Halogen-free Guideline

HDP User Group International, Inc. Halogen-free Guideline Date 08-25-2008 Rev A

Halogen-free Guideline

© 2008 HDP User Group International, Inc. All rights reserved

HDP User Group International, Inc Page 1 of 67

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Halogen-free Guideline

Date: August 25, 2008

Table of Contents 1.0 Preface .................................................................................................................................... 6 2.0 Halogen-free Drivers ............................................................................................................... 6 3.0 Halogen-Free Flame Retardants .......................................................................................... 12 4.0 Definition of “Halogen-free” Electronic Products and Product Categories ............................ 23 5.0 Printed Circuit Board Assembly (PCBA) Materials ............................................................... 24 6.0 Cable Base Materials ............................................................................................................ 39 7.0 Mechanical Plastics .............................................................................................................. 48 8.0 Optical Films, Tapes and Adhesives ..................................................................................... 53 9.0 Thermoplastic Films in Electrical & Electronic Applications .................................................. 58 10.0 Industry Enablement Activities to Transition to Halogen-free Products .............................. 62 11.0 Appendices ......................................................................................................................... 65

ACKNOWLEDGEMENTS The HDPUG Halogen-Free Guideline represents the efforts of 25 companies that contributed to its development over a 15 month period. Such a comprehensive and informative Guideline would not have been possible without the extensive expertise and collaboration by all who parti-cipated. The project included representatives from the following organizations:

INTERNATIONAL R




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1.0 Preface

Flame-retarded plastics are commonly needed to meet strict fire safety codes for electronic equipment. Certain halogenated compounds, such as brominated flame retardants, or BFRs, are used as flame retardants in a variety of applications including thermoplastics, insulation ma-terials, component mold compounds, solder masks and printed circuit board laminates. In addi-tion, polyvinyl chloride, or PVC, a resin that contains the halogen (chlorine), is a commonly used base resin for certain cable jacketing. However, concerns have arisen that these materials may pose certain risks to health or the environment particularly at end-of-life. In response, “halogen-free” alternative materials are either available on the market or in development. At this time, there is little knowledge on the performance characteristics, supply chain readiness, costs and/or environmental and human health aspects of certain “halogen-free” alternative materials. This Guideline is intended to address this knowledge gap to enable companies to make more informed decisions with respect to material substitution.

2.0 Halogen-free Drivers

2.1 Legislative Requirements

There are no general legal restrictions on the use of all halogenated flame retardants in any part of the world but laws have been enacted in the past several years that restrict the use of certain halogenated flame retardants in certain applications. Nonetheless, there has been considerable discussion and public concerns about flame retardants in general and halogenated flame retar-dants in particular. The focus on halogenated flame retardants possibly started with the obser-vation that polychlorinated biphenyls (PCBs) and polybrominated biphenyls (PBBs) had an ad-verse effect on the environment due to their persistence, toxicity and ability to bioaccumulate. Brominated flame retardants (BFRs) became a topic of environmental concern in the early 1990‟s, when it was discovered that some BFRs could form halogenated dioxins and furans when subjected to extreme thermal stress, such as might occur during an accidental fire or dur-ing uncontrolled combustion. The severity of the concern is a matter of debate, because the amount of dioxins formed depends on the combustion conditions and only some of the products formed, those containing halogen in the 2,3,7,and 8 positions, are of toxicological interest. The environmental and health properties of not only BFRs, but also other types of flame retardants have been studied extensively. The most widely used organic flame retardants (brominated and phosphorus based) have also become the subject of European Union-administered risk as-sessments. A European Union Risk Assessment has concluded that the most widely-used brominated flame retardant, tetrabromobisphenol-A (TBBPA), does not present a risk to human health or to the environment when used as a reactive-type flame retardant, such as in printed wiring boards. More recently, the fate of electronic waste material, which could contain Pb, Cr (IV), Cd, Hg, PBBs and PBDEs (polybrominated diphenylethers), has gained increasing political attention and has led to the WEEE and RoHS Directives in Europe. Other regions of the world have or are about to follow with similar legislation. The following table summarizes the relevant regulatory activities:


Europe:

RoHS As from 01-July-2006 the European “Directive 2002/95/EC of the European Parliament and of the Council of 27 Janu-ary 2003 on the restriction of the use of certain hazardous substances in electrical and electronic equipment” (RoHS) bans the use of lead (Pb), mercury (Hg), hexavalent chro-mium (CrVI), Cadmium (Cd), polybrominated biphenyls (PBB) and polybrominated diphenylethers (PBDE) in elec-tric and electronic equipment. Maximum allowable concen-trations per “homogeneous material” are 0.01 % by mass for Cadmium and 0.1 % for all others (2005/618/EC). De-ca-BDE was exempted from RoHS by 2005/717/EC pub-lished in Oct-2005. The State of Denmark and the Euro-pean Parliament have challenged the exemption before the European Court of Justice, which ruled in April 2008 that, due to procedural irregularities, the exemption must be lifted and DecaBDE again be included in the restricted substances under RoHS for electronic products placed on the EU market on or after July 1, 2008. In general, all ex-emptions need to be re-examined every four years. The European Commission started stakeholder consultations at the end of 2007 and commissioned studies to examine the existing 28 exemptions under RoHS and to determine if other potentially hazardous substances should be added to the list.

Penta- and Octa-BDE

Directive

The Directive 2003/11/EC prohibits the marketing of any substance, preparation or article containing Penta- or Octa-BDE as of 15-Aug-2004, also with a limit of 0.1 % by mass.

Risk Assessments Extensive human health and environmental testing has been performed on various brominated flame retardants, and to a lesser extent on other types of flame retardants. The above amendment to the marketing and use Directive (Penta- and Octa-BDE Directive) was a result of the Euro-pean Risk Assessment of these substances..The two pri-mary brominated flame retardants used in Electronic prod-ucts that have gone through the European Union Risk As-sessment are Decabromodiphenyl ether (Deca-BDE) and Tetrabromobisphenol A (TBBPA). Results of these Risk Assessments confirm that Deca-BDE has no risks identi-fied and is safe for continued use, and TBBPA does not present a risk to human health or the environment in its reacted form, such as in PWBs. Concerns about environ-mental impacts of when TBBPA is used as an additive to ABS plastics are confined to one plant, which have been addressed by imposing an environmental permit require-ment Other FRs with relevance for E&E applications under risk assessment are hexabromocyclododecane (HBCD) and antimony trioxide (ATO). http://ecb.jrc.it/existing-chemicals/risk-assessment/

http://ecb.jrc.it/existing-chemicals/risk-assessment/


WEEE The Directive 2002/96/EC of 27 January 2003 on waste electrical and electronic equipment was introduced in Eu-rope to enhance the recycling of E&E waste and set up appropriate industry-financed recycling schemes in Mem-ber States. Flame retardants are affected by the first part of Annex II which lists materials and parts that must be re-moved and treated separately before further treatment of the WEEE: […] plastic containing brominated flame retar-dants. Printed circuit boards of mobile phones generally, and of other devices if the surface of the printed circuit board is greater than 10 square centimeters, must also be removed and treated separately irrespective of the type of any flame retardant contained. These separation require-ments are very costly in practice and a revision is under discussion.

National legislation Sweden had issued a ban of Deca-BDE since 01-Jan-2007 in textiles, furniture and some cables with the exception of E&E and automotive applications. However, this regulation has been withdrawn. The Norway Pollution Control Authori-ty (SFT) has proposed bans on 10 chemicals, including medium chain chlorinate paraffins (MCCPs) and HBCCD. TBBPA has been removed from the list proposed for re-strictions. Norway adopted a ban on Deca-BDE in Decem-ber 2007.

REACH The Regulation 1907/2006/EC of 18 December 2006 “con-cerning the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH), establishing a Euro-pean Chemicals Agency, […]” comprises the new Euro-pean chemicals law entering into force on 01-June-2007. All chemicals marketed in quantities above 1 ton per year need to be registered and information on toxicological and environmental properties needs to be supplied depending on production volumes. REACH also refers to “chemicals in articles”, so that under certain conditions flame retar-dants (like any other substance) which are imported in fi-nished goods like computers or cars can be affected.

North America:

California RoHS The Electronic Waste Recycling Act of 2003 created Cali-fornia‟s RoHS law, which is codified in section 25214.10 of the Health and Safety Code. The California RoHS law re-quired the Department of Toxic Substances Control (DTSC) to adopt regulations by January 1, 2007 prohibiting “…an electronic device from being sold or offered for sale in this state if [it] is prohibited from being sold or offered for sale in the EU [under] Directive 2002/95/EC … due to the presence of certain heavy metals.” On January 1, 2007, DTSC‟s regulations, also known as the California RoHS regulations, became effective. The California RoHS regula-


tions only prohibit the heavy metals Pb, Hg, Cd and CrVI (same as EU-RoHS) in covered electronic devices – halo-genated flame retardants are not restricted. Other States have considered similar legislation; a Federal regulation has also been discussed.

Canada In December 2006, the Canadian government amended the list of “Toxic Substances to Schedule 1 to the Canadian Environmental Protection Act, 1999” to include all bromi-nated diphenylethers, including Deca-BDE. In July 2008, the Canadian government issued “Polybrominated Di-phenyl Ethers Regulations” [SOR/2008-218] which ban the production of all PBDEs in Canada. With the exception of Deca-BDE, no PBDEs may be produced, imported or mar-keted in Canada. No restrictions apply for finished imported articles containing PBDEs. Environment Canada is consi-dering further measures on Deca-BDE. http://canadagazette.gc.ca/partII/2008/20080709/pdf/g2-14214.pdf

China:

RoHS The “Administrative Measure on the Control of Pollution Caused by Electronic Information Products” (China-RoHS) entered into force in March 2007. The legislation is appli-cable to import, manufacture and sale of products in China, but products for export are specifically excluded. Many product types that are not within the scope of the EU RoHS are within the scope of the China RoHS and vice versa. In addition, the initial disclosure, declaration and exemption requirements for a RoHS certificate are different from the EU RoHS. However, the same six hazardous substances are regulated (lead, cadmium, chromium(VI), mercury, po-lybrominated biphenyls and polybrominated diphenyl eth-ers, with the exception of deca-BDE), but the Chinese list can be amended in the future. More detailed materials test-ing is required in the China RoHS and is accepted only if performed by certified Chinese labs. A table in the product documentation must identify which hazardous substances are contained and which components are present. http://www.aeanet.org/chinarohs

2.2 Market Driven Requirements

Ecolabels

Ecolabels have been introduced since the 1970‟s as voluntary measures in order to promote environmentally conscious products. The idea is that the consumer can make an informed deci-sion for such products, if they are labeled according to an accepted and respected scheme. Worldwide, today, there are about 25 ecolabel organizations and schemes (see: http://www.gen.gr.jp ). Even in Europe there are several national labels in addition to the EU

http://www.aeanet.org/chinarohs

http://www.gen.gr.jp/


flower. Other parts of the world have followed and developed their own systems. Ecolabels were quite successful in product areas which consumers easily link to environmental effects, e.g. re-cycled paper, solvent versus water based paints. Product categories with less evident differen-tiation of environmental effects, such as consumer electronics, have gained much less attention. Ecolabels are specifically designed to go beyond legal requirements like RoHS, because they are meant to endorse the “best in class” and advance environmental benchmarks. Judgments as to what constitutes “best in class” or what constitutes advancement in environmental protec-tion are subjective to a certain degree. Many ecolabel systems do not approve the use of specific or all halogenated flame retardants in their criteria for electronic products (e.g. EU label, Blue Angel in Germany, Nordic Swan in Scandinavia, TCO in Sweden). Though these labels may not be based on a legal ban of a given list of substances, ecolabels will not be used on products that contain the substances above a given threshold or criteria. For example, though risk assessments has been provided to ap-prove the use of TBBPA, it has been targeted for removal by some ecolabel requirements. Even with the labeling requirements, exemptions for TBBPA such as when used as a reactive flame retardant in epoxy printed wiring boards or in small parts of less than 25 or 10 grams (mass dependent on label) are allowed. In addition, some ecolabel organizations demand flame retardants used in products are declared to them even on a confidential basis.

In recent years, most European ecolabel schemes have adopted a different approach to restrict-ing flame retardants in their criteria: they prohibit the use of flame retardants with certain “risk phrases” which are defined by chemical regulations in Europe, see Appendix 1. The term “risk phrases” is misleading, because in fact they are hazard statements (see examples in bullet points below). In Europe, various stakeholders are currently (2008) discussing a harmonization of the treatment of flame retardants within the different ecolabel systems.

Industry Declaration systems of environmental performance (eco-declarations)

Because of short product life cycles and the need to apply for each ecolabel separately, the industry has developed voluntary declaration systems which allow them to present environmen-tally relevant information in a standardized and traceable manner, so that a purchaser can make an informed decision. In 1996, the Swedish IT industry association decided to establish a self-declaration system, the IT Eco Declaration. The declaration now covers about 80% of customer inquiries, and includes reasonable and IT industry accepted criteria found in the most important European Eco labels including plastics and some of their additives including flame retardants (see www.itecodeclaration.org). The IT Eco Declaration resembles a questionnaire, there are no fail-pass criteria. Questions related to flame retardants are as follows:

Compliant with EU-RoHS substance restrictions?

All cover/housing plastic parts >25g are halogen-free?

All printed circuit boards (without components) >25g are halogen-free?

Chemical specifications of flame retardants in cover / housing plastic parts >25g accord-ing ISO 1043-4?

Chemical specifications of flame retardants in printed circuit boards (without compo-nents) >25g according ISO 1043-4?

http://www.itecodeclaration.org/


Plastic parts >25g are free from flame retardant substances/preparations above 0.1% classified as R45 (may cause cancer)/46(may cause heritable genetic damage), R50(very toxic to aquatic organisms)/51(toxic to aquatic organisms)/53(may cause long-term adverse effects in the aquatic environment) and R60/(may impair fertility)/61(may cause harm to the unborn child) (67/548/EEC)?

Note that these voluntary declarations are based on customer requests, mainly expressed in public tenders. In the USA, an “Electronic Product Environmental Assessment Tool” (EPEAT) was developed and published as IEEE 1680 standard. By declaring product properties according to this stan-dard and registering with the Green Electronics Council (GEC) a declaration system is set up which ranks compliant products in categories of bronze, silver and gold. There are two types of criteria: required ones are a must, optional ones can earn you additional ranking points. Criteria relating to flame retardants are:

Compliant with EU-RoHS substance restrictions (required)

No Short Chain Chlorinated Paraffins (SCCPs) (required)

Large plastic parts (> 25 g) free of flame retardants classified as hazardous under Euro-pean Council Directive 67/548/EEC (optional)

www.epeat.net

Public procurement Public procurement has become a major topic in Europe, because public institutions have de-fined policies of “greening their supplies”. For example, cities have joined in a global network on green procurement, see www.cities21.com/iclei.htm . The European Commission has published a „Buying Green‟ handbook on environmental public procurement in October 2004 (http://europa.eu.int/comm/environment/gpp/ ) as well as a new publication on green public procurement in July 2008 (http://ec.europa.eu/environment/gpp/index_en.htm) including a prod-uct sheet for office IT equipment1 which refers to certain ecolabel criteria and Risk Phrases from the European chemicals‟ regulations. A similar product sheet of the United Nations Environment Programme (UNEP) specifically rewards products which do not contain brominated flame retar-dants2.

