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EP0964893A1 - Naphtalenedicarboxylate contenant un melange de polyamide/polyester a propriete de retention de saveur amelioree - Google Patents

Naphtalenedicarboxylate contenant un melange de polyamide/polyester a propriete de retention de saveur amelioree

Info

Publication number
EP0964893A1
EP0964893A1 EP98908969A EP98908969A EP0964893A1 EP 0964893 A1 EP0964893 A1 EP 0964893A1 EP 98908969 A EP98908969 A EP 98908969A EP 98908969 A EP98908969 A EP 98908969A EP 0964893 A1 EP0964893 A1 EP 0964893A1
Authority
EP
European Patent Office
Prior art keywords
acid
polyamide
molecular weight
nylon
diol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98908969A
Other languages
German (de)
English (en)
Inventor
Timothy Edward Long
Steven Lee Stafford
Emily Tedrow Bell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Publication of EP0964893A1 publication Critical patent/EP0964893A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • acetaldehyde acetaldehyde
  • AA acetaldehyde
  • the container market for carbonated and still mineral water requires exceptionally low levels of acetaldehyde (AA) in the container side wall in order to avoid the diffusion of the AA into the water leading to an undesirable water taste.
  • AA is an inherent side product which is generated during the polymerization melt phase and subsequent processing steps.
  • variables such as catalyst selection influence the amount of residual AA.
  • this level of AA is still perceived to be too high for some applications.
  • taste testing has indicated that humans can taste 20 ppb differences in AA. Consequently, there has been significant interest in reducing the residual AA content as low as possible.
  • Bottle sidewall color is typically reported as a b* unit which reflects the level of yellow color in the bottle.
  • containers prepared from virgin PET resin have values ranging from 0.8-1.2 b* units. Consequently, significant attention has been devoted to the production of beverage containers which demonstrate both low AA and low color.
  • U.S. Pat. No. 4,837,115 discloses a thermoplastic composition containing polyethylene terephthalate and high molecular weight polyamides which act to reduce the residual acetaldehyde contained in the polyester.
  • U.S. Pat No. 4,837,115 states that the molecular weight of the polyamide is not critical so far as the polyamide has a film-forming property. Such polyamides, therefore, must have high enough molecular weights to form a film. It is well known in the art that polyamides having molecular weights of at least 12,000 are necessary to form a film.
  • the present invention comprises semi-crystalline polyester blend compositions having improved flavor retaining properties, comprising: (A) 98.0 to 99.95 weight percent of a polyester which comprises
  • a dicarboxylic acid component comprising repeat units from at least 50 mole percent naphthalenedicarboxylic acid derived from at least one dimethylester of naphthalenedicarboxylic acid respectively;
  • a diol component comprising repeat units from at least 50 mole percent ethylene glycol, based on 100 mole percent dicarboxylic acid and 100 mole percent diol;
  • the present invention further comprises a process for forming a polymer/polyamide blend comprising blending
  • (A) about 80 to about 99 weight % of a base polyester comprising (1) a dicarboxylic acid component comprising repeat units from at least about 85 mole percent naphthalenedicarboxylic acid thereof, wherein said acid is derived from terephthalic acid or naphthalenedicarboxylic acid respectively; and (2) a diol component comprising repeat units from at least about 85 mole percent ethylene glycol, based on 100 mole percent dicarboxylic acid and 100 mole percent diol; and B) about 1 to about 20 weight % of a concentrate comprising: 1) about 1 to about 99 weight % of a carrier resin comprising repeat units from at least about 60 mole percent naphthalenedicarboxylic acid and mixtures thereof, and a diol component comprising repeat units from at least about 50 mole percent ethylene glycol, based on 100 mole percent dicarboxylic acid and 100 mole percent diol; and (2) about 1 to about 99 weight% of a polyamide which displays a melting point
  • the present invention involves naphthalenedicarboxylate polyester/polyamide blends having surprisingly low AA.
  • the present invention further discloses naphthalenedicarboxylate containing polyester/polyamide blends which are formed by mixing a polyester base resin with a concentrate containing the polyamide.
  • polyester (A), of the present invention is selected from polyethylene naphthalenedicarboxylate (PEN) or copolyesters thereof.
  • the acid component of polyester (A) contains repeat units from at least about 50 mole percent naphthlenedicarboxylic acid and at least about 50 mole percent ethylene glycol, based on 100 mole percent dicarboxylic acid and 100 mole percent diol.
  • naphthalenedicarboxylate repeat unit is supplied from the diester.
  • the dicarboxylic acid component of the polyester may optionally be modified with up to about 50 mole percent and more preferably 15 mol% of one or more different dicarboxylic acids.
  • additional dicarboxylic acids include aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, or cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms.
  • dicarboxylic acids examples include: terephthalic acid, phthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like. Polyesters may be prepared from two or more of the above dicarboxylic acids.
