INVISTA North America v. M&G et. al.

8/3/2019 INVISTA North America v. M&G et. al.

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IN THE UN ITED STATES D ISTRICT COU RTFOR THE DISTRICT OF DELAW AREINVISTA NORTH AMERICA S.AR.L.,

Plaintiff,C.A. No.

V.

M & G U S A C O R P O R A T I O N a n dM & G P O L Y ME R S U S A , L L C , J U R Y T R IA L D E M A N D E DDefendants.

C O M P L A I N T F O R P A T E N T IN F R I N G E M E N TPlaintiff INVISTA North America S.t r.l., by its attorney, Fish & Richardson P.C., for its

complaint against Defendants M&G USA Corporation and M&G Polymers USA, LLC ("M&G"or "Defendants"), alleges as follows:

The Nature of the Action1. This is an action for infringement of United States Patent Nos. 7,943,216 ("the

'216 patent") and 7, 879,930 ("the ' 930 patent") (collectively, the "IN VI S TA PE T P atents").The Parties

2. Plaintiff INVISTA North America S.it r.1. ("INVISTA") is a corporationorganized and existing under the laws of Luxembourg, with its corporate headquarters located at4123 East 37th Street North, Wichita, Kansas. INVISTA is one of the world's largest integratedproducers of polymers. INVISTA is registered to do business in the State of Delaware with aplace of business at Three Little Falls Centre, 2801 Centerville Road, Wilmington, Delaware19808.


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3. On information and belief, Defendant M&G USA Corporation, is a corporationorganized and existing under the laws of the State of Delaware, with a principal place of businessat State Route 2, Apple Grove, West Virginia 25502.

4. On information and belief, Defendant M&G Polymers USA, LLC, is a whollyowned subsidiary of M&G USA Corporation and is a corporation organized and existing underthe laws of the State of Delaware, with a principal place of business at 6951 Ridge Road, SharonCenter, Ohio 44274.

Jurisdiction and Venue5. This action arises under the patent laws of the United States of America, United

States Code, Title 35, Section 1, et seq. This Court has subject matter jurisdiction over the actionunder 28 U.S.C. 1331 and 1338.

6. Based on the facts and causes alleged herein, this Court has personal jurisdictionover Defendants.

7. Venue is proper in this Court under 28 U.S.C. 1391 and 1400(b).The Patents-in-Suit

8. The '216 patent, entitled "Method to Make Single-Layer PET Bottles with HighBarrier and Improved Clarity," issued to Zhenguo Liu, Sanja Mehta, Xiaoyan Huang, and DavidA. Schiraldi on May 17, 2011. INVISTA, as the assignee, owns the entire right, title, andinterest in the '216 patent. A copy of the '216 patent is attached to this complaint as Exhibit A.

9. The '930 patent, entitled "Colored Oxygen Scavenging Polymers," issued toZhenguo Liu on February 1,2011. INVISTA, as the assignee, owns the entire right, title, andinterest in the '930 patent. A copy of the '930 patent is attached to this complaint as Exhibit B.


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Additional Facts Relevant to All Counts10. On information and belief, M&G sells PET resins throughout the United States,

including this judicial district. Two of these resins are M&G's PoliProtect APB and PoliProtectJB products.

11. On information and belief, M&G manufactures, sells, offers to sell, and exportsPoliProtect APB and PoliProtect JB for use in the manufacture of food packaging articles.

12. On or around August 9, 2008, M&G submitted a food contact notification (FCNNo. 851) with the United States Food and Drug Administration to provide for the safe use of

hexanedioic acid, polymer with 1,3-benzenedimethanamine in conjunction with up to 0.015weight percent cobalt neodecanoate as a modifier of ethylene phthalate polymers, which may beused in the manufacture of food contact containers.

13. On or around September 30, 2005, M&G submitted a food contact notification(FC N N o. 546) to the Un ited S tates Food and D rug Adm inistration to provide for the safe use of1,3-Benzenedicarboxylic acid, 5-sulfo-, monolithium salt as a modifier ofpoly(ethylenephthalate) polymers and copolymers, which may be used in the manufacture of soda and beerbottles.

14. On information and belief, hexanedioic acid, polymer with 1,3-benzenedimethanamine in conjunction with up to 0.015 weight percent cobalt neodecanoate as amodifier of ethylene phthalate polymers and 1,3-Benzenedicarboxylic acid, 5-sulfo-,

monolithium salt as a modifier of poly(ethylene phthalate) polymers and copolymers arecomponents in PoliProtect APB and PoliProtect JB resins and PoliProtect APB and PoliProtectJB food packaging articles.


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15. On information and belief, M&G's customers make, use, sell, offer to sell and/orimport PoliProtect APB and PoliProtect JB food packaging articles in the United States.

16. M&G states on the PoliProtect APB Data Sheet:If colorants are to be used with M&G PoliProtect APB Polyester Resin pleasecontact your M&G technical contact as some colorants have been found to bedetrimental to the active portion of the oxygen barrier. Your M&G technicalcontact can determine if the colorant is on the list of tested colors.17. M&G states on the PoliProtect JB Data sheet:If colorants are to be used with M&G PoliProtect APB Polyester Resin pleasecontact your M&G technical contact as some colorants have been found to bedetrimental to the active portion of the oxygen barrier. Your M&G technicalcontact can determine if the colorant is on the list of tested colors.18. On information and belief, M&G manufactures, offers for sale, and sells

PoliProtect APB and PoliProtect JB resins in the United States and encourages its customers tocombine colorants with the PoliProtect APB and PoliProtect JB resins.

Count I(Direct Infringement of the '216 Patent under 35 U.S.C. 271(a))

19. Paragraphs 1 to 18 are incorporated herein as set forth above.20. Upon information and belief, M&G has knowledge of the '216 patent through at

least its continued participation in a European Opposition of the European counterpart to the'216 patent, E P 1 663 630.

21. Defendants have been and are now infringing directly one or more claims of the

'216 patent in this District and elsewhere in the United States by making, using, selling, offeringto sell, and/or importing PET products, including without limitation their PoliProtect APB andPoliProtect JB resins, covered by one or more claims of the '216 patent, to the injury ofINVISTA. Defendants' acts of infringement have injured and damaged INVISTA.


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22. Defendants' infringement of the '216 patent has been and continues to be willful.23. Defendants' infringement has caused irreparable injury for which monetary

damages are inadequate and will continue to cause irreparable injury unless and until Defendantsare enjoined from further infringement by this Court.

Count II(Indirect Infringement of the '216 Patent under 35 U.S.C. 271(b) and (c))


least its continued participation in a European Opposition of the European counterpart to the'216 patent, E P 1 663 630.

26. Defendants have been and are now infringing by contributing to or inducing theircustomers to make, use, sell, offer to sell, and/or import, in this District and elsewhere in theUnited States, PET products, including without limitation their PoliProtect APB and PoliProtectJB resins and PoliProtect APB and PoliProtect JB food packaging articles, covered by one ormore claims of the '216 patent, all to the injury of INVISTA. The PoliProtect APB andPoliProtect JB resins have no substantial non-infringing use and are specially designated to workwith the patented invention. Defendants' acts of infringement were done with knowledge of theINVISTA PET patents and with the intent to encourage infringement. Defendants' acts ofinfringement have injured and damaged INVISTA.

27. Defendants' infringement of the '216 patent has been and continues to be willful.28. Defendants' infringement has caused irreparable injury for which monetary

damages are inadequate and will continue to cause irreparable injury unless and until Defendantsare enjoined from further infringement by this Court.


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Count III(Indirect Infringement of the '930 Patent under 35 U.S.C 271(b) and (f))


least its continued participation in a European Opposition of the European counterpart to the'930 patent, EP 1 778 791. COBARR S.p.A. is the opponent in the opposition ofEP 1 778 791.E P 1 778 791 w as issued from W O 2005 U S 29297, which was also the application from whichthe '930 patent issued. Upon information and belief, COBARR S.p.A. is a wholly owned

subsidiary of M&G Finanziaria S.r.1., which is also the parent of M&G.31. Defendants have been and are now infringing by inducing their customers to

make, use, sell, offer to sell, and/or import, in this District and elsewhere in the United States,PET products, including without limitation, PoliProtect APB and PoliProtect JB resins withcolorants, as covered by one or more of the claims of the '930 patent, all to the injury of1NVISTA. Defendants' acts of infringement have injured and damaged INVISTA.

32. Defendants have been and are now infringing by inducement one or more claimsof the '930 patent in this District and elsewhere by supplying or causing to be supplied orexporting all or a substantial portion of the components of the invention covered by one or moreclaims of the '930 patent, including without limitation their PoliProtect APB and PoliProtect JBresins, and by inducing the combination of such components outside of the United States, all to

the injury of INVISTA. Defendants' acts of infringement were done with knowledge of theINVISTA PET patents and with the intent to encourage infringement. Defendants' acts ofinfringement have injured and damaged INVISTA.

33. Defendants' infringement of the '930 patent has been and continues to be willful.

6


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34. Defendants' infringement has caused irreparable injury to INVISTA for whichmonetary damages are inadequate and will continue to cause irreparable injury unless and untilDefendants are enjoined from further infringement by this Court.

Prayer for ReliefWHEREFORE, Plaintiffs request the following relief:a. Judgment that Defendants infringe the '216 patent;b. Judgment that Defendants infringe the '930 patent;c. An injunction permanently enjoining and restraining Defendants, and their

successors, assigns, officers, agents, servants, employees, attorneys, and persons in activeconcert or participation with them, including any affiliated entities, during the term of thepatents-in-suit (the '216 patent and the '930 patent), from infringing and from inducing,contributing to, or otherwise causing the infringement of the patents-in-suit by making, using,selling, or offering to sell in the United States, importing into the United States or exporting outof the United States any products that infringe any claims of the patents-in-suit, including thePoliProtect APB and PoliProtect JB resins and food packaging articles, or by supplying orcausing to be supplied any products that induce or contribute to the same by others, includingthird parties outside of the United States.

d. That judgment be entered against Defendants for money damages sufficient tocompensate 1NVISTA for Defendants' infringement of the '216 patent and the '930 patent in an

amount to be determined at trial, including lost profits;e. That any such money judgment be trebled as a result of the willful nature of

Defendants' infringement;f. That this Court declare this case an exceptional case pursuant to 35 U.S.C. 285;


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g. For an accounting for any infringing sales not presented at trial and an award bythe Court of additional damages for any such infringing sales; and

h. That this Court award INVISTA costs and attorneys' fees and such other relief asis just.

JU R Y D E M A N DINVISTA demands trial by jury.

Dated: October 21, 2011 FISH & RICHARDSON P.C.

By:William J. Marsden,Douglas E. McCann (#382)AnnaMartina Hiifnal (#2771)222 Delaware Avenue, 17th FloorP.O. Box 1114Wilmington, DE 19801Telephone: (302) 652-5070Facsimile: (302) [email protected]@[email protected] E. SingerFISH & RICHARDSON P.C.60 S outh Sixth Street3300 R BC P lazaMinneapolis, MN 55402(612) [email protected]

ATTORNEYS FOR PLAINTIFFINVISTA NORTH AMERICA S.)k R.L.