Ecolabels and their restrictions on certain flame retardants can come into play, because EU Public Procurement Directives 2004/17/EC article 35 and 2004/18/EC article 23 explicitly allow for the use of the underlying specifications of ecolabels, provided:

the specifications are appropriate and covered by the contract

these are based on scientific information

the eco-labels are adopted with participation of all stakeholders (not met by all labels)

they are accessible to all interested parties (some private labels might not be allowed). It is however not allowed to

request eco-label certified products

1 http://ec.europa.eu/environment/gpp/pdf/toolkit/office_IT_equipment_GPP_product_sheet.pdf

2 http://www.iclei-europe.org/index.php?id=6608&no_cache=1, [email protected],

criterion C4.3

http://www.epeat.net/

http://www.cities21.com/iclei.htm

http://europa.eu.int/comm/environment/gpp/

http://ec.europa.eu/environment/gpp/index_en.htm

http://ec.europa.eu/environment/gpp/pdf/toolkit/office_IT_equipment_GPP_product_sheet.pdf

http://www.iclei-europe.org/index.php?id=6608&no_cache=1

mailto:[email protected]


be fully compliant with a certain eco-label as some criteria are not related to the pur-chased product

relate to general management principles and ethical and similar issues. From mid 2005 an increasing number of EU Member States ‟cut and paste‟ ecolabeling criteria into the call for tender documents and use these as the environmental specifications that sup-pliers are evaluated and rated against, and in some cases even be excluded.

3.0 Halogen-Free Flame Retardants

The term "halogen-free" is often used as if it covered a class of products having all the same characteristics and properties. Although there are 5 halogens contained within the Periodic Ta-ble of Elements, the two focused on for “halogen-free” or “low halogen” requirements are Bro-mine (Br) and Chlorine (Cl) and in particular the BFR and PVC material sets that have historical-ly been used within industry. However, a wide range of chemistries is behind these flame retar-dants3 4 which therefore have different properties and characteristics.

Fig. 2.1: Diagram of the main factors which determine the choice of a flame retardant.

Changing one of the factors often has an effect on the others as well. A flame retardant should be carefully chosen not only for flame retardancy effectiveness but also for its effects on the overall properties of the polymer system. Two considerations should also be made when identifying possible flame retardants: the mode of flame retardancy and its

3 Weil and Levchik (2004): A Review of Current Flame Retardant Systems for Epoxy Resins

Journal of Fire Sciences.2004; 22: 25-40 3 Doering et al. (2007): Halogen-free flame retardants for electric and electronic applications.

Karlsruhe Research Centre, Germany. www.halogenfree-flameretardants.com

flame retardant

compatibility with

polymer and

processing

fire safety

toxicology and

environmentcost

http://www.halogenfree-flameretardants.com/


means of interaction in the polymer system. The mode of flame retardancy can be either physi-cal or chemical. Possible physical interactions by a flame retardant include cooling the polymer below combustion temperatures, forming a char layer over the polymer to exclude oxygen in the system (intumescence), and diluting the amount of fuel in the system by the presence of an inert material. Chemical interaction includes mechanisms taking place in the gas phase, interfering and prohibiting the continuation of the combustion process, and mechanisms occurring in the solid phase, which can either break down the polymer or chemically form a carbon layer on the surface. In general, chemical interactions have been found to be most effective for fire retardan-cy. Also important is the additive or reactive interaction of the flame retardant with the polymer sys-tem. The interaction of the flame retardant with the resin material affects not only polymer prop-erties but also processing and environmental issues. Reactive flame retardants are chemically built into the polymer structure and thereby provide a consistent structure for fire retardancy and substrate properties. TBBPA is an example of a reactive brominated flame retardant widely used in PWB manufacture, whereas DOPO (see below) is an example of a phosphorus-based FR. Additive flame retardants are incorporated by mechanical means and need to be uniformly dispersed in the system. There is also the possibility of “blooming” out of the system. Inconsis-tent properties, including flame retardancy, could result, as well as adverse environmental ef-fects. There are, however, several effective products based on additive flame retardants that do not suffer from these potential problems. Non halogenated products include three main chemical families:

Phosphorus based chemicals: their flame retardant mechanism operates primarily in the solid phase of a polymer, by removing water and creating a carbon-rich char on the surface of the polymer. This FR mechanism means that there is usually very low smoke density and no release of corrosive, acid gases into the gas phase (like HCl or HBr for halogenated products). On a weight-% basis, phosphorus is also more effective than bromine: UL 94 V-0 is achievable with a final P-content of 2.5 to 4 %.

Nitrogen based compounds work differently and have an effect both in the gas phase (by releasing non flammable nitrogen, which dilutes the oxygen concentration) and in the condensed phase, especially when combined with phosphorus compounds, helping the formation of a more stable, cross-linked char.

Mineral flame retardants include mainly aluminium trihydroxide (ATH) and magnesium dihydroxide (MDH). Both share the same mechanism: when exposed to the heat, they will decompose to release water vapor, which will cool down the system, dilute flamma-ble gases in the flame zone and create an oxide layer at the surface. MDH has a higher temperature of decomposition than ATH and has found some limited use in engineering thermoplastics. Although these compounds are the most environmentally friendly, they provide processing difficulties due to their additive nature and the high loadings usually required to achieve the necessary fire performance. With proper dispersing (use of high shear mixing and wetting agents) and utilizing the proper particle size, these compounds can be used effectively.

Other mineral FRs include Boehmite (alumina monohydrate, more temperature stable but less effective than ATH) and borates, which can only be used in synergy with more powerful FRs, namely phosphorus and/or nitrogen based ones. Silica (SiO2) is some-times referred to as a flame retardant. However, it is just an inert filler which dilutes the combustible polymer and does not undergo any chemical reactions in a fire.


Halogen-containing flame retardants are effective due to their interference with the radical chain mechanism in the gas phase combustion process. Bromine and chlorine are especially favored due to ideal timing for interference attributed to the particular bonding strength to carbon. Other halogens are not ideal, as they do not interact at the appropriate time in the combustion process because of bonding to carbon that is too strong (carbon-fluorine) and too weak (carbon-iodine). This chapter will only discuss the chemistry and technology of halogen-free flame retardants. For an evaluation of their environmental and health properties please refer e.g. to the US-EPA project on “Flame Retardants in Printed Circuit Boards” (http://www.epa.gov/dfe/pubs/projects/pcb/index.htm) and the website www.halogenfree-flameretardants.com which presents some fact sheets on flame retardants. Further general in-formation on flame retardants, with links to producing companies: www.flameretardants.eu

3.1 Halogen-Free Flame Retardants for Laminate Materials

Not all halogen-free additives are able to fulfill all technical requirements for CCLs, and usually, it is necessary to use a combination of different chemicals to cover the requirements of the vari-ous applications, which are defined by different criteria or industry standards (e.g. automotive (specific thermal cycles), broadband telecom, buried capacitance, burn in board, high Tg). A wealth of development work took place over the last years, so that some halogen-free CCLs are in their 2nd or 3rd generation already. Here is an overview of the currently used systems:

Aluminum Trihydroxide ATH Al(OH)3 is a low cost filler that begins to break down at 180°C to 215°C, depending on the type of ATH. The decomposition is an endothermic (1051 J/g) reaction that releases water and performs all three physical interactions for fire retardancy: cooling of the polymer, form-ing an insulation layer over the substrate absorbing smoke particles, and diluting the fuel remaining in the system. The disadvantage of using this material alone is that very high levels of loading are often required to achieve the desired flame retardancy, and consequently, ATH is not used as a stand-alone FR. It is typically used in combination with halo-genated or non-halogenated flame retardants to decrease the loading requirement. At moderate loadings, ATH can impart improved physical properties, such as reduced thermal ex-pansion in the z-axis, to the laminate. New high thermal sta-bility grades of ATH, such as Martinal TS-702, decompose about 15°C higher than standard grades and can be used in some applications requiring higher thermal stability. ATH is supplied e.g. by Albemarle and Nabaltec.

Al(OH)3

http://www.epa.gov/dfe/pubs/projects/pcb/index.htm



http://www.flameretardants.eu/


Alumina monohydrate (boehmite) can replace ATH in applica-tions requiring exceptionally high thermal stability. Boehmite is thermally stable to 340°C. Boehmite is a less efficient FR than ATH and is typically used in novolac epoxy resins in combination with other FRs. Boehmite is available e.g. from Nabaltec.

AlOOH

Magnesium (di-)Hydroxide MDH decomposes in the same endothermic (1315 J/g) manner as ATH, yet at a higher tem-perature (330°C). It forms an insulating layer during combus-tion. MDH is typically not used in PWBs, because of its reac-tivity during the acid etching process. It could be potentially used with a base etching system.

Mg(OH)2

DOPO (Dihydro oxaphosphaphenanthrene) is a cyclic hydro-genphosphinate containing a P-H bond. It is mono-functional, but several modifications are possible, which allow DOPO to be grafted to C=C linkage or reacted with epoxy groups. To-day, DOPO can be regarded as the major building block used to make phosphorus containing epoxy resins (Tg up to 150°C). DOPO is commercially available from different suppliers and global capacities have consequently increased over the past 2 years to respond to the increasing market demand from PWB. DOPO itself is mono-functional, but the derivative shown below (called DOPO-HQ or HCA-HQ) is bi-functional. The higher price of DOPO has been a limiting factor in its growth. Major suppliers are Sanko Chemical, JP and Schill & Sei-lacher, D

DOPO

HCA-HQ

Organophosphates such as triphenyl phosphate, resorcinol diphenylphosphate (RDP) and bisphenol-A diphenylphos-phate (BDP) have found use as non-halogen flame retardants for electronic enclosures made, primarily, from alloys such as PC/ABS and PPE/HIPS. In Japan, an aryl phosphate mar-keted as PX 200 by Daihatchi has found some application in PWBs due its good hydrolytic stability and heat resistance. Other aryl phosphates like triphenyl phosphate (TPP) are more susceptible to degradation, but mentioned as well in the literature for PWB applications. These phosphates are com-monly used in combination with ATH. Major suppliers of aryl phosphates are Chemtura, Supresta, Lanxess, Daihachi and Albemarle.

Structure of PX 200 and

triphenyl phosphate

(TPP).

P OO

H

P OO

OHOH

O

OP

O

O

OP

O

OO

O

OP

O

O

http://www.nabaltec.com/

http://www.sanko-inet.co.jp/hca.html

http://www.schillseilacher.de/

http://www.schillseilacher.de/

http://www.chemtura.com/

http://www.supresta.com/

http://www.lanxess.com/

http://www.daihachi-chem.co.jp/eng/index.html

http://www.albemarle.com/


An oligomeric aryl phosphonate is marketed by Supresta un-der the name of Fyrol PMP. Due to its hydroxyl groups it can react into the polymer and act as a curing agent for epoxies. It is recommended to be used in combination with ATH. PMP is reported to have a high thermal stability. (high Tg, pressure cooker test).

Structure of Fyrol PMP

Metal phosphinates: They were primarily developed for engi-neering thermoplastics (glass filled polyamides and polyest-ers), but can also be used in rigid and flexible PWB applica-tions. Key aspects are a high phosphorus content (> 23 %), no affinity to water and a good thermal stability (330°C) which makes them compatible with lead-free soldering operations. Electrical properties show virtually no impact on Dk / Df even at frequencies well above one GHz. However, due to a low density and high surface area, phosphinates can not be used alone and therefore, they are usually combined with modified (phosphorus or nitrogen containing) epoxy resins, with N-synergists such as melamine polyphosphate or blends with other polymers (cyanate esters, benzoxazines, PPE or oth-ers). The “Lewis-acidity” of some metal phosphinates requires an adjustment of the epoxy resin processing chemistry to achieve a desired resin Tg and effective cure rate. Available from Clariant

General structure of

Phosphinates

Melamine polyphosphate (MPP) is an additive-type flame retardant based on a combination of phosphorus and nitrogen chemistries. It is an effective synergist with high thermal sta-bility (355°C) suitable for lead-free processing. Melamine po-lyphosphate will not change the performance characteristics of the formulation especially the Tg or the electrical properties (tested in standard epoxy laminated for-mulations at 1GHz). MPP functions best in halogen-free flame retardant blends to lower load levels of other ingredients which are necessary to achieve UL-94 V0.

Structure of melamine

polyphosphate

(HO)n O P

O

CH3

O O P

O

O

CH3

(OH)m

p m,n = 0 or 1

P

R 1

R 2

O

O

n

_

M n+

http://www.supresta.com/

http://www.exolit.com/


In Japan, high purity grades of phosphazene are reported to be commercially used. However, their high cost (up to 40 U$/kg) seems to restrict their use to a limited number of nich-es. Several patents tend to confirm the technical suitability in various formulations.


phosphazenes

Organophosphorus anhydrides: Anhydride molecules like oxaphospholane (2-methyl-2,5-dioxo-1,2-oxaphospholane) may have potential for use as reactive components for suita-ble epoxy resins and/or as a curing agents. Thanks to a high phosphorus content (23%), it is very effective as demonstrat-ed by a V-0 rating (UL 94) with a final P-content as low as 2,5 %. It is available from Clariant

Structure of oxaphos-

pholane

Phenylphosphonic acid esters: A number of patents suggest that it is possible to graft phosphorus molecules into the epoxy backbone through the reaction of diglycidyl ester of phenylphosphonic acid. The modified epoxy resins show ac-ceptable electrical and mechanical properties, which makes them suitable for use in electronic applications. The raw ma-terials are available from different suppliers, suggesting that this technology is commercially available. Further molecules like Amgard V19 from Rhodia (www.rhodia.com, a cyclic di-phosphonate) are also reported to give V-0 rated laminate showing a Tg of 145-150°C and passing the Pressure Cooker Test. The market relevance of these technologies can not be assessed yet.

Red Phosphorus has been used as an additive and imparts fire retardancy by forming a protective char due to phospho-rus‟ affinity for oxygen. However, red phosphorus can form trace amounts of toxic phosphine and acids, particularly un-der conditions of higher temperatures and humidity. Because these acids can cause corrosion and electrical problems, red phosphorus manufacturers like Clariant recommend not to use it for PWB applications. When there is a request for “phosphorus-free” flame retardants, what is meant is really “free of red phosphorus”, because of the problems mentioned above.

Since many potential halogen-free FRs are of a filler type, and the amount of fillers is limited per se, the role of modified resins must be emphasized. Besides traditional modifications of epoxies with DOPO, numerous variations are possible. In addition to the epoxy chemistry, many blends or pure systems are used or could be used. These include long known cyanate esters (CE), bismaleimide triazine (BT), polyphenylene ether (PPE) or the recently developed benzoxazines (Azyral from Huntsman) which are commercially available since 2006. These benzoxazines can


http://www.rhodia.com/

http://www.huntsman.com/


be homo-polymerized leading to high Tg (200°C), and reach UL 94 V-0 without additives. When combined with epoxies, they may offer a more balanced price-performance profile; the epoxy-containing solution will typically need an FR booster. Overall, a range of different resin chemistries and flame retardant systems is now becoming available as a “halogen-free toolbox” which the CCL and PWB manufacturers can use to create optimized solutions for various applications. Efforts to establish performance reliability of these new CCL and PWB products are ongoing5.