  • glycol component (A)(2) may optionally be modified with up to about 50 mole percent and more preferably up to about 15 mole percent, of one or more different diols other than ethylene glycol.
  • additional diols include cycloaliphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms.
  • diols to be included with ethylene glycol are: diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propane- 1,3-diol, butane- 1,4-diol, pentane-l,5-diol, hexane-l,6-diol, 3- methylpentanediol-(2,4), 2-methylpentanediol-( 1 ,4), 2,2,4-trimethylpentane-diol- (1,3), 2-ethylhexanediol-(l,3), 2,2-diethylpropane-diol-(l,3), hexanediol-(l,3), 1,4- di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4- dihydroxy-l,l,3,3-tetramethyl-cyclobut
  • the resin may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art.
  • the carrier and base resins of the present invention should have molecular weights which are sufficient to insure that bottles may be formed from the resin. More preferably the resins have IN. which are between about 0.60 and about 1.3 dl/gm, as determined in a 70:30 phenol :trichloroethane cosolvent.
  • the PEN based polyesters of the present invention can be prepared by conventional polycondensation procedures well-known in the art. Such processes include direct condensation of the dicarboxylic acid(s) or diester(s) with the diol(s).
  • the polyesters may also be subjected to solid state polymerization methods.
  • the second component of the present invention is a polyamide capable of decreasing the AA which is generated during the production of the base resin and subsequent processing steps. Suitable polyamides display a melting point below the melting point of the polyester (PEN homopolymer, copolymer or blends).
  • said polyamide is selected from the group consisting of low molecular weight partially aromatic polyamides having a number average molecular weight of less than 15,000, low molecular weight aliphatic polyamides having a number average molecular weight of less than 7,000 and wholly aromatic polyamides.
  • partially aromatic polyamide it is meant that the amide linkage of the partially aromatic polyamide contains at least one aromatic ring and a nonaromatic species.
  • the partially aromatic polyamides have an IN. of less than about 0.8 dL/g.
  • the IN. of the partially aromatic polyamides is less than about 0.7 dL/g and the number average molecular weight is less than about 12,000.
  • the aliphatic polyamides have an IN. of less than about 1.1 dL/g.
  • the IN. of the aliphatic polyamides is less than about 0.8 dL/g and the number average molecular weight is less than about 6,000.
  • Wholly aromatic polyamides comprise in the molecule chain at least 70 mole % of structural units derived from m-xylylene diamine or a xylylene diamine mixture comprising m- xylylene diamine and up to 30% of p-xylylene diamine and an ⁇ -aliphatic dicarboxylic acid having 6 to 10 carbon atoms, which are further described in Japanese Patent Publications No. 1156/75, No. 5751/75, No. 5735/75 and No.
  • composition or articles of the present invention may contain up to about two weight percent of the low molecular weight polyamides and preferably less than about one weight percent. It has been determined that the use of polyamides at greater than about two weight percent based on the weight of the polyester cause undesirable levels of haze.
  • polyamides used in the present invention are derived from 2,6-naphthalenedicarboxylic acid either alone or in combination with other acids such adipic acid.
  • the low molecular weight polyamides may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromellitic dianhydride, or other polyamide forming polyacids and polyamines known in the art.
  • Preferred low molecular weight partially aromatic polyamides include: poIy(/ «-xylylene adipamide), poly(hexamethylene isophthalamide), poly(hexamethylene adipamide-co-isophthalamide), poly(hexamethylene adipamide- co-terephthalamide), and poly(hexamethylene isophthalamide-co-terephthalamide).
  • the most preferred low molecular weight partially aromatic polyamide is poly( ⁇ w - xylylene adipamide) having a number average molecular weight of about 4,000 to about 7,000 and an inherent viscosity of about 0.3 to about 0.6 dL/g.
  • Preferred low molecular weight aliphatic polyamides include poIy(hexamethylene adipamide) and poly(caprolactam).
  • the most preferred low molecular weight aliphatic polyamide is poly(hexamethylene adipamide) having a number average molecular weight of about 3,000 to about 6,000 and an inherent viscosity of 0.4 to 0.9 dL/g.
  • Low molecular weight partially aromatic polyamides are preferred over the aliphatic polyamides where clarity and dispersibility are crucial.
  • Preferred low molecular weight aliphatic polyamides include polycapramide (nylon 6), poly- ⁇ -aminoheptanoic acid (nylon 7), poly- ⁇ -aminonanoic acid (nylon
  • polyundecane-amide (nylon 11), polyaurylactam (nylon 12), polyethylene- adipamide (nylon 2,6), polytetramethylene-adipamide (nylon 4,6), polyhexamethylene-adipamide (nylon 6,6), polyhexamethylene-sebacamide (nylon 6,10), polyhexamethylene-dodecamide (nylon 6,12), polyoctamethylene-adipamide (nylon 8,6), polydecamethylene-adipamide (nylon 10,6), polydodecamethylene- adipamide (nylon 12,6) and polydodecamethylene-sebacamide (nylon 12,8).
