WO2011037361A8 - Composition de polyester et procédé de production associé - Google Patents

Composition de polyester et procédé de production associé Download PDF

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Publication number
WO2011037361A8
WO2011037361A8 PCT/KR2010/006347 KR2010006347W WO2011037361A8 WO 2011037361 A8 WO2011037361 A8 WO 2011037361A8 KR 2010006347 W KR2010006347 W KR 2010006347W WO 2011037361 A8 WO2011037361 A8 WO 2011037361A8
Authority
WO
WIPO (PCT)
Prior art keywords
polyester composition
acid
polyester
composition
polyfunctional compound
Prior art date
Application number
PCT/KR2010/006347
Other languages
English (en)
Korean (ko)
Other versions
WO2011037361A2 (fr
WO2011037361A3 (fr
Inventor
김남일
김상묵
최연주
Original Assignee
에스케이씨 주식회사
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 에스케이씨 주식회사 filed Critical 에스케이씨 주식회사
Publication of WO2011037361A2 publication Critical patent/WO2011037361A2/fr
Publication of WO2011037361A8 publication Critical patent/WO2011037361A8/fr
Publication of WO2011037361A3 publication Critical patent/WO2011037361A3/fr

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Classifications

    • 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
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • 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
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • Polyester composition and its manufacturing method FIELD OF THE INVENTION The present invention relates to a polyester composition which can be used in fields such as a film for forming a container, a film for display optics, and a method for producing the same.
  • PET Polyethylene terephthalate
  • PET which is a representative polyester, has excellent transparency, heat resistance, mechanical properties, chemical resistance, etc., and is excellent in workability.
  • biaxially stretched PET film has been used for several years since optical properties such as liquid crystal display (LCD), plasma display (PDP), projection display, and LCD protective film and release film used in manufacturing optical products. come.
  • the color of polyester is largely affected by the metal compound used as polymerization catalyst.
  • the antimony (Sb) -based catalyst is used in the form of antimony trioxide or antimony acetate, and since antimony is reduced to form antimony metal particles, the color of polyester is darkened and light transmittance is reduced. have.
  • the germanium (Ge) -based catalyst is excellent Although it may have color tone and transparency, the cost of the catalyst due to the revolving metal is high, and the cost of producing the polyester polymer is greatly increased, and the improvement of the brightness when the optical film is actually produced is not sufficient. There is a problem.
  • an aluminum (A1) catalyst Japanese Patent Laid-Open Publication No. 2006-096789, etc., claims that a polyester polymer having excellent color and transparency can be obtained. However, this method is also difficult to manufacture a catalyst and has a high cost. There is this.
  • polyester is semicrystalline, transparency is generally lowered as it is crystallized.
  • the method of suppressing crystallization to the maximum is mainly used.
  • a small amount of copolymers such as isophthalic acid (IPA) is used to reduce the crystallinity of PET and prevent crystals from forming even after molding.
  • IPA isophthalic acid
  • polymers prepared in this manner may cause problems in dimensional stability when manufactured as optical biaxially oriented films.
  • An object of the present invention is to provide a polyester composition excellent in color and transparency that can be used for the preparation of an optical biaxially stretched polyester film, and a method for producing the same.
  • the present invention provides a polymer comprising a polymer in which an aliphatic catalyst is polycondensed with ethylene glycol, an aliphatic dihydric alcohol, terephthalic acid or dimethyl terephthalate, and an aromatic dihydric acid and a polyfunctional compound having a trivalent or more semi-ungung group.
  • the ester composition the polyfunctional compound is contained in an amount of 50 to 2500 ppm, the difference between the color tone L value and the b value is 55 or more, and an extreme limit with the polyester composition having the same melt viscosity and composition without containing the polyfunctional compound. It provides a polyester composition, wherein the difference in viscosity is 0.015 dL / g or less.
  • the present invention comprises the step of reacting the esterification by mixing ethylene glycol which is an aliphatic dihydric alcohol and terephthalic acid or dimethyl terephthalate which is an aromatic divalent acid, and the reaction product is polymerized by an antimony catalyst.
  • the method for producing a polyester composition comprising the step of obtaining a final polymer composition, 50 to 2500 polyfunctional compounds having a trivalent or more semi-ungung group at the beginning or end of the esterification reaction step, or at the beginning of the polymerization reaction step It provides a method of producing a polyester composition, comprising the step of adding the reaction in ppm.
  • the polyester polymer composition of the present invention is excellent in color and transparency than conventional polymers, and maintains excellent color and transparency even after processing, so that it can be processed into a polyester film or a transparent container to exhibit excellent performance.
  • the present invention is a polyester composition
  • ethylene glycol which is an aliphatic dihydric alcohol, terephthalic acid or dimethyl terephthalate which is an aromatic dihydric acid