3.2 Halogen-Free Flame Retardants For Enclosure Resins

Electronic enclosures are a market segment which includes televisions, desktop or notebook computers, monitors, printers, copiers, household appliances, etc. These housings are made of different types of polymer resins and may or may not contain flame retardants. Common poly-mer resins are high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymers (ABS), an ABS alloy with polycarbonate (PC/ABS) and a HIPS alloy with polyphenylene ether (PPE/HIPS). Another plastic resin alloy that is increasingly being used in high-end TV enclo-sures is the alloy of ABS with poly(methyl methacrylate) (PMMA). Not all flame retardants work in all polymer systems. Plastics suppliers need to optimize resin performance vs. fire safety to meet the most stringent OEM performance and various regional regulatory requirements. HIPS and ABS A suitable halogen-free flame retardant for these resins has been the subject of research for many years by resin and FR manufacturers, and no efficient and cost effective products have been identified. Both HIPS and ABS resins are non-charring polymers that require an effective vapor-phase active flame retardant, and only halogenated flame retardants can meet the most stringent UL-94 V-0 rating. Condensed-phase flame retardants are not effective in these resins, so commercially available phosphorus-based flame retardants cannot be used. For some audio and game equipment, a less stringent UL-94 V-2 requirement can be met by the use of phos-phorus flame retardants in ABS resin. Aromatic phosphate esters (see table) derived from phe-nol (TPP), resorcinol (RDP), Bisphenol-A (BPADP or BDP) and dimethylphenol (PX-200) are the halogen-free products available. Formulators need to adjust resin properties to compensate for the plasticizing effect of the phosphates. With a switch to alloys of HIPS and ABS, suitable halogen-free flame retardants for stricter fire safety requirements are available. PC/ABS and PPE/HIPS Polycarbonates (PC) and polyphenylene ethers (PPE) are inherently less flammable polymers, but they are more expensive than commodity resins. They are tough materials and require very high processing temperatures. They cannot be used alone to produce very intricate enclosure designs and require other additives to meet the appropriate mechanical and flow properties. Resin producers have combined the inherent flame resistant property of these resins with the good processing capabilities of ABS and HIPS resins into two alloys: PC/ABS and PPE/HIPS. Because of the high PC and PPE content of these less flammable alloys, halogen-free flame retardants can be used to produce V-0 rated materials. Aromatic phosphate esters derived from

5 See iNEMI project on technical performance of halogen-free CCL, expected to finish in mid

2008; HDPUG initiated a project on reliability of halogen-free components in late 2007.


phenol (TPP), resorcinol (RDP), Bisphenol-A (BPADP) and dimethylphenol (PX-200) are the halogen-free solutions available. Of the two alloys, PC/ABS is most widely used for flame-retardant electrical and electronic enclosures, and BPADP is a preferred flame retardant be-cause of high hydrolytic stability compared with the competitive RDP product. TPP has been nearly phased out because of the unfavorable health & environment profile and some perfor-mance deficiencies.

In PC/ABS blends, the required loadings of phosphate ester flame retardant depend on the ratio of PC and ABS. A phosphate concentration of 8-15% is typically used in 75:25 PC/ABS blends to achieve an UL-94 V-0 rating. Approximately 0.5% PTFE is also used to retard dripping. A phosphate concentration of 10-20% is used in the typical 30:70 PPE/HIPS blend. The aryl phosphates, RDP and BPADP, are large, oligomeric molecules and therefore do not have a propensity to migrate from the polymer.

PMMA/ABS The alloy of ABS with poly(methyl methacrylate) is increasingly being used in enclosures, espe-cially high-end flat panel TV displays. PMMA is a very flammable polymer and is very difficult to flame retard. No successful flame retardant is available for this alloy without sacrificing some aesthetic and mechanical properties of the resin, so some OEM‟s have been using this alloy only for markets where there is no strict flame retardant requirement.

Triphenyl Phosphate has a phosphorus content of 9.5 % and is a solid with a melt-ing point of 49 °C. It has the lowest thermal stability of the phosphates presented here.

O P O

3

Resorcinol bis (diphenyl phosphate) (RDP) is a liquid flame retardant with a phos-phorus content of 10.8 %. It is less plasticizing than TPP.

O

O P

O

O P O

O O n

n = 1-7

O


Bis-phenol A bis(diphenyl phosphate) (BDP) is a liquid flame retardant with a phosphorus content of 8.9 %. Less plasticizing than TPP.

3.3 Halogen-Free Flame Retardants for Connectors and Mechanical Plastic Parts

For connectors and mechanical parts, often engineering thermoplastics like polyamides, po-lyesters or polycarbonates are used because of good toughness and rigidity. In connectors this enables the design of so-called “living hinges” that need to be opened and closed easily without breaking, whereas toughness is particularly important in snap fits for terminal blocks to allow easy assembly. Polyamides typically also perform well regarding heat ageing, which is impor-tant because of the increasing temperatures due to miniaturization of electrical components. Polyesters like Polybutylene terephthalate (PBT) on the other hand offer the benefit of good dimensional and hydrolytic stability. The following table presents an overview of flame retar-dants used for these polymers:

Metal phosphinates: These are well suited for glass fibre reinforced polyamides and polyesters and are added at levels of about 20 % - often combined with nitrogen synergists. Key aspects are a high phosphorus content (> 23 %), no affini-ty to water and a good thermal stability (up to 330°C) which make them compatible with lead-free soldering operations. Available from Clariant.


Phosphinates

Melamine Polyphosphate (MPP) is especially suited for glass fibre reinforced polyamide 6,6, where it is added at ca. 25 % for UL 94 V0 per-formance. It has a good thermal stability (ca. 300 °C). MPP is often used as synergist in combina-tion with phosphorus FRs in glass filled PA and PBT MPP is supplied e.g. as Melapur 200 from Ciba (application patent for M200 for GF PA) or Budit 3141 from Budenheim.

melamine polyphosphate

P

R 1

R 2

O

O

n

_

M n+

n

O O P

O

O

O P

O

O

O

n = 1-2


http://www.cibasc.com/melapur


Melamine cyanurate (MC) is especially suited for unfilled and mineral filled polyamides. UL V0 can be achieved with 6 to 15 % in unfilled PA and up to 20 % for UL V2 in low glass filled PA 6. MC is also used as synergist in combination with phos-phorus FRs. It is available from Ciba, Budenheim and others.

melamine cyanurate

Red phosphorus is a polymeric form of elemental phosphorus. It is used mainly in glass fibre rein-forced PA 6,6 at 5 to 8 % addition level. Due to Its inherent colour, compounds are limited to red or black colours. Since pure red phosphorus powder is highly reactive and even flammable, special workplace precautions have to be taken. Major suppliers have also developed delivery forms which are easier and safer to handle (e.g. masterbach-like concentrates, micro-encapsulated versions). Available from Clariant, Italmatch and others.

generic structure of red

phosphorus

Aryl phosphates and phosphonates: their main use is styrenic blends at 10 to 20 % addition level for UL 94 V0. They are often used as co-components in FR-formulation. Their limitations are possible plasticizing effects and a certain volatility at high processing temperatures. Bloom-ing can have a negative influence on electrical properties. See enclosures chapter above for more information on aryl phosphates. They are available e.g. from Supresta, Lanxess, Albe-marle, Chemtura.

e.g. RDP

Magnesium hydroxide (MDH): high filler levels of about 45 to 50% are necessary to reach UL 94 V0. Because of its limited temperature stability, it is mainly used in low glass fibre PA 6. MDH is available from Albemarle (Martinswerke), Nabal-tec, and others

Mg(OH)2

3.4 Halogen-Free Flame Retardants for Cable Resins

The choice of polymer (thermoplastic, thermoset, thermoplastic elastomers) and flame retardant system depends on the physical, chemical and electrical properties needed to meet specific cable design requirements. Traditionally, cables have been the domain of the thermoplastic po-lymer polyvinyl chloride (PVC). For a variety of reasons, cables based on polyolefins and ethy-lene vinyl acetate (EVA) are now replacing PVC in many applications. Polyolefins, however, are

O P O

O

O

O P O

O

O

n = 1...7


much more flammable than PVC and need fire retardant additives to meet safety requirements. Metal hydroxides are commonly used, because they represent the most economic solution, even when high loadings are necessary to achieve the required classification. Other commonly used FR additives are:

Flame retardant Polymers

Aluminium-tri-hydroxide (ATH) Magnesium-dihydroxide (MDH) Boehmite (AlOOH) (aluminium-oxide-hydroxide)

Low density polyethylene Ethyl vinyl acetate Polyolefins

Phosphorus flame retardants Used in fire resistant coatings for cables

Zinc borate Synergist with ATH

Phosphate esters (eg. Tricresyl Phosphate TCP)

Rubber

Melamine cyanurate, melamine phosphate,

Polyamides Polypropylene

To meet most critical flame test standards, the wire insulation in cables must pass the stringent UL VW-1 vertical flame test. Wire insulation containing halogen based compounds can easily meet this test. The non-halogen systems based on mineral fillers and nano clays can pass the VW-1 flame test if used at very high filler loadings. At high loadings, the physical and electrical properties of the cable may be significantly compromised. Consequently, in several applications, particularly those involving a wet environment, there is an increasing trend to use both haloge-nated and mineral based flame retardants. This gives the best balance of physical and flame performance along with reduced smoke and corrosive gases. Another option is to maintain physical and electrical properties is to use surface-coated mineral fillers. The fatty acid coated grades help lower compound viscosity and increase throughput rates. The vinyl-silane coatings help improve physical and electrical properties and are generally used for insulation compounds to meet wet electrical requirements. The amino-silane coating is recommended for polar poly-mers, such as EVA and polyamides. Magnesium hydroxide (MDH) is recommended in applica-tions where the processing temperature exceeds the decomposition temperature of ATH, i.e., above 200 °C.

3.5 Halogen-Free Flame Retardants for Films, Labels, Mylars

These applications cover polymers similar to the ones covered in previous sections. Therefore, the flame retardants discussed before should also be suitable for these articles. For thin films the particle size of solid FRs can of course be a limitation, but most suppliers also offer fine qualities. Flame retardants which rely on surface effects for their mechanism may face inherent difficulties, e.g. if a char layer needs to be formed for a phosphorus flame retardant, there must be enough material to do so. Reactive flame retardants developed for other applications like fibers may also be suitable, e.g. DOPO and oxaphospholane (see PWB section above) in po-lyester films.


4.0 Definition of “Halogen-free” Electronic Products and Product Cat-egories

4.1 Halogen-Free Standards

To date, there are three existing industry standards that define maximum concentration values for halogens (bromine and chlorine) in printed circuit board materials only. Fluorine, iodine, and astatine (other Group VIIA halogens) are not included in these definitions.

JPCA-ES-01-1999 Japan Printed Circuit Association (JPCA) defines criteria and method for “Halogen-free” as fol-lows: Br < 0.09wt% (900ppm) Cl < 0.09wt% (900ppm) IEC 61249-2-21 International Electrotechnical Commission (IEC) for Materials for printed circuit boards and other interconnecting structures defines “Halogen-Free” as follows: 900 ppm max Cl 900 ppm max Br 1500 ppm max total Cl + Br IPC -4101B Has adopted the IEC definition of “Low Halogen” within printed circuit boards as follows: 900 ppm max Cl 900 ppm max Br 1500 ppm max total Cl + Br Additional standards will likely be developed to cover non-PCB laminate materials, such as the IPC J-STD 709 that is currently in development.

4.2 Electronic Products That Historically Contain Halogens

Currently, most electronic products and components are treated with a chemical compound called a flame retardant. The UL standard provides a basis for indicating the degree of flame retardancy required. A flame-retardant level of V-0 or V-1 is required normally for materials used in electronic products and parts. Certain halogenated compounds (of which brominated flame retardants, or BFRs, are a subset) are used as flame retardants in a variety of applications including thermoplastics, insulation ma-terials, component mold compounds, solder masks and printed circuit board laminates. In addi-tion, polyvinyl chloride or PVC (a resin that contains chlorine) is a commonly used base resin for certain cable jacketing.

Table 1 (below) describes general uses of halogens in electronic products (this list is not ex-haustive).


Table 1 – General Use of Halogens in Electronics

Part Type Potential Halogen Use

Mechanical plastic parts BFRs/CFRs used in certain flame-rated ABS, HIPS, PC, PS and PBT resins

Cables BFRs used in cable/wire insulation material PVC used in cable/wire jacketing and overmold

Printed circuit boards BFRs used in FR-4 epoxy resins and solder masks. Epichlorhydrin used in commercial manufacture of epoxy resins

Electronic components BFRs used in FR-4 epoxy resins, mold compounds, plastic packages. Inorganic bromine/chlorine in solder masks, thermal interface materials, die attach, underfills

Connectors BFRs used in certain flame-rated PBT and PA resins

Films, tapes, mylars BFRs used in certain flame-rated resins PVC used in certain magnetic tapes

5.0 Printed Circuit Board Assembly (PCBA) Materials

5.1 General Description of Halogen (Bromine & Chlorine) Use in PCBA Base

Materials

Suppliers to the electronics industry are increasingly being asked by consumer electronic manu-facturers to provide materials for the manufacture of halogen-free products. There has been considerable debate concerning the use of brominated epoxy resins, such as those typically used in the PWB industry. The concerns are based on the generation of hydrogen bromide gas and halogenated dioxins during combustion of brominated epoxy resins during improper recy-cling procedures. These concerns are not based on hard scientific evidence of environmental or documented health problems, however there are projects underway to better understand these potential impacts. Indeed the latest EU risk assessment has concluded that the use of TBBPA in PCBs presents no risk to human health or the environment. Restrictions on TBBPA in this appli-cation are not currently proposed in the EU. The technical and economical aspects of manufacturing “Green Laminates” have been chal-lenging, particularly in relation to cost and moisture absorption characteristics. Brominated epoxy materials are the current industry standard and are able to satisfy the Pb-free require-ment of the EU RoHS directive. These materials are cost-effective, with good chemical, thermal and mechanical performance. Phosphorus-based materials may allow for improvements in thermal stability, provided performance reliability can also be demonstrated. Reliability of halo-gen-free alternatives must be measured in comparison to current bromine-based materials. More rigorous testing may be needed for measuring properties affected by the higher moisture absorption characteristics of some phosphorus-based materials. Higher moisture absorption can be an issue for filler type flame retardants and should be qualified accordingly.


Table 2 - Anticipated Halogen (Bromine & Chlorine) Use in PCBA Material Sets

Guideline Section - Material Potential Halogen Use

Section 5.2 – PCB Laminates BFRs used in laminate resins

Section 5.3 – Solder Masks Inorganic bromine/chlorine

Section 5.4 - Solder Alloys Halogen use not expected

Section 5.5 - Solder Flux & Paste Inorganic chlorinated and brominated com-

pounds used in flux activators

Section 5.6 – Component Mold Compounds BFRs used in compounds

5.2 PCB Laminates

Background Halogenated flame retardants have been used for PCB laminates for many years. All of them are TBBPA and epoxy derivatives of TBBPA even though there had been a few examples of using other brominated flame retardants for Paper/Phenolic or CEM laminates. Even TBBPA itself has seldom been listed on the FR-4 formulation since epoxy resins of TBBPA are the main components of the varnish and there is no need for additional TBBPA to achieve V-0 level. There are two types of brominated epoxy resins from TBBP: the low brominated and the high brominated. The low brominated epoxy resin is made from the reaction between TBBPA and BPA type epoxy resin (BADGE: Bisphenol A diglycidylether). On the other hand, high bromi-nated epoxy resin is made from TBBPA and epochlorohydrin. In most cases, the low bromi-nated type is preferred because of good processability and reliability. However, the high bromi-nated type is often adapted to accommodate a high loading of non-brominated multi-functional resin. In either case, the bromine content of 18~19% is needed to reach V-0 flame retardancy. As a result, TBBPA is incorporated as the backbone of the epoxy resin for PCB laminates. HF PCB Laminate Industry Overview While there are many types of HF flame retardants, they can be grouped into 3 general types; inorganic fillers, phosphorus compounds and nitrogen compounds. Among those three, the phosphorus compounds can be divided into reactive and additive types depending on their reac-tivity. The typical examples of each group, its flame retardancy mechanism, and effects on lami-nate properties are shown on Table 3.