  • the low molecular weight polyamides are generally prepared by melt phase polymerization from a diacid-diamine complex which may be prepared either in situ or in a separate step. In either method, the diacid and diamine are used as starting materials. Alternatively, an ester form of the diacid may be used, preferably the dimethyl ester. If the ester is used, the reaction must be carried out at a relatively low temperature, generally 80 to 120°C, until the ester is converted to an amide. The mixture is then heated to the polymerization temperature.
  • caprolactam either caprolactam or 6-aminocaproic acid can be used as a starting material and the polymerization may be catalyzed by the addition of adipic acid/hexamethylene diamine salt which results in a nylon 6/66 copolymer.
  • adipic acid/hexamethylene diamine salt which results in a nylon 6/66 copolymer.
  • the molecular weight is controlled by the diacid-diamine ratio. An excess of diamine produces a higher concentration of terminal amino groups. Conversely, an excess of the diacid leads to a higher concentration of terminal acid groups. If the diacid-diamine complex is prepared in a separate step, excess diamine is added prior to the polymerization.
  • the polymerization can be carried out either at atmospheric pressure or at elevated pressures.
  • the process for preparing the polyester/polyamide blends of the present invention involve preparing the polyester and low molecular weight polyamide, respectively, by processes as mentioned previously.
  • the polyester and polyamide are dried in an atmosphere of dried air or dried nitrogen, or under reduced pressure.
  • the polyester and polyamide are mixed and subsequently melt compounded, for example, in a single or twin screw extruder.
  • Melt temperatures must be at least as high as the melting point of the polyester and are typically in the range of about 260 to about 310°C.
  • the melt compounding temperature is maintained as low as possible within said range.
  • the extrudate is withdrawn in strand form, and recovered according to the usual way such as cutting.
  • the polyester and polyamide may be dry-blended and heat-molded or draw-formed into plastic articles.
  • the polyamide can be added in the late stages of polyester manufacture.
  • the polyamide can be blended with the molten polyester as it is removed from the polycondensation reactor, before it is pelletized. This method, however, is not desirable if the polyester/polyamide blend will be subjected to solid state polymerization since undesirable color and/or haze may develop during extended time at elevated temperatures.
  • the polyamide may also be added as part of a polyolefin based nucleator concentrate where clarity is not critical such as in crystallized thermoformed articles.
  • the polyamide may also be as a component of a polyester concentrate.
  • the concentrate carrier resin may use either the acid or ester form of the acid component of the polyester. Preferably the carrier resin is derived from the acid form.
  • the concentrate comprises about 1 to about 99 weight % of a carrier resin comprising repeat units from at least about 60 mole percent naphthalenedicarboxylic acid and a diol component comprising repeat units from at least about 50 mole percent ethylene glycol, based on 100 mole percent dicarboxylic acid and 100 mole percent diol and about 1 to about 99 weight% of a polyamide described above. More preferably the carrier resin is about 20 to about 99 and most preferably about 50 to about 99 weight percent.
  • the blends of this invention serve as excellent starting materials for the production of moldings of all types by extrusion or injection molding. Specific applications include various packaging applications such as thermoformed or injection molded trays, lids and cups; injection stretch blow-molded bottles, film and sheet; extrusion blow-molded bottles and multilayer articles. Examples of package contents include, but are not limited to, food, beverages, and cosmetics. Many other ingredients can be added to the compositions of the present invention to enhance the performance properties of the blends.
  • crystallization aids for example, crystallization aids, impact modifiers, surface lubricants, denesting agents, stabilizers, antioxidants, ultraviolet light absorbing agents, metal deactivators, colorants such as, but not limited to titanium dioxide and carbon black, nucleating agents such as polyethylene and polypropylene, phosphate stabilizers, fillers, and the like, can be included herein. All of these additives and the use thereof are well known in the art and do not require extensive discussions. Therefore, only a limited number will be referred to, it being understood that any of these compounds can be used so long as they do not hinder the present invention from accomplishing its objectives.
  • Suitable colorants can be added to either component of the blend during polymerization or added directly to the blend during compounding. If added during blending, the colorant can be added either in pure form or as a concentrate. The amount of a colorant depends on its absorptivity and the desired color for the particular application.
  • a preferred colorant is l-cyano-6-(4-(2- hydroxyethyl)anilino)-3-methyl-3H-dibenzo(F,I,J)-isoquinoline-2,7-dione used in an amount of from about 2 to about 15 ppm.
  • Desirable additives also include impact modifiers and antioxidants.
  • typical commercially available impact modifiers well-known in the art and useful in this invention include ethylene/propylene terpolymers, styrene based block copolymers, and various acrylic core/shell type impact modifiers.
  • the impact modifiers may be used in conventional amounts from about 0.1 to about 25 weight percent of the overall composition and preferably in amounts from about 0.1 to about 10 weight percent of the composition.