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Exhibit A


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I I I I l l l I I I I l l l I I I I I I I I I l l l l l l l l l l l l I l l i l l lUS007943216B2(12) United S tates Patent

Liu et al.(lO) Patent No.: US 7,943,216 B2(45) Date of Patent: May 17, 2011

( 5 4 )

( 7 5 )

( 7 3 )(*)

METHOD TO MAKE S INGLE-LAYER PETBOTTLES WITH HIGH BARRIER ANDIMPROVED CLARITYhwentors: Zhenguo Liu, Flanders, NJ (US ); SanjaMehta, Spartanburg, SC (US); XiaoyanHuang, Marietta, GA (US); David ASchiraldi, Shaker Heights, OH (US)Assignee: INVISTA North Americal S.ar.l.,W ilmington, DE (US )

( 6 0 )( 5 1 )

( 5 6 )

( 5 2 )( 5 8 )

( 6 2 )

( 2 1 )( 2 2 )( 6 5 )

Notice: Sub ject to aw disclaimer, the term of thispatent is extended or adjusted under 35U.S.C . 154(b) by 0 days.Appl. No.: 12/768,541Filed: Apr. 27, 2010

Prior Publication D ataUS 2010/0209641 AI Aug. i9, 2010

Related U.S. Application DataDivision of application No. 10/569,614, filed asapplication No. PCT /US 2004/025257 on Aug. 5,2004.Provisional application No. 60/498,311, filed on Aug.26, 2003.Int. C1.C08K 5/00 (2006.01)B32B 27/34 (2006.01)B32B 2 7/08 (2006.01)B65D 23/00 (2006.01)B65D 23/02 (2006.01)U.S. C1 ...................... 428/34.1; 428/35.7; 428/36.9;5 2 4 / 4 1 3 ; 5 2 4 / 4 3 5 ; 5 2 4 / 5 3 8 ; 5 2 5 / 4 2 5Field of Classificatlon Search .......... ........ 525/425;524/413,435, 538; 428/34,1, 35.7, 36.9See application file for complete search history.

References CitedU . S. PATEN T D OC U M EN TS

4,187,358 A4,499,262 A4,501,781 A4,837,115 A4,957,980 A5,021,515 A5,258,233 A5,266,413 A5,281,360 A5,300,572 A5,340,884 A

211980 Kyo2/1985 F agerbttrg2/1985 Kushida6/1989 Igarashi9/1990 Kobayashi6/1991 Coclu'an11/1993 Mills11/1993 Mills1/1994 Hong4/1994 Tajima8/1994 Mills

FOREIGN PATENT DOCUMENTSEP 0301719 2/1989JP 02-135259 9/1988JP 63-288993 1111988JP 402135259 A * 511990JP 2663578 10/1997W O W O 01/090238 1112001

5,623,047 A 4/1997 Yuo5,639,815 A 6/1997 Cochran5,650,469 A 7/1997 Long5,866,649 A 2/1999 I-long5,955,527 A * 9/1999 Cochranetal ....... ...... ... 524/4136,083,585 A 7/2000 Ca hill6,239,233 B1 5/2001 Bell6,288,161 B1 9/2001 Kim6,346,307 B1 2/2002 AI Ghatta6,346,308 BI 2/2002 C ahill6,406,766 B1 6/2002 Rotter6,506,463 B1 1/2003 Ca hill6,509,436 B1 1/2003 Ca hill6,444,283 B1 912003 Tamer6,933,055 B2* 8/2005 Share et al ................ . 428,/474.42002/0063238 AI 5/2002 Cochran200310134966 A1 7/2003 Kim

200410013833 AI* 1/2004 Leeetal ....... ........ ....... 428/35,7

OTHER PUBLICATIONSMitsubishi Gas Chemical Company, Inc., Nylon-MXD6, SuperiorPerformance in Barrier Packaging; website--www.mgc-a.com/Pages/MXD6!media/Mxd6brAr.pdf.* cited by examinerPrimary Examiner -- Ana L Woodward(74) Attorney, Agent, or Firm -- Craig M. Sterner(57) ABSTRACTThe present invention comprises a blend of polyester and apartially aromatic polyamide with ma ionic compatibilizerand a cob alt salt. This blend can be processed into a containerthat has both active and passive oxygen barrier and carbondioxide barrier properties at an improved color and claritythan containers known in the art. The partially aromaticpolyamide is preferably meta-xylylene adipamide. T he ioniccompatibilizer is preferably 5-sodiumsulfoisophthalic acid or5-zincsulfoisophthalic acid, or their dialkyl esters such as thedimethyl ester (SIM) mid glycol ester (SIPEG ). The cobaltsalt is selected foma the class of cobalt acetate, cobalt carbon-ate, cobalt chloride, cobalt hydroxide, cobalt napltthenate,cobalt oleate, cobalt l inoleate, cobalt octoate, cobalt stearate,cobalt nitrate, cobalt phosphate, cobalt sulfate, cobalt (ethyl-ene glycolate), or mixtures of two or more of these. Thepartially aromatic polyamide is present ha a range from about1 to about I0 wt. % of said composition. The ionic compati-bil izer is present in a range from abo ut 0.1 to about 2.0 m ol-%of said composition. The cobalt salt is present in a range fromabout 20 to ab out 500 ppm of said composition.

15 Claims, 2 Drawing Sheets


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U.S. Patent May 17, 2011 Sheet 1 0f2 US 7,943,216 B2

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U.S. Patent May 17, 2011 Sheet 2 of 2 US 7,943,216 B2

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US 7,943,216 B21METHOD TO MAKE S INGLE-LAYER PETBOTTLES WITH HIGH BARRIER ANDIMPROVED C LARITYCROSS REFERENCE TO RELATEDAPPLICATION

This applicationis a division ofU,S , patent application SenNo. 10/569,614 filed Feb. 24, 2006; which is a 371 of PCT/US04125257 filedAug. 5, 2004; which claims benefit ofpri- 10ori ty lom U.S . Provisional Appl ication Ser. N o. 601498,311filed Ang. 26, 2003,

BACKGROUND OF THE INVENTION1) Field of the hlventionThe invention relates to compatibilized blends of polya-

mides in polyesters, a method for forming such compositions,and to containers made from such compositions. Specificallythe compositions have less yellowness than previous blend s.The blends can be used as passive gas barriers, or activeoxygen scaven gers with the addition of a transition metalcatalyst.2) Prior Art

Plastic materials have bee n replacing glass and metal pack -aging materials due to their lighter weight, decreased break-age compared to glass, and potentially lower cost. One majordeficiency with polyesters is its relatively high gas permeabi!-ity. This restricts the shelf life of carbonated soft drinks andoxygen sensitive materials such as beer and lmit juices.

Multilayer bottles containing a low gas permeable polymeras an inner layer, with polyesters as the other layers, havebeen connnercialized. Blends of these low gas permeablepolymers into polyester have not been successfffl due to hazeformed by the domains in tM two-phase system. The pre-ferred polyamide is a partially aromatic polyamide contain-ing meta-xylylene goups, especially poly (m-xylylene adi-pamide), MXD6.The MX D6 b ulletin (TR N o. 0009-E) from Mitsubishi GasChcntical Company, Inc., Tokyo Japan, dearly shows that thehaze of a multilayer bottle containing a layer of 5 wt-%MXD6 is -1% compared to 15% for a blend of the sanle 5wt-%.

However, the use of partially aromatic polyamides as thelow gas permeable polymer gives an increase in the yellow-ness of the resultant container.

U.S . Pat. No. 4,501,781 to Kushida etal. discloses a hollowblow-molded biaxially oriented bottle shaped container com-prising a mixture of polyethylene terephthalate (PET) resinmid a xylylene gruup-containing polyamide resin. Bothmonolayer mid mnltilayer containers are disclosed, but thereis no information on the color of the bottles.

U.S. Pat. No. 5,650,469 to Long etal. discloses the use ofa terephthalic acid based polyester blended with low levels(0.05 to 2.0 wt-%) ofa polyamide to rednce the acetald&ydelevel of the container. These blends produced lower yellow-ness containers than a corresponding blend made from adimethyl terephthalate based polyester, but are still tmsatis-factory for the higher levels required to significantly lower(decrease) the gas permeability.

U.S. Pat. Nos. 5,258,233, 5,266,413 and 5,340,884 to Millset al. discloses a polyester composition comprising 0.05 to 2.0wt-% of low molecular weight polyamide. At a 0.5 wt-%blend of MXD6 the haze of the bottle increased from 0.7 to1.2%. No gas permeation or color data is given.

U.S. Pat. No. 4,837,115 to Igarashi et al. discloses a blendof amino terminated polyamides with PET to reduce acetal-

2dehyde levels. There was no increase in haze with the add itionof 0.5 wt-% MXD6, but at 2 wt-% the haze increased from 1.7to 2.4%. N o gas permeation or color data is given.

U.S. Pat. No. 6,239,233 to Bell et al. discloses a blend of5 acid temtinated polyamides with PET that has reduced yel-lowness compared to amino terminated polyamides. No gaspermeation data is given.

U.S . Pat. No. 6,346,307 to A1 G hatta et al. discloses tbe useof a dimthydride of a tetmcarboxylic acid to reduce the dis-persed domain size of a blend of MXD6 in PET. Theexamples did not give color data, but at a 10 wt-% MXD6blend level the oxygen permeability was rednced from 0.53 to0.12 ml/bottle/day/aml and the carbon dioxide permeabilitywas reduced from 18.2 to 7.02 ml/bottle/day/atm.

U.S. Pat. No. 6,444,283 to Tnruer et al. discloses that low15 molecular weight MXD 6 polyamides have lower haze thanhigher molecular weight MXD 6 when blended with PET . Theexamples did not give color data, but at a 2 wt-% MXD6(MitsubisN C hemical Company grade 6007) the oxygen per-meability of an oriented film was reduced from 8.1 to 5.7

20 cc-mil/100 ina-atm-day compared to 6.1 for the low molecu-lar weight MXD6.U.S. Pat. No. 4,957,980 to Koyayashi et al. discloses theuse ofmaleic anhydride grafted copolyesters to compatibilize

polyester-MXD6 blends.25 U.S . Pat. No. 4,499,262 to Fagerburg et al. discloses sulfo-modified polyesters that give an improved rate of acetalde-hyde generation and a lower critical planar stretch ratio.Blends with polyamides were not discussed.

Japanese Pat. No. 2663578 B2 to Katsumasa et al. dis-closes the use of 0.5 to 10 mole % 5-sulfoisophthalte copoly-0 mers as compatibilizer ofpolyester-MXD6 blends. No colordata was given.