Table 3 - Comparison of Halogen-Free Flame Retardants

Flame Retardants Examples Mechanism Effects on PWB Materials

Positive Negative

Inorganic Fillers Metal Hy-droxide Zinc Borates

Release of Water

Relatively in-expensive Can be used as a synergist

High loading Tg Reduction Low copper adhesion

Additive Phos-phorus Com-pounds

Aromatic phosphates Aromatic phosphates

Char formation High Flame Retardancy Widely availa-ble

Tg reduction Increased Moisture sensi-tivity Low copper adhesion

Reactive Phos-phorus Com-pounds

HCA(DOPO) Phosphine oxide (PPQ)

Char formation Low loading Good thermal performance

Tg reduction High cost Increased moisture sensi-tivity

Nitrogen Com-pounds

Melamine Triazines

Endothermic Release of Flame resistant Gas

Relatively in-expensive Can be used as hardener

Tg Reduction Increased moisture sensi-tivity

Although there are many other HF flame retardants such as silicon compounds or highly aro-matic compounds, these compounds are rather expensive and used in limited applications. The first generation of HF FR-4 laminates appeared in the late 1990‟s in Japan where red phos-phorus was used as a flame retardant. However, red phosphorus can undergo disproportiona-tion reactions in hot and humid environments which lead to corrosive acids and traces of toxic (and malodorous) phosphine gas. Therefore, red phosphorus is not recommended any more for application in electronic parts like PWBs. The current generation of HF FR-4 was first developed by Hitachi, followed by Matsushita in 1999. The reactive phosphorus FR combined with filler has been adapted. However, HF lami-nates were not widely accepted at the beginning because of high cost and concerns for reliabili-ty. Moreover, the electronic industry recession during the early 2000‟s hindered their progress. It gained momentum only after several years, when the cost went down by increased awareness, development and volume production, which increased the market for HF FRs and its availability. From that time, makers from other regions offered HF laminates applying similar chemistry. As a result, HF PCB laminates are now widely available. On the other hand, laminate for packaging substrate is not readily available because it can not use phosphorus compound unlike HF FR-4 laminate. Special flame resistant resin with high filler load is adapted though special resin tends to be very expensive and rare. However, despite its rapid growth, HF laminate still occupies less than 10% of FR4 laminates. There are some doubts whether HF laminate can keep its momentum after the EU‟s recent rul-ing on TBBPA. However, it seems that the increased use trend will continue for some time, con-sidering the fact that the HF PCB‟s concept is based more on marketing rather than science.


Therefore, the HF portion is expected to increase for years even though there will be a limit for the HF market expansion. (Fig. 1)

Figure 1. HF FR-4 Laminates Market trend (JMS 2006) [US dollars]

Properties of HF PCB Laminates With the enactment of EU RoHS in 2006, there has been a considerable increase in the use of lead-free solder. As the lead free SnAgCu soldering process requires higher temperatures, the PCB experiences a more intense thermal stress, which may have adverse effects on its reliabili-ty. Therefore, HF PCB laminates should have high thermal stability in addition to the necessary electrical, mechanical and thermal properties essential for PCB laminates. When TBBPA as the backbone is substituted by phosphorus-based compound, the properties of the laminates may change as shown in Table 3.

Table 4 - Basic Properties of FR-4 and HF FR-4

Properties Unit FR-4 HF FR-4

Mechanical Peel Strength (1oz Cu) kgf/cm 2.0 1.6 z-CTE (before Tg / after Tg) ppm/℃ 50 / 270 35 / 200 Flexural Modulus GPa 22 ~ 25 24 ~ 27 Flexural Strength MPa 450 ~ 550 460 ~ 560 Electrical Dielectric Constant @1GHz 4.4 4.8 Dissipation Factor @1GHz 0.015 0.01 Volume Resistivity ohm-cm 1E14~1E15 1E14~1E15 Surface Resistivity ohm 5E13~5E14 5E13~5E14 Thermal Tg (DSC) ℃ 140~150 145-155 Pressure Cooker Pass Pass Chemical / Physical Water Absorption % 0.10~0.15 0.06~0.11 Flammability V-0 V-0

Sample: 1.6t

0

100

200

300

400

500

600

5%

6%

7%

8%

9%

10%

2005 2006 2007 2008

Value($M)

HF Portion


As the data indicates, major areas showing differences are copper adhesion, thermal expan-sion, and Dk/Df. All of these are closely related with filler and phosphorus backbone. Application of phosphorus compounds tends to have adverse effects on Tg, water absorption and thermal stability. Multifunctional resin has been adopted to overcome these drawbacks. Since phosphorus FR is expensive, filler such as metal hydroxides has been added to compen-sate for the insufficient flame retardancy due to the low dose of phosphorus FR. Filler can decrease Df, CTE and water absorption. Phosphorus also seems to contribute to the decrease of Df and CTE. Low CTE can have positive effects on the reliability of the laminate. Moreover, low Df can be helpful when application is signal loss sensitive despite the increase in Dk because of heavier dependence of signal loss on Df. In fact, HF PCB laminates can be more cost effective than middle Dk/Df for some high frequency applications. The only inferior property of HF FR-4 seems to be low copper adhesion. The effect can be sig-nificant with low or no profile copper even if the difference is small. The effect of low copper adhesion may become a factor for halogen-free boards especially during lead-free BGA/CSP rework where increased board pad pull out can be observed. Equipped with low CTE and long T260 materials, the HF PCB laminates producers claim that their material is reliable enough to be lead free process compatible. Most HF laminates do ap-pear to be capable to be used for general applications like PC and LCD boards. However, the set of halogen-free laminate materials starts to reduce as the fabrication becomes complex. Therefore, the halogen-free laminates should be checked for its reliability in the case of high-end board applications. Processing of HF PCB Laminates Since HF FR-4 is quite different from conventional FR-4, there seems to be no process that is unaffected by the conversion. However, it is reasonable to assume that there are more impacts on the processes which treat the inside of the laminate, such as drilling, desmearing and plating. In fact, there is hardly any difference in treating HF PCB laminates for the other steps. Among the three, the drilling process is the most eminent because of the high drill wear com-pared with the conventional FR4. Most HF laminate makers are aware of this issue and have improved the HF laminates. However, there will be more drill wear than conventional FR4 even with the improved versions due to the filler used for HF. As far as desmearing and plating processes are concerned, it is hard to predict what the impact will be. Nevertheless, the effects seem marginal, which requires some fine tuning of the chemistries used. In summary, the impacts of HF conversion on the PCB fabrication process are limited at best. Even drilling, the most influential process, can be managed without major adjustment if a PCB fabricator has experience with filled laminates, which are more prevalent these days. Prepreg Storage/Shelf Life Some HF systems use hardeners that change the shelf life of the prepreg. Standard Dicy-cured brominated FR-4 systems will easily last 3-6 months or longer when stored properly. HF mate-rials will meet the requirements for shelf life in IPC-4101, but may not pass recertification testing as easily.


Inner Layer Scaling Factors FR-4 scaling factors vary with design, construction, manufacturer and resin system. This is more so for HF materials which may or may not contain inorganic fillers. Fabricators need to qualify each manufacturers material to make sure their existing scale factors are adequate. Inner Layer Bond Enhancement Inner layer to prepreg adhesion may be lower due to the higher modulus of the resin system. The use of Reverse Treat will typically increase the bond strength by approximately 1 to 1.5 lbs as compared to standard copper foil. If immersion tin adhesion treatments are used, the fabri-cator should test the coating to verify adequate bond strength. Pre-Lamination Pull vacuum for 20 minutes prior to heating the package. This is due to moisture effects on cure and adhesion for some HF systems. Lamination HF materials require slightly longer cure cycles than standard FR-4. The amount of time at cure temperature, cure temperature will be affected by the thickness of the multilayer package being produced. Very thick boards will require a longer cure times. Use of a 60 minute cure for sub-assemblies and boards less than 0.0125" is normally adequate. An 80 minute cure may be ap-propriate for high layer count boards or boards exceeding 0.125” in thickness. Removal of flash should be performed by routing rather than shearing to minimize crazing along the panel edges. Drilling In general higher modulus HF materials drill differently than standard FR-4. Due to the in-creased thermal decomposition of the resin system, the drill debris remains as free particles (dust) and may be difficult to remove with standard tool geometries. To effectively remove de-bris during drilling, undercut drill geometries and high helix tools may help. On high layer count or thicker boards, peck drilling may be necessary. Stack heights and hit counts will vary with the construction and overall thickness of the boards being drilled. Standard .060” thick boards have been successfully stacked 3 high for bit diame-ters down to 13.5 mils. As a general guideline, the sum of the board thickness in a multilayer drill stack should not exceed 200 mils. Maximum hit count for a small drill diameter is 1000. For drill diameters of 13.5 mils and greater, maximum hit count is 1500 Desmear Although the processing of halogen-free materials has been stated as equivalent to those of FR4, caution should be exercised with the desmear and metallisation steps. In general, these materials are more chemically resistant than FR4, and successful processing requires close cooperation between supplier and PCB fabricator. Conventional permanganate desmear sys-tems are effective for removal of HF resin from interconnect posts. Dwell times and tempera-tures typically used for most FR-4 materials should be satisfactory but some systems require different parameters.


Plasma can be used with or without a single permanganate pass (to be determined by each fabricator). Care must be exercised to avoid excessive resin removal if both plasma and per-manganate are employed together. Plasma processing tends to improve overall hole quality, particularly in thick and/or high aspect ratio boards. Standard plasma gas mixtures and cycles are satisfactory. Secondary Drilling The use of entry and backer material may be necessary during the secondary drilling of larger hole sizes to avoid crazing/ fracturing at the hole perimeter.Additionally, sharper plunge point angle geometries may be necessary to avoid crazing around secondary drilled hole perimeters. Routing and Scoring Modifications of the final PWB rout fabrication process may be necessary. For PWB designs requiring scored geometries, the testing of various Tgs and resin content ma-terials has determined that adjustments to the process will be necessary. As the modulus strength of materials increases, the maximum resultant web thickness (dependent on the scored edge depth) must be decreased to avoid excessive fracturing upon breaking away the scored materials. Individual board designs/stackups may require adjustment of score depth geometries. Thinner web thicknesses are typically required. This is influenced by layer count, glass types and retained copper in the design

Section 5.3 - Solder Masks

Background: For solder mask materials, traditionally flame retardants have not been added to their formula-tions. Although solder mask, especially for rigid PCBs, is usually required to have a UL rating, the rating is obtained when coated on a flame retardant substrate such as FR-4. Since the solder mask coating is usually significantly thinner than the base laminate, the coated PCB re-lies upon the flame retardant in the laminate to provide flammability protection for the PCB. Consequently it may be difficult to achieve a satisfactory UL rating in cases of very thin con-structions or with very thick solder mask coatings. Since flame retardants such as BFRs are not added to solder masks, any halogens present are introduced as elemental bromine and/or chlorine in typical ingredients or impurities. These ha-logens generally come from additives such as pigments and/or from residual catalysts from re-sins manufacturing. Pigments with lower halogen content (<900 ppm chlorine, <900 ppm bro-mine, combined 1500 ppm bromine and chlorine) are available for most colors (often at higher cost) and have been utilized in halogen-free solder masks. Likewise, resins with lower residual catalyst are available, again at higher cost. Formulating products with lower halogen content has not affected the performance of solder mask materials. Properties and Performance of HF Solder Masks: Solder mask materials generally must meet specific performance criteria. The most commonly used specifications for solder masks are the IPC-SM-840, “Qualification and Performance Spe-cification of Permanent Solder Mask” and Underwriters Laboratories Inc. UL Standard 94, “Standard for Tests for Flammability of Plastic Materials for Parts in Devices and Appliances.” These requirements are for all solder mask products regardless of their composition so they


apply equally to halogen-free products. Typically the properties of a halogen-free version of a solder mask have not differed from a version that is not halogen-free. The one area where halogen-free base materials could cause a difference is in UL-94 burn test-ing with solder mask-coated samples. Because the rating of the solder mask is dependent upon the flame retardancy of the base material, it could be more difficult to achieve the desired flam-mability rating if the base material is not as flame retardant. Since the rating is also dependent upon the ratio of the solder mask thickness to the base material thickness, the maximum allow-able coating thickness for the solder mask may be more limited when utilizing halogen-free base materials. However, it must be noted that the halogen level of the solder mask has no effect upon the flammability as the halogen content is from inorganic forms and not flame retardants. Processing of HF Solder Masks: Experience has shown little to no difference in processing parameters for a halogen-free solder mask compared to a non halogen-free version of the same solder mask. Any difference may be attributed to a possible change in pigment that could have a minor effect upon the exposure of a photoimageable solder mask. This difference would usually be undetectable. All other processes should be unchanged. Availability and Cost Implications of HF Manufacturers typically have a wide selection of halogen-free products readily available. Nearly half of North American production utilizes halogen-free solder mask in 2008 and most new products are halogen-free. The cost of halogen-free products is comparable to those that are not halogen-free. Production volumes are similar to non-halogen-free products so there is no small volume penalty for main-line products.

Section 5.4 - Solder Alloys

It is not expected that solder alloys would contain bromine or chlorine above the industry-proposed 900 ppm threshold limits.

Section 5.5 - Solder Pastes and Fluxes

Background Inorganic halogens (bromine and/or chlorine) are used in solder pastes and fluxes because they are very effective activators used for oxide removal. At the advent of no-clean products, the in-dustry was very concerned about halogens remaining on the circuit board because ionic Cl and Br could cause corrosion. However, SIR and electromigration testing have shown that the use of rosins and covalently bonded halides can produce very benign residues. It has also been documented that non-halogenated fluxes may also cause corrosion if not formulated or processed properly. Therefore, it is not a safe assumption that halogen-free fluxes and solder pastes will produce residues that are more reliable than those containing halogens. The current trend toward halogen-free is based on the environmental concerns surrounding Cl and Br. Even though flux residue remaining on the circuit board is very insignificant relative to the entire assembled PCB, if an XRF is used directly onto the residue surrounding a solder joint, high Br or Cl readings could be detected if that flux or paste contained halogens


The current test methods for halogen detection in fluxes and solder pastes are from the IPC/J-STD-004. There are two major challenges here:

1. The J-STD-004 specifies halide free as having less than 500ppm of total halide in the raw flux. As a specification, this is more stringent than the 900/900/1500 being used for circuit boards

2. The test methods used in J-STD-004 are designed to look for the ionic species of halo-gen because those are more likely to a reliability issue than covalently bonded halides. Since the majority of fluxes and pastes that are halogenated contain covalently bonded halides, the current test methods in J-STD-004 are not sufficient to determine true halide content of a material. This creates confusion in the industry as statements such as “ha-lide free by titration,” “halide free per J-STD-004,” or “halide free per ion chromatogra-phy” may not necessarily mean the solder paste of flux contains no halogens. It only means that none were detected by the test method used.

To determine the actual halogen content, much of the industry recommends an oxygen bomb combustion followed by ion chromatography test. This test burns the flux at a high temperature which breaks the covalent bonds and volatilizes all of the organic content of the flux. The ash remaining will consist of the halogens and other inorganic content. Ion chromatography can then be used to detect the actual halide content of the flux. There is still discussion in the indus-try as to whether this test should be run on the raw flux or reflowed flux residue. Testing of the flux residue may give an accurate representation of halogens left on the PCB. However, it adds a degree of complexity to the testing. Any time flux residue is scraped from a surface, there is potential for outside contamination (such as from the solder mask on the PCB), so testing of the raw flux used in soldering would probably be preferred as the best method to use..

Cost and availability of halogen-free materials Truly halogen-free solder pastes and fluxes are currently available in the market today but in limited quantities. The cost of using one of these materials is very difficult to assess because it is dependent on the type of product being assembled. The two major challenges facing halo-gen-free pastes and fluxes are:

1. Wetting/hole fill: Cl and Br are used in fluxes because they are very effective at oxide removal. Elimination of halogens will typically mean that the process window relative to wetting and hole fill may be more narrow. Some example challenges that may be seen when using halogen-free materials when trying to wave solder thick boards with OSP, when using oxidized parts, or through long, hot reflow or rework processes.

2. Because halogens are very effective activators, a significantly higher quantity of halo-gen-free activator would be necessary to achieve equivalent wetting. This results in a greater challenge for solder paste and flux manufacturers as it may limit other design characteristics such as printability/stencil life, probe testability, solids content, and even possibly reliability. Therefore, the use of halogen-free materials most likely means a sa-crifice in wetting or some other performance characteristic.

For certain low complexity products, it may be feasible to implement halogen-free solder pastes and fluxes. As complexity increases, costs and soldering issues may become more apparent. For example, the use of nitrogen may be needed in reflow and wave processes when it was not used before.