  • a polymer in which a polyfunctional compound having a trivalent or more semi-ungung group is polycondensed by an antimony-based catalyst, 50 to 2500 ppm of the multifunctional compound is contained, the difference between the tint L value and the b value is 55 or more, the difference in the ultimate viscosity with the polyester composition having the same melting viscosity and composition without containing the polyfunctional compound is 0.015 It provides a polyester composition that is dL / g or less.
  • the polyfunctional compound When the polyfunctional compound is added below 50ppm, the effect of improving color and transparency is not sufficient, and when it is added more than 2500ppm, the effect of improving color or transparency is not obtained, and the degree of polymerization of the actual polymer (extreme viscosity) It is not preferable because the melt viscosity rises too much compared to), and the adverse effect is obtained due to high shear shear during the melt extrusion process of the polymerization process and film forming. More preferably, the polyfunctional compound is in the range of 150 to 2000 ppm It is good to add.
  • the difference between the L value indicating the whiteness and the b value indicating the yellowness in the color index measured by the color meter indicates 55 or more, and preferably may have a difference value of 55 to 65. The larger the difference between the L value and the b value, the better. If the difference is less than 55, the brightness is not required by the present invention.
  • the excellent color and transparency of the polyester composition of the present invention are believed to be due to the action of the polyfunctional compound added during polymerization on the crystal structure. That is, it is presumed that the polyfunctional compound increases the crystallinity by producing very small crystals as the crystals restrict the growth of large crystals.
  • the composition of the present invention exhibits a difference (additional viscosity) of intrinsic viscosity from the polyester composition having the same composition and melt viscosity and no polyfunctional compound (0.01 dL / g or less), preferably 0 To 0.015 dL / g. If the value of the viscosity exceeds 0.015 dL / g, the point at the end of the reaction in the polymerization step should be changed, especially in the case of continuous polymerization, it is difficult to produce a polymer having an accurate degree of polymerization. In addition, deterioration occurs due to excessive shear force (shear) in the release of the melt pressure in the film manufacturing process is not preferable because it is a problem.
  • a composition was prepared with the same ingredients and contents as the composition of the present invention, but the polymer was prepared without the addition of a polyfunctional compound to prepare a polymer. do. At this time, it is necessary to terminate the reaction at the same stirring power value during the polymerization reaction so as to have the same melt viscosity as the composition of the present invention.
  • the multifunctional compound used in the present invention is not particularly limited as a compound having a trivalent or higher acid component or a trivalent or higher alcohol component.
  • the molecular weight of the multifunctional compound is too high, the effect of color improvement is improved even in a small amount. Without this, the melt viscosity of the polymer may rise too much, causing process problems in the polymerization step and the melt extrusion step for producing the film.
  • preferred multifunctional compounds used in the present invention include tris-2-hydroxyethyl isocyanurate (THIC), pentaerythritol (PEL), trimellitic acid (trimellitic). acid, TMA) and combinations thereof.
  • a running property improving agent can be added to the composition of this invention.
  • the runnability enhancer is not particularly limited, but inorganic particles or organic particles may be used.
  • inorganic particles such as silica gel, calcium carbonate, and alumina having an average particle diameter of 0.1 to 10.0 / may be included in consideration of optical properties of the film. It is good to let.
  • each polymer may further contain additives required for post-processing applications.
  • additives required for post-processing applications For example, when it is aimed at producing a biaxially oriented film, an appropriate amount of metal acetate may be added as an electrostatic agent to produce an unstretched sheet.
  • the polyester composition of the present invention may contain 15% by weight or less of repeating units polymerized from other divalent acid and diol components. There is no need to limit it, but it is preferable to select a component that lowers the crystallinity and does not excessively increase the shrinkage after heat setting of the film manufacturing process.
  • divalent acid components that may be used in the film of the present invention, isophthalic acid (IPA), succinic acid, glutaric acid, adipic acid, suitsic acid ( suberic acid), azel
  • IPA isophthalic acid
  • succinic acid glutaric acid
  • adipic acid adipic acid
  • schweric acid suberic acid
  • azel One or more kinds of azelaic acid, sebacic acid and ester derivatives thereof can be used.
  • a single polymer obtained by copolymerizing the respective components may be applied, or various polymers may be used in combination so as to contain the respective compositions.
  • Such a polyester composition of the present invention esterification of ethylene glycol, which is an aliphatic dihydric alcohol, and terephthalic acid or dimethyl terephthalate, which is an aromatic dihydric acid, and polymerization reaction of the reaction product by an antimony-based catalyst to give a final polymer.