The use of a transition metal catalyst to promote oxygenscavenging in polyamide mnltilayer containers, and blendswith PET , has been disclosed in the following patents, for

5 example.U.S. Pat. Nos. 5,021,515, 5,639,815 and 5,955,527 toCochran e t al. disclose the use of a cob alt salt as the preferred

transition metal catalyst and MXD6 as the preferred polya-mide. There is no data on the color or haze of the polyamide

40 blends.U.S. Pat. Nos. 5,281,360 and 5,866,649 to Hong, and U.S,Pat. No. 6,288,161 to Kim discloses blends of MX D6 with

PE T and a cobalt salt catalyst. There is no data on the color orhaze of the polyamide blends.45 U.S . Pat. No. 5,623,047 to You et al. discloses the use of a

catalyst composition containing an alkali metal acetate, pref-erably 30 ppm cobalt acetate to mask the yellowness in poly-esters polymerized from terephthalic acid.US Pat. Application 2003/0134966 A1 to Kim etal. dis-

5o closes the use of cobalt octoate and xylene group-containingpolyamides for use in multi-layer extrusion blow-molding forimproved clarity. Extrusion blow-molding ntinimizes the ori-entation of the polyamide doma in size compared to in.]ectionstretch blow molding containers. No color data is given.

s5 There is a need for an improved gas barrier polyester com-position that can be injection stretch blow molded as a mono-layer container that has reduced yellowness and adequatehaze. This is particularly required for containers that requirea long shelf life, such as beer a nd other oxygen sensitive

60 materials. None of these patents disclose how tiffs balance ofproperties can b e achieved.

SUMMARY OF THE INVENTION6s The present invention is an improvement over polyester/polyamide blends lcnown in the art in that these compositions

have reduced yellowness.


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US 7,943,216 B23In the broadest sense the presem invention comprises a

compatibilized b lend of polyester and a partially aromaticpolyamide with an ionic compatibilizer and a cobalt salt.The b roadest scope of the present invention also comprises

a container that has both active and passive oxygen barrierand carbon dioxide barrier properties at an improved colorand clarity than containers known in the art.

In the broadest sense the present invention also comprisesa container in which the balance of gas barrier properties andcolor can be independently balanced.

In the broadest sense the present invention is a method toblend polyester and polyamides with an ionic compatibilizerand a cobalt salt.The drawing is to aid those skilled in the art in tmderstand-ing the invention and is not meant to limit the scope of theinvention in any mmmer beyond the scope of the claims.

FIG. 1 shows a graph of the oxygen permeation rate ofselected runs of Example 3.

FIG. 2 shows a graph of the oxygen permeation rate of theruns of Example 4.

DETAILED DESCRIPTION OF THE INVENTIONCom positions of the present invention comprise: polyester,partially aromatic polyamide, ionic com patibilizer, and a

cobalt salt.Geuerally polyesters can be prepared by one of two pro-

cesses, namely: (1) the ester process and (2) the acid process.The ester process is where a dicarboxylic ester (such as dim-ethyl terephthalate) is reacted with ethylene glycol or otherdiol in an ester interchange reaction. Beca use the reaction isreversible, it is generally necessary to remove the alcohol(methanol when dimethyl terephthalate is employed) to com-pletely convert the raw materials into monomers. Certaincatalysts are well known for use in the ester interchangereaction. In the past, catalytic activity was then sequesteredby introducing a phosphorus compound, for example poly-phosphoric acid, at the end of the ester interchange reaction.Primarily the ester interchange catalyst was sequestered toprevent yellowness from occurring in the polymer.

Then the monomer undergoes polycondensation and thecatalyst employed in this reaction is generally an antimony,germanium or t i tanium compound, or a mixture of these.In the second method lbr malting polyester, an acid (such asterephthalic acid) is reac ted with a d iol (such as ethyleneglycol) by a direct esterification reaction producing monomerand water. This reaction is also reversible like the ester pro-cess and thus to drive the reaction to completion one lnustremove the water. The direct esterification step does notrequire a catalyst. The monomer then und ergoes polyconden-sation to form polyester just as in the ester process, and thecatalyst and conditions employed are generally the sane asthose for the ester process.

For mo st container applications this melt phase p olyester isfarther polymerized to a higher molecular weight by a solidstate polymerization.

In smmnary, in the ester process there are two steps,nmnely: (1) an ester interchange, and (2) polycondensation.Inthe acidpmcess there are also two steps, nmn ely: (1) directesterification, and (2) polycondensation.

Suitable polyesters are produced from the reaction of adiacid or diester component comprising at least 65 tool-%terephthalic acid or CI-C4 dialkylterephthalatc, preferably atleast 70 mol-%, more preferably at least 75 m oI-%, evcnmorepreferably, at least 95 tool-%, and a d iol component compris-ing at least 65% mol-% ethylene glycol, preferably at least 70mol-%, more preferably at least 75 mol-%, even more pref-

4embly at least 95 tool-%. It is also preferable that the d iacidcomponent is terephthalic acid and the diol component isethylene glycol, thereby forming polyethylene terephthalate(PET). ",'he mole percent for all the diacid component totals

5 100 mol-%, and the mole percefitage for all the diol compo-nent totals 100 mol-%,

Where the polyester components are modified by one ormore diol components other than ethylene glycol, suitablediol components of the described polyester may be selected

l0 from 1,4-cyclohexandedimethanol, 1,2-propanediol, 1,4-bu-tanediol, 2,2-dimethyl-l,3-propanediol, 2-methyl-l,3-pro-panediol (2MPDO) 1,6-hexanediol, 1,2-cyclohexanediol,1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cy-clohexanedimethanol, and diols containing one or more oxy-

15 gen atoms in the chain, e.g., diethylene glycol, triethyloneglycol, dipropylene glycol, tripropyleue glycol or m ixtures ofthese, and the like. In general, these diols contain 2 to 18,preferably 2 to 8 carbon atoms. Cycloaliphatic diols can beemployed in their cis or trans cmtflgumtion or as nfixture of

20 both lbrms. Preferred modifying diol components are 1,4-cyclohexanedimethanol or diethylene glycol, or a mixture ofthese.

Where the polyester components are modified by one ormore acid components other than terephthalic acid, the suit-

25 able acid components (aliphatic, alicyclic, or aromatic dicar-boxylic acids) of the linear polyester may be selected, forexample, t?om isophthalic acid, 1,4-cyclohexanedicarboxy-lic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid,glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic

30 acid, 2,6-naphthalenedicarboxylic acid, bibenzoic acid, ormixtxtres of these and the like. In the polymer preparation, itis often preferable to use a ftmctional acid derivative thereofsuch as the dinethyl, diethyl, or dipropyI ester of the d icar-boxylic acid. The 'mhydrides or acid halides of these acids

35 also may be employed where practical. These acid modifiersgenerally retard the crystallization rate compared to tereph-thalic acid.Also particularly contemplated by the present invention isa modified polyester made by reacting at least 85 tool-%4o terephthalate from either terephthalic acid or d imethyl-terephthalate with any of the above comonomers.In add ition to polyester made from terephthalic acid (ordimethyl terephthalate) and ethylene glycol, or a modifiedpolyester as stated above, the present invention also includes

4s the use of 100% of an aromatic diacid such as 2,6-naphtha-lene dicarboxylic acid or bibenzoic acid, or their diesters, anda modified polyester made by reacting at least 85 mol-% ofthe dicarboxylate from these aromatic diacids/diesters withany of the above comonomers.

5o Preferably the polyanfide used as the gas barrier compo-nent of the blend is selected from the group of partiallyaromatic polyamides is which the anfide linkage contains atleast one aromatic ring and a non-aromatic species. Preferredpartially aromatic polyamides inchde: poly(m-xylylene adi-55 pamide); poly(hexanlethylene isophthalmnide); poly(hexam-ethylene adipamide-co-isophthalamide); poly(hexamethyl-ene adipamide-co-terephthalamide); poly(hexamethyleneisophthalamide-co-terephthalamide); or mixtttres of two ormore of these. The most preferred is poly(m-xylylene adipa-60 lnide).The preferred range ofpolyamide is 1 to 10% by weight ofthe composition depending on the required gas barrierrequired for the container.

The ionic compatibilizcr is preferably a copolyester con-6s talning a metal sulfonate salt group. The metal ion of the

sulfonate salt may be Na+, Li+, K+, Zn++, Mn++, Ca++ andthe like. The sulfonate salt group is attached to an aromatic


15/26

US 7,943,216 B25acid nucleus such as a benzene, naphthalene, diphenyl, oxy-diphenyl, sulfonyldiphenyl, or methylenedipheny! nucleus.Preferably, the aromatic acid nucleus is sulfophthalic acid,sulfoterephthalic acid, sulfoisophthalic acid, 4-sulfonaphtha-lene-2,7-dicarboxylic acid, and their esters. Most preferably,the sulfomonomer is 5-sodinmsuffbisophthalic acid or5-zincsullbisophthalic acid and most preferably their dialkylesters such as the dimethyl ester (SIM ) and glycol ester(SIPE G). T he preferred range of 5-sodimnsulfoisophthalic or5-zincsulfoisophthalic acid to reduce the haze of the con-tainer is 0.1 to 2.0 mol-%.

Suitable cobalt compounds for use with the present inven-tion include cobalt acetate, cobalt carbon ate, cobalt chloride,cobalt hydroxide, cobalt naphthenate, cobalt oleate, cobaltl inoleate, cobalt octoate, cob alt stearate, cobalt tfitmte, cobaltphosphate, cobalt sulfate, cobalt (ethylene glycolate), andmixtures of two or more of these, among others. As a transi-tion metal catalyst for active oxygen scavenging, a salt of along chain fatty acid is preferred, cobalt octoate or stearatebeing the most preferred. For color control of passive gasbarrier blends any cobalt compound can b e used, with cobaltacetate being preferred.It has surprisingly been found that the ionic compatibilizer,in addition to improving gas b arrier properties and improvinghaze, in combination with a cobalt salt significantly reducesthe yellowness of the resin, pretbrm and container. The pre-ferred range of Co for blends containing 1 to I 0 wt-% par-tially aromatic polyamide mad 0.1 to 2.0 reel-% of an iolficcompatibilizer is 20 to 500 ppm.Although not required, additives may be used in the poly-ester/polyamide blend. Conventional known additivesinclude, but are not limited to an additive of a dye, pigment,fi l ler, branching agent, reheat agent, anti-blocldng agent, an ti-oxidant, anti-static agent, biocide, blowing agent, couplingagent, flame retardant, heat stabilizer, impact modifier, UVand visible light stabilizer, crystallization aid, lubricant, plas-ticizer, processing aid, acetaldehyde and other scavengers,and slip agent, or a nfixture thereof.The b lend of polyester, imfic compatibilizer, cobalt salt andpartially aromatic polymnide is conveniently prepared byadding the components a re the throat of the injection moldingmachine that produces a preform that can be stretch blowmolded into the shape of the container. If a conventionalpolyester base resin designed for polyester containers is used,then one method is to prepare a master batch of a polyestercontaining the ionic compatibilizer, and optionally a transi-tion metal catalyst for active scavenging, together with thepartially aromatic polymnide using a gravimetric feeder forthe three compone nts. Alternatively the polyester resin can b epolymerized with the ionic compatibilizer, mad optionally atransition metal catalyst for active scavenging, to lbrm acopolymer. This copolymer can be mixed at the injectionmolding machine with the partially aromatic nylon. Alterna-tive all the blend components can b e blended together, or as ablend of master batches, mad fed a s a single material to theextruder. The mixing section of the extruder should be of adesign to produce a homogeneous b lend. 'h is can be deter-mined by measuring the thermal properties of the preformand ob serving a single glass transition temperature in con trastto two separate glass transition temperatures of the partiallyaromatic polyamide and polyester.These process steps work well for forming carbonated softdrink, water or beer bottles, and containers for hot fill appIi-cations, for example. The present invention can be em ployedin any of the conventional llown processes for producing apolyester container.