5.6 Flip Chip CPU Base Materials

5.6.1 Solder resist Solder resist contains inorganic filler and barium compound as flame retardant. These fil-lers do not contain Bromine. However, they contain chlorine in the pigment and residue in the resin. Thus, new halogen-free solder resists are being developed to eliminate the chlorine content. The typical value for the key properties to be considered as successful candidate as halogen-free solder resist are

- Dielectric constant: 2.5 to 3.7 - Dissipation factor: 0.015 to 0.030 - Tg: 95C to160C - CTE (α1) ppm/C:55 to 65 - CTE (α2) ppm/C: 130 to 180 - Moisture absorption: 1.5% to 0.8% - Thermal conductivity (W/mK): 2.2 to 3.0 - Modulus: 3 to 4 Gps

5.6.2 Buildup Buildup material has phosphorus as flame retardant. The halogen-free buildup material has been in production for at least three years. Next generation buildup material is under development for eliminating phosphorus. But, it is in very early development stage. The key properties for the current material are:

- Dielectric constant: 3.3 to 3.5 - Dissipation factor: 0.019 to 0.030 - Tg: 150 to 160C - CTE (X, α1 ) ppm/C:45 to 60 - CTE (Y, α1) ppm/C:45 to 60 - CTE (Z, α1) ppm/C: 45 to 60 - Moisture absorption: 1.0 to 1.9% - Thermal conductivity (W/mK): 1.5 to 2.3 - Modulus: 3 to 4 Gps

5.6.3 Laminate material Halogenated laminate materials generally contain BFRs. Most of the halogen-free lami-nate materials use phosphorus-containing FR and aluminum hydroxide as the flame re-tardant. The typical value for key properties to be considered as successful candidate as halogen-free solder resist are

- Dielectric constant: 4.6 to 5.0 - Dissipation factor: 0.012 to 0.019 - Tg: 160C to 250C - CTE (X) ppm/C:11 to 15 - CTE (Y) ppm/C:11 to 15 - CTE (Z) ppm/C: 30 to 33 - Moisture absorption: 0.11 to 0.25% - Thermal conductivity (W/mK): 0.6 to 0.9 - Modulus: 25 to 30 Gps


5.6.4 Underfill material Underfill material does not contain flame retardant material. Also, it does not contain any bromine or chlorine elements. The key properties for the typical current material are:

- Dielectric constant: 3.2 to 3.8 - Dissipation factor: 0.005 to 0.012 - Tg: 90C to 140C - CTE (α1) ppm/C: 30 to 36 - CTE (α2) ppm/C:100 to 130 - Moisture absorption: 1.0 to 1.5% - Thermal conductivity (W/mK): 0.3 to 0.4 - Modulus: 6 to 12 Gps

5.7 Wire Bond Package Based Material

The substrate materials used for wire bond package are the same as those used for the flip chip package. Thus, same solder resist and laminates are used for both flip chip and wire bond packages. The major difference is that molding compound and die attach adhesive are normally only used for wire bond package and underfill is used for flip chip package. The information de-scribed in Section 5.6 not only applies to the packages for CPU based products, but also ap-plies to other packages, such as CSP, BGA and stack die packages which are used in cell phone, wireless, ASIC, networking, etc.

5.7.1 Molding compounds For current material, brominated and non-brominated flame retardants are used. Mold-ing with bromine-free flame retardants have been in production for some companies since 2005. For the most of the halogen-free molding compounds, multi Aromatic resin is used as the replacement for BFR. The halogen-free molding compounds are available from most of the molding compound suppliers. These compounds have been qualified for produc-tion. Their reliability, electrical properties, mechanical properties are similar to non halo-gen-free molding compounds. The assembly process between non halogen-free and ha-logen-free is the same. As such, no new investment in the semiconductor assembly process is required for the conversion. The cost is slightly higher than non halogen-free molding compounds due to smaller volume. But as the volume becomes larger due to the conversion from non halogen to halogen, the cost should come down to the same level as non halogen-free. For most of the semiconductor houses, halogen-free molding compound will be used for launching of new products. As for legacy products, they may remain to be non halogen-free depending on the business situation. Similar to non halogen-free molding compounds, their properties slightly vary depending on applications. The key properties for typical halogen-free mold compound are:

- Dielectric constant: 4.0 to 4.5 - Dissipation factor: 0.015 to 0.020 - Tg: 140C to 180C - CTE (α1) ppm/C: 8 to 14 - CTE (α2) ppm/C: 25 to 40 - Moisture absorption: 0.1 to 0.4%


- Thermal conductivity (W/mK): 0.8 to 1.2 - Modulus: 19 to 25 Gps

5.7.2 Die attach adhesive Die attach adhesive does not contain flame retardant material. Also, it does not contain any elemental bromine or chlorine. The key properties for the typical current material are:

- Dielectric constant: N/A - Dissipation factor: N/A - Tg: -20C to 60C - CTE (α1) ppm/C: 48 to 65 - CTE (α2) ppm/C:130 to 200 - Moisture absorption: 0.2 to 0.6% - Thermal conductivity (W/mK): 0.6 to 3.5

5.8 Connector Base Materials

Background: The typical use of any halogen Bromine, Chlorine, Fluorine, Iodine, Astatine) in connectors would be as a flame retardants (FR), lubricants, or stabilizers in certain plastics. Bromine and chlorine are commonly used in flame retardant packages, with bromine being the most preva-lent. It is important to note that the delineated bromine compounds described in this section do not fall into the PBB and PBDE compounds banned by existing EU RoHS legislation. Underwriters Laboratory (UL) 94-V0 flammability ratings are required for many connectors. Many plastics require the addition of a flame retardant “package” in order to achieve this rating. LCP and PPS would be the exception to this rule as these families of plastics can achieve a V0 rating without the addition of FRs. The bromine compounds in flame retardant “packages” are typically present at levels of 15-35% which far exceed the 0.09% limits proposed by certain in-dustry associations and manufacturers. Fluorine and iodine are less frequently found as lubricants or stabilizers in certain plastics. As-tatine is not typically used due to cost and rarity. These elements were not considered in this assessment as industry definitions of halogen-free have focused on bromine and chlorine. It is important to note that certain plastics suppliers are evaluating these “other” halogens for use in flame retardant packages intended to be marketed as “halogen-free”. The criticality of establish-ing an industry accepted standard definition of halogen-free cannot be overstated. Plastics used in a particular connector product are determined by a variety of criteria:

• Mechanical properties

• Moldability – fill characteristics like thin walls, etc.

• Solder process requirement – wave solder vs. reflow process. Note that lead free processing requirements have introduced additional high temperature requirements

• Cost

• Global availability


Nylons and PBTs are extensively used in the connector industry due to meeting many of these criteria. Both would typically contain halogenated flame retardants. It is also important to note that plastics are not typically “drop-in” replacements due to differing shrink rates, fill characteristics and mechanical properties (e.g. for latches). Mold and potentially design modifications are typically required when changing plastic materials, especially when changing between plastic families (e.g. high temperature nylons to LCP). As a result, many plastic material changes require major capital investment and significant product and process qualification testing.


Table 5 - Current Usage of Halogens in Typical Connector Product Families: The following table is a snapshot of the variety of plastics with/without Bromine or Chlorine FRs typically used by the Connector Consortia in the Product families shown. The list is not exhaustive.

Defintions/Abbreviations

LCP Liquid Crystal Polymer

PBT Polybutylene Terephthalate

PCT Polycyclohexylenedimethylene Terephthalate

PPA Polyphthalamide

PPS Polyphenylene Sulfide

ABS Poly(Acrylonitrile Butadiene Styrene)

PPO Polyphenylene Oxide

PP Polypropylene

PC Polycarbonate

PE Polyethylene

contains halogenated flame retardants

no halogenated flame retardants

LCP LCP

PBT PPS

PCT PBT

Nylon PPA

PCT

LCP

PPS Nylon

PBT PCT

PPA

LCP LCP

Nylon PC

PBT

PCT PBT

PPA PPA

ABS

PBT

LCP Nylon

Nylon LCP

PPO

PBT LCP

PCT PPA

Nylon

LCP

Nylon

PPA

PCT

PBT

PP

PPO

ABS

PC

Modjack

FFC

Memory (e.g DDR)

Board-to-Board

Memory Card

I/O (e.g. USB, IEEE1394, PCI, PCI Exp. Gb Ethernet)

Disk Drive (e.g. Serial ATA, SCSI, Fibre Channel)

Signal/Backpl. (e.g. DIN, IEC stds, VME, Multibus)

Processor/Chip Sockets (e.g. uPGA, PLCC)

Power (includes VRM)


The following bullets will provide some background to the information in the Table.

• Halogen usage is pervasive across the product families

• The variation in types of plastics used is caused by the following factors: o Large differences in types of products even within families influence plastic selec-

tion due to factors described above. o Represents a composite of usage of all companies in Connector Consortia; how-

ever, it is expected that fairly limited variation exists on specific products. o As indicated above, new plastics have been introduced into product families to

deal with the higher temperature requirements of lead free processing. Existing tin lead compatible products have not gone away.

o Legacy – newly available materials may have been used on the newer products within a product family. In addition, products acquired via corporate acquisition have their own legacy materials.

Note also that as indicated above, although there may be both halogen containing and halogen-free products within a connector family. This would typically be due to product specific issues and drop in substitution would not be feasible.

The PPS resins do not contain intentionally added bromine or chlorine for flame retar-dant purposes. However, PPS resins typically contain 600 – 1500 ppm chlorine, in the form of residual salt, as a by-product of the manufacturing process of the resin. This chlorine by-product is present in the form of inorganic NaCl (the structure of common ta-ble sale) and poses no known threat to the environment. Unfortunately, as currently de-fined in the existing industry standards for “halogen-free”, PPS would not be permitted when the chlorine content exceeds 900 ppm. An exemption for this environmentally-benign form of chlorine should be established for the continued use of PPS in “halogen-free” connector applications. Another approach could be to create a new industry stan-dard to apply to PPS resins and other connector resins (existing industry standards are specific to PCB laminates only).

Halogen-free Alternatives: Transition to a halogen-free plastic has historically meant moving to a material such as LCP which significantly impacts product cost. While still true to a large extent, in the past 18 months several plastic manufacturers have been developing “halogen-free” versions of nylon resins. It is a technical challenge to identify combinations of halogen-free compounds that will provide the required FR characteristics along with a readily moldable resin with acceptable mechanical strength. Connector companies are evaluating these new resins and are working with suppliers to optimize the formulations. More work is needed to finalize the resin formulations before the plastics suppliers scale up to volume production. Implications of a move to halogen-free connectors: As plastics suppliers continue to make halogen-free materials available, more options are avail-able to the connector manufacturer. However, for the foreseeable future we believe the follow-ing to be true:

Transition to halogen-free will continue to bear a cost/price premium. In additional to the increased plastic cost, capital costs for tooling changes will be significant

Material changes in most cases will require product re-qualification including UL approv-al (if required on the product)

New materials will not be drop in replacements, thus requiring mold modifications and/or product design changes to accommodate

Halogen-free alternatives are typically less moldable than current versions


Limited selection of halogen-free alternatives will result in reduced connector perfor-mance. The lack of options limits flexibility in balancing requirements of strength, com-pliance needs (latching, interference fits without cracking), compression strength, mold-ing requirements, coloration, etc.

Connector industry cannot support yet another product variation (both halogen-free and halogen containing versions). Until cost parity exists, this is a major risk

6.0 Cable Base Materials

6.1 Scope

The scope of this section will only address the types of wire and cable found in computing de-vices. Specifically, AC/DC power cords, internal wire and cable, and data cables.

6.2 Background

For the wire and cable applications mentioned, the predominate plastic material used today for insulation, jacket and plugs is PVC. As previously discussed, PVC is coming under increasing environmental pressure for replacement. The primary concerns are 1) the halogenated nature of PVC and the emission of corrosive HCl gas and/or dioxins when burned and 2) the use of phthalates as plasticizers used to make flexible PVC. PVC is a commodity plastic which has been optimized over decades for use in wire and cable. Therefore, similar to the discussion on connectors, there is no drop in replacement for PVC that does not come without compromises. The primary implications of conversion to PVC free, ha-logen-free alternatives include cost, performance and regulatory compliance. There are seven major types of materials used in coated wire and cables:

(1) resins (thermoplastic and thermoset compounds) for insulation and jacketing; (2) plasticizers to make the plastic flexible and easy to process (and impart other qualities such as impact resistance and abrasion resistance); (3) stabilizers to provide heat resistance during manufacturing as well as visible light, UVrays and heat resistance during product use; (4) flame retardants to slow the spread of an accidental fire and reduce the amount of heat and smoke released; (5) fillers to reduce formulation costs and improve insulation resistance; (6) lubricants to improve the ease of processing; and (7) colorants to give the desired color, which is crucial for identification purposes.


Table 6 - Anticipated Halogen (Bromine & Chlorine) Use in Major Cable Material Sets

Material Potential Halogen Use

Resins BFRs used in cable/wire insulation material PVC used in cable/wire jacketing and over-mold

Plasticizers Halogen use not expected

Stabilizers Halogen use not expected

Flame retardants BFRs used in cable/wire insulation material

Fillers Halogen use not expected

Lubricants Halogen use not expected

Colorants Halogen use not expected

6.3 General Material Performance Requirements for Wire & Cable

• A specified level of flame retardancy on extruded cable insulation/jacket, such as UL VW-1, FT2 or other regional equivalents

• Some level of flame retardancy on injection molded plugs/strain reliefs, like UL 94 V-0 or regional equivalent

• Flexibility

• Mechanical Performance such as tensile strength and tensile elongation

• Aging performance to ensure functionality over time

• Cold bend and heat shock

• Electrical performance, such as spark test, dielectric strength and insulation resistance

• Conductor corrosion

6.4 PVC-Free, Halogen-Free Alternatives

The development of PVC-free, halogen-free alternatives in wire and cable has intensified over the past 12 months. The leading halogen-free material candidates include Thermoplastic Elas-tomers (TPE‟s), modified PPE based alloys, and Polyethylenes/Polyolefins. These materials are being commercially used in some wire and cable applications today. However, they are not used as broadly across all types of computing device wire and cable as PVC. Thermoplastic Elastomers (TPE’s) Themoplastic Elastomers (TPE‟s) are a very broad category of materials and generally includes the following groups: Styrenic Block Copolymer Blends: These are normally blends of hydrogenated styrene-butadiene-styrene block copolymers with FR additive to provide the appropriate FR perfor-mance. In wire coating, they have good processability and nice surface appearance. Currently, some of the challenges include robust FR performance and good dielectric performance. Thermoplastic Polyurethane Blends: These blends typically have very good chemical and oil resistance. They also have good elasticity, especially at low temperatures, making them poten-


tially good candidates for jacketing. Some of the challenges include processability, robust FR performance, and limited use for insulation due to high dielectric constant. TPU‟s have a limited temperature rating up to 80C, as listed in UL1581. Thermoplastic Vulcanizates and Blends: These are normally crosslinked EPDM dispersed in a polypropylene continuous phase. TPV‟s typically have good flexibility, processability, and ade-quate chemical resistance. Challenges include the ability to get robust FR performance due to the inherently high polyolefin base and the retention of tensile properties after aging. Copolyesters (TPEE) and Blends: Copolyester elastomers are block copolymers composed of alternating hard (typically PBT) and soft segments (amorphous glycol). Although final properties can be tailored, the PBT segments exhibit high heat resistance and good chemical resistance (particularly to oils and greases), while the soft segments contribute impact strength and good flexural modulus. One of the challenges is to balance halogen-free FR with dielectric performance. mPPE based Alloys A relatively new entrant in wire and cable includes blends of mPPE (polyphenylene ether) with other soft building blocks and FR additives. As a resin, mPPE has inherent FR capability, there-fore the FR additive package is significantly lower than in other halogen-free alternatives. The resulting blends offer a good balance of flexibility, mechanical performance, robust FR and low specific gravity. These alloys have reasonable processability, and very good dielectric perfor-mance including high dielectric strength and volume resistance in water immersion. Also, they have good temperature performance – 105C without crosslinking. Some challenges include chemical resistance to hydrocarbons and odor during processing. Polyethylene/Polyolefins Polyethylene is a lightweight, water-resistant, chemically inert, and easy to strip resin. The dif-ferent types of polyethylene used in the wire and cable industry include low-density (LDPE), linear low-density (LLDPE), medium-density (MDPE), high-density (HDPE), chlorinated polye-thylene (CPE) and cross-linkable polyethylene (XLPE). Polyethylene‟s low dielectric constant allows for low capacitance and low electrical loss making it the choice for audio, radio frequency, and high voltage applications. In terms of flexibility, PE can be rated stiff to very hard, depending on molecular weight and density. As PE is less inhe-rently flame retardant, traditionally brominated flame retardants were added to provide robust FR. However, new formulations have been accepted, particularly in Europe, that use non-halogen flame retardants and moisture-cured XLPE for insulation and jacketing in some flexible cords, appliance wires, and building wire. The use of inexpensive aluminum trihydrate (Al(OH)3) and/or magnesium hydroxide (MgOH) flame retardant additive is quite common. Calcium carbo-nate can also be used as a filler to provide a PE compound that is price-competitive with PVC compounds. The challenge is the high loading of FR that is required, sometimes >40-50%, which can compromise processability, flexibility, and abrasion resistance. Maintaining adequate FR performance while achieving the desired flexibility is one of the major hurdles with using FRPE as a jacketing material.