  • a polyester composition comprising the step of obtaining a composition, 50 to 2500 ppm of a polyfunctional compound having a trivalent or more semi-atom group at the beginning or end of the esterification reaction step, or at the beginning of the polymerization reaction step. It is prepared by a method comprising the step of adding and reacting.
  • the polyfunctional compound is preferably added at the beginning of the esterification reaction step, and the esterification reaction step is preferably carried out while removing water as a by-product. In this, it is preferable to use a melt polymerization reaction.
  • the multifunctional compound is tris-2-hydroxyethyl isocyanurate (THIC), pentaerythritol (pentaerythritol, PEL), trimellitic acid (TMA) and It is preferable to select from the group which consists of these mixtures.
  • THIC tris-2-hydroxyethyl isocyanurate
  • PEL pentaerythritol
  • TMA trimellitic acid
  • the polyester composition of the present invention can be produced as a biaxially stretched polyester film through a melt extrusion and biaxial stretching process, the film thus produced has a light transmittance of 70% or more at 350nm measured in accordance with ASTM D 1003 It can represent more than 86% at 450nm.
  • Such a biaxially stretched polyester film comprises the steps of: melt extruding and rapidly solidifying the polyester composition of the present invention to obtain an unstretched sheet; Stretching the unstretched sheet in the longitudinal and transverse directions and then relaxing and heat-setting to obtain a stretched sheet; And cooling the stretched sheet.
  • the polyester polymer of the present invention described so far has excellent color and transparency, and in particular, even if the antimony-based catalyst and phosphorus-based stabilizer are used as it is, no degradation in color and transparency occurs. As a result, it maintains excellent color and transparency even after processing, and thus can be used in a variety of applications requiring transparent containers, polyester films, and other transparency.
  • the present invention will be described in more detail with reference to Examples. However, the following examples are merely to illustrate the present invention, but not to limit the content of the present invention.
  • Esterification reaction vessel (primary reaction vessel) equipped with a layered separation tower capable of stirring at 200 rpm and separating ethylene glycol and water from the reaction mixture, and Polyethylene terephthalate polycondensation semi-rigidizer with both inverter type stirrer capable of stirring at 10-50 rpm and condensation polymerization reactor (secondary reactor) equipped with vacuum pump and vacuum pump It was used as manure.
  • triethylphosphate (TEP) was added as a stabilizer to 230 ppm based on the total polymer-to-phosphorus (P) component and stirred for about 5 minutes.
  • antimony trioxide (Sb 2 0 3 ) was added in an amount of 190 ppm based on antimony (Sb) relative to the entire polymer, and stirred for about 5 minutes.
  • the primary reaction product thus obtained was transferred to a secondary reaction machine to carry out polymerization reaction under vacuum of 28 C and 0.5 torr or less. The reaction was terminated when the load of the stirrer motor became 20 kW to obtain the final polyester composition.
  • each polymer was precrystallized in a paddle dryer at a temperature of 12 CTC and then dried in a tower dryer using 18 CTC dry air. It was melt extruded at 285 ° C. and then quenched from above with cooling maintained at 26 ° C. through a T-die to obtain an amorphous sheet.
  • the amorphous sheet was stretched 3.2 times in the longitudinal direction using the circumferential speed difference between in a stretching roll at 100 ° C. while auxiliary heating with a radiator heater. This was preheated while rising to 110-12CTC in the tenter, and stretched 3.6 times in the transverse direction under the hot air through the stretching section divided into 13CTC and 14CC.
  • the stretched sheet was heat-set in a hot air at 230 ° C., and then cooled with 3.5% relaxation at 18 CTC to obtain a biaxially stretched polyester film having a thickness of 185 iin.
  • (3) Polymer Hue Each polymer composition was measured in reflection mode through color meter (Model: SE2000, Nippondenshoku) to obtain whiteness (L) and yellowness (b), respectively. The average value was taken.
  • the polyester composition according to Examples 1 to 4 of the present invention exhibited excellent color tone (Lb) and viscosity, and produced a biaxially stretched polyester film The excellent light transmittance was shown at 350 nm and 450 nm.
  • the polyester compositions according to Comparative Examples 1 and 3 with little or no addition of the multifunctional compound appeared poor in terms of color tone (Lb) and light transmittance of the film.
  • the polyester composition according to Comparative Example 2 in which the polyfunctional compound was added in excess was poor in terms of viscosity.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de polyester, qui comprend un polymère pouvant être obtenu par la polycondensation d'un alcool aliphatique dihydrique, d'un diacide aromatique et d'un composé polyfonctionnel trivalent ou plus par les moyens d'un catalyseur à base d'antimoine, qui a une tonalité chromatique et une transparence remarquables et qui peut améliorer la transmittance de la lumière lorsqu'elle est utilisée dans le moulage de récipients ou dans la production d'un film optique pour l'affichage.
PCT/KR2010/006347 2009-09-24 2010-09-16 Composition de polyester et procédé de production associé WO2011037361A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020090090486A KR101127951B1 (ko) 2009-09-24 2009-09-24 이축연신 폴리에스터 필름 및 이의 제조방법
KR10-2009-0090486 2009-09-24