  • Examples of typical commercially available antioxidants useful in this invention include, but are not limited to, hindered phenols, phosphites, diphosphites, polyphosphites, and mixtures thereof. Combinations of aromatic and aliphatic phosphite compounds may also be included.
  • Acetaldehyde generation was determined by the following method. After crystallizing for 30 minutes at 180°C, the pelletized polyester was dried overnight at 120°C. in a vacuum oven. A Tinius-Olsen melt indexer was loaded with 5 grams of the polyester and held at the test temperature for five minutes. The molten polyester was extruded into water and stored at a temperature of -40°C. until grinding. The sample was ground to 20 mesh or finer and 0.5 grams was placed in a sample tube which was immediately sealed. The sample was analyzed by dynamic headspace gas chromatographic analysis using a Hewlett- Packard 5890 Gas Chromatograph with a Perkin Elmer Automatic Thermal Desorption ATD-50 as the injection system. Acetaldehyde was desorbed by heating the sample at 150°C. for ten minutes. The gas chromatography column had a 30 m by 0.53 mm inside diameter.
  • Acetaldehyde concentration after extrusion was determined by grinding the pellets or sheet to 20 mesh or finer and measuring the acetaldehyde concentration by the same gas chromatographic method as described for acetaldehyde generation. Color was determined according to ASTM D2244 using a Hunter Color Lab instrument. Color measurements are reported as Rd, a and b.
  • Haze was determined by ASTM D1003. Haze values of greater than 3.0% indicate visible haze.
  • Inherent viscosity was measured at 25°C using 0.50 grams of polymer per 100 ml of a solvent consisting of 60% by weight phenol and 40% by weight tetrachloroethane.
  • Poly(/n-xylylene adipamide) was prepared by the following procedure.
  • the mixture was placed in a polymerization reactor under a nitrogen atmosphere.
  • the mixture was heated with stirring to reflux for 30 minutes.
  • the mixture was heated to 120°C. and held for 60 minutes while water was distilled off.
  • the temperature was then increased to 275°C. over a period of 3.25 hours.
  • the mixture was stirred at 275°C. for 30 minutes.
  • the poly(m- xylylene adipamide) was extruded into water, ground and dried.
  • the number average molecular weight and IN. of the poly(/w-xylylene adipamide) was determined to be 2,300 and 0.27 dL/g, respectively.
  • Poly( M-xylylene adipamide) prepared according to the above procedure was used to prepare a concentrate containing 25 weight percent of the polyamide in POLYESTER A.
  • the polyamide was pulverized and subsequently dried at 120°C. for 16 hours in a vacuum oven.
  • PEN containing the low AA concentrate was prepared as follows: Three samples of PEN homopolymer having an IN. of 0.56 dL/g were modified with an amount of concentrate sufficient to deliver the amount of polyamide listed in Table 1 below.
  • the low AA concentrate prepared in Example 1 was added just prior to extrusion to form polymer pellets at 295°C and the resulting polymer was molded into pellets.
  • the AA concentration after extruding was measured and compared to the control reported in Table 2 to determine the % AA reduction as and is shown in Table 1, below.
  • PEN homopolymer and a copolymer of 92 mole% N, 8 mole%T and 100 mole %EG
  • Examples 5-7 report the amount of AA present in the unmodified base polymers.
  • Examples 8-10 were prepared as above, except that the amount of polyamide delivered was kept constant (0.5 wt%) and the carrier resin (or concentrate) resin used was the same as the base polymer.
  • Table 2 shows the amount of AA in the extruded pellets and the corresponding %AA reduction compared to the controls (Examples 5-7).
  • PEN is generally processed at temperatures which are 10-20° greater than those for PET due to PEN's higher melting temperature.
  • the amount of AA generated in a polymer derived or containing ethylene glycol nearly exponentially increases as the processing temperature is increased.
  • the amount of AA generated in PET at 295°C is nearly double the amount generated at 275°C.
  • the AA reducing agents of the present invention could still produce significant reductions in AA in PENT and PEN polymers despite their higher required processing temperatures and corresponding higher rates of AA generation.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne des compositions à mélange de polyesters présentant des propriétés de rétention de saveur et de couleur améliorées comprenant (A) 98,0 % à 99,95 % en poids d'un polyester constitué (1) d'un composant d'acide dicarboxylique comprenant des unités de répétition d'au moins 50 % en moles d'acide naphtalénedicarboxylique; et (2) un composant de diol comprenant des unités de répétition d'au moins 50 % en moles d'éthylène glycol sur la base de 100 % en moles d'acide dicarboxylique et de 100 % en moles de diol; et (B) 2,0 % à 0,05 % en poids d'un polyamide dans lequel les poids associés de (A) et (B) font un total de 100 %.
EP98908969A 1997-03-05 1998-03-05 Naphtalenedicarboxylate contenant un melange de polyamide/polyester a propriete de retention de saveur amelioree Withdrawn EP0964893A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US3600897P 1997-03-05 1997-03-05
US36008P 1997-03-05
US3398998A 1998-03-03 1998-03-03
US33989 1998-03-03
PCT/US1998/004311 WO1998039388A1 (fr) 1997-03-05 1998-03-05 Naphtalenedicarboxylate contenant un melange de polyamide/polyester a propriete de retention de saveur amelioree

