WO1999051660A1 - Polyester, procede de production associe, et son utilisation comme modificateur de polymere - Google Patents

Polyester, procede de production associe, et son utilisation comme modificateur de polymere Download PDF

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Publication number
WO1999051660A1
WO1999051660A1 PCT/JP1999/001695 JP9901695W WO9951660A1 WO 1999051660 A1 WO1999051660 A1 WO 1999051660A1 JP 9901695 W JP9901695 W JP 9901695W WO 9951660 A1 WO9951660 A1 WO 9951660A1
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Prior art keywords
polyester
acid
weight
polymer
alicyclic dicarboxylic
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PCT/JP1999/001695
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English (en)
Japanese (ja)
Inventor
Shizuo Kitahara
Atsushi Hayashi
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Nippon Zeon Co., Ltd.
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Publication of WO1999051660A1 publication Critical patent/WO1999051660A1/fr

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    • 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
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • 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

  • Polyester its production method, and its application as a polymer modifier
  • the present invention relates to a polyester, a method for producing the same, and an application thereof as a modifier for a polymer.
  • the present invention relates to a polyester obtained by polycondensing a specific polycarboxylic acid and a polyhydric alcohol; a method for producing the polyester; a polymer modifier composition containing the polyester as an active ingredient A polymer composition comprising the polymer modifier composition and a polymer; and a molded article of the polymer composition.
  • Polyolefin resins such as polypropylene and ethylene rubber such as ethylene-propylene copolymer rubber (hereinafter, polyolefin resin and ethylene rubber are sometimes collectively referred to as “polyolefin”) have excellent physical properties and are relatively Since it is inexpensive, it is used in many applications as a compact. However, since polyolefin and the like do not have a polar group, there is a problem in that when a paint is applied to the surface of the molded body, the adhesion of the paint is low. Further, when a molded article such as polyolefin is adhered to, for example, a vulcanized rubber molded article, there is a problem that practical adhesive strength cannot be obtained.
  • the present inventor has already found that by blending a polyester having a high molecular weight and a high hydroxyl value with a polypropylene resin, the paintability of the resin surface can be improved. (WO9739906). However, further improvements in the paintability of the surface of the resin to be coated and the adhesion strength to the coating film are desired.
  • the molded article of the composition in which the polyester described in WO9739496 was blended with the polyolefin had a low flexural modulus but little change in the low-temperature impact strength as compared with the polyolefin to which the polyester was not added. Was extremely reduced. W
  • An object of the present invention is to improve the coating properties of a molded article of the polymer, the adhesive strength with a coating film, and the balance between flexural modulus and low-temperature impact strength by blending the polymer with the polymer.
  • Polyester useful as an agent a modifier composition for a polymer containing the polyester as a modifier; a polymer composition obtained by blending the modifier composition with a polymer; and a polymer composition formed by molding the polymer composition. It is an object of the present invention to provide a molded article comprising
  • Another object of the present invention is to provide a method for efficiently producing a high molecular weight polyester useful as a polymer modifier.
  • the present inventors have focused on a polyester obtained by a polycondensation reaction between 4-ethylhexahydrofuric anhydride and 2-ethyl-2-butyl-1,3-propanediol.
  • the weight-average molecular weight was generally less than 10,000, and the weight-average molecular weight was reduced by polycondensation using tandust (VI) phosphoric acid hydrate as an esterification catalyst.
  • VI tandust
  • a polyvalent carboxylic acid (A) and a polyhydric alcohol (B) are obtained by polycondensation, and have a hydroxyl value of 5 to 200 mg K ⁇ HZg, weight average in terms of standard polystyrene.
  • Polyester having a molecular weight of 100,000 to 500,000, in which a polyvalent carboxylic acid (A) has a carboxyl group bonded to two mutually adjacent carbon atoms And at least one selected from alicyclic dicarboxylic acids and functional derivatives thereof having a modified molecular structure, wherein the polyhydric alcohol (B) has two carbon atoms each having a hydroxyl group bonded thereto.
  • a polyester comprising an alkanediol having a molecular structure in which a carbon atom to which a hydrogen atom is not bonded is interposed.
  • the present invention includes at least one selected from dicarboxylic acids having a molecular structure in which a carboxyl group is bonded to two mutually adjacent carbon atoms and functional derivatives thereof.
  • a method for producing a polyester comprising polycondensing a polycarboxylic acid (a) and a polyhydric alcohol (b) in the presence of a heteropolyacid. It is.
  • a polymer modifier composition comprising, as an active ingredient, a polyester obtained from the above polycarboxylic acid (A) and polyhydric alcohol (B).
  • a polymer composition comprising a polymer and the above-mentioned modifier composition for a polymer.
  • a molded article obtained by molding the polymer composition is provided.
  • the polyester of the present invention is obtained by polycondensation of a polyvalent carboxylic acid (A) and a polyhydric alcohol (B), and the polyvalent carboxylic acid (A) is bonded to two carbon atoms adjacent to each other by a lipoxyl group.