Publications (3)

Publication Number Publication Date
WO2011037361A2 WO2011037361A2 (fr) 2011-03-31
WO2011037361A8 true WO2011037361A8 (fr) 2011-06-03
WO2011037361A3 WO2011037361A3 (fr) 2011-11-03

Family

ID=43796352

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Application Number Title Priority Date Filing Date
PCT/KR2010/006347 WO2011037361A2 (fr) 2009-09-24 2010-09-16 Composition de polyester et procédé de production associé

Country Status (2)

Country Link
KR (1) KR101127951B1 (fr)
WO (1) WO2011037361A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101694892B1 (ko) * 2014-11-18 2017-01-10 롯데케미칼 주식회사 폴리에스테르 수지의 제조 방법

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0931217A (ja) * 1995-07-20 1997-02-04 Nippon Ester Co Ltd ポリエステルフィルム
JP2003268093A (ja) * 2002-03-15 2003-09-25 Toyobo Co Ltd ポリエステルの製造方法およびその成形体
US7358322B2 (en) * 2004-03-09 2008-04-15 Eastman Chemical Company High IV melt phase polyester polymer catalyzed with antimony containing compounds
KR101222791B1 (ko) * 2005-12-14 2013-01-15 에스케이케미칼주식회사 공중합 폴리에스테르 수지를 이용한 압출 성형 제품

Also Published As

Publication number Publication date
KR101127951B1 (ko) 2012-03-23
WO2011037361A2 (fr) 2011-03-31
KR20110032807A (ko) 2011-03-30
WO2011037361A3 (fr) 2011-11-03

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