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Ashland Specialty Ingredients

Regulatory up date on biocides

Gilles PRADIER

New Products Leader APT Seminar April 4th 2014

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Ashland Specialty Ingredients

Overview

• Introduction about Ashland Biocides

• Technical support

• Re-Classification of Formaldehyde

• Impact on Ashland’s FH-donors classification?

• New labeling contrains (CLP regulation)

• Ashland’s solutions to avoid EU H208

• Conclusion,

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Ashland Specialty Ingredients

1. Introduction

Ashland’s Biocides

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Ashland Specialty Ingredients

2002: Acquired

Degussa’s Biocides

business

2004: Acquired Biochema

Schwaben

2006: Added businesses

of Milker & Grüning,

Progiven,

2007: Acquired

Bode Chemie

Nuodex/Tenneco/

Creanova/Degussa

2011

ISP

acquisition

History of Ashland’s Biocides

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Ashland Specialty Ingredients

Memmingen, Germany Leaside, Canada

Chatham, USA Horhausen, Germany

Biocides manufacturing facilities

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Ashland Specialty Ingredients

WET-STATE PROTECTION

Nuosept ®

Bodoxin, Bacillat, Ebotec

DRY FILM PROTECTION

Fungitrol ®

Cinon, Fongal

Ashland ‘s brands

• Nuosept ® : IN-CAN biocides

ensure “wet-state preservation”

of water-based products

•Fungitrol ® : DRY-FILM biocides

ensure film protection against

fungi & algae defacements

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Active substances supported by Ashland in Europe

Active substances CAS N° Product

Types(PT)

Rapporteur

Member

State

Dossier submitted by /

companies

EG-Form (EU)

(Ethylendioxy) dimethanol

3586--55--8 2, 6, 11,

12*, 13

Poland ASI in task force

* ASI

HHT (EU/US)

(Hexahydrotriazin)

4719-04-4 6,

11*,12*,

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Poland ASI in task force

*ASI

TMAD (EU)

(Tetra Methylol Acetylene Diurea)

5395-50-6 2, 6, 11,

12, 13

Spain ASI in task force

Na-N(hydroxymethylglycinate)

(EU/US/CDN)

70161-44-3 6 Austria ASI

BIT (EU/US/CDN) 2634-33-5 6, 12, 13 Spain Data access

IPBC (EU/US/CDN)

(Iodo propynyl butyl carbamate)

55406-53-6 6, 7, 8, 9,

10, 13

Denmark ASI in task force

Folpet) EU/US/CDN)

(N-(trichloromethylthio)phthalimide)

133-07-3 7, 9 Italy Data access

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2. Technical support

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Technical support

Biocide

selection

Plant Hygiene

Bio-audit

Challenge tests

HPLC analysis

Optimal

preservation

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Technical support/In-Can challenge tests

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Technical support/ Dry film biocides

• Bio-resistance tests :

Fungus resistance EN 15457

Algae resistance EN 15458

• Yellowing (L*a*b ; Yi measurement)

• On site expertise/strain identification

• Fence test exposure (Memmingen)

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Fungus resistance test/ Façade paints

Unprotected paint Protected protected

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Algae resistance test of façade paints

Unprotected render Protected render

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Technical support/Dry film challenge tests

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3. Re-classification of Formaldehyde

& FH-donors

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Reclassification of Formaldehyde

and related effects on FH Donors mixtures

• Formaldehyde will be reclassified from 1st April 2015 :

carcinogen category 2 H351 to a carcinogen category 1B H350

• Formaldehyde Donors and Formaldehyde donors containing

mixtures will be reclassified as carcinogen category 1B H350 if

containing > 0.1% “Free Formaldehyde” (NMR analysis)

No labeling impact to paints when FH-donors are used at

recommended levels

Handling restrictions for CAR Cat 1B mixtures

(limited storage for plants below “Seveso” classification)

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¤ O-FORMAL

EDDM or EG-formal (Bodoxin)

Fast releasing FA-Donor / release factor 49%

Free FH content > 0,1% for most of EDDM-biocides

Most of EDDM-biocides will be classified as CAR Cat 1B

Might limit storage in plant sites not classified « SEVESO »

¤ N-FORMAL

TMAD (Bacillat )

Slow releasing FA-Donor / release factor 26%

Premium quality TMAD available with less than 0,1% Free FH

Most of Bacillat will not get re-classified Car Cat 1B

No handling & storage restriction

Impact on Ashland’s FH Donors

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5. Impact of the new labeling regulation (CLP)

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•Labeling rules will change for mixtures containing skin sensitizing substances from 1st June 2015

• New Information statement « EU H208 » will prevent end-users about the presence of skin sensitizing substances if their concentrations exceed 1/10 of current labelling limits

“Contains (name of sensitizing substance)

May produce an allergic reaction”