  • the polyester of the present invention has a weight average molecular weight (Mw) in terms of standard polystyrene of 10,000 to 500,000, preferably 10,000 to 300,000, as measured by gel permeation chromatography (GPC). More preferably, it is in the range of 10,000 to 200,000. If the molecular weight is excessively small, the adhesion strength between a molded body obtained from a polymer composition prepared by blending the polyester as a modifier with another polymer and a coating material such as a paint decreases, and If it is large, the effect of improving the paintability is poor, and neither is preferable.
  • Mw weight average molecular weight
  • the hydroxyl value of the polyester ranges from 5 to 200 mgKOHZg, preferably from 10 to 150 mgKOH / g, more preferably from 30 to 8 OmgKOHZg.
  • the softening point of the polyester is usually 10 or more, preferably 30 to 300 °, more preferably 50 to 200 ° (: most preferably in the range of 60 to 150 ° C. When, the operability is excellent and suitable.
  • polyester When the polyester is oil-soluble, it generally has better compatibility with many polymers to be modified, including polyolefin, and is suitable.
  • oil-soluble means that the light transmittance of the polyester solution is 80% or more, preferably 85% or more. The method for measuring the light transmittance will be described later. Also, the Gardner one hue of the polyester is usually :! ⁇ 6, preferably :! ⁇ 3.
  • the polyvalent carboxylic acid (A) used in the synthesis of the polyester of the present invention is an alicyclic dicarboxylic acid having a molecular structure in which a carbonyl group is bonded to two carbon atoms adjacent to each other (hereinafter, simply referred to as an “aliphatic”). Cyclic dicarboxylic acid ”) and / or a functional derivative thereof.
  • the alicyclic dicarboxylic acid includes, as its basic skeleton, a saturated alicyclic dicarboxylic acid having a saturated aliphatic hydrocarbon ring such as a cyclopentane ring, a cyclohexane ring, a norpolnanane ring, an adamantane ring, and the like.
  • the basic skeleton thereof includes, for example, unsaturated alicyclic dicarponic acids having an unsaturated aliphatic hydrocarbon ring such as a cyclohexene ring and a norpolenene ring.
  • Examples of the functional derivative of the alicyclic dicarboxylic acid include a halide, an anhydride, an ester and a salt. Of these, acid anhydrides are preferred.
  • saturated alicyclic dicarboxylic acid examples include hexahydrophthalic acid (1,2-cyclohexane'diacid), 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, and 2,2-methylhexahydrophthalic acid.
  • unsaturated alicyclic dicarboxylic acids include tetrahydrophthalic acid, 3-methyltetrahydrofluoric acid, 4-methyltetrahydrofuric acid, and 2,3-norpolpolene diacid; Tricyclo [5.2.1.0 2 ⁇ 6 ] deca-3-ene-8,9-dicarboxylic acid and the like.
  • saturated alicyclic dicarboxylic anhydride examples include hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride and 2,3- Specific examples of unsaturated alicyclic dicarboxylic anhydrides include tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, and 4-methyltetanoic anhydride. Lahydrophthalic anhydride and 2,3-norporene diacid anhydride.
  • alicyclic dicarboxylic acid ester examples include dimethyl ester of hexahydrophthalic acid, dimethyl ester of 3-methylhexahydrophthalic acid, dimethyl ester of 4-methylhexahydride, dimethyl ester of 2,3-norbornane dinitrate Dialkyl esters of saturated and unsaturated alicyclic dicarboxylic acids such as esters and 4-methyltetrahydrophthalic acid dimethyl ester; 4-methylhexahydrofuranoic acid methyl ester, 2,3-norpornan diacid methyl ester and 4- Hapesters of saturated and unsaturated alicyclic dicarboxylic acids such as methyl tetrahydrophthalic acid ethyl ester; and the like.
  • alicyclic dicarboxylate examples include saturated and unsaturated salts of potassium hexahydrofurate, sodium 3-methylhexahydrophthalate, potassium 4-methylhexahydrophthalate and potassium 4-methyltetrahydrophthalate.
  • Alkali metal salts of unsaturated alicyclic dicarboxylic acids and the like.
  • hexahydrophthalic acid 3-methylhexahydrofuric acid, 4-methylhexahydrofuric acid, 2,3-norpolnanodiacid
  • hexahydrofuranic anhydride, 4-methylhexahydrid phthalic anhydride, 3-methylhexahydrofuric anhydride and 2,3-norbornanediacid anhydride are used.
  • Polyester is particularly suitable because of its high compatibility with many polymers to be modified such as polyolefin.
  • the alicyclic dicarboxylic acids and functional derivatives thereof can be used alone or in combination of two or more.
  • the proportion of the alicyclic dicarboxylic acid and the functional derivative thereof in the polycarboxylic acid (A) is usually at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight. It is.
  • polycarboxylic acid (A) other polycarboxylic acids (that is, other dicarboxylic acids and Z or trivalent or higher carboxylic acids) and the same may be used as long as the effects of the present invention are not impaired.
