WO2005068531A1 - Resine polyester avec proprietes d'absorption de l'infrarouge ameliorees - Google Patents

Resine polyester avec proprietes d'absorption de l'infrarouge ameliorees Download PDF

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Publication number
WO2005068531A1
WO2005068531A1 PCT/KR2004/003379 KR2004003379W WO2005068531A1 WO 2005068531 A1 WO2005068531 A1 WO 2005068531A1 KR 2004003379 W KR2004003379 W KR 2004003379W WO 2005068531 A1 WO2005068531 A1 WO 2005068531A1
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WO
WIPO (PCT)
Prior art keywords
polyester resins
infrared
polymerization
red iron
iron oxide
Prior art date
Application number
PCT/KR2004/003379
Other languages
English (en)
Inventor
Jin-Gi Lee
Yeon-Suk Kim
Byeong-Ok Choi
Kyeong-Jin Park
Original Assignee
Taekwang Ind Co., Ltd
Daehan Synthetic Fiber Co., Ltd
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 Taekwang Ind Co., Ltd, Daehan Synthetic Fiber Co., Ltd filed Critical Taekwang Ind Co., Ltd
Publication of WO2005068531A1 publication Critical patent/WO2005068531A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G17/00—Connecting or other auxiliary members for forms, falsework structures, or shutterings
    • E04G17/06—Tying means; Spacers ; Devices for extracting or inserting wall ties
    • E04G17/065—Tying means, the tensional elements of which are threaded to enable their fastening or tensioning
    • E04G17/0651—One-piece elements
    • E04G17/0654—One-piece elements remaining completely or partially embedded in the cast material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0822—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/006—PBT, i.e. polybutylene terephthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids

Definitions

  • the present invention is related to thermoplastic polyester (hereinafter referred to as 'PET') resins having superior colors and infrared-absorbing efficiency and the methods of manufacture of these resins.
  • PET resins are materials of which amounts of use for containers for various kinds of carbonated drinks, natural water, and fruit juices, and for sheet, etc. are on the increasing trend day by day since they have superior physical properties in stability, strength, etc. Therefore, there has been an increasing demand for resins that have been transparent and have had superior colors while increasing productivity during molding.
  • PET containers for drinks There are a few methods of manufacture of PET containers for drinks including a method of manufacture of high-pressure blowing before resins are solidified completely after they are ejected from a machine, and a method of ejection of preforms in the first step and re-heating of these preforms and high-pressure blowing in molding frames in the second step.
  • the 2-step method is utilized mostly owing to the productivity and variety of the kinds of containers.
  • the core requisite for increasing productivity is shortening of the re-heating time.
  • 4,535,118 are methods of improving absorbancy of infrared light by adding carbon black during re-heating of preforms; and disclosed in the U.S. Patents No. 5,925,710 and No. 6,034,167 and Laid-Open No. 2001-0,043,209 are methods of improving absorbancy of infrared light by adding graphite.
  • the use of carbon black or graphite is problematic in that it is extremely difficult to disperse them since they are non-polar, and therefore, they may appear in the form of black spots, and the color tends to be darker even if a small amount is added.
  • a method of combining antimony particles, phosphorus compounds, etc. is disclosed in the U.S. Patent No. 5,419,936.
  • the elements to be equipped by the resins in the manufacture of molded containers in the 2-step method are not only that the time of re-heating should be shortened by improving absorbancy of infrared light in order to improve productivity, but also that the colors, transparency, and homogeneous molding capacity should be satisfied.
  • an object of the present invention is to provide with thermoplastic PET resins containing the red iron oxide compound coated with manganese oxide having improved productivity, as well as superior colors and transparency, by increasing absorbancy of infrared light so that preforms are heated higher than the glass transition temperature in a shorter time compared to using general PET resins having no additives added when manufacturing containers through reheating and blow molding of preforms after they are made, and to provide with the methods of manufacture of these resins.
  • Another object of the present invention is to provide with preforms manufactured by using thermoplastic PET resins containing the red iron oxide compound coated with manganese oxide.
  • Still another object of the present inention is to provide with containers manufactured with thermoplastic PET resin preforms containing the red iron oxide compound coated with the above manganese oxide.
  • the main component of MFO which is the additive of the present invention, is the compound of red iron oxide and manganese oxide. And a small amount of a part of the compound of silicon oxide and/or aluminum oxide is mixed and sintered at a high temperature. It is a black heat-resistant inorganic oxide containing 50 to 90 weight % of the red iron oxide compound, 8 to 43 weight % of the manganese oxide compound, and 2 to 5 weight % of the silicon oxide and/or aluminum oxide compound as another component.
  • the above MFO is dispersed and distributed evenly in the resins irrespective to when it is added, i.e., in the early stage or at any time of a reaction, during the polymerization of PET resins, since it has superior heat resistance and dispersibility. And it has superior colors since its colors are not changed.
  • the efficiency of absorbance of infrared light is improved if MFO is added compared to the case that it is not added.
  • the amount of input of MFO in the present invention it is preferable to have 3 to 100 ppm of MFO contained with respect to the amount of PET resins, more preferably, 5 to 50 ppm of MFO, in order to produce resins having improved absorbancy of infrared light and colors. If its concentration is lower than 3 ppm, its efficiency of absorbance of infrared light is lowered although its colors may be improved; and if its concentration is greater than 100 ppm, it is not desirable in that white turbidity occurs during blow molding and it becomes opaque since its color becomes inferior and the speed of crystallization becomes faster.
  • the particle size of MFO in the present invention it is preferable to maintain 0.1 to 20 microns (micrometers), more preferably, 0.1 to 10 microns. If the particle size is too small, the ratio of generation of sub-standard products during blow molding is increased and black spots are found in molded products since particles are aggregated, dispersion becomes uneven, and the absorbancy of infrared light of preforms is deviated; and if the particle size becomes too large, the surface of molded products is not smooth and opaque.
  • the present invention is illustrated in detail below:
  • the resins according to the present invention are applicable to both of thermoplastic homopolymers and copolymers that may be crystallized.
  • thermoplastic polymers in the present invention are PET resins, that are thermoplastic polymers produced by the stoichiometric reaction of dicarboxylic acid and/or its derivatives and diol components.
  • known methods of manufature of PET resins include a method of production of bis(2-hydroxyethyl) terephthalate (hereinafter referred to as 'BHET') through transesterification of dimethyl terephthalate (hereinafter referred to as 'DMT') and ethylene glycol (hereinafter referred to as 'EG') in the presence of catalysts such as manganese, calcium, lithium, sodium compounds, etc., or a method of manufacture through the production of BHET according to the direct esterification of terephthalic acid (hereinafter referred to as 'TPA') and EG, and then, the condensation polymerization reaction of this BHET at 265 to 295°C under the vacuum below 1 torr in the presence of condensation polymerization catalysts
  • the main components that may be used for the synthesis of the resins according to the present invention include dicarboxylic acids and their derivatives such as phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, naphthalene-2,6-dicarboxylic acid, sebacic acid, adipic acid, succinic acid, etc.; anhydrides and esters corresponding to the above; diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, 1,3- propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-l,3- propanediol, 2,2-diethyl-l,3-propanediol, 2-methyl-l,4-pentanediol, 1,3
  • reaction catalysts one or more kinds of catalysts selected from transesterification catalysts in the above-described DMT method such as manganese, calcium, lithium, sodium, zinc, cobalt compounds, etc. and polymerization condensation reaction catalysts such as antimony, titanium, germanium, etc. may be combined and used. It is also acceptable to add complementary coloring agents such as cobalt acetate, etc., heat resistance agents such as phosphorus compounds, etc., charging prevention agents, UN cut-off agents, fluorescence enhancing agents, coloring agents, etc.
  • transesterification catalysts in the above-described DMT method such as manganese, calcium, lithium, sodium, zinc, cobalt compounds, etc. and polymerization condensation reaction catalysts such as antimony, titanium, germanium, etc.
  • complementary coloring agents such as cobalt acetate, etc., heat resistance agents such as phosphorus compounds, etc., charging prevention agents, UN cut-off agents, fluorescence enhancing agents, coloring agents, etc.
  • the present invention is illustrated in still more detail below:
  • a reator 40 to 45 moles of terephthalic acid, 80 to 90 moles of ethylene glycol, and 0 to 5 moles of isophthalic acid are put, mixed for about 10 minutes, heated to 230 to 240°C, and made to have the maximum pressure of the inside of the reactor of below 4.5 kg f /cm 2 in order to perform esterification.
  • esterification is progressed 97 to 98% with respect to the throughput of water produced during the reaction, the pressure inside of the reactor is increased slowly by controlling a valve.
  • Thermoplastic PET resins are manufactured by reacting at 285 to 290°C for the final-stage temperature of the polymerization condensation reaction for 130 minutes in a vacuum state below 1.0 torr, where the intrinsic viscosity of polymers is at a level of 0.58 to 0.65 dl/g.
  • MFO which is an additive for the improvement of absorbancy of infrared light disclosed in the present invention is input in the early stage or during a reaction in the above process.
  • the degree of polymerization should be increased by performing a separate polymerization process in a solid state after the liquid-phase polymerization process.
  • the surface of resin chips is crystallized by putting the chips manufactured according to the above-described liquid-phase polymerization into a rotary solid-phase polymerization reactor, and heating slowly up to 160°, while rotating at 20 rpm.
  • the solid-phase polymerization is performed at 160 to 210°C for 10 to 15 hours, where the degree of vacuum is maintained below 0.5 torrs, and the intrinsic viscosity of polymers having the solid-phase polymerization completed is made to be greater than 0.70 dl/g.
  • Preforms are manufactured by ejecting solid-phase-polymerized chips at 280 to 290°C, and bottle molded products are manufactured through high-pressure blowing of the above preforms after measuring the temperature of the surface of the preforms by using an infrared thermometer after passing them through an infrared heater in a 2-cavity-2-stage blow molder (Frontier).
  • Acetaldehyde amount (AA) Into a container having an inner volume of 50 ml, 5.0 g of a resin sample is weighed precisely and input. And thermal extraction is performed at 16°C for 2 hours after adding 10 ml of distilled water and closing tightly with nitrogen. The amount of acetaldehyde in the solution thus extracted is analyzed quantitatively through gas chromatography (HP 5890-11) by using isobutyl alcohol as the standard material.
  • IR absorbance efficiency (%) 100 x (a - b) / b where a is the temperature measured of the surface of preforms manufactured by inputting additives; and b is the temperature measured of the surface of preforms manufactured without inputting additives.