Publications (1)

Publication Number Publication Date
EP0964893A1 true EP0964893A1 (fr) 1999-12-22

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EP98908969A Withdrawn EP0964893A1 (fr) 1997-03-05 1998-03-05 Naphtalenedicarboxylate contenant un melange de polyamide/polyester a propriete de retention de saveur amelioree

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Country Link
EP (1) EP0964893A1 (fr)
JP (1) JP2001514681A (fr)
BR (1) BR9808301A (fr)
WO (1) WO1998039388A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6239233B1 (en) * 1998-10-09 2001-05-29 Eastman Chemical Company Polyester/polyamide blends with improved color
US6191209B1 (en) * 1999-06-30 2001-02-20 Ciba Specialty Chemicals Corporation Polyester compositions of low residual aldehyde content
AU6505000A (en) * 1999-07-30 2001-02-19 Eastman Chemical Company Polyester-polyamide blends with reduced gas permeability and low haze
WO2001023475A1 (fr) 1999-09-27 2001-04-05 Ciba Specialty Chemicals Holding Inc. Compositions de polyester possedant une teneur limitee en aldehyde residuel
IT1318600B1 (it) 2000-06-28 2003-08-27 Sinco Ricerche Spa Preparazione di resine poliestere impieganado masterbatch dipoliarilenammidi.
JP2004517187A (ja) 2000-12-29 2004-06-10 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 低残存アルデヒド含量のポリエステル組成物
US6908650B2 (en) 2001-03-02 2005-06-21 Ciba Specialty Chemicals Corporation Polyester and polyamide compositions of low residual aldehyde content
WO2003016401A1 (fr) 2001-08-13 2003-02-27 Ciba Specialty Chemicals Holding Inc. Compositions de polyester a faible contenu en aldehyde residuel
US7041350B1 (en) * 2002-08-30 2006-05-09 The Coca-Cola Company Polyester composition and articles with reduced acetaldehyde content and method using hydrogenation catalyst
CA2513686C (fr) * 2003-01-31 2011-09-27 M & G Polimeri Italia S.P.A. Article comprenant une composition absorbant la lumiere afin de masquer un trouble visible et procedes associes
JP2008543610A (ja) * 2005-06-17 2008-12-04 イーストマン ケミカル カンパニー シクロブタンジオールと均一ポリアミド配合品を含むポリエステルを含有する多層透明製品の製造法

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US5258233A (en) * 1992-04-02 1993-11-02 Eastman Kodak Company Polyester/polyamide blend having improved flavor retaining property and clarity
US5650469A (en) * 1995-10-25 1997-07-22 Eastman Chemical Company Polyester/polyamide blend having improved flavor retaining property and clarity

Non-Patent Citations (1)

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Title
See references of WO9839388A1 *

Also Published As

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JP2001514681A (ja) 2001-09-11
BR9808301A (pt) 2000-05-16
WO1998039388A1 (fr) 1998-09-11

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