6.5 Implications of Halogen-free Alternatives

Product Safety Requirements One of the biggest challenges in validating a halogen-free alternative is navigating the various regional regulations that govern safety compliance. In most cases, the standards were written years before the halogen-free movement, and with PVC in mind. Another challenge is that many criteria within the standards were written, not based upon application needs, but upon the capability of the incumbent material. For the US market, first and foremost, the alternative material must be recognized and meet the material performance profiles outlined by UL1581, Table 50. See appendix A for a short over-view. Materials Included in Table 50 of UL1581 – Green denoting potential for Halogen-free Secondly, for Appliance Wire, such as DC charger, USB cable and internal wire, the application requirements must be met via UL758. See Appendix B for a short overview. For AC Power cords, there are over a dozen different regional regulatory bodies that must be satisfied in order to be recognized globally. The following are three of the majors: US Market: UL62 Flexible Cords and Cables This standard specifies the requirement of flexible cords with 600V maximum. It defines:

Cable construction and relevant codes

Performance & test requirements, including material performance as outlined by UL1581, Table 50.

Marks Today, UL62 recognizes the following thermoplastic material categories for cable jackets: PVC and TPE. For cable insulation, the only thermoplastics recognized are PVC, PE, TPE and FEP. If a new material does not fall within one of the categories mentioned, then a new category must

60C 80C 90C 105C 125C 150C

mPPE-PE mPPE mPPE

PVC PVC PVC PVCPVDF PVDF

FR-PE FR-PE FR-PEXL XL XL

LD-HDPE XLPO XLPO XLPOPP PP

TPU TPU TPU FEPTPE TPE ETFE ETFE


be created which can take at least 9 months. This new material/category must also be recog-nized by the National Electrical Code, NFPA 70. Even when a material falls within a category, there can be a challenge with the new halogen-free formula meeting the performance profiles that were originally established, most likely with a halogenated formulation, in UL1581, Table 50. The result is time delay due to the need for further product development, or the less desired route of launching the cable as “unlisted”. European Market: VDE HD21.14S1 This standard defines the cables of rated voltage up to and including 450/750V:

Scope: Only Halogen-free Material

Cable constructure and relevant codes

Performance & test requirement

Guide to use(informative) Unlike UL62, this standard was written for halogen-free materials, and is mainly based on per-formance in application. If the material in the application passes the requirements, it is relatively easy and straightforward to get certified. Japan Market: Den-An-Ho (Electrical Appliance and Material Safety Law) This law defines the requirements of flexible AC Power cords of voltage up to and including 600V. It is more similar to UL in that it does recognize only certain material categories.

Scope: Wire & Cable performance made from Rubber mixtures. Wire & Cable perform-ance made from Polymeric materials: PVC, PE and blends, PO and blends, Fluoro-polymer materials.

PSE (Product Safety Electrical Appliance and Materials) Mark certification

Cable constructure and relevant codes

Performance & test requirement

Guide to use (informative) Suppliers or cable manufacturers have to declare their material identification to JET/JECTEC. If their product fits into one of the established categories, they can move forward with certification. If the suppliers or cable manufacturers judge that they are not categorized under a current category for AC power cord, then they need to generate a new category. In the case of PO which was recently created, the process took more than 3 years. Basically, the wire industry believes it is nearly impossible to create a new category without strong lobbying activity with the government. Regardless of geography, the typical power cords are SPE; SVE; H03Z1Z1-F ; H05Z1Z1-F; OFF; OCCTFK

And the typical performance requirements include

Tensile Strength & tensile elongation before /after aging

Heat shock & Heat deformation

Dielectric resistance


Bending & Pulling as Figure 7 & 8

Flame retardant ,eg VW-1 as Figure 9

Migration as Figure 10

Abrasion

6.6 Summary: Performance, Regulatory, Processing, and Cost

PVC has been optimized over decades as a wire and cable material. One of the strengths of PVC is its inherent robust flame retardant performance. Most of the halogen-free alternatives rely exclusively on the halogen-free FR additive packages to deliver similar FR performance. The issue is that, in many cases, the loading of the FR additive package is extremely high (>40%) and often times will compromise flexibility, scratch/abrasion performance and processa-bility. With that said, the product development activity on halogen-free flexible materials has intensified, and dramatic improvements are being made daily. If the intent of the electronic companies is to launch globally, attention must be paid to all of the regional regulatory bodies. In some parts of the world, PVC is the only recognized material! Initially, the process will be painful. However, the expectation is that once the new materials can perform in existing categories, or new categories are created, it will eventually become as routine as PVC. While the same extrusion lines can be used, the line speeds of the highly filled materials can be 40% less than that of PVC. In addition, the high filler loading increases the specific gravity of the material. Therefore, care must be taken when comparing resin prices on a weight basis. Based on system cost studies, the cost of converting from PVC to a halogen-free solution varies widely from 1.5X to 7X. Regardless of the spread, two things are certain: First, the initial cost of transitioning to a halogen-free alternative will be more than PVC. Second, the system cost delta will reduce over time as the volume of halogen-free alternatives increases, the market be-comes more competitive, and the wire extruders optimize around halogen-free materials. Appendix A: UL 1581 - Reference Standards for Electrical Wires, Cables, and Flexible Cords In this standard, the following items are defined:

• Definition of application test procedures • Definition of physical property tests for insulation and jacket materials • List of approved materials and short term test standards (section 50) • Definition of long term physical property test for non-listed materials (section 481)


Figure 2 shows the relationship between the continuous use temperature and the required test temperatures:

Use Rating ST Temp(C)

LT Temp(C) HD Temp(C)

80 113 87 100

90 121 97 121

105 136 113 121

Figure 2. Relationship between Short Term (ST), Long Term (LT) and Heat Distortion (HD) Temperature vs. UL End Use Rating.

Appendix B - Appliance Wiring Materials :UL758 3.21In this standard, the following items are defined:

• Defines use codes for wires • Defines wire construction • Defines application test requirements based on previous 2 points • Refers to UL 1581 for detailed test definitions • Refers to UL 1581 for insulation/jacket physical property requirement for recognized mate-

rials • Refers to UL 1581 for insulation/jacket materials physical property requirements for unlisted

materials 3.22Some typical examples of wires that are governed by UL 758 are shown in Figure 3 below. (Should we replace the USB cable with a 105C internal wire photo?)

Figure 3. Examples of applications that fall under UL 758.


3.23UL 758 uses so-called Style Pages to define the construction and use codes of various wire&cable configurations. This is shown in Figure 4.

Figure 4. Schematic overview of the elements within a UL Style Page.

In addition to describing the basic construction and use conditions of the wire&cable, a UL 758 Style Page also defines the type of markings to be used and the basic tests that need to be per-formed on that wire and cable assembly. Figure 5 shows an example of a UL 758 Style Page.

UL 758 Style Pages - Use Codes: 6 Categories

• Use rating: I,II,F,S

• Mechanical Rating: A,B,C

• Dry Temperature rating: (xxxC)

• Voltage

• Flame: H, V, VW-1, FT1, FT2, NR

• Special Rating: oil, wet, sunlight resistance, etc.

UL 758 Style Pages - Basic Construction Types:

• Single or multiple conductor w/extruded insulation – table 3.3

• Single conductor w/other than extruded insulation – table 3.4

• Parallel cord w/extruded insulation and jacket – table 3.5

• Multiple conductor cable – non-integral jacket – table 3.6

• Bonded or laminated flat ribbon cable – table 3.7

• High voltage DC wire w/extruded insulation – table 3.8

Each Table defines:

• Conductor material & size

• Insulation material & thickness

• Jacket material

• Markings

• Basic test requirements

Material physical property tests de-fined in UL 1581:

• recognized materials – section 50

• new materials require testing according to section 481


Figure 5. Example of a UL 758 Style Page. UL 758 Use Codes are often printed on the jacketing of the cable construction. Figure 6 below shows an example of a Use Code.

Use Code: I B 80C 300V VW-1 O 60C • Use rating • Mechanical rating • Dry temperature

rating • Voltage rating • Flame rating • Special ratings

I – Internal Wiring B – evaluated for normal han-dling 80C 300V VW-1 Oil rated for 60C

Figure 6. Example of a UL 758 Use Code.

+


Figure 7. Typical Bending Test procedure

Figure 8. Typical Pulling Test procedure

Figure 9: VW-1 Test Figure 10: Migration Test

7.0 Mechanical Plastics

The design of an electronic device such as a desktop computer, laptop computer or a monitor is a challenging and iterative process. A design team must consider the fit, form and function of the product against an increasingly complex set of material viables that range from part toler-ance and part cost to product aesthetics and product environmental impact. The product devel-opment process must take a comprehensive look at a products life cycle and select materials that appropriately meets the specified performance requirements. In the following section we will take a closer look at the smaller subset of mechanical plastics that are used in today‟s consum-er electronics. In addition, we will discuss potential non- halogen material alternatives that fit these major mechanical plastic application segments. The final selection of any material is


based on a balance of price, performance, brand image, corporate values and consumer de-mand. Figure 11. is a diagram which illustrates both the variety and the complexity of applications and underscores the importance of material selection.

Figure 11: Application Spectrum

Figure 12: Application Schematic

The polymeric materials used in these devices are numerous and cover the spectrum of both thermoplastics and thermosets. The following discussion will focus on thermoplastics will the realization that printed circuit board as a thermoset will be discussed in another section/chapter. It is not uncommon for a single device to contain more than one dozen different plastic material types (see Figure 2). The plastics used in these devices often are a mix of commodity materials such as PolyVinyl Chloride, (PVC) and High Impact PolyStyrene, (HIPS) which are often posi-tioned on price and to Engineering ThermoPlastics or (ETPs) which are positioned on perfor-mance. For an example you could have a device such as a computer monitor that would employ a commodity HIPS as an enclosure with numerous internal components using a more perfor-mance tailored ETP such as polycarbonate for a transparent cover plate. In order to better understand material selection we first most understand some basic polymer science. Thermoplastic materials can be divided or categorized into three basic groups Amorphous Polymers, Semi-Crystalline Polymers and Amorphous/Crystalline Blends. Figure 13. illustrates the main property attributes of the various polymers. It must be noted that the specification of these base materials for various applications is further augmented by the addition of specialty fillers such as glass, minerals and other additives. The use of additives and their specialty compounding can result in polymer solutions that have uniquely tailored performance attributes such as improved strength to weight ratios, tighter di-mensional stability, improved impact, Flame Retardancy (FR) performance and lubricity to name a few.

Application Challenges

Ma

teri

al

Perfo

rm

an

ce

Application Challenges

Ma

teri

al

Perfo

rm

an

ce


Amorphous Polymers

Semi-Crystalline Poly-mers

Amorphous/Crystalline Blends

- Broad softening point - Very good mechanical

properties. - Dimensional stability - Intrinsically transparent - Consistent shrinkage

- Sharp melting point - Resistance to some Severe chemical environments - Differential Shrinkage - Very good electrical

properties

- Tailored Products - Characteristics dependent on blend ratio - General balance of performance

Example Materials - PC - PVC - HIPS - ABS - PS

Example Materials - PBT - PA

Example Materials - PC/ABS Blends - PC/PBT Blends

Figure 13 - Inherent properties of the various polymer categories. Understanding the polymer classification is important for two fundamental reasons. One, it gives an indication of how a part will likely perform from a physical property standpoint and two, the base polymer often will dictate the flame retardant package that is efficient and compatible with the resin system. The degree of difficulty to make a non-FR resin FR varies greatly and is de-pends on the base resin system. Unfortunately there are few resins that are inherently flame retardant. Since the focus to this discussion is non-halogen solutions let‟s focus on device com-ponents that are using flame retarded plastic materials. Flame retardancy is an important consideration in material selection for both internal and exter-nal device components. Plastic part flame performance requirements for electronic devices are often set by industry recognized standards development organizations such as the IEC, Interna-tional Electrotechnical Commission. Furthermore, Underwriters Laboratory (UL) has a standard flame test protocol and classification system that rates plastics flammability which is UL 94, The Standard for Flammability of Plastic Materials for Parts in Devices and Appliances (Visit www.UL.com) See Figure 4 for a brief overview of UL94 plastic materials flame performance definitions. Therefore an industry or national standard will dictate the required flame perfor-mance of a device and a materials UL94 rating will dictate the possible materials available for a particular part design.

http://www.ul.com/


Figure 14: UL94 Flame Performance Classifications for Plastic Materials

Selecting the right material for a particular FR part design is a function of many important ma-terial attributes. Those attributes include but are not limited to transparency, use of a filler, wall thickness, UL94 flame rating, flow and aesthetics. Generally, the driving factors are a combina-tion of UL94 rating, wall thickness and flow. Thickness plays an important factor in FR perfor-mance. Therefore the effectiveness of FR additives in thin wall parts such as connectors is very critical to overall performance. The addition of the desire for a non-halogen FR system further narrows the materials available to a designer. Non-halogen or halogen-free for the context of this discussion is defined to be a polymer material that is either inherently flame retardant or that contains no brominated or chlorinated flame retardant. It is important to note that given this defi-nition it is possible to have elemental bromine or chlorine present in addition to a halogen. As an example fluorine is a halogen that is often used as an antidrip agent and can be present at <= 0.5%. The halogen-free FR polymer landscape continues to evolve on two fronts -regulation and inno-vation. Pressure from environmental groups and regulatory developments are creating market-ing pressure that is having an impact on the use of traditional halogen FR systems particularly within the electrical and electronic industry. In response to this pressure FR suppliers and plas-tic materials suppliers are working collaboratively to innovate and deliver non-halogen FR pack-ages in both their traditional portfolios and with new materials. Figure 15. is a materials matrix of FR polymers commonly used in the consumer electronic market space. From the chart a few general observations can be made. Non-halogen alterna-tives for amorphous resins exist. Technology is still emerging for semi-crystalline and blended polymers.

Least stringent

Most stringent

HB: Horizontal Burn – HB materials do not self extinguish. Tests rate of flame

progression (<75mm/min for materials <3mm, 40mm/min otherwise)

V-2: Vertical Burn – 2, 30 sec applications of ¾” flame. V-2 materials are permitted to

drip but must self extinguish within 30sec.

V-1: same flame applicat ion and self extinguish limit but no drips permitted.

V-0: same flame applicat ion but <10 sec self extinguishing & no drips.

5VB: 5” Vertical Burn: 5, 5 second applications of 5” flame. Bars must self extinguish

<60sec with no drips. Plaques can form a hole.

5VA: same flame applicat ion as 5VB, self extinguish limit & no drips.

Plaques must not form a hole.

Least stringent

Most stringent

HB: Horizontal Burn – HB materials do not self extinguish. Tests rate of flame

progression (<75mm/min for materials <3mm, 40mm/min otherwise)

V-2: Vertical Burn – 2, 30 sec applications of ¾” flame. V-2 materials are permitted to

drip but must self extinguish within 30sec.

V-1: same flame applicat ion and self extinguish limit but no drips permitted.