  • Esterification is performed by inputting 6,688 g of terephthalic acid (TPA), 5,120 g of EG, 160 g of isophthalic acid (IPA), and 104 g of diethylene glycol (DEG) into a stainless steel reactor having an inner volume of 20 liters, stirring for 10 minutes, and inputting 20 ppm of the red iron oxide compound (Bayferrox '303T' of Bayer AG Company) coated with manganese oxide which is dispersed into EG in advance to have a concentration of 0.5 weight %.
  • TPA terephthalic acid
  • IPA isophthalic acid
  • DEG diethylene glycol
  • Esterification is performed at 235°C while maintaining 4.5 kg f /cm 2 for the maximum pressure inside of the reactor, and terminated by controlling slowly the pressure valve and opening it completely after it is confirmed from the amount of water generated that the esterification reaction is progressed to the degree of 97%. Thereafter, 114 ppm of cobalt acetate, 540 ppm of antimony trioxide, and 70 ppm of phosphoric acid are input, and the temperature is increased to 270°C throughout 60 minutes while reducing the pressure slowly. The final-stage temperature of the polymeerization condensation reaction is 285°C, and the reaction is continued for 130 minutes under a vacuum of 0.8 torrs.
  • chips having a diameter of 2.5 mm and a length of 3 mm are manufactured by ejecting polymers through a 5-hole nozzle to a 20- °C cooling water bath, cooling, and cutting with a cutter.
  • the intrinsic viscosity (IN) of these polymers is 0.61 dl/g.
  • the chips manufactured in the above method are made through solid-phase polymerization in order to increase the degree of polymerization.
  • the chips manufactured in the above are put into a 20-liter rotary solid-phase polymerization reactor, rotated at 20 rpm, heated slowly up to 160°C in order to prevent coagulation among chips, and solid-phase polymerized at 160 to 210°C for 12 hours, where the final degree of vacuum is 0.2 torrs, and the intrinsic viscosity of polymers is 0.79 dl/g.
  • Preforms are manufactured by ejecting solid-phase-polymerized chips at 285°C, and bottle molded products are manufactured through high-pressure blowing of the above preforms after measuring the temperature of the surface of the preforms by using an infrared thermometer after passing them through an infrared heater in a 2-cavity-2-stage blow molder (Frontier).
  • Liquid-phase polymerization condensation reaction, solid-phase polymerization, and manufacture of preforms and bottle molded products are performed in the same method as that of Preferred Embodiment 1 except that the amounts of input of the red iron oxide compound coated with manganese oxide are changed as shown in Tables 1 and 2.
  • Liquid-phase polymerization condensation reaction, solid-phase polymerization, and manufacture of preforms and bottle molded products are performed in the same method as that of Preferred Embodiment 1 except that the red iron oxide compound coated with manganese oxide is input after the esterification reaction is terminated, not in the early stage of the esterification reaction, in an amount of 30 ppm.
  • the results are shown in Tables 1 and 2.
  • Liquid-phase polymerization condensation reaction, solid-phase polymerization, and manufacture of preforms and bottle molded products are performed in the same method as that of Preferred Embodiment 1 except that the red iron oxide compound coated with manganese oxide is input after the esterification reaction is terminated, not in the early stage of the esterification reaction, in an amount of 5 ppm.
  • the results are shown in Tables 1 and 2.
  • the present invention is applicable extensively to the manufacture of various kinds of PET containers in that not only the productivity in molding of containers may be improved but also their colors, transparency, and molding capacity are superior by improving the absorbancy of infrared light by adding the red iron oxide compound coated with manganese oxide in the early stage or in the middle of a reaction during polyester polymerization. It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed processes and products without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Chemical & Material Sciences (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne des résines polyester destinées à la fabrication de récipients et des procédés de fabrication de ces résines, dans lesquels la productivité peut-être améliorée par une augmentation de l'efficacité de l'absorption de la lumière infrarouge pendant le moulage des récipients polyester. Cette invention se caractérise en ce que les couleurs des résines polyester ne sont pas modifiées pendant la polymérisation polyester et les composés oxyde de fer rouge revêtus avec de l'oxyde de manganèse très dispersible et thermorésistant sont entrés avant ou pendant la réaction de polymérisation dans une quantité de 100 ppm. L'efficacité de l'absorption de la lumière infrarouge des préformes fabriquées avec les résines polyester de l'invention après leur passage à travers la zone de chauffage infrarouge est améliorée de plus de 7 % comparée à celle des résines sans additifs. Les préformes fabriquées selon cette invention présentent des couleurs, une transparence et une capacité de moulage supérieures.
PCT/KR2004/003379 2004-01-16 2004-12-21 Resine polyester avec proprietes d'absorption de l'infrarouge ameliorees WO2005068531A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2004-0003432 2004-01-16
KR10-2004-0003432A KR100455456B1 (ko) 2004-01-16 2004-01-16 적외선 흡수성이 개선된 폴리에스테르 수지