6Testing Procedures1. Oxygen and Carbon Dioxide Permeability of Films,Passive

Oxygen flux of film samples, at zero percent relative5 hunfidity, at one atmosphere pressure, and at 25o C. wasmeasured with a Mocon Ox-Tran model 2/20 (MOCON Min-

neapolis, Minn.). A mixture of 98% nitrogen with 2% hydro-genwas used as the carrier gas, and 100% oxygenwas used asthe test gas. Prior to testing, specimens were conditioned in

t0 nitrogen inside the unit for a minimmn of twenty-four honrsto remove traces of atmospheric oxygen dissolved in the PE Tmatrix. The conditioning was continued until a steady baseline was obtained where the oxygen flux changed by less thanone percent for a thirty-minute cycle. Subsequently, oxygen

i5 was introduced to the test cell. The test ended when the fluxreached a steady state where the oxygen flux changed by lessthan 1% during a 30 m inute test cycle. Calculation of theoxygen permeability was done according to a literaturemethod for permeation coefl]cients for PET copolymers,20 from Fick's second law of diffusion with appropriate bomad-ary conditions. The literature documents are: Sekelik et al.,Journal of Polymer Science Part B: Polymer Physics, 1999,Volume 37, Pages 847-857. The second literature document isQureshi et al., Journal of Polymer Science Part B: Polymer2s Physics, 2000,Volume38,Pages 1679-1686.Thethirdlitera-tare document is Polyakova, et aL, Journal of Polymer Sci-ence PartB: Polymer Physics, 2001, Volume 39, Pages 1889-1899.The carb on dioxide permeability of films was measured in

30 the same m anner, replacing the oxygen gas with carbon diox-ide and using the M econ Permatran-C 4/40 instrument.All film permeability values are reported in units of (cc(STP).cm)/(mZ.atm,day)).

2. Oxygen Permeability of Films, Active Scavenger.35 The same method was used as for passive oxygen perme-ability above with the exception that the oxygen flux did not

necessarily equilibrate to a steady state. A fter the introductionot" the oxygen into the cell, the reduction in the amount ofoxygen was measured from 0 to at least 350 hour. Treatment40 of the data generated an Apparent Permeation Coefficient(APC), as a function of time with oxygen exposure (cc(STP).cm)/(m2.atm.day). The generated APC data is not a steadystate value in normal permeation coefficients. APC is datagenerated that describes oxygen permeation at a fixed point in45 time, even though this coefficient is changing slowly withtime. These changes are too small to be detected during thetime necessary for mea suring their value at any fixed point intime. Calculation of the AP C was done according to a l i tera-tore method for pemaeation coefficients for PET copolymers,

5o from Fick' s second law of diffusion with appropriate bound-ary conditions, in the same manner as described for passivebarrier permeability.3. Carbon Dioxide Permeability of Bottles.

Carbon dioxide permeability of bottles was measured_s5 using a MO CO N Permatran C-200 CQ Permeation System,Tests were conducted at 22o C . The bottles were purged withnitrogen and then pressurized with CQ a t a pressure of 60 psi(4.01 MPa). The bottles were left in ambient conditions for 3days and the pressure measured. Bottles in which the pressure0 had dropped below 56 psi (3.75 Mpa) were rejected, other-wise the bottles were repressurized to 60 psi (4.0i MP a) andplaced in the testing chamber, which has been purged withnitrogen for at least 5 hours. After a day, me asurements of theCOx in the test chamber were taken over a 30 minute time

65 frame, over an eight hour time period, The nitrogan flow rateto the sensor was 100 cm3/min, and to the carrier stremn was460 cm3/min. Results are reported as cm/bottle/day.


16/26

US 7,943,216 B274. Intrinsic Viscosity (IV)Intrinsic viscosity (IV) is determined by dissolving 0.2

grams of an anmrphous polymer composition in 20 milli l itersof dichloroacetic acid at a temperature of 25" C . and using anUbbelhode viscometer to determine the relative viscosity 5(RV). R V is converted to IV using the equation: IV=[(RV-1)x0.691]+0.063.

5. ColorThe haze of the preform and bottle walls was measured

with a Hunter Lab ColorQuest II instrument. D65 illuminant 10was used with a CIE 1964 10standard observer. The haze isdefined as the percent of the CIE Y diffuse transmittance tothe CIE Y total transmission. The color of the prelbnn andbottle walls was measured with the same instrument and isreported using the CIELAB color scale, L* is a measure of 15brightness, a* is a measure ofredness (+) or greemless (-) andb* is a measure ofyellowness (+) or blueness (-).6. Diethylene Glycol (DE G)The D EG (diethylene glycol) content of the polymer isdetermined by hydrolyzing the polymer with an a queoussolution of ammonium hydroxide in a sealed reaction vesselat 220+_5 C. for approximately two hours. The liquid portionof theThe D EG (diethylene glycol) content of the polymer isdetermined by hydrolyzing the polymer with an aq ueoussolution of atImmnimn hydroxide in a sealed reaction vesselat 220-5 C. for approximately two hours. The liquid portionof the hydrolyzed product is then analyzed by gas chroma-tography. The gas chromatography apparatus is a FID Detec-tor (HP5890, HP7673A) from H ewlett Packard. The amino- 3onium hydroxide is 2.8 to 30% by weight anmonimnhydroxide from Fisher Scientific and is reagent grade,7. Isophthalic mad Naphthalene Dicarboxylic AcidThe percent isophthalic acid and naphthalene dicarboxylicacidpresent in the amorphous polymer was determined at 285 35nanometers using a Hewlett Packard Liquid C hromatograph(HPLC) with an ultraviolet detector. An amorphous polymersample was hydrolyzed in diluted sulfuric acid (10 ml acid in1 liter deionized water) in a stainless steel bomb at 2300 C. for3 hours. After cooling, an aqueous solution from the bombwas mixed with three volumes of methanol (HPLC grade) andan internal standard solution. The mixed solution was intro-duced into the HPLC for analysis,

8. Metal ContentThe metal content of the ground polymer samples wasmeasured with an Atom Scan 16 ICP Emission Spectrograph.The sample was dis solved by heating in ethanolamine, and oncooling, distilled water was added to crystallize out the

terephthalic acid. The solution was centrifaged, and thesupematant liquid analyzed. Comparison of atomic emis- 5osions from the samples tinder analysis with flaose of solutionsof known m etal ion concentrations was used to d etermine theexperinlental values of metals retained in the polymersamples.9. Preibrm and Bottle Process 55

After solid state polymerization, the resin of the presentinvention is typically, dried for 4-6 hours at 170-1800 C.,melted and extruded into prefomls. Each preform for a 0.59l iter soft drink bottle, for example, employs about 24 gram s ofthe resin. The preform is then heated to about 100-120 C. andblown-molded into a 0.59 liter contour diameter giving astretch ratio of twelve (2x6). Since the bottle size is fixed,differant preform sizes can be used for obtaining differentstretch ratios.

10. Scmming Electron MicrographFilms were prepared by compression molding by heating at2750 C. in a press for 3 minutes without pressure, then the

8pressure was cycled several times between 0 and 300 psi andthen held at 300 psi for 4 minutes. The film was quenched inice water. These films were notched with a razor b lade on thefilm surface to facilitate a brittle failttre, immersed in liquidnitrogen for 15 minutes, removed mad fractured by hand per-pendicular to the thinkness direction. Fractnre surfaces werecoated with 100 angstrom of gold and were observed using aJEO L 840A scm ming electron microscope.

The tbllowing examples are given to illustrate the presentinvention, and it shall be understood that these examples arefor the purposes of illustration and are not intended to limitthe scope of the invention.

EXAMPLESVarious polyester (PET) resins reflecting typical connner-

cial recipes were produced. Comonomers included isoph-thalic acid (or its dimethyl ester) (IPA) and diethylene glycol(DEG) as crystallization retardants and naphthalene dicar-20 boxylic acid (or its dimethyl estm:) (ND C) to improve thetemperature at wlfich a container can be fil led.

,norphous polyester was first produced with an IV ofabout 0.6, this was daen solid phase polymerized to the finalresin IV. The additives used were, manganese acetate, zinc

as acetate, cobalt acetate, antimony trioxide and poly-phospho-ric acid. The ana lyses of these resins are set forth in Table 1.TABLE 1

Resin IdentificationA B C D

Process TAt DMT DMT DMTIV 0,83 0.82 0.84 0.81IPA, wt-% 2,5 3,1 0 0NDC, wt-% 0 0 5 5DEG, wt-% 1,5 0,7 0,6 0,6Cobalt, ppm 30 40 100 0

A series of copolyesters were made containing various40 amounts of 5-sulfoisophthalic acid (S IPA), either the ester orthe gylcolate of SIPA was used. The melt phase polymeriza-tion was conducted in the normal way, but the amorphousresin was not solid state polymerized for resin $3. In the caseof Resin S1, zinc acetate was used in place of manganese

45 acetate as the ester-interchange catalyst. The analyses ofthese resins are set forth in Table 2.

ProcessIV8IPA, tool-%Cobalt, pprn

TABLE 2Resin Identification

S1 82 83DMT DMT DMT0.84 0.82 0.560.11 1.3 1.70 0 40

A m aster batch of the cobalt salt to be used as the transitionmetal catalyst for active oxygen scavenging was mad e by late

6o addition of 2 wt-% cobalt octoate to a polyester preparedusing 75 ppm Zn (as zinc acetate), 250 ppm Sb (as antimonytrioxide, 60 ppm P (as poly-phosphoric acid) and 2.5 wt-%IPA. Tls material had an IV of 0.35-0.40.60 ppm P (as poly-phosphoric acid) and 2.5 wt-% IPA. This

65 material had an IV of 0.35-0.40.Ufless otherwise stated the partially aromatic nylon usedin the blend was Type 6007 from Mitsubishi Gas Chemical,


17/26

US 7,943,216 B29Tokyo Japan. Type 6007 has a number average molecularweight of 25, 900 and its melt viscosity at 271C. and 1000sec-1 is 280 Pa's.