  • Functional derivatives may be included. Their allowable amount is usually 50% by weight or less, preferably 30% by weight or less, more preferably 10% by weight or less in the polycarboxylic acid (A).
  • the optionally used divalent carboxylic acid and its functional derivative include aromatic dicarboxylic acid and its functional derivatives, for example, halides, anhydrides, esters and the like.
  • aromatic dicarboxylic acids and their functional derivatives include phthalic acid, terephthalic acid, isophthalic acid, 3-methylphthalic acid, 4-methylphthalic acid, phthalic anhydride, and 3-methylphthalic anhydride. And 4-methylphthalic anhydride.
  • divalent carboxylic acids and their functional derivatives include, for example, succinic acid, adipic acid, maleic acid, itaconic acid, pimelic acid, methylmalonic acid, dimethylmalonic acid, suberic acid, azelaic acid, sebacin Acid, brassic acid, polyalkenyl succinic acid, polymerized fatty acid dimer acid (hereinafter abbreviated as "dimer monoacid") and its hydrogenated product, 1,3-cyclohexane 'diacid, 1,4- Cyclohexane 'diacid, and esters and anhydrides thereof.
  • succinic acid adipic acid
  • maleic acid itaconic acid
  • pimelic acid methylmalonic acid
  • dimethylmalonic acid dimethylmalonic acid
  • suberic acid suberic acid
  • azelaic acid sebacin Acid
  • brassic acid polyalkenyl succinic acid
  • polymerized fatty acid dimer acid hereinafter abbre
  • trivalent or higher carboxylic acid and the functional derivative thereof used as desired include, for example, trimellitic acid, pyromellitic acid, trimethylvalivalic acid, camphoronic acid, trimesic acid, etc., and esters and anhydrides thereof. And the like.
  • monovalent carboxylic acid and its functional derivative may be used in addition to the polycarboxylic acid (A) as long as the effects of the present invention are exerted.
  • the allowable amount is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less in the total rubonic acid component.
  • monovalent carboxylic acid and its functional derivative optionally used include formic acid, acetic acid, butyric acid, 2-methylpropanoic acid, valeric acid, isooctylic acid, isononanoic acid, lauric acid, myristic acid, and palmitic acid. Acids, stearic acid, isostearic acid, arachinic acid, linoleic acid, oleic acid, elaidic acid, tall fatty acids, and the like, and derivatives thereof such as esters thereof.
  • the polyhydric alcohol (B) used in the synthesis of the polyester of the present invention has a molecular structure in which a carbon atom to which no hydrogen atom is bonded is sandwiched between two carbon atoms to which a hydroxyl group is bonded.
  • Alkanediol hereinafter sometimes referred to as “hindered glycol”.
  • an alkyl group having 1 to 50 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms is bonded to the above carbon atom to which no hydrogen atom is bonded.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, an amyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
  • Dodecyl group tridecyl group, pendecyl group, octadecyl group, eicosyl group and the like.
  • methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, amyl, hexyl, heptyl, octyl, nonyl and decyl are preferred, and especially ethyl.
  • Groups, propyl, butyl, amyl, hexyl and heptyl groups are preferred.
  • alkanediols are 2,2-dimethyl-1,3-propanediol, 2,2-getyl- 1,3-propanediol, 2,2-dipropyl-1,3-propanediol, 2,2-diisopropyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, 2,2- Diisobutyl-1,3-propanediol, 2-methyl-2-hexyl-1,3-propanediol, 2-methyl-2-pentyl-1 3-propanediol, 2-methyl-2, dodecyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-pentyl-1,3-propanediol, 2_ Propyl-2-pentyl-1,3-propanediol.
  • 2,2-diethyl-1,3-propanediol, 2,2-dipropyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol and 2-ethyl-2-butyl-1 , 3-propanediol is preferred.
  • the amount of hindered glycol in the polyhydric alcohol (B) is appropriately selected depending on the purpose of use, but is preferably 50 to 100% by weight, preferably 60 to 100% by weight of the total polyhydric alcohol component. To 100% by weight, more preferably 70 to 100% by weight. If the amount of the hindered glycol is excessively small, the compatibility with the resin or rubber is inferior, which is not preferable.
  • polyhydric alcohols ie, other dihydric alcohols and trihydric or higher polyhydric alcohols
  • the allowable amount of the polyhydric alcohol used in combination is usually 40% by weight or less, preferably 30% by weight or less, more preferably 25% by weight or less in the total polyhydric alcohol (B).
  • dihydric alcohols used in combination include, for example, ethylene glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5- Alkanediols other than hindered glycol, such as pentanediol, 1,8-octanediol, 1,9-nonanediol; cyclopentane-1,2-diol, cyclopentane-1,3-diol, cyclohexane — 1,2-diol, cyclohexane— 1,3-diol, cyclohexane-1,4-diol, cyclooctane-1,4-diol, 2,5-norpolnandiol, 1,4-cyclohexanedimethanol , 2,5-cycloalkanediols such as norbornane
  • trihydric or higher alcohols optionally used include, for example, glycerol compounds such as glycerol, diglycerol and polyglycerol; saccharides such as sorbitol, darcose, mannitol, sucrose and glucose; and ditrimethylolpropane and dipen Erythritol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and the like.