V-0: same flame applicat ion but <10 sec self extinguishing & no drips.

5VB: 5” Vertical Burn: 5, 5 second applications of 5” flame. Bars must self extinguish

<60sec with no drips. Plaques can form a hole.

5VA: same flame applicat ion as 5VB, self extinguish limit & no drips.

Plaques must not form a hole.


Materials suppliers and FR suppliers often work together to find and optimize FR systems. The technical innovation cycle for new resin and FR systems is typically 12 to 24 months. The inno-vation cycle includes optimizing the material formulation percentages, demonstrating molding capability, testing mechanical performance and assuring UL compliance. Material solutions have to be both technically sound and commercially viable. Removing halogens while maintain-ing cost and total overall performance may be difficult to achieve in the short term. The con-sumer electronics industry must consider all aspects and requirements pertaining to non-halogen alternatives so that designers and consumers alike have the information they need to make the product and purchasing decisions that best fit their respective expectations.

Figure 15 - Materials Matrix

* Non- Halogen= Non Chlorinated and Non Brominated FR System

Polymer Chemistry Material Typical Non- Halogen* Potential Observations

Description Selection Drivers Applications FR Alternatives Suppliers Comments

PC- Polycarbonate transparency lenses Yes SABIC IP, Lexan Resin Slight Price Up

impact housings Bayer, Dow, Idemitsu

Modified PPO electrical properties flexible wirings Yes SABIC IP, Noryl Resin

Polyphenylene Ether low water absorption fan impeller Ashahi

ABS, Acrylonitrile- surface quality housings Yes SABIC IP, Cycolac Resin UL-94, HB

Butadiene-Styrene range of colors internal parts

PVC, PolyVinyl price internal parts No Chlorine present

Chloride wire coatings in base polymer

HIPS, High Impact price No FR typically

Polystrene brominated

PBT, Polybutylene electrical properties connectors Yes, SABIC IP, Valox Resin Slight Price Up

Terephalate chemical resistance fan housings Limited Ticona

PA, Polyamide internal parts Yes, DuPont, BASF, DSM

connectors Limited

PC/ABS low temp. impact enclosures Yes SABIC IP, Cycoloy Resin Slight Price Up

high flow bezels Bayer, Dow, Idemitsu

Common Thermoplastic Materials Serving Consumer Electronics

Am

orp

ho

us P

oly

mers

Am

orp

ho

us/C

rysta

llin

e

Po

lym

er

Ble

nd

s

Se

mi-C

rysta

llin

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Po

lym

ers


8.0 Optical Films, Tapes and Adhesives

This section evaluates the use of halogens in certain optical films, tapes and adhesives typically used in electronic products including a brief overview of usage, availability of alternatives, and implications of moving to low halogen products.6 For the purpose of this section, “low halogen” is defined as having less than 900 ppm bromine, less than 900 ppm chlorine, and/or less than 1500 ppm bromine and chlorine, based on the de-finition used in IEC 61249-2-21 (a standard developed for properties of “nonhalogenated epox-ide woven e-glass reinforced laminated sheets”). Generally Optical films, tapes and adhesives are used in many areas of electronic devices. It is very rare for optical films, tapes or adhesives to contain brominated or chlorinated flame retardants. Brominated flame retardants have been a focus of regulations, most notably the European Un-ion‟s Restriction on Hazardous Substances (“RoHS”) Directive, China RoHS, and Korea RoHS law, all of which focus on the polybrominated flame retardants PBBs and PBDEs. As part of marketing or other product campaigns (see IPC White Paper TR-584A, by the IPC 4-33 Halo-gen-Free Materials Subcommittee), some companies have gone beyond the brominated or chlorinated flame retardants, to focus more generally on the levels of bromine or chlorine in products. Below is a discussion of certain optical film, tape or adhesive products known to be used in electronic devices and whether they contain bromine and chlorine content. Optical Films Background Below is a diagram of a typical LCD panel showing the location of several of the film types that might be used.

6 This discussion is intended as a brief overview of low halogen considerations in certain films, tapes and

adhesives based on reasonably anticipated uses in electronics products, and is not intended to cover all potential applications in all areas of this industry. This discussion is not intended as legal or regulatory advice. All statements and technical information, and recommendations contained in this discussion are believed to be reliable. 3M does not warrant the accuracy or completeness of this information. 3M re-serves the right to change, at any time and without prior notice, any information contained herein.

Enhancement film

Enhancement film Diffuser film Lightguide

Reflector- may be film

Panel

Adhesive Tape


Underwriters Laboratory (UL) Flammability Standards Optical films themselves generally do not carry UL flammability ratings because they are part of larger assemblies. These larger assemblies, rather than individual components, are required to meet UL flammability standards. However there are some films that will meet and carry the UL HB (Horizontal Burn) rating. Key Requirements of Display Application Films The following properties define suitability for use of display application films

Optical properties

Heat stability

UV stability

Mechanical properties

Cost

Global availability Current Usage of Halogens in Typical Optical Film Product Families: The following is a snapshot of the variety of optical films with/without Bromine or Chlorine typi-cally used in electronics in the product families shown. The list is not exhaustive. Prism Films/Turning film

• These films do not contain brominated flame retardants above impurity levels. The im-purity flame retardants are not the PBB and PBDE flame retardants that are the focus of EU, China, and Korea RoHS. The impurity levels of these flame retardants would meet the definition of low halogen stated above.

• These films may contain intentionally added bromine above the 900 ppm requirement of this guideline. This bromine is a brominated polymer used to improve optical properties.

• These films may include impurity chlorine. This chlorine level is generally below the 900 ppm level. The chlorine is a residual from the manufacture of the brominated polymer.

Reflective Polarizers

These films are unlikely to contain bromine and chlorine

Diffuser Sheets (cover and bottom)

These films are unlikely to contain bromine or chlorine

Reflectors-


Iodine Polarizers


Front Surface Films (privacy, anti-reflection)

These films are unlikely to contain bromine or chlorine above impurity levels

These films would meet the definition of low halogen stated above. Reflective Polarizer/ Prism Film-

• These films do not contain brominated flame retardants above impurity levels. The im-purity flame retardants present are not the PBB and PBDE flame retardants that are the


focus of EU, China, and Korea RoHS. These flame retardant impurity levels would meet the definition of low halogen stated above.

• These films may contain intentionally added bromine above the 900 ppm level. This bromine is a brominated polymer used to improve optical properties

• These films generally include a chlorinated acrylate polymer used to improve prism du-rability. The level of chlorine from this use is generally below 900 ppm; however, levels can be near the 900 ppm level so care should be taken to control other potential impurity sources of chlorine in the film.

• These films may also include impurity chlorine. This chlorine level is generally below 900 ppm. The chlorine is a residual from the manufacture of the brominated polymer.

Other Optical Film considerations: Optical films are often used in cooperation with adhesives and tapes (example: rim tapes). These adhesives and tapes may be used with the film or attached to the films. Some of these adhesives and tapes may contain chlorine above 900 ppm. These materials would need to be evaluated on a case by case basis for halogen content. Low Halogen Products In the past few years several manufacturers have been developing low halogen alternatives to Display films that contain halogens. This has been a significant cost to manufacturers in R&D and qualification work. A move to low halogen optical films may create the following trade-offs:

• Optical properties

• Heat stability

• UV stability

• Mechanical properties

• Cost incurred in creating new low halogen films with equivalent properties to films with halogens may lead to more costly products.

• Global availability- In general, supply of certain low halogen display films is low. Until additional capacity can be created, availability and cost of these films may be affected.

Any of the properties listed above are frequently achievable in low halogen versions, but when certain performance at a particular cost is needed, it will be much more difficult to find a product that meets the low halogen criteria. Tapes, Adhesives, and Related Products Background Tapes, adhesives and related products used in electronics assembly are generally selected for desirable mechanical properties, cleanliness, favorable application processes, appropriate envi-ronmental stability and price. With the recent attention given to halogen content of these types of products, a number of general trends are notable and are discussed below. This product segment comprises a variety of tape constructions, curable liquid adhesives, and pressure sensitive adhesives (PSAs). These varied products in turn are formulated from di-


verse raw material streams, hence the halogen content can be generalized on the basis of the raw materials used. Trends and product examples are given below. Key requirements of tapes, adhesives, and related products The following properties define suitability for use of tapes, adhesives, and related products

Desirable mechanical properties

Cleanliness

Favorable application processes

Appropriate environmental stability

Cost Underwriters Laboratory (UL) Flammability Standards Tapes, adhesives and related products in this electronics segment generally do not contain flame retardants; therefore no halogens are introduced from brominated or chlorinated flame retardants. A UL rating of 94 HB is sometimes required of products for electronics assembly applications. Addition of flame retardants is not usually required to meet this UL rating. General Materials Trends with Regard to Halogen Content

• Tapes, adhesives and related products in this segment based on epoxy resins present substantial issues with regard to halogen content. Epoxy resins contain certain chlori-nated residues as a by-product of the epoxy synthesis. These chlorinated residues are benign towards the mechanical and environmental performance (e.g., humidity/ tem-perature durability testing) of the cured epoxy, and have only recently gained attention as a result of the industry halogen initiatives. Adhesives and tapes containing epoxy re-sins as raw materials may therefore be well above the 900 ppm level for chlorine and re-quire reformulation. Successful reformulation to reduce chlorine content is sometimes possible by reducing the epoxy content, using lower chlorine-content epoxy resins, or both. Some low-chlorine epoxy resins are available for this type of application. These low-chlorine resins are relatively expensive at this time as they have not attained the economies of scale. It is notable that numerous epoxy resins of tailored functionality and properties are currently used in formulation of electronics adhesives. Only a few of these have been produced in “lowered halogen” content to-date, making across-the-board reformulation difficult at this point in time.

• Generally speaking, adhesives, tapes and related products not addressed by the issues presented above are found to meet the low halogen definition. Adhesives based on acrylics, natural rubbers, and polyurethanes are typically low in halogen content and meet the low halogen definition, if not formulated with flame retardants. Tape backings such as polyesters or polyolefins also have halogen content well below the standard. In summary, adhesives and tapes not based on epoxy resins, or intentionally-added chlori-nated materials (PVC, flame retardants, etc) generally will meet the definition of low ha-logen.

• With the advent of low-halogen customer requirements for the electronics assembly segment, this product segment is now additionally differentiated from others. For exam-ple, aerospace, construction, printing and consumer markets may use similar products but without the low-halogen standard. Products have migrated into electronics assembly from these other applications areas and may be unsuitable for low-halogen applications. In aerospace applications, PVC (polyvinylchloride), for example, is preferred as an ad-


hesive backing due to the requirement of decades of product service life. The excep-tional environmental stability of PVC, Neoprene, and other chlorinated polymeric mate-rials make them favored for aerospace, construction, transportation and other environ-mentally demanding product application areas. It must be recognized that the halogen initiatives further differentiate electronics assembly products from other segments. Ac-cordingly, this will make supply chains more complex, increase the number of raw mate-rials required for product formulation, and add cost.

Current Usage of Halogens in tapes, adhesives, and related products: The following is a snapshot of the variety of tapes, adhesives, and related products with/without Bromine or Chlorine typically used in electronics in the product families shown. The list is not exhaustive. Films- Assembly Applications

• Labeling Facestock- may contain bromine or chlorine in coatings, with the total con-struction well below the definition of low halogen stated above.

• Warning/ Identification labels- Products used in this segment generally meet the defi-nition of low halogen stated above.

• Carriers/liners for tapes- Products used in the assembly segment generally meet the definition of low halogen stated above.

Tapes

• Rim Tapes- may contain bromine or chlorine in the adhesive above the definition of low halogen stated above.

• Conductive tapes- Most products meet the definition of low halogen stated above.

• Structural tapes- May contain bromine or chlorine in the adhesive above the definition of low halogen stated above if they are formulated with epoxy resins.

• Double sided tapes- Will meet the definition of low halogen stated above if not formu-lated with conventional epoxy resins.

• Adhesive transfer tapes- These are generally acrylic-based and meet the definition of low halogen stated above.

Adhesives

Form-in-place gaskets These are epoxy-based and can be reformulated to meet the definition of low halogen stated above, with some difficulty.

Neoprene Pressure Sensitive Adhesives (PSAs)- Neoprene adhesives are halogen-based and will not meet the definition of low halogen stated above.

Epoxy-based Adhesives including liquid epoxies- These will have chloride content above the definition of low halogen stated above, if based on conventional epoxy resins. Reformulation with low-halogen epoxy resins is possible, with some difficulty and poten-tial loss of properties.

Acrylic adhesives unlikely to contain bromine or chlorine above the definition of low ha-logen stated above.

Optical mounting adhesives unlikely to contain bromine or chlorine above the defini-tion of low halogen stated above.

Rubber-based PSAs unlikely to contain bromine or chlorine above the definition of low halogen stated above.


Film laminating/ optically clear adhesives unlikely to contain bromine or chlorine above the definition of low halogen stated above.

Conductive Adhesives unlikely to contain bromine or chlorine above the definition of low halogen stated above.

Low Halogen Alternative Summary: Moving to low halogen optical films, labels, tapes and adhesives may require substantial in-vestment and significant product and process qualification testing. This can affect product cost, availability, and project timelines significantly. In addition, there may be changes to perfor-mance of products based on reformulations to reduce bromine and chlorine content, as totally analogous low-halogen raw material alternatives are not always available. Another impact of the low-halogen initiatives is that further differentiation/specialization of products within the elec-tronics assembly segment, may lead to lower sales volumes and higher prices for these particu-lar specialized products that do not have the benefit of economies of scale.

9.0 Thermoplastic Films in Electrical & Electronic Applications

Background Flame retardant films are widely used in electrical & electronic devices (E&E). Good dielectric properties, high temperature and chemical resistance, good die-cut, thermoforming / cold form-ing ability, good compatibility with adhesives and ink are critical requirements for proper applica-tion in these environments. E&E flame retardant film applications, the Eco drivers, and the main E&E flame retardant films available in the current market will be discussed in the following para-graphs.

Main Applications EMI/RFI Shielding U.S. and European agencies continue to tighten regulations on EMI (electromagnetic interfe-rence) /RFI (radio frequency interference) emissions. Metallized polymer films can offer a low-cost, lightweight solution, while maintaining UL recognition. Die-cut insulators and spacers Good temperature and chemical resistance are its typical material properties. The films should also be easily thermoformed into complex, three-dimensional parts or cold-formed and show compatibility with many fastening and laminating adhesives. Insulation Barriers FR films are used as insulators in adapters, servers, inverters, batteries, and computers. Excel-lent thermal and electrical insulation properties are required. These films also offer important opportunities for weight/gauge and size reduction while maintaining UL recognition. Labels and overlays FR films can also be used in wide range of labels, nameplates and overlays, which require high temperature resistance, excellent electrical properties and compatibility with both UV-curing and conventional inks.


Printed circuits FR films used in printed circuits typically require low moisture absorption, high temperature re-sistance and resistance to a broad range of organic solvents and chemical detergents.

ECO Drivers Traditionally brominated or chlorinated flame retardant agents are widely used because of their high flame retardant efficiency and low price. Recently, some end users of E&E flame retardant films have posted more strict limitations, beyond EU RoHS requirements, to bromine and chlo-rine flame retardant agents. Now, though the E&E films with bromine or chlorine content still dominate the market, the bromine and chlorine-free E&E films are growing within the market.

Popular E&E Flame Retardant Films

Polycarbonate (PC) Film Polycarbonate flame retardant films usually use brominated flame retardant agents to achieve UL-94 V0 rating down to 10 mil gauge and UL-94 VTM0 rating down to 2 mil gauge. The films can be transparent, translucent or colored opaques. The films have high puncture resistance, low moisture absorption, high continuous use temperatures (RTI >120C) and excellent dielectric strength making them particularly suitable for adapter, inverter and server insulation applications . They can be produced in a variety of surface textures and easily fabricated into shaped articles through forming, lamination and in-mold decoration processes. The films can also be metallized for EMI/RFI shielding applications. Translucent and opaque bromine and chlorine-free V2, VTM-2 and VTM-0 PC films have re-cently been introduced to the market, and development efforts are under way for halogen-free, transparent V0 solutions.