Unless otherwise stated the preforms were prepared on anArburg injection molding machine using 24 g of material, and sblown into a 0.59 liter contour bottle on a Sidel SBO2 stretchblow molding machine. The bottle sidewall thickness is about0,25 ram.

10TABLE 6

Run Co, Preform BottleNo. Resin ppm ivIXD6, wt-% SIP& mol-% b* b12 C 100 0 0 0.4 0.813 8I 100 0 0,11 -1,8 !.114 C 200 3 0 !.4 2.415 8! 200 3 0,11 -7.4 1.916 C 200 4 0 1.0 2.817 S1 200 4 0,!1 -7.8 2,018 C 200 5 0 3,2 3.219 S1 200 5 0.11 -6,i 2.6

Exanaple 110The effect of the interaction of S]PA with Co on the yel-lowness of preforms and bottles was studied by blendingeither polyester resin D or S 1 with the cobalt master batch andMXD6. The yellowness vahle (b*) of the preforms mad bottlesidewalls are set forth in Table 3 (lower or negative b* values 15

correspond to less yellowness).TABLE 3

Pre- Bet-Run Co, MXD6, SIPA, form tie 20No. Resin ppm wt-% reel-% b* Delta b* Delta2

At all levels of MXD6 the incorporation of an iolfiC com-patibilizer reduced the yellowness.The oxygen permeab ility of the bottle sidewalls was mea-sured and the results plotted in FIG. 1. This shows that theionic compatibilizer decreases the permeability at eachkbXD6 concentration. Surprisingly there is a non-linear rela-tionship of oxygen permeability with MXD 6 concentrationwith extremely low values at 5 wt-% MXD6.

12345678

Example 4

0.11 mol-% SIPA, there is a synergistic effect and the Co saltis markedly m ore effective in offsetting the yellowness.

1 ,Difference in b of the preform compared to the eonkeL2Difference in b* of the bottle compared to the control,

25 In order to better define the oxygen permeab ility as a ftmc-tion of MXD6 concentration a series of blends were preparedusing polyester A as the base resin. The concentration ofMXD6 used was 1, 2, 3, 4, 4.5 and 5 wt-%, each containing100 ppm cob alt octoate. The oxygen permeability of the

30 bottle sidewalls was measured and the results shown in FIG,2. This illustrates that there is a surprising reduction in oxy-gen permeability between 4.5 and 5 wt-% MXD6.

Exanaple 2 35 Example 5

D 0 0 0 11 Control 3.6 ControlD 0 5 0 19.3 8.3 7.1 3.5D 100 0 0 0,7 -10.3 1 -2.6D 200 5 0 4.2 -6.8 3.5 -0.1S1 0 0 0.11 16.3 Control 4.6 Control81 0 5 0.11 17,5 1.2 5.5 0.981 100 0 0.11 -0,8 -17.1 1.1 -3.581 200 5 0.11 -6,6 -22.9 2 -2.6

A sinfilar trial was conducted using resin C as the controlmad the results set forth ha Table 4.

TABLE 4Run MXD6, SIPA, PretbrmNo. Resin Co, ppm wt-% tool-% b' Bottle b*

9 C 100 0 0 -0.1 1.210 C 200 5 0 3.6 5.711 S1 200 5 0.11 -3.5 3.6

The haze of these preforms mad bottle sidewalls are set forthin Table 5,TABLE 5

Ran Co, Preform BottleNo. Resin ppm MXD6, wt-% SIP& mol-% haze, % haze, %9 C 100 0 0 9,5 1,310 C 200 5 0 16.4 13.911 S1 200 5 0.!1 14,3 8,2

Another trial was rtm in which the level of MX D6 was heldconstant at 5 wt-% and the concentration of SIPA changed,the results are set forth in Table 7. In these runs the base4o polyester resin was A and the master batch of S IPA polymer$2 was used.

TABLE 7Run Co, MXD6, Preform45 No, Resins ppm wt-% $IPA, reel-% b* Bottle b*20 A 30 0 0 3,8 1.021 A 130 5 0 0,5 4.122 A/S2 130 5 0.13 -2,5 3.623 A/S2 130 5 0.26 -2.9 3,7

50 24 A/S2 130 5 0.65 -3.6 3.325 S2 100 5 1.3 -9.1 2.8

55These results show that the ionic compatibilizer can be

used as a master batch to obtain the synergistic reduction ofyellowness with cobalt, as well as a copolym er that was usedin the previous Examples 1-3.

The results again show the synergistic effect of the ioniccompafibilizer on the cobalt salt as a means to reduce yellow-ness, in addition the ionic compatibilizer reduced the haze of 60the bottle sidewall containing 5 wt-% M XD 6.

Example 3

Example 6Instead of using sodium as the SIPA salt, a copolyester

using the divalent zinc ester was made using the process thatwas used for copolymer S1. Since this Zn copolyester wasmore yellow than S 1 no com parison of the relative differencebetween Na-SIPA and Zn-SJPA can be given. However the

AnothertrialwasconductedinwhichtheamountofMXD6 65 hazeofbottlesidewallsmadewithPETresinAasthecontrol,was varied at a constt SIPA level of 0.11 mol-%, and the using 0.11 reel-% SIPA (the rtms containing MXD6 con-results set forth in Table 6 tained 100 ppm Co) are compared in Table 8 below.


18/26

US 7,943,216 B211TABLE 8

12TABLE 11

Run No. MXD6, wt-% SIPA type Haze, %26 0 none 5.527 5 none 14.228 5 Na 12.029 5 Zn 9,6

MXD6, wt-% SIP& tool-% Domain size, 10 0 0.8-1,520 0 2,2-4,520 1.35 0,2-0,510 0,03 0,5-1,510 0.08 0.5-1.510 0.16 0.2-0.5

It would appe ar that the divalent ionic compa tibilizer ismore effective than the monovalent in reducing the bottle lOsidewall haze. This shows that at a low level of SIP A, less than 0.2 tool-%,the domain size of a blend containing 10 wt-% MXD6 is

reduced to less than 0.5 jan.Example 7

32 C 20033 C 20034 C 20035 C 20036 $I 20037 S1 200

Run Co, MXD6 MXD6, SIPA, PrefornlNo. Resin ppm type wt-% tool-% b* Bottle b*

TABLE 9

A low molecular weight MX D 6 was prepared.A mixture of438 g of adipic acid, 428.4 g ofm-xylylenediamine mad 500 gof deionized water were charged in a 2-liter autoclave undernitrogen atmosphere. The mixture was stirred lbr 15 minutesthen heated to reflux for 30 minutes. Water was distilled offand the temperature was increased to 275C , over a period of60-90 nfinutes. The mixture was stirred at 2750 C. ibr 30minutes bekb re extrusion. This polymer had a viscosity of 9.5Pa.s at 1000 sec-1 and 27i C. (compa red to 280 Pa.s for thecommercial 6007).

The procedure of Exanlple 3 was followed, using this lowmolecular weight MXD6 (LM W ) compared to the conmner-cial 6007. The results are set forth in Table 9.

Example 8A series of bottles were produced using C as the base PETresin, the $3 SIPA eopolyester and 6007 MXD6. The passiveoxygen permeability, at 0% Relative Humidity, of the bottle

20 sidewalls was meas ured and the results set forth in Table 12.

25

3 O

TABLE 12o2 Permeability(ec(STP). cm)/Run No. MXD6, wt-% SIP& mol-% (m2' am' day)

38 0 0 0,18039 2.5 0 0,18140 2.5 0.3 0,16441 5 0 0,13842 5 0.3 0.13143 5 06 014544 I0 0 0.07945 i0 0.3 0.05446 i0 0.6 0,051

6007 3 0 2.0 2.5LMW 3 0 3.4 2.1 35 This shows that the ionic compatibilizer is improving the6007 5 0 4.2 3.5 oxygen gas barrier at a given MXD6 level, possibly due to theLMW 5 0 1.1 3.6 reduction in domain size, wlfich increases the nnmber of6007 5 0.11 -6.1 2.6LMW 5 0.11 -6.6 2.0 domains, as shown in Example 7.

This illustrates that the color is b etter (less yellow) with thelow molecular weight MXD 6 than 6007.The haze of these runs was also measured and the resultsset forth in Table 10 below.

TABLE 10Run Co, MXD6 MXD6, SIPA Preform BottleNo. Resin ppm Type wt-% tool-% Haze, % Haze, %32 C 200 6007 3 0 50.3 10.933 C 200 LMW 3 0 48.3 7,734 C 200 6007 5 0 50,1 14.035 C 200 LMW 5 0 49,9 11.836 $1 200 6007 5 0,11 49,3 11.137 $1 200 LMW 5 0,11 45.4 7.4

The use of the lower molecular MXD 6 in conjunction withSIPA markedly reduces the haze of the bottle sidewalls.

40 Example 9Following the procedure of Example 7 a polyamide wasproduced in which 12% of the adipic acid was replaced withisophthalic acid. The melt viscosity of this polyamide at 17145 C. and 1000 sec- was 237 Pa.s. This polyanfide was blended

at a 5 wt-% level with PETresin C and ionic compatibilizer $3to give a level of SIPA of 0.6 mol-% in the blend. B ottles wereprepared from this blend and the oxygen permeation ratemeasures at 0.155 (cc(STP).cm)/(m2.atm.day). This can be

50 compared with a lower oxygen permeation rate of 0.145measured on run 43 achieved with 5 wt-% MXD6.

Exarnple 10The carbon dioxide transmission rate of 0.5 liter bottles

made from PET resin A were measured to be 8.6 cc&ottle/day. The addition of 5 wt-% M XD 6 decreased this rate to 4.5cc/bottle/day.60 Exalnple 11Example 7

Master batches using cobalt stearate and cobalt naphthen-In order to deterufine the effect of the ionic compatibilizer ate in place of cobalt octoate were prepared using the same

on MXD6 domain size, a series of films were prepared and metbod as described above for cobalt octoate. Using PETfractured. PETresinBwasusedtogetherwithblondswiththe 65 baseresinD,bottleswerepreparedusingdifferentamountsof$3 SIPA copolyester and 6007 MXD 6. The domain size was MXD 6 and different concentrations of cobalt octoate, cobaltmeasured and the results set forth in Table 11. stearate and cobalt naphthenate. The bottle wall oxygen per-


19/26

US 7,943,216 B213meability was measured and the va lue after 100 hours (at thistime the rate is at equilibrium, see FIG. 1) is set forth in Tab le13.