  • glycerol compounds such as glycerol, diglycerol and polyglycerol
  • saccharides such as sorbitol, darcose, mannitol, sucrose and glucose
  • ditrimethylolpropane and dipen Erythritol trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and the like.
  • tetrahydric or higher alcohols having an ether bond in the molecule such as dipentaerythritol and ditrimethylolpropane, are particularly preferred.
  • a polyhydric alcohol (B) an alkanediol having a molecular structure in which a carbon atom without a hydrogen atom is sandwiched between two carbon atoms each having a hydroxyl group, and an ether bond in the molecule
  • a molded article of a polymer composition containing the obtained polyester as a modifier exhibits remarkably high adhesion strength to a coating material.
  • the mixing ratio of the tetravalent or higher alcohol having an ether bond in such a polyhydric alcohol mixture is preferably from 0.1 to 20% by weight, more preferably from 1 to 10% by weight.
  • monohydric alcohol may be used in addition to the polyhydric alcohol (B) as long as the effects of the present invention are exerted.
  • the allowable amount is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less in the total alcohol component.
  • the monohydric alcohol optionally used in combination may be, for example, methanol, ethanol, isopropanol, butanol, t-butanol, neopentyl alcohol, 3-methyl_3-pentanol, or 3-ethyl alcohol. 3-pentanol, 2,3,3-trimethyl-2-butanol, 1-decanol, nonyl alcohol, and the like.
  • the method for producing a polyester according to the present invention comprises at least one type of dicarboxylic acid having a molecular structure in which a carboxyl group is bonded to two carbon atoms adjacent to each other and a functional derivative thereof. Wherein polycondensation is carried out between a polycarboxylic acid (a) containing a compound and a polyhydric alcohol (b) in the presence of a heteropolyacid.
  • catalysts such as conventionally known brenstead acid, organometallic compounds, and metal oxides
  • side reactions such as an elimination reaction are very likely to occur, which makes it difficult to obtain a high molecular weight polymer.
  • a polycondensation reaction is carried out at a temperature of 200 or more using these conventionally known catalysts, there is a problem that a colored polyester is obtained.
  • the above dicarboxylic acid and polyhydric alcohol are polycondensed using heteropoly acid as a catalyst, a high molecular weight and colorless polyester can be easily obtained.
  • Dicarbonic acid and its functional derivatives having a molecular structure in which a carbonyl group is bonded to each of the carbon atoms used are used without any particular limitation.
  • Aliphatic, alicyclic and aromatic dicarboxylic acids and their derivatives Is mentioned. These dicarboxylic acids can be used alone or as a mixture of two or more. Among these, cyclic dicarboxylic acids and derivatives thereof are preferred.
  • dicarboxylic acids having a molecular structure in which a carbonyl group is bonded to mutually adjacent carbon atoms specific examples of the aliphatic dicarboxylic acids include succinic acid, dicarboxylic acid, maleic acid, and polycarboxylic acid. Alkenyl succinic acid and the like can be mentioned.
  • Specific examples of the aromatic dicarboxylic acid include phthalic acid, 3-methylphthalic acid, 4-methylphthalic acid, and 2,3-naphthylene diacid.
  • Specific examples of the alicyclic dicarboxylic acid include those similar to the alicyclic dicarboxylic acid exemplified in the section of the polyester (1) and the polyvalent carboxylic acid (A) of the present invention.
  • the polyvalent carboxylic acid (a) used in the present invention has a molecular structure in which a carbonyl group is bonded to carbon atoms adjacent to each other as long as the effects of the present invention are exerted.
  • the dicarboxylic acid having a carboxylic acid and a functional derivative thereof other dicarboxylic acid, a tri- or higher carboxylic acid, and a functional derivative thereof may be included.
  • the tolerable amount of such optionally used polycarboxylic acid and its functional derivative is usually not more than 20% by weight, preferably not more than 10% by weight, more preferably not more than 10% by weight in the total polyvalent carboxylic acid (a). Or less than 5% by weight.
  • polycarboxylic acids and functional derivatives thereof used as desired include, for example, aromatic polycarboxylic acids, linear or branched aliphatic polycarboxylic acids, alicyclic polycarboxylic acids and these. And derivatives such as esters, halides and anhydrides.
  • aromatic polycarboxylic acids include terephthalic acid, isophthalic acid, naphthaleno, 2,6-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthylene-1,5-dicarponic acid, Naphthylene-1,6-dicarboxylic acid, naphthylene-1, merge force Rubonic acid, naphthylene-1,8-dicarboxylic acid, diphenylmethane-4,4'-dicarbonic acid, diphenylether-4 Aromatic dicals such as 4,4'-dicarboxylic acid and benzophenone-1,4'-dicarboxylic acid, diphenylpropane-4,4'-dicarboxylic acid And boric acid.