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WO2005068531A1 true WO2005068531A1 (fr) 2005-07-28

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7662880B2 (en) 2004-09-03 2010-02-16 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic nickel particles
US7745512B2 (en) 2005-09-16 2010-06-29 Eastman Chemical Company Polyester polymer and copolymer compositions containing carbon-coated iron particles
US7776942B2 (en) 2005-09-16 2010-08-17 Eastman Chemical Company Polyester polymer and copolymer compositions containing particles of titanium nitride and carbon-coated iron
US7838596B2 (en) 2005-09-16 2010-11-23 Eastman Chemical Company Late addition to effect compositional modifications in condensation polymers
CN102190786A (zh) * 2011-03-28 2011-09-21 黄山永佳三利科技有限公司 一种消光聚酯树脂及其制备方法
US8039577B2 (en) 2004-11-12 2011-10-18 Grupo Petrotemex, S.A. De C.V. Polyester polymer and copolymer compositions containing titanium nitride particles
US8987408B2 (en) 2005-06-16 2015-03-24 Grupo Petrotemex, S.A. De C.V. High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates
US9267007B2 (en) 2005-09-16 2016-02-23 Grupo Petrotemex, S.A. De C.V. Method for addition of additives into a polymer melt

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58185630A (ja) * 1983-03-25 1983-10-29 Mitsubishi Petrochem Co Ltd 透光性及び保温性の良好な農業用合成樹脂フイルム
JPH0249611A (ja) * 1988-08-11 1990-02-20 Sun A Chem Ind Co Ltd 電子レンジ調理用食品容器
JPH05254281A (ja) * 1992-03-13 1993-10-05 Tomoegawa Paper Co Ltd 磁気記録媒体及びその情報処理方法
JPH08165444A (ja) * 1994-12-15 1996-06-25 Kansai Paint Co Ltd ガラスに適した一時保護用光線遮蔽剤
KR20010043209A (ko) * 1998-05-01 2001-05-25 시펫 소시에따 이딸리아나 폴리에틸렌 테레프탈라토 에스. 피. 에이. 적외선 흡수재를 포함하는 폴리에스테르
KR20010107971A (ko) * 1999-09-21 2001-12-07 나까니시 히로유끼 폴리에스테르 수지 조성물제 블로우 성형체용 프리폼,폴리에스테르 수지 조성물제 블로우 성형체 및 그 제조 방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58185630A (ja) * 1983-03-25 1983-10-29 Mitsubishi Petrochem Co Ltd 透光性及び保温性の良好な農業用合成樹脂フイルム
JPH0249611A (ja) * 1988-08-11 1990-02-20 Sun A Chem Ind Co Ltd 電子レンジ調理用食品容器
JPH05254281A (ja) * 1992-03-13 1993-10-05 Tomoegawa Paper Co Ltd 磁気記録媒体及びその情報処理方法
JPH08165444A (ja) * 1994-12-15 1996-06-25 Kansai Paint Co Ltd ガラスに適した一時保護用光線遮蔽剤
KR20010043209A (ko) * 1998-05-01 2001-05-25 시펫 소시에따 이딸리아나 폴리에틸렌 테레프탈라토 에스. 피. 에이. 적외선 흡수재를 포함하는 폴리에스테르
KR20010107971A (ko) * 1999-09-21 2001-12-07 나까니시 히로유끼 폴리에스테르 수지 조성물제 블로우 성형체용 프리폼,폴리에스테르 수지 조성물제 블로우 성형체 및 그 제조 방법

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7662880B2 (en) 2004-09-03 2010-02-16 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic nickel particles
US8039577B2 (en) 2004-11-12 2011-10-18 Grupo Petrotemex, S.A. De C.V. Polyester polymer and copolymer compositions containing titanium nitride particles
US8987408B2 (en) 2005-06-16 2015-03-24 Grupo Petrotemex, S.A. De C.V. High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates
US7745512B2 (en) 2005-09-16 2010-06-29 Eastman Chemical Company Polyester polymer and copolymer compositions containing carbon-coated iron particles
US7776942B2 (en) 2005-09-16 2010-08-17 Eastman Chemical Company Polyester polymer and copolymer compositions containing particles of titanium nitride and carbon-coated iron
US7838596B2 (en) 2005-09-16 2010-11-23 Eastman Chemical Company Late addition to effect compositional modifications in condensation polymers
US9267007B2 (en) 2005-09-16 2016-02-23 Grupo Petrotemex, S.A. De C.V. Method for addition of additives into a polymer melt
CN102190786A (zh) * 2011-03-28 2011-09-21 黄山永佳三利科技有限公司 一种消光聚酯树脂及其制备方法

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