This information statement might be a problem for DIY

market and more particularly for premium quality paints

CLP Regulation/ New EU H208 Info statement

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New labeling limits EU H208

Substances EU H208 triggers EU Ecolabel

CMIT/MIT 1.5 ppm 15 ppm/ Iso total<500ppm

IN-CAN TOTAL <600ppm

OIT 50 ppm <500ppm

IN-CAN TOTAL <600ppm

BIT 50 ppm <500ppm

IN-CAN TOTAL <600ppm

MIT 100 ppm 200 ppm: Iso total<500ppm

IN-CAN TOTAL <600ppm

DCOIT 100 ppm Dry film total < 0,1% Indoor

Dry film tottal < 0,3% outdoor

EDDM 410 ppm* <10ppm free FH VdL 03

TMAD 760 ppm* <10 ppm free FH VdL 03

DBDCB 1000 ppm IN-Can tital < 600ppm

IPBC 1000 ppm 1000p pm indoor

6500 ppm outdoor

BRONOPOL Non skin sensitizing <10 ppm Free FH VdL 03

IN-CAN TOTAL <600ppm

Zinc Pyrithione Non skin sensitizing

500ppm

IN-CAN TOTAL <600ppm

Phenoxy Ethanol Non skin sensitizing IN-CAN TOTAL <600ppm

*Max. values recommended by ASI to avoid exceeding 200ppm free Formaldehyde in end products

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Ashland’s solutions to avoid EU H208

a. Formaldehyde-donors biocides

b. Bronopol-Biocides

c. Formaldehyde-free Biocides

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Ashland Specialty Ingredients

• 0,1-0,2% Nuosept TBM 40 max. (760ppmTMAD +50ppm BIT+ 50ppm MIT)

Ideal for replacing CMIT/MIT + FH-Donors and/or BIT+ FH-Donors

• 0.15-0.28% Bacillat TK : Max. (760ppm TMAD+ 50ppm MIT)

Booster recommended in combination with 0,1% Nuosept BM22) (5%BIT+ 5%MIT)

Flex solution 50ppm BIT+ 100ppm MIT+ 760 ppm TMAD

• 0.15-0.3% Bacillat TOK: Max. ( 250 ppm TMAD+ 100ppm MIT+ 50ppmOIT)

Low emission FH <100ppm/, Enhanced fungicidal resistance

• 0.05-0.13% Bacillat + 0.1% Nuosept BM22 :

max. (760ppmTMAD +50ppmBIT+ 50ppmMIT)

Flex. Solution/Possible adjustment of active contents

a.Labeling free solutions/ FH-Donors

N-Formal Actives EUH208

“statement”

trigger

Nuosept TBM 40 (NEW) TMAD + BIT+ MIT 0,20%

Bacillat TK TMAD + MIT 0,28%

Bacillat TOK TMAD + MIT + OIT 0,33%

Bacillat TMAD 0,13%

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Nuosept TBM40

•Solution of BIT/MIT/TMAD in a non VOC carrier

•No CAR Cat 1B classification

•No EUH208 to customer end-products

•Liquid solution/easy to pour & handle

•Low odor

•Highly concentrated/High performances

•Broad spectrum of efficacy vs bacteria/yeasts/molds

•Head space protection

•Typical use : 0,1-0,2%

a.Labeling free solutions/ FH-Donors

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PRODUCT name

Actives NEW

EU H308

triggers

Nuosept KMB (NEW) BIT/MIT/BNPD 0.2%

Ebotec KB MIT/BNPD 0.5%

b. Labeling free solutions/Bronopol

• Nuosept KMB :

Broad spectrum of activity

Fast speed of kill

Eu Ecolabel compliance

Cost effective

• Ebotec KB :

Booster recommended at the early stage of the production

in combination with BIT/MIT

0,1-0,2% Ebotec KB + 0,1% Nuosept BM22

Max. 50ppm BIT+ 100ppm MIT+ 200 ppm BNPD

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FA-free products

Actives EU H208

“statement”

trigger in %

Nuosept BM22 BIT/MIT 0,10%

Nuosept BMZ (NEW) BIT/MIT/ZnPt 0,2%

c. Labeling free solutions/FH-Free biocides

• Nuosept BMZ: BIT + MIT + ZnPt

Broad spectrum of efficacy

Enhanced fungicidal properties

protection of the interface liquid/head space

Cost effective preservation

Ideal substitution of preservation based on

BIT+ MIT + CMIT/MIT

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• Ashland offers FH-donors biocides which will not get

reclassified as CAR Cat 1B

• Ashland offers various biocide solutions in line with Eu-

Ecolabel & without EU H208 Infop statement to your

paints

• For more information and discuss the most adequate

solutions to your needs, please contact :

BRENTAG Portugal

or directly gpradier@ashland.com

Conclusion

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Thanks for your

attention

Any question?