  • linear or branched aliphatic dicarboxylic acids include, for example, daltaric acid, adipic acid, pimelic acid, methylmalonic acid, dimethylmalonic acid, suberic acid, azelaic acid, sebacic acid, isosebacic acid, brassic acid, dodecanedicarboxylic acid And hydrogenated products of dimer monoacid and dimer acid.
  • Examples of alicyclic dicarboxylic acids in which a carboxylic acid group is not bonded to two carbon atoms adjacent to each other include 1,3-cyclopentane 'diacid and 1,3-cyclohexane.diacid. , 1,4-cyclohexane 'diacid and the like.
  • examples of the trivalent or higher polycarboxylic acid include trimellitic acid, tricarballylic acid, camphoronic acid, trimesic acid, 1,2,5-, 2,3,6- or 1,8,4-naphthane
  • examples thereof include tri- or higher-valent carboxylic acids such as phosphorus tricarboxylic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and trimeric acid of a polymerized fatty acid, and esters and anhydrides thereof.
  • a functional derivative such as a monovalent carboxylic acid and an ester thereof may be used in combination as long as the effects of the present invention are not impaired.
  • the allowable amount is usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less in the total rubonic acid component.
  • Specific examples of such a monovalent carboxylic acid and its functional derivative include the monovalent carboxylic acid and its functional derivative exemplified in the section of the polyester (1) and the polyvalent carboxylic acid (A) of the present invention.
  • the polyhydric alcohol (b) used in the production method of the present invention is an alcohol having two or more hydroxyl groups in the molecule, and is not particularly limited as long as it is used in ordinary polyester synthesis.
  • the polyhydric alcohol (b) is used alone or as a mixture of a dihydric alcohol and a trihydric or higher alcohol, and is preferably used as a mixture of a dihydric alcohol and a trihydric or higher alcohol.
  • Examples of the polyhydric alcohol (b) include dihydric alcohols such as hindered glycols, alkane diols other than hindered glycols, cycloalkane diols, diols having an ether bond in the molecule, aromatic diols, and the like. And the like.
  • hindered glycol, alkanediol other than hindered glycol, cycloal Preferred are candiols and diols having an ether bond in the molecule, and especially an alkanediol having a molecular structure in which a carbon atom to which a hydrogen atom is not bonded is sandwiched between two hydrocarbons each having a hydroxyl group bonded thereto. That is, hindered glycol is preferred.
  • hindered glycol examples include carbons in which a hydrogen atom is not bonded between two carbon atoms to which a hydroxyl group is bonded, as exemplified in the section of the polyester (1) and the polyvalent alcohol (B).
  • Alkandiols having a molecular structure in which atoms are sandwiched include the same ones.
  • alkane diols other than hindered glycol include the above-mentioned polyester (1) and polyhydric alcohol (B). Examples of the above are given.
  • the polyhydric alcohol (b) used in the present invention has a molecular structure in which a carbon atom to which a hydrogen atom is not bonded is sandwiched between two hydrocarbons each having a hydroxyl group bonded thereto. It is preferable to include an alkanediol or a cycloalkanediol, particularly an alkanediol having a molecular structure in which a carbon atom to which a hydrogen atom is not bonded is sandwiched between two carbon atoms to which a hydroxyl group is bonded. The amount is preferably from 80 to 100% by weight based on the weight of the total polyhydric alcohol.
  • a mixture of such an alkanediol and a tetravalent or higher alcohol having an ether bond in the molecule is particularly preferable.
  • Specific examples and preferred mixing ratios of the tetravalent or higher alcohol are the same as those described in the section of the polyester (1) and the polyhydric alcohol (B).
  • a monohydric alcohol may be used in combination with the polyhydric alcohol (b) as long as the effects of the present invention are not impaired.
  • the allowable amount is usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less in the total polyhydric alcohol component.
  • Specific examples of the monohydric alcohol include those exemplified in the section of the polyester (1) and the polyhydric alcohol (B).
  • the heteropolyacid used as the polycondensation catalyst in the production method of the present invention is , A compound having a polynuclear structure in which two or more oxo acids are condensed, which is a condensed acid containing oxygen and two or more elements.
  • the heteroatoms of the heteropolyacid include phosphorus, gay silicon, boron, aluminum, germanium, titanium, zirconium, cerium, cobalt, iron, chromium, arsenic, nickel and the like. Of these, phosphorus or gayne is preferred.
  • the polyacid atom is at least one element selected from molybdenum, tungsten, vanadium, niobium, and tantalum. Of these, tungsten, molybdenum and vanadium are preferred.
  • heteropolyacids include tandustric phosphoric acid, tundastokeic acid, tundastoboric acid, tungstogermanic acid, tandustaluminic acid, tungstocobaltate, tandustrate, and tungstotitanate, tandustarsenate, and molybdrin.