Polypropylene (PP) Films These films typically use brominated flame retardant agents. They have low moisture absorp-tion, excellent dielectric strength, good score and folding ability, and lower price. However, their heat resistance is lower than PC films. They are typically used in insulation applications that do not require continuous use temperatures greater than 100C.

Polyester/Polycarbonate Blend Films These opaque films typically use brominated flame retardant agents. They have outstanding dielectric strength, chemical resistance and ease of fabrication (i.e.: thermoforming, embossing, clean-edge die-cutting, folding and bending), which makes them excellent for a wide range of electrical electronic and medical applications.

Polyetherimide (PEI) films They are bromine and chlorine-free flame retardant films. They have high modulus, high tem-perature resistance, low moisture absorption and excellent dielectric properties. These make them a popular choice for high-voltage internal insulation, high-temperature PSA (pressure sen-sitive adhesive) tapes, speaker cones, motor-slot liners and wedges, and transformer wraps. These products can also be directly metallized for EMI/RFI shielding applications.


Polyphenylene Ether (PPE) films Polyphenylene Ether films are another group of halogen-free flame retardant films. They have excellent temperature resistance, outstanding dielectric strength, ease of fabrication such as thermoforming, embossing, clean-edge die-cutting, score and bend. They are more cost effec-tive compared to PEI films.

Graphic films

Background Graphic films are characterized by a variety of surface finishes and textures as functional and/or aesthetic element. Standard or high performance polymer grades & colors also determine the end use application of graphic films. E.g. films made from polycarbonate (PC) offer outstanding optical clarity, material strength, consistent printability and ease of processing. Typical applica-tions of these films are as varied as in mold decorated parts to eye catching, cost effective dis-plays, automotive dials, labels for industrial equipment, control panels & digital media applica-tions. The use of halogenated additives in this product portfolio depends on the end use application. Graphic films need following attributes:

1. Printability: Graphic films should possess ability to achieve a variety of surface effects/ intricate designs through screen/offset printing. Printing on single/dual surface across a range of gages is desired with excellent ink adhesion to solvent based, UV, water based & IR inks. Typically polyest-ers/polycarbonate do not require any pre processing of the surface as opposed to polyolefin films, which require heat/plasma treatment for ink adhesion.

2. Optical Clarity: High light transmission & low haze is required. Light transmission equal to or greater than 90% is desired for LED/LCD window applications. Optical clarity across all the gages is also desira-ble in the graphic film portfolio.

3. Formability: High heat resistance, melt strength & dimensional stability are essential to allow close tolerance registration after repeated heating & drying samples. The material should offer ability to pro-duce deep drawn, three-dimensional parts using various vacuums forming processes and em-bossing operation.

4. Design freedom: Graphic films need to possess ability to replicate multiple textures. Textures can be a functional element for light management or they can hide scratches, defects, fingerprints & marring in heavy use application. They can also eliminate „hot spots‟ in back lit applications and facilitate coating application. Additionally, they can also provide aesthetic value to the end use applica-tion.


Graphic Films used in In-Mold decoration (IMD) applications

Background These films are used as decorative overlays, covers, outer skins in consumer electronic devices such as cell phones, laptops & portable media players. IMD offers many design flexibility and productivity advantages versus other decoration methods done after molding. These benefits include design flexibility; multiple colors, effects, and textures with a single operation; long-lasting graphics manufacturing productivity; and systems cost reductions.

1. Design Flexibility This allows your customers to express their personalities, while you easily manufacture products with radically different looks.

2. Multiple Colors, Effects, & Textures with a Single Operation

IMD allows you to achieve different colors, effects, and textures that are complete when the part comes out of the mold. When any of these factors need to change, there is no need to re-tool or change resin color. Simply change the film and you can change the appearance or texture dramatically.

3. Long-lasting Graphics

"Long-lasting" graphics are encapsulated between film and resin with IMD. Unlike tradi-tional 1st surface graphics that can wear off, 2nd surface IMD graphics can not be re-moved without destroying the part.

4. Manufacturing Productivity

Manufacturing gains can include: - Reduced secondary operations and labor - Production that molds and decorates in one operation - Elimination of adhesive (cost and process) - Lower system costs in many applications - Reduced inventory with capability to stock only one color of resin.

Underwriters Laboratory (UL) Flammability Standards IMD Films themselves generally do not carry UL flammability ratings because they are part of larger assemblies. These larger assemblies, rather than individual components, are required to meet UL flammability standards. Therefore, products in this segment generally do not contain flame retardants; hence no halogens are intentionally introduced from brominated or chlorinated flame retardants. Commonly available films are based on Polymethylmethacrylate, Polycarbo-nate, Polyesters or their blends.

Key requirements The following properties define suitability for use of films in electronics IMD applications:

• High Light Transparency and clarity

• Scratch resistance

• Chemical resistance on the outer surface

• Printability on the second surface without pre-treating


• Deep Draw Formability

• UV Weatherability

• Desirable mechanical properties

• Cleanliness

• Need for textured surface

• Appropriate environmental stability

• Cost

High Performance Coated Polycarbonate films

High performance coated polycarbonate films are design to offer better surface hardness, resis-tance to chemical attack, scratch and abrasion than equivalent non-coated polycarbonate film. These coated films are good candidates for a wide range of applications, for example flat mem-brane switch overlays, lenses and display windows for cell phones and other hand held devices, labels, automotive displays etc. They offer productivity gain when compared to post-coating processes. They are also use for extensively in graphic applications where the film can be printed on the second or first surface. These printed films can be subsequently use in a 2D in-mold-decoration process. Due to the inherent brittle nature of the hard coat on polycarbonate film, they are not typically used in 3 dimensional in-mold-decoration process or see only very limited use in smaller parts with shallow draw depth and very gentle edge radius. Development of more flexible coating allows the use of coated film in application where relatively deeper draws are feasible. Additional functionality can also be incorporated into the coating such as anti-fog capability and water shedding properties. Halogens such as Bromine or Chlorine are typically not incorporated into hard coated film where coating primary function is to increase the inherent surface chemical resistance, surface hardness and abrasion resistance. Hence, these hard coated films are typi-cally halogen-free.

10.0 Industry Enablement Activities to Transition to Halogen-free Products

10.1 General

The following non-technical issues are addressed in this section:

The Transition to Halogen-free Products

Potential Combinational Issues Affecting Reliability and Functionality

Availability and Volume Ramp up Issues

Supplier Information about the Technical Properties of Halogen-free Products The section is also an introduction to other services HDP User Group is providing.


10.2 The Transition to Halogen-free Products

Several of the HDP User Group members have ambitious environmental profiles. They want to comply with future more stringent market and legislative environmental requirements before they are forced to do so. The process of making the transition to Halogen-free products is complex. Many interactions between the supply chain companies and system integrators are needed.

10.3 Potential Combinational Issues Affecting Reliability and Functionality

The experience gained by HDP User Group (and other industry consortia) when preparing the transition to Lead-free solder joints is that there could be side effects when making broad ma-terial changes. One example is that the elevated temperature of the Lead-free assembly process influenced the reliability of via connections in the printed wiring boards. There is a po-tential risk that the new Halogen-free materials have different mechanical and electrical proper-ties. Examples are different dielectric constants of PCB laminate materials and less adherence of molding compounds to component leads. It is therefore important to investigate any possible combinational effect by assembling test ve-hicles of typical products and conducting comprehensive reliability and functionality testing. HDP User Group is planning several projects aimed at getting more knowledge about any po-tential reliability and/or functionality issues. The first project of this kind is focused on building a halogen-free PWB (board + components) for a notebook computer. Additional projects will ad-dress other typical products.

10.4 Availability and Volume Ramp-up Issues

The global infrastructure is facing the “Chicken and Egg Problem” with respect to halogen-free materials and components. Suppliers want to ensure there is adequate business opportunities before they can make investments. The users (OEMs) want to ensure technical feasibility, supply chain capability and suitable costs before they ramp-up in high volumes. The HDP User Group strategy is to facilitate the communication between all players within the supply chain. This shall be done by:

• Facilitate suppliers to display the properties of their Halogen-free products. See informa-tion in 6.5 Supplier Information about the Technical Properties of Halogen-free Products.

• Facilitate for suppliers to get information about potential opportunities from potential cus-tomers by assembling a “Halogen-free Transition Roadmap”.

The two activities would help enable suppliers to develop new Halogen-free products and in-crease production to meet market demands, particularly from OEMs who have established pub-lic commitments to phase-out the use of certain halogenated compounds, namely BFR and PVC. It is important to note that 7 of the top 10 global PC manufacturers have set goals to phase-out BFR and PVC; these 7 manufacturers represent over 50% of the worldwide market share for PCs (per IDC WW Quarterly PC Tracker for Q12008). For a list of OEM public commitments, please see below. Individual company websites include the latest information and take precedent over the information listed below.


Company Public Commitment Website for More Information

Acer Eliminate BFRs and PVC by 2009

http://global.acer.com/about/sustainability.htm

Apple Eliminate BFRs and PVC by end 2008

http://www.apple.com/environment/materials/

Dell Eliminate BFRs and PVC by 2009

http://www.dell.com/environment

HP Eliminate BFRs and PVC in new products in 2009

http://www.hp.com/hpinfo/globalcitizenship/environment/index.html

Lenovo Eliminate BFRs and PVC by 2009

http://www.pc.ibm.com/ww/lenovo/about/sustainability/environment/index.html

LG Eliminate BFRs and PVC by 2010

http://www.lge.com/about/sustainabili-ty/environmental_management.jsp

Philips Eliminate BFRs and PVC by 2012

http://www.philips.com/about/sustainability/index.page

Samsung Eliminate BFRs and PVC by 2010

http://www.samsung.com/us/aboutsam-sung/corpcitizenship/index.html

Sharp Eliminate BFRs and PVC by 2010

http://sharp-world.com/corporate/eco/environment_and_sharp/index.html

Sony Eliminate BFRs and PVC by 2010

http://www.sony.net/SonyInfo/Environment/index.html

Toshiba Eliminate BFRs and PVC by 2009

http://www.toshiba.co.jp/pc_env/index.html

Figure 16 – OEM Public Commitments on BFR and PVC

10.5 Supplier Information about the Technical Properties of Halogen-free

Products

It is important for system integrators planning to design halogen-free system products to have access to information about electrical and mechanical properties of the products they want to assemble. The suppliers usually supply this information but in different forms making it difficult for the users to compare the products and their suitability for the intended purpose. HDP User Group is therefore designing a distributed “Product Property Database” enabling users to get access to the properties of the products connected suppliers have available. The database will have lists of:

• Suppliers connected to the HDP User Group entry point at the HDP User Group website

• Classes of products in the database

• Properties to be displayed

• Test methods to be used by the suppliers when generating the properties





http://www.dell.com/environment






http://www.lge.com/about/sustainability/environmental_management.jsp





http://www.samsung.com/us/aboutsamsung/corpcitizenship/index.html











11.0 Appendices

APPENDIX 1

Flame retardant restrictions in European eco-label systems - April 2006 German Blue Angel Multifunctional devices RAL-UZ 114 Edition January 2005 Bans all PBBs & PBDEs in plastic parts (>25g) Used FRs to be declared by CAS numbers Not contain any substances which are classified in TRGS 905 or are classified as mutagenic, teratogenic, carcinogenic Printed wiring board material: No halogenated FRs Copiers RAL-UZ 62 Edition January 2005 Bans all PBBs & PBDEs in plastic parts (>25g) Used FRs to be declared by CAS numbers Not contain any substances which are classified in TRGS 905 or are classified as mutagenic, teratogenic, carcinogenic Printed circuit boards‟ base material: No PBBs, PBDEs or chloroparaffins Printers RAL-UZ 85 Edition January 2005 Bans all PBBs & PBDEs in plastic parts (>25g) Used FRs to be declared by CAS numbers Not contain any substances which are classified in TRGS 905 or are classified as mutagenic, teratogenic, carcinogenic Printed circuit boards‟ base material: No PBBs, PBDEs or chloroparaffins Portable computers RAL-UZ 93 Edition February 2004 Halogenated organic compounds (flame proofing agents) are prohibited Used FRs to be declared by CAS numbers Not contain any substances which are classified in TRGS 905 or are classified as mutagenic, teratogenic, carcinogenic The carrier material of printed circuit boards must not contain any PBBs, PBDEs or chlorinated paraffins Workstation computers RAL-UZ 78 Edition February 2004 Halogenated organic compounds (flame proofing agents) are prohibited Used FRs to be declared by CAS numbers Not contain any substances which are classified in TRGS 905 or are classified as mutagenic, teratogenic, carcinogenic The carrier material of printed circuit boards must not contain any PBBs, PBDEs or chlorinated paraffins Visual display unit (Workstation computers RAL-UZ 78 Edition February 2004) Not contain any substances which are classified in TRGS 905 or are classified as mutagenic, teratogenic, carcinogenic Halogenated organic compounds (flame proofing agents) are prohibited


Used FRs to be declared by CAS numbers Not contain any substances which are classified in TRGS 905 or are classified as mutagenic, teratogenic, carcinogenic Reprocessed Toner modules RAL-UZ 55 Edition February 2004 New parts added: No halogenated plastics. (No PBBs or PBDEs as FRs) Not contain any substances which are classified in TRGS 905 or are classified as mutagenic, teratogenic, carcinogenic Printed wiring board No criteria found Criteria exists for each IT products and print supplies No PBBs, PBDEs or chloroparaffins (Base material) Televisions No criteria found EU-Flower Televisions (2002/255/EG) Edition March 25th 2002 No FRs with specific CASno7 (PBDEs only) R45, R46, R50, R51, R52, R53, R60, R61 (LCD-screens, Hg restrictions only) Validity: March 2007 according to Kerstin Sahlén, SIS Miljömärkning Nordic Swan Toner cartridges Edition 2.4 April 22nd 1999 – April 11th 2007 (New edition in progress, Lena Rogeman) No chlorinated plastics (replaced parts) Televisions (Audiovisual Equipment, edition 2.2 March 19th 2003 – March 31st 2009) Chlorinated plastic parts not permitted (exception of electrical components in circuit boards) Halogenated FRs must not be added to the plastics Other FRs specified with CASno Other FRs in plastic parts >25g, R45, R46, R60, R61

7 * Casnumbers (PBDEs): 13654-09-6, 101-55-3, 2050-47-7, 49690-49-0, 40088-47-9, 32534-81-9,

36483-60-0, 68928-80-3, 32536-52-0, 63936-56-1, 1163-19-5, 85538-84-8


APPENDIX 2 European eco labelling systems, IT products and prints supplies – flame retardant re-strictions in plastic parts >25g status April 2006

Copier/printer/ fax/mfp

PC, mobile PC system, desktop

VDU Toner car-tridges

PWB printed Televisions

EU Flower

No criteria R45, R46, R60, R61, R50, R50/R53 R51/53

R45, R46, R60, R61, R50, R50/R53 R51/53

R45, R46, R60, R61, R50, R50/53 R51/53

No crite-ria

No criteria R45, R46, R50, R51, R52, R53, R60, R61

German Blue Angel

R40, R45, R49 R46, R68 R60, R61, R62, R63

R40, R45, R49 R46, R68 R60, R61, R62, R63

R40, R45, R49 R46, R68 R60, R61, R62, R63

R40, R45 R49, R46, R68 R60, R61 R62, R63

R40, R45 R49, R46, R68 R60, R61 R62, R63

No criteria No criteria

Nordic Swan

R40, R45, R46, R48, R49, R60, R61, R62, R63

R45, R46, R60, R61

R45, R46, R60, R61

R45, R46, R60, R61

Bans all chlori-nated plastics

R45, R46, R60, R61

R45, R46, R60, R61

TCO Bans all brominated and chlorinated substances Used FRs to be declared by CAS numbers

No crite-ria

No criteria No criteria

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