TABLE 13Oxygen Permeability @

100 hours,MXD6, (cc(STP), cm)/Run No. wt-% Cobalt salt Co, ppm 0n2. arm. day)

47 0 -- -- 0,15048 1.75 Oetoate 200 0,09849 1,75 Octoate 400 0,12050 . 1.75 Stearate 100 0,09851 1.75 Stearate 200 0,12252 3.0 Octoate 400 0.12053 3.0 Octoate 60 0.04854 5.0 Octoate 100 0.00555 5,0 Stern'ate 30 0.00556 5,0 Stearate 50


20/26

Exhibit B


21/26

I I I I I I I I I l l l l l l l I f I l l l I I I l l I l l l l l I l l l l l lUS007879930B2(121 United States Patent

Liu (10) Patent N o.: U S 7,879,930 B2(45) Date of Patent: Feb. 1, 2011( 5 4 )( 7 5 )( 7 3 )(*)

COLOR ED OXYGEN SCAVENGINGPOLYMERS

( 2 1 )( 2 2 )( 8 6 )

Inventor: Zhenguo Liu, Greet, SC (US)Assignee: INVISTA North America S.a r.l.,Wilnfington, DE (US)Notice: Subject to any disclaimer, the term of this

patent is extended or adjusted under 35U.S.C . 154(b) by 922 days.Apph No,: 111659,053PCT Filed: Aug. 17, 2005PCT No.: PCT/U S2005/029297 3 7 1 ( c ) (i ),(2), (4) Date: Jan. 31, 2007

( 6 0 )( 5 1 )

(87) PCTPub. N o.: WO 2006/023583

( 6 5 )PCT Pub, Date: Mar. 2, 2006

Prior Publication D ataUS 2009/0030115 A1 Jan. 29, 2009

Related U.S. Application DataProvisional application No. 60/602,272, filed onAug.17, 2004.Int. C1.C08L 67/00 (2006.01)C08L 77/00 (2006.01)B32B 27/34 (2006.011B32B 27/36 (2006.01)

(52) U.S. C1 .. ......... ......... ...... 524/87; 524/157; 524/186;5 2 4 / 1 9 0 ; 5 2 4 / 3 5 6 ; 5 2 4 / 3 5 7 ; 5 2 4 / 3 5 8 ; 5 2 4 / 5 1 3 ;5 2 4 / 5 1 4 ; 5 2 4 / 5 1 5 ; 5 2 4 / 5 2 7 ; 5 2 4 / 5 3 8 ; 5 2 4 / 5 3 9 ;5 2 4 / 6 0 1(58) Field of Classification Search ................... 524/87,524/157, 186, 190, 356, 357, 358, 513,514,524/515,527, 538, 539, 601

See application file for complete search history.(56) References Cited

U . S. P ATEN T D OC U M EN TS5,021,515 A5,281,360 A5,314,987 A5,340,884 A5,639,815 A

6/1991 Cochran etal.1/1994 Hong et ah5/1994 Kim8/1994 Mills et al.6/1997 Cochram eta!.

EP 0301719 2/1989W O W O 93/23474 11 /1993WO 95/06677 3/1995WO W O 98/012244 3/1998W O W O 99/048963 9/1999

5,866,649 A 2/1999 Hongetal.5,955,527 A 9/1999 Co&ranet al.6,083,585 A 7/2000 Cahill et al.6,288,161 B1 9/2001 Kim et al.6,365,247 B1 4/2002 Cahill et aL6,444,283 B1 9/2002 Turner et al.2002/0063238 AI 5/2002 Coc lu'an et al,2002/0173591 AI 11/2002 Cifisholmetal.2003/0031815 A1 2/2003 Schiraldi et al.

FOREIGN PATENT DOCUMENTS

OTHER PUBLICATIONSSekelik et al., Journal of Polymer Science Part B: Polymer Physics,1999, vol. 37, pp. 847-857.Qureshi et al., Journal of Polymer Science Paxt B: Polymer Physics,20(10, voh 38, pp. 1679-1686,Polyakova et al., Journal of Polymer Science Part B: Polymer Phys-ics, 2001, vol. 39, pp. 1889-1899.INVISTA press release of JuL 20, 2004 (DI2).PolyShMdTM presentation PET World Congress at Drirdtec Sep.12, 2005 (DI4).Slide presentations Nova Pack Europe 2004, entitled "Beer inPolyShMd--The Monolayer Miracle" (D20).Desentation--Nova-Pack Europe 2003 by DIPOL Chemical Inte>national entitled "Prospects for PET Barrier Packaging for Beer inEastern European Market" (D22).Smmnary from Plastics Technology of Sep. 1, 2003 entitled"Monolayer PET Bottles Emerge in Barrier Uses" (D24).Document entitled "International Events" which presents the date ofNove-Pack Em'ope 2004 as being Oct. 18/19, 2004 (D29).

Primary Examiner--Aria L Woodward(74) Attorney, Agent, or Firm-q2raig M. Sterner(57) ABSTRACTThe presem invention relates to a melt blend of a base poly-mer, an oxidizable organic polymer, a transition metal saltcatalyst and a colorant that does not completely deactivate thecatalyzed oxidation. A preferred colorant, yields in ml articlemade from the polymer melt bland a Catalyst DeactivationFactor (CD F) of less than ab out 0.25, preferably less than0.15, more preferably less than 0.1, and most preferred lessthan 0.05. The present invention also comprises a coloredmonolayer art icle having the described C DF , such as a fi lm,themlotbrmed tray, or blow molded container, that has activeoxygen scavenging properties. The colorant, after melt blend-ing a base polymer, an oxidizable organic polymer, a transi-tion metal catalyst, does not increase the binding energy of thetransition metal catalyst ion by more than 1 eV.

15 Claims, No Drawings


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US 7,879,930 B21COLOR ED OXYGEN SCAVENGINGPOLYMERS

BACKGROUND1) Field of the hwentionThis invention relates to colored oxygen scavenging poly-

mers and articles made from such polymers. In particular itrelates to polymer blends containing a base polymer, an oxi-dizable organic polymer, a transition metal catalyst, and acolorant. The colorant is selected from a group of colorantsthat do not completely deactivate the transition metal catalyst.A pretErred colorant, yields in an article made from the meltpolymer blend, a Catalyst Deactivation Factor (CDF) of lessthm about 0.25, preferably less than 0.15, more preferablyless than 0.1, and most preferred less than 0,05. The presentinvention also comprises a co!ored monolayer article madefrom such polymer blends having the described CDF , such asa film, thermoformed tray, or blow molded con tainer, that hasactive oxygen scavenging properties.2) Prior Art

Typical polymers used in making film, thermoformedtrays, or blow molded containers, are prhnarily based onpolyester due to its physical properties. Suitable polyesterscan be homopolymers such as polyethylene terephthalate(PET), polyethylene naphthalate (PEN), or copolymers ofeither or both. For blow molded containers, polyethyleneterephthalate isophthalate copolyester (PET/IP) is particu-larly useful.

Oxygen scavenging polymers are well lmown and are espe-cially useful in the food packa ging business. It is known thatoxygen can have an effect on the odor and taste of packagedfood thereby shortening the shelf life of the food. Oxygenscavenging packaging ma terials, on the other hand, react withoxygen that is in the process of traversing the packagingbarrier. Thus the oxygen scavenging packaging materialreduces or eliminates the odor and/or undesirable taste offood or beverages excessively exposed to oxygen.

Typical oxygen scavenging compounds are oxidizableorganic polymer molecules containing allylic positions suchas polybutadiene based polymers, or polyethylene/cyclohex-ene copolymers, or containing banzylic positions such asm-xylylamine-based polyamides, or mixtures of these. Theuse of oxidizable organic polymers by themselves results in avery slow oxidative process, but such polymers lack thedesired physical properties of PET, for example, and a re verycostly compared with PE T. The incorporation of oxidationcatalyst into the oxidizable polymer solves this prob lem.

W ith respect to the oxidizable organic polymers mentionedearlier, poly(m-xylylene adipamide) (known conmlerciallyas MX D6) is widely known. Add itionally, the prior art dis-closes that the oxidizable organic polymers need a transitionmetal catalysts to make it actively scavenge oxygen. The mostcommon transition catalyst described by the prior art is acobalt salt.PC T Patent Application W O 98/12244 in the nanle ofinventors Cahill et al. mad assigned to Amoco Corporationdiscloses an oxygen scavenging composition wherein thecritical oxidizable organic polymer is polybutadiene and thecatalyst for the oxidizable organic polymer is transition metalsalts or other compounds. T his application discloses the use-fulness of such a composition as a blend with polymers forpackaging films and containers for the food and beveragcindustry.PC T P atent Application W O 99/48963 in the name ofChing et al. and assigned to Chevron Chemical Companydiscloses an oxygen scavenging composition including a

2polymer or oligomer having at least one cyclohexene group orfunctionality. This application also discloses the use of tran-sition elements as a catalyst to activate the oxygen scavengingcomposition. The transition metal catalysts are employed in

5 the forna of salts and other compositions. This reference alsonotes that cobalt, a transition metal catalyst, is preferred.

The use of a traasition metal catalyst to promote oxygenscavenging in polyamide multilayer containers, and blendswith polyethylene terephthalate (PET), lms been disclosed in

o the following patents, for example.U.S. Pat. Nos. 5,021,515, 5,639,815 and 5,955,527 to

Cochran et al. disclose the use of a cob alt salt as the preferredtransition metal catalyst and poly(m-xylylene adipamide)(MXD6) as the preferred oxidizable organic polymer.15 U.S. Pat. Nos. 5,281,360 mad 5,866,649 to Hong, and U.S.Pat. No. 6,288,161 to Kim also discloses blends of IVLXD6with PET and a cobalt salt catalyst.Until recently these oxidizable orgmfic polymers have been

used as a n imaer layer in m ultilayer fihns, thermofonned trays20 or blow molded containers. For colored articles, such as

green, blue or mnber bottles, the colorant is mixed in thenon-scavenging outer and ilmer layers. In such multilayerarticles there is no reaction between the colorant and thetransition metal catalyst contained in the oxygen scavenging

25 layer. There is a need for colored monolayer films, sheets andcontainers to reduce the cost ofmultilayer processes.It is generally accepted that the oxidation of polymersinvolves a free radical reaction with the lbrmation of hydro-peroxides. "ikansition metal ions catalyze the decomposition

30 of hydroperoxides to radical species that greatly acceleratethe rate of oxidation and thus the rate of oxygen scavanging.

Surprising it has been lbund that certain colorants deacti-vate the catalyst, after melt blending and thereafter (such as inan article), making them less effective as a catalyst. Thus only

35 certain colorants can be used for mon olayer oxygen scaveng.ing articles since the colorant is intimately mixed in a meltphase with the transition metal catalyst, unlike prior multi-layer film, thermofonned trays, or blow molded containers.

SUMMARY OF THE INVENTIONThe present invemion relates to the use of ce rtain colorantsthat do not completely deactivate the catalyst in monolayer

active oxygen scavenging melt blended polymeric systems.In the broadest sen se the present invention comprises a blend45 of a b ase polymer, an oxidizable orgmzic polymer, a transitionmetal catalyst, and a colorant that does not completely deac-tivate the catalyst after melt blending. Optionally a compati-bilizer can be included in the blend.