  • Acids molybdocheic acid, molybdoboric acid, molybdogermanic acid, molybdoceric acid, molybdenum stostophosphoric acid, molybdo tangosteoic acid, molybdo tandust boric acid, titano tangostophosphoric acid, vanad molybdo phosphoric acid, vanado molybdenum acid Acids, vanadotandust caiic acid, vanadotandustolinic acid, vanadotandust boric acid, vanadotandust germanic acid and the like can be mentioned.
  • evening gustolinic acid, tandustic acid, molybdophosphoric acid, molybdocaieic acid, molybdotandustoleic acid, molybdotandusteic acid, molybdotanguestoborate, vanadomolybdophosphate, vanadomolybdateeca, vanadotandustakee Acids and vanadotandustric acid are preferred, and more preferred are guststophosphoric acid, gustuccinic acid, molybdophosphoric acid and molybdic acid.
  • the heteropolyacid used in the present invention may be a salt formed by reacting these compounds with an alkali or the like.
  • the salt of the heteropolyacid include an acid metal salt and an acid salt.
  • the acidic metal salt include salts of alkali metals such as sodium, potassium, rubidium, and cesium; salts of metals belonging to Group II of the periodic table such as beryllium and magnesium; salts of alkaline earth metals such as calcium, strontium, and barium; Examples include salts of transition metals such as silver, zinc, and mercury; and salts of typical elements such as aluminum, thorium, tin, and lead.
  • the acidic sodium salts include ammonium salts with amines and ammonia, and phosphonium salts. Can be mentioned.
  • heteropolyacid used in the present invention those having water of crystallization in the molecule can also be used.
  • heteropolyacid used in the present invention when used as a catalyst for a polycondensation reaction, these compounds may be used alone, or two or more kinds may be used in combination. Further, other catalysts used for ordinary polycondensation reaction of polyester can be used in combination as long as the effects of the present invention are not impaired.
  • catalysts include, for example, Bronsted acids such as paratoluenesulfonic acid, sulfuric acid and phosphoric acid; calcium acetate, zinc acetate, manganese acetate, zinc stearate, alkyltin oxide, dialkyltin oxide, titanium alkoxide. And the like; and metal oxides such as tin oxide, antimony oxide, titanium oxide, and vanadium oxide.
  • the allowable amount of these combined catalysts is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less of all the catalyst components.
  • the amount of the heteropolyacid used in the present invention is usually in the range of 50,000 to 10 ppm based on the total weight of the polycarboxylic acid (a) and the polyhydric alcohol (b). Preferably, it is in the range of 10,000 ppm to 50 ppm, more preferably 5, OOO ppm to 50 ppm. An excessively large amount is not preferable because the polyester polymer is significantly colored. If the amount is too small, the catalytic activity is significantly reduced, which is not preferable.
  • the polyvalent carboxylic acid (a) and the polyvalent alcohol (b) are polycondensed in the presence of a heteropolyacid.
  • the polycondensation reaction is not particularly limited, but usually a method of synthesizing a polyester by collectively polymerizing a polycarboxylic acid and a polyhydric alcohol is employed.
  • the polycondensation reaction may be carried out according to a conventional method, and is usually carried out at a reaction temperature of 100 to 300, preferably 150 to 280, and particularly preferably in the presence of an inert gas. If necessary, a water-insoluble organic solvent azeotropic with water, such as toluene or xylene, may be used, and the reaction is carried out under reduced pressure (usually 0.1 to 50 OmmHg, preferably 0.5 to 200 mmHg, more preferably:! ⁇ 5 OmmHg). In the polycondensation, all monomers obtained by adding all polyhydric carboxylic acids and all polyhydric alcohols
  • the ratio of the total number of alcoholic reactive groups (X) to the total number of carboxylic acidic reactive groups (Y) is usually an equivalent ratio of (X) / (Y), usually 70 to 1.30, preferably 0.80. To 1.20, more preferably 0.90 to 1.10.
  • the equivalent ratio of (X) / (Y) is usually 1.00 or more, preferably 1.01 to 3.5.
  • the alcoholic reactive group is an alcoholic functional group that forms an ester bond, and usually includes a hydroxyl group.
  • the carboxylic acid reactive group is a carboxylic acid functional group that forms an ester bond, and usually includes a carboxyl group, an ester group, an acid anhydride, and the like. In the case of an acid anhydride, the number of carboxylic acid-reactive groups is twice the number of carboxyl groups.
  • the polyester produced by the above production method of the present invention usually has a number average molecular weight in terms of standard polystyrene of 2,500 or more, preferably 3,000 or more, and a weight average molecular weight (Mw in terms of standard polystyrene). ) Is from 10,000 to 500,000, preferably from 10,000 to 300,000, more preferably from 10,000 to 200,000.
  • the acid value of the polyester is usually 5 mgKOHZg or less, preferably 2 mgK ⁇ H / g or less.
  • the hydroxyl value of the polyester is usually 5 to 20 OmgKOH / g, preferably 10 to: L5 OmgKOHZg.
  • the glass transition temperature (Tg) of the polyester is not particularly limited, but is usually 10 to 30 O, preferably 30 to 200.
  • the polymer modifier composition of the present invention contains the polyester as an active ingredient.
  • the polymer modifier composition of the present invention is usually used in the form of granules, pellets, a solution dissolved in an organic solvent, a dispersion dispersed in a poor solvent, or an emulsion prepared using an emulsifier.
  • concentration of the polyester in the polymer modifier is usually 1 to 90% by weight, preferably 5 to 70% by weight.
  • a polymer composition is prepared by blending a polymer modifier composition containing the polyester of the present invention as an active ingredient with a polymer to be modified such as polyolefin.
  • the amount of the polymer modifier composition to be blended with various polymers is not particularly limited, but usually, the polymer modifier composition is added to 100 parts by weight of the polymer to be modified.
  • the content of the above polyester is in the range of 0.01 to 50 parts by weight, preferably 0.1 to 30 parts by weight, and more preferably 0.1 to 25 parts by weight.
  • the polyester of the present invention is effective for modifying an olefin polymer, particularly an olefin copolymer rubber and / or an olefin resin.
  • the amount of the polyester used is appropriately selected depending on the blending amount of the olefin polymer rubber and the olefin resin.
  • the preferred amount of the polyester used for modifying the hard polymer mixture composed of 100 parts by weight of the olefin resin and 5 to 30 parts by weight of the olefin copolymer rubber is: It is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the hard polymer mixture.
  • the suitable amount of the polyester used for the modification of the soft polymer mixture consisting of 100 parts by weight of the olefin resin and 300 to 300 parts by weight of the olefin copolymer rubber is as follows.
  • the amount is usually 0.1 to 50 parts by weight, preferably 0.5 to 25 parts by weight with respect to 0 parts by weight.
  • the olefin copolymer rubber is not particularly limited, but may be an ⁇ -olefin and a copolymer rubber thereof with a copolymerizable monomer or a copolymer rubber of two or more ⁇ -olefins.
  • a Mooney viscosity of 30 to 170, preferably 50 to 150, and an iodine value of 100 or less, preferably 50 or less is used.
  • Examples of the ⁇ -olefin used in the preparation of the copolymer rubber include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, and 4-methyl.
  • _ 1 Pentene and the like.
  • the amount of ⁇ -olefin in the copolymer rubber is usually at least 50% by weight, preferably from 60 to 100% by weight, more preferably from 80 to 100% by weight.
  • Examples of the monomer copolymerized with hyolefin include a conjugated diene compound and a non-conjugated diene compound.
  • Examples of the conjugated diene compound include butadiene, isoprene, and 1,3-pentene diene, and examples of the non-conjugated diene compound include ethylidene encompassorpolene, dicyclopentadiene, and 1,4-hexadiene. Among them, ethylidene norporene is preferred.
  • the bonding amount of these copolymerizable monomers in the copolymer rubber is usually 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less.
  • the olefin copolymer rubber examples include ethylene-propylene copolymer rubber, ethylene-butene-11 copolymer rubber, ethylene-octene-11 copolymer rubber, propylene-butene-11 copolymer rubber, and ethylene-ethylene copolymer rubber.
  • examples include propylene-conjugated copolymer rubber, isobutylene-conjugated copolymer rubber, ethylene-propylene-non-conjugated copolymer rubber.
  • IIR isobutylene-isoprene copolymer rubber
  • EPDM ethylene-propylene-ethylidene norportene copolymer rubber
  • olefin copolymer rubber In addition to the olefin copolymer rubber, other rubbers can be used if necessary. As other rubbers, gen-based rubbers such as natural rubber, polybutadiene rubber, polyisoprene rubber, and styrenebutadiene copolymer rubber are preferable. It is also possible to use acrylonitrile-lubutadiene copolymer rubber, hydrogenated acrylonitrile-butadiene copolymer rubber, or an olefinic thermoplastic elastomer.
  • gen-based rubbers such as natural rubber, polybutadiene rubber, polyisoprene rubber, and styrenebutadiene copolymer rubber are preferable. It is also possible to use acrylonitrile-lubutadiene copolymer rubber, hydrogenated acrylonitrile-butadiene copolymer rubber, or an olefinic thermoplastic elastomer.
  • the olefin resin examples include ⁇ -olefin homopolymers such as ethylene, propylene, butene-1, pentene-11, hexene1-1, 4-methylpentene-11, and octene-11; ethylene and propylene Or copolymers of two or more ⁇ -olefins, such as other copolymers with ⁇ -olefins.
  • ⁇ -olefin homopolymers such as ethylene, propylene, butene-1, pentene-11, hexene1-1, 4-methylpentene-11, and octene-11
  • ethylene and propylene Or copolymers of two or more ⁇ -olefins such as other copolymers with ⁇ -olefins.
  • homopolymers of ethylene or propylene and copolymers containing ethylene or propylene as a main component are preferable, and those containing propylene as a main component are particularly preferable.