5o The broadest scope of the present invention also comprisesa colored monolayer article, such as a film, thermofomledtray, or blow molded container, that has active oxygen scav-enging properties.

The b roadest scope of the present invention also comprisesan article made from a melt blended polymer resin compris-55 .mg a base polymer, an oxidizable organic polymer, a transi-tion metal catalyst, mad a colorant that has a Color Deactiva-tion Factor of less than about 0.25.

The b roadest scope of the present invention also comprisesa melt blanded polymer resin comprising a base polymer, an6 O oxidizable organic polymer, a transition metal catalyst, and acolorant that does not increase the binding energy of thetransition metal catalyst ion by more than 1 eV.

65DETAILED DESCRIPTION OF THE INVENTION

Melt blended compositions or polymer resins of this inven-tion comprise: abase polymer, an oxidizable organic poly-


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US 7,879,930 B23mer, a transition metal catalyst, a colorant that does not deac-tivate the catalyst, and optionally a compatibilizer.' i11e base polymers used for packaging include, but are notlimited to, polyethylene such as, for example, low densitypolyethylene, very low density polyethylene, ultra-low den-sity polyethylene, high density polyethylene, and linear lowdansity polyethylene; polyesters such as, for example, (PET ),(PEN) and their copolymers such as PET/IP; polyvinyl chlo-ride (PVC); polyvinylidene chloride (PVDC ); and ethylenecopolymers such as ethylene/vinyl acetate copolymer, ethyl-ene/alkyl (meth)acrylate copolymers, ethylene/(meth)acrylicacid copolymers, and ionomers. Blends of different basepolymers also can be used.The preferred b ase polymer is polyester, and in pa rticularPET mad its copulymers. Generally polyesters can be pre-pared by one of two processes, nmnely: (1) the ester processand (2) the acid process. Tile ester process is where a dicar-boxylic ester (such as dimethyl terephtlmlate) is reacted withethylene glycol or other did in an ester interchange reaction.Because the reaction is reversible, it is generally necessary toremove the alcohol (methanol when dimethyl terephthalate isemployed) to completely convert the raw materials intomonomers. Certain catalysts are well known for use in theester interchange reaction. In the past, catalytic activity wassequestered by introducing a phosphorus compound, forexample polyphosphoric acid, at the end of the ester inter-change reaction. Primarily the ester interchange catalyst wasseqnestered to prevent yellowness from occurring in the poly-mer.

Then the monomer undergoes polycondensation and thecatalyst employed in this reaction is generally an antimony,gemaanium, or titanimn compound, or a mixmre of these.

Inthe second method for making polyester, an acid (such asterephthalic acid) is reacted with a diol (such as ethyleneglycol) by a direct esterificationreaction producing monomerand water. This reaction is also reversible like the ester pro-cess and thus to drive the reaction to completion the watermust be removed. The direct esterification step does notrequire a catalyst. The monomer then tmdergoes polyconden-sation to form polyester just as in the ester process, mad thecatalyst and conditions employed are generally the stone asthose for the ester process.

The temperatures, pressures, and associated equipmentwith the ester or acid process are well "known to those skilledin the art. For most packaging applications this melt phasepolyester is cooled and further polymerized to a highermolecular weight by a solid state polymerization.

In smmnary, in the ester process there are two steps,namely: (1) an ester interchange, and (2) polycondensation.In the acidprocess there are 'also two steps, na mely: (I) directesterifieation, and (2) polycondensation. Solid state polymer-ization is often used to increase the molecular weight.

Suitable polyesters are produced from the reaction of adiacid or diester component comprising at least 65 mol-%terephthalic acid or C -C4 dialkylterephthalate, preferably atleast 70 mol-%, more preferably at least 75 mol-%, evenmorepreferably, at least 95 mol-%, and a diol component compris-ing at least 65% mol-% ethylene glycol, preferably at least 70mol-%, more preferably at least 75 mol-%, even more pref-erably at least 95 tool-%. It is also preferable that the diacidcomponent is terephthalic acid and the diol component isethylene glycol, thereby forming polyethylene terephthalate(PET). The mole percent for all the diacid component totals100 tool-%, and the mole percentage for all the diol compo-nent totals 100 tool-%.

Where the polyester components are modified by one ormore diol components other than ethylene glycol, suitable

4dioI components of the described polyester may b e selectedfrom 1,4-cyclohexandedhnethanol, 1,2-propanediol, 1,4-bu-tanediol, 2,2-dhnethyl-l,3-propanediol, 2-methyl-l,3-pm-panediel (2MPDO), 1,6-hexanediol, 1,2-cyclohexanediol,

5 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cy-clohexanedimethanol, and diols containing one or more oxy-gen atoms in the chain, e.g., diethylene glycol, triethyleneglycol, dipropylene glycol, tripropylene glycol, or mixturesof these, and the like. In general, these diols contain 2 to 18,

to preferably 2 to 8 carbon atoms. Cycloaliphatic diols can beemployed in their cis or tmns configuration, or as a m ixture ofboth forms. Preferred modifying did components are 1,4-cyclohexanedimethanol or diethylene glycol, or a mixture ofthese.

15 W here the polyester components are modified by one ormore acid cmnponents other than terephthalic acid, the suit-able acid components (aliphatic, alicyclic, or aromatic dicar-boxylic acids) of the linear polyester may be selected, forexmnple, from isophthalic acid, 1,4-cyclohexanedlcarboxy-

2o lic acid, 1,3-cyclohexmledicarboxylic acid, succinic acid,glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioicacid, 2,6-naphthalenedicarboxylic acid, bibenzoic acid, ormixtures of these and the like. In the polymer preparation, itis often preferable to use a ftmctional acid derivative thereof25 such as the dimethyl, diethyl, or dipropyl ester of the dicar-boxylic acid. The anhydrides or acid halides of these acidsalso may be employed where practical. These acid modifiersgenerally retard the crystallization rate compared to tereph-thalic acid. Most preferred is the copolymer of PET and30 isophthalic acid. Generally the isophthalic acid is presen tfrom about 1 to about 10 mole %, andpreferably abont 1.5 to6 mole % of the copolymer.Also particularly contemplated by the present invention isa modified polyester made by reacting at least 85 mol-%75 terephthalate from either terephthalic acid or dimethyl-terephthalate with any of the above comonomers.In add ition to polyester made from terephthalic acid (ordimethyl terephthalate) and ethylene glycol, or a modifiedpolyester as stated above, the present invention also includes40 the use of 100% ofoaa aromatic diacid such as 2,6-naphtha-lane dicarboxylic acid or bibenzoic acid, or their diesters, anda modified polyester made by reacting at least 85 mol-% ofthe dicarboxylate from these aromatic diacids/diesters withany of the above comonomers.45 Suitable oxidizable orgatfic polymers are polymer mol-ecules containing allylic positions such as polybutadienebased polymers or polyethylene/cyclohexene copolymers, orcontaining benzylic positions such as m-xylylamine-basedpolyamides, or mixtures of these,50 Preferably the oxidizable organic polymer is selected fromthe group of partially aromatic polyamides is whichthe mfidel inkage contains at least one aromatic ring and a non-aromaticspecies. Preferred partially aromatic polyamides include:poly(m-xylylene a dipamide); poly(hexamethylene isoph-55 thalamide); poly(hexamethylene adipamide-co-isophthala-mide); poly(hexmnethylene adipmnide-co-terephthalamide);poly(hexamethylene isophthalmnide-co -terephthalamide);or nfixtares of two or more of these. The most preferred ispoly(m-xylylene adipanfide) otherwise known commercially

0 as MXD6.The preferred range of oxidizable organic polyamide is 1 to10% by weight of the composition depending on the requiredgas barrier required for the container.

In combination with the polymeric component and the6s oxidizable organic polymer, the composition of the present

invention includes a transition metal compound as the cata-lyst, thus creating an oxygen scavenging bIen d after melt


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US 7,879,930 B25blending. The catalyst makes the blend an "active" oxygenscavenging polymeric blend. The transition metal catalystcan be a salt which includes a metal selected from the first,second, or third transition series of the Periodic Table. Themetal preferably is Rh, Ru, or one of the elements in the seriesof Sc to Zn (i.e., Sc, Ti, V, Cr, Ma, Fe, Co, Ni, Cn, and Zn),more preferably at least one ofMn, Fe, Co, Ni, and Cu, andme st preferably Co . Suitable anions for such salts include, butare not limited to, chloride, acetate, octoate, oleate, stearate,palmitate, 2-ethylhexanoate, neodecanoate, a nd naphthenate.The preferred amoun t of the transition metal catalyst is in therange of about 25 to ab out 300 ppm by weight, based on thepolymer blend.

In the case where the oxygen scavenging polymer isincompalible with the base polymer, an ionic compafibilizercan he used to reduce the domain size of the oxidizableorganic polymer, thus reducing the haze of the article. Theionic compatibilizer is preferably a copolyester containing ametal sulfomte salt group, The m etal ion of the sulfonate saltmay be Na+, Li+, K+, Zu++, Mu++, Ca++ and the like. Thesulfonate salt group is attached to an aromatic acid nucleussuch as a benzene, naphthalene, diphenyl, oxydiphenyl, sul-fonyldipheny!, or methylenediphenyl nucleus.

Preferably, the aromatic acid mlclans is sulfophthalic acid,sulfoterephthalic acid, sulibisophthalic a cid, 4-sulfonaphiha-lene-2,7-dicarboxylic acid, and their esters. Most prelbmbly,the sulfomonomer is 5-sodiumsulfoisophthalic acid or5-zincsullbisophthalic acid, and m ost pre[brably their dialkylesters such as the dimethyl ester (SIM) and glycol ester(SIPE G). T he preferred range of 5-sodimnsulfoisophthalic or5 -zincsulfoisophthalic acid to reduce the haze of the article is0.1 to 2.0 tool-% of the blend or composition.

Although not required, additives may be used in the basepolymer/oxidizable organic polymer blend. C onvcntimmlknown additives include, but are not limited to an additive ofa filler, branching agent, reheat agent, anti-blocking agent,antioxidant, anti-static agent, biocide, blowing agent, cou-pling agent, flame retardant, heat stabilizer, impact modifier,UV and visible light stabilizer, crystallization aid, hibricant,plasticizer, processing aid, acetaldehyde and other scaven-gers, and slip agent, or a rhixtnre thereof. As in the case of thecolorant, these additives must be chosen not to deactivate thetransition metal catalyst.

The melt blend of base polymer, oxidizable organic poly-mer, transition metal catalyst (and optionally an ionic com-patibilizer) is convaniently prepared by adding the compo-nents at the throat of the injection molding machine that: (i)produces a preform that can be stretch blow molded into theshape of the container, (ii) produces a film that can be orientedinto a packaging film, (iii) produces a sheet that can b e ther-moformed into a food tray, or (iv) produces an injectionmolded container. The mixing section of the extruder shouldbe of a design to produce a homogeneous blend.These process steps work well for forming carbonated softdrink, water or beer bottles, packaging films and thermo-formed trays. The present invention can be employed in mayof the conventional known processes for producing a poly-meric container, film or tray.

After considerable research, it has been found that certaincolorants bind with the transition metal catalyst after meltblending and thereafter. Each transition metal catalyst has anion capable of reacting with compounds that m ay form a morestable compound. Although not bound by theory, it is thoughtthat tltis binding of the transition metal catalyst ion to certaindyestuffs prevents the transition metal catalyst from acting asa catalyst for the oxidation of the oxidizable polymer.

6Transition metals are mfique in that the electronic configu-

ration of the elements is characterized by having thll outerorbitals and the second outermost orbitals incompletelyfilled. This allows the transition metals to form a formidable5 munber &oxidation states, and the ease of moving from one

valence state to another is believed to be the reason that theycatalyze the oxidation of oxidizable polymers. It is wellknown that transition metals ions can bind ligands to give acoordination compound or com plex. It is believed that certain

10 colorants have ligands that will form such coordination com-pounds with the transition metal ion.Proof of such binding with colorants was shown usingX-ray Photoelectron Spectroscopy (NIPS ). The bindingenergy of the tansition metal ion in the presence of a colorant15 that did not deactivate the oxidation catalytic behavior ofthetransition metal did not cha nge, whereas in the presence of acolorant that did deactivate the oxidative catalytic behavior ofthe transition metal, the binding energy of the ion increasedby 1 to 2 electron volts. This indicates that the transition metal

20 ion, in the presence o f a colorant that deactivates the oxidationof an oxidizable polymer, is being homed to the colorant.Testing Procedures

1. Oxygen and Permeability25 Oxygan flux of fihn samples, at zero percent relative

hmnidity, at one atmosphere pressure, and at 23C. wasmeasured with a Mocon Ox-Tran model 2/21 (MOCON Min-neapolis, Mira1.). A mixture of 98% nitrogen with 2% hydro-gen was used as the carrier ga s, and 100% oxygen was used a s

30 the test gas. Prior to testing, specimens were conditioned innitrogen inside the unit for a minimum of twenty-four hoursto remove traces of atmospheric oxygen dissolved in the PETmatrix. The coMitioning was continued until a steady baseline was obtained where the oxygen flux changed by less than

5 one percent for a thirty-ntinute cycle. Subseqnently, oxygenwas introduced to the test cell. The reduction in the amount ofoxygen was measured from 0 to 50 hours. Treatment of thedata generated an A pparent Permeation Coefficient (APC), asa fimction of time with oxygen exposure (CC(STP)'cm)/

4O (m2'atm'day), these units normalize the permeance throughmeasurement of the film thickness. The generatedAPC data isnot a steady state value in normal permeation coefficients.APC is data generated that describes oxygen permeation at afixed point in time, even though this coefficient is changing

4s slowly with time. These changes are too small to be detectedduring the time necessary for measuring their value at anyfixed point in time. Calculation of the oxygen permeabilitywas done according to a literature method for permeationcoefficients lbr polymers, from Fick's second law ofdilsion

s0 with appropriate boundary conditions. The literature docu-ments are: Sekelik et al., Journal of Polymer Science Part B:Polymer Physics, 1999, Volume 37, Pages 847-857. The sec-ond Iiteratre docmnent is Qureshi et al., Journal of PolymerScience Part B: Polymer Physics, 2000, Volume 38, Pages55 1679-1686. The third literature document is Polyak ova, et al.,Journal of Polymer Science Part B: Polymer Physics, 2001,Volnme 39, Pages 1889-1899.

All film permeability values are reported in units of(cc(s).cm)/(ma.atm.day). The Catalyst Deactivation Factor60 (CDF) is dethed as:(oxygen permeability of base polymer, oxidizable organic

polymer, transition metal catalyst and 0.25 weight % colo-rant)/(oxygen permeability of base polymer and oxidizableorganic polymer).65 A CDF of 1 corresponds to complete deactivation, and aCD F of 0 corresponds to no deactivation of the oxidation

catalyst.


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US 7,879,930 B272. XPS AnalysisA 200 ppm solution of the transition salt and approxi-mately 1% by weight of the colorant was prepared in 5 g4n of

trifluoroacetic acid, The sohttion was shaken to achieve ahomogeneous solution.

This homogeneous sohttion obtained above was spincoated on a glass slide lxl cm in size. The volume of thesohttion used for coating was a pprox, i 00 lxl. The spin coaterused for the purpose of coating was from Spee dline Teclmolo-gies Model 6708D. T he glass slide was placed on the rotatingdisk and the solution was dropped after the glass slide wasrotating at a constant speed of 1200 rpm. It was allowed torotate further at the same speed of 1200 rpm for another 30seconds followed by ramping the speed to 1500 rpm in 2seconds and rotating at ttmt speed for 10 secon ds. Thereafterthe rotating disk was brought to stop in 6 seconds. The spincoated samples were placed under vacuum at 50-600 C. for6-8 hours for the removal of solvent. The glass slide contain-ing the transition metal salt and colorant were analyzed byX P S.The XPS instrument used was a Perldn Elmer ESC A andconditions were: Pass Energy--93eV, Chamber Pressure--10-8 Torr with an irradiation electrode ofA1 Ka (1486.6 eV).Fifty scans in the ran ge of the binding en ergy of the transitionmetal were taken and averaged.

8anthraquinone blue dye has a CDF of 0.017 whereas ananthraquinone green colorant had a C DF of 1.00. A colorantwith a CD F of less than ab out 0.25 is within the scope of thepresent invention.

Example 2Solutions of cobalt acetate tetrahydrate (control), with Sol-

vent Red 195 and with Solvent Green 3 were prepared andlC analyzed by XPS as discussed above. The 2p3/2 bindingenergy of cobalt metal is 778. l eV (CRCHandbookofChem-istry and Physics, 8Ft E dition). The binding energy of thecontrol Co(lI) oxidation state was measured to be 780.8 eV,and in the presence of Solvent Red 195 (CDF of 0.014)

is remained at 780.8 eV, while ha the presence of Solvent Green3 (CD F of 0.899) the binding energy increased to 783.2 eV.This analysis, shows that a colorant that deactivates thetransition metal catalyst in the oxidation of an oxidizablepolymer exhibits a coordination b ond with the transition

20 metal ion.Although particular embodiments of the invention have

been described in d etail, it will be understood that the inven-tion is not limited correspondingly in scope, but includes allchanges and modifications coming within the spirit and terms25 of the claims a ppended hereto.Example !

A commercial PET bottle resin T2201 (INVIST A S partan-burg, S.C. USA) was used as a base resin, blended with a 30sodium 5-sulfoisophthalic acid copolyester to ve 0.11 mole% sulfoisophthalic acid. T he oxidizable organic polymer wasType 6007 poly(m-xylylene adipamide) (MXD6) from Mit-snbishi Gas Chemical, Tokyo Japan at a concentration of 5weight %, based on the weight of the total blend. T he transi- 35tion metal was cobalt stearate at a level of 60 ppm cobalt,based on the weight of the total blend. This blend of ba seresin, MXD6, and cobalt stearate was melt blended withvarious colorants at a concentration of 0.25 weight %, basedon the weight of the blend, and injection molded into pre- 40lbrms. These prefbrms were stretch blow molded into stan-dard 0.6 liter bottles. The oxygen permeability of the bottlesidewall was measured after 50 hours and compared to apermeability of 0,133 and 0.0004 (cc(sTP).cm)/(m2.atm.day)for the PET control with 5 wt-% 1VEKD6, and the PET-- 4sMXD6 with a transition metal salt (60 ppm Co), both withouta colorant, respectively. The results using colorants fromvarious suppliers and various types are set tbrth in Table 1.

TABLE 1Permeability(CC(STP) em)iColor Index Colorant Type (m2, attn. day) CDF

None 0.000 0 55SelventYellow 114 Qulnoline dye 0.000 0,000Solvent Red 195 Azo dye 0.002 0.015Solvent Blue 97 Althraquinone dye 0.002 0.017SolventYelIew !14 Quinophthalonedye 0.005 0.038Solveztt Red 179 Perinone dye 0.008 0.058Solvent Red 135 Periuone dye 0.050 0,374Solvent Brown 53 Azomethine dye 0,056 0,42! 60SelventYellow 93 Methine dye 0.057 0,431Pigment Blue 15:3 Ptthalocyanine pigment 0.106 0,797Solvent Green 3 Anthraquinone dye 0.133 1,000Solvent Blue 57 Phthalocyeafine pigment 0.133 1,000

As this tab le illustrates, there is no correlation of the C DFwith the (chemical) type of coloram. For instance, an

What is claimed is:1. A melt blended resin for packaging articles comprising:

a base polymer, oxidizable orgamc polymer, transition metalcatalyst, and a colorant, such that an article made from saidmelt blended resin has a catalyst deactivation factor of lessthan 0.25, and further wherein said base polymer is selectedfrom the group consisting ofpolyethylene, polyester, polyvi-nyl chloride, polyvinylidene chloride, ethylene copolymers,and blends thereof.

2. The me lt blended resin of claim 1, wherein said colorantdoes not increase the binding energy of the transition metalcatalyst ion by more than 1 eV.3. The melt blended resin of claim 1, wherein said basepolymer is polyester.

4. The melt blended resin of claim 3, wherein said polyesteris a copolyester of polyethylene terephthalate.5. The melt blended resin of claim 1, wherein said oxidix-able organic polymer is a partially aromatic polyanfide.6. The melt blended resin of claim 5, wherein said partiallyaromatic polyanfide is MXD 6.7. The melt blended resin of claim 1, wherein said oxidiz-able orgmic polymer is polybutadiene.8. The melt blended resin of claim 1, wherein said transi-tion metal catalyst is a coba lt salt.9. The melt blended resin of claim 8, wherein said cobalt

salt is cobalt stearate.10. The melt blended resin of claim 1, wherein said resincontains an ionic eompatibilizer, wherein the ionic compati-

blizer reduces the haze of the paclcaging articles.11. The melt blended resin of claim 10, wherein said com-patibilizer is a copolyester containing a metal sulfonate salt.12. The melt blended resin of claim 11, wherein said metalst!lfonate salt is 5-sodiumsulfoisophthalic acid.13.A monolayer film, having an oxygenpermeation rate ofless than 0.01 (cc(stp).cm)/(m2.atm.day), said film formed

from a melt blend of a base polymer, oxidizable orgmficpolymer, transition metal catalyst, and a colorant, whereinsaid base polymer is selected from the group consisting ofpolyethylene, polyester, poiyvinyl chloride, polyvinylidenechloride, ethylene copolymers, and blends thereof.


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US 7,879,930 B2914. A polymer blend for packaging articles comprising: a

melt blend of a base polymer, oxidizable organic polymer,transition metal catalyst, md a colorant, such t

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