  • olefinic resins include, for example, graft copolymerization of a, ⁇ -unsaturated sulfonic acid such as acrylic acid or maleic acid and its anhydride onto a homopolymer or copolymer of ⁇ -leufin. Graft copolymerized modified olefin resin; block copolymer obtained by block copolymerization of ⁇ -unsaturated carboxylic acid such as acrylic acid or maleic acid and its anhydride with the above-mentioned ⁇ -olefin homopolymer or copolymer.
  • ⁇ -unsaturated sulfonic acid such as acrylic acid or maleic acid and its anhydride
  • Graft copolymerized modified olefin resin block copolymer obtained by block copolymerization of ⁇ -unsaturated carboxylic acid such as acrylic acid or maleic acid and its anhydride with the above-mentioned ⁇ -olefin homopolymer or copoly
  • Polymerized modified olefin resin ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-crotonic acid copolymer, ethylene-maleic acid copolymer, ethylene-acrylic acid ester copolymer Polymers, ethylene / methacrylic acid ester copolymers, ethylene / vinyl acetate copolymers, etc. And a copolymer of focus ethylenically unsaturated saturated monomer.
  • polymers include thermosetting resins such as phenolic resin, cresol resin, urea resin, melamine resin, alkyd resin, furan resin, unsaturated polyester resin, epoxy resin, polyurethane resin; and Polystyrene resin, polyacrylic resin, polyphenylene ether resin, polyester resin, polycarbonate resin, polyacetal resin, polyamide resin, modified polyphenylene oxide resin, polybutylene terephthalate resin, polysulfone resin, Thermoplastic resins such as polyphenylene sulfide resin are exemplified.
  • thermosetting resins such as phenolic resin, cresol resin, urea resin, melamine resin, alkyd resin, furan resin, unsaturated polyester resin, epoxy resin, polyurethane resin
  • Polystyrene resin polyacrylic resin, polyphenylene ether resin, polyester resin, polycarbonate resin, polyacetal resin, polyamide resin, modified polyphenylene oxide resin, polybutylene terephthalate resin, polysul
  • polymer composition of the present invention in addition to the above components, if necessary, commonly used inorganic fillers, vulcanizing agents, vulcanization accelerators, vulcanization aids, reinforcing agents, plasticizers, lubricants Various additives such as UV inhibitors, UV stabilizers, UV stabilizers, heat stabilizers, antistatic agents, nucleating agents, flame retardants, organic pigments, inorganic pigments, and fillers can be blended. It is determined as appropriate within a range that does not impair the effects of the invention.
  • the polymer composition of the present invention is prepared according to a usual method, and can be produced, for example, by kneading the above components in a mixer.
  • kneading machine include extruders such as a single-screw extruder and a twin-screw extruder, Banbury, Brabender, Plastmill, calendar, 21st-roller, roll, extruder, multi-screw kneader, double helical repone Stirrer etc. Can be used.
  • the molded article of the present invention is obtained by molding the above-mentioned polymer composition by an ordinary method.
  • a molding method for example, any known method such as injection molding, blow molding, extrusion molding, compression molding, and rotational molding may be used.
  • paints include solvent-type thermoplastic acrylic paints, solvent-type thermosetting acrylic paints, modified acrylic alkyd paints, epoxy paints, acrylic urethane paints, silicon-modified urethane paints, polyurethane paints, and alkyd melamine. And poether melamine paints. Water-based paints can also be used. Furthermore, it can be firmly bonded to other molded bodies by using a suitable adhesive. Examples of the adhesive include an epoxy adhesive, a urethane adhesive, an acrylic adhesive, a cyanoacrylate adhesive, and a vulcanized adhesive.
  • the weight average molecular weight and the number average molecular weight of the polyester were calculated as standard polystyrene equivalent amounts according to the gel permeation (GPC) method.
  • the hydroxyl value and the acid value of the polyester were measured according to the following standards described in “Standard Fat and Oil Analysis Test Method” (Japan Oil Chemical Association).
  • the hue of the polyester was measured by the Gardner colorimeter method.
  • the softening point of polyester is measured according to the ring and ball method specified in JIS K2531. Was.
  • the light transmittance of the polyester was measured by the following method. That is, 5 g of polyester and 95 g of toluene are mixed and dissolved in a nitrogen atmosphere while stirring at 80 ° C for 1 hour, and then cooled to 20 ° C. This toluene solution is allowed to stand in a constant temperature room at 20 ° C for 24 hours, and then stirred again, and then the transmittance is measured using a turbidity meter (ANA-14S, manufactured by Tokyo Koden Co., Ltd.). A tungsten incandescent lamp (6 V, 6 A) is used as the light source, and a 20 mm square glass cell is used as the cell. The transmittance is 0 when the shutter is closed, and the transmittance of the toluene used for dilution is 100 (unit:%). The higher the value, the better the light transmittance.
  • the light transmittance is a measure that the polyester is oil-soluble, and it can be said that the polyester solution is oil-soluble when the light transmittance of the polyester solution is 80% or more.
  • the melt index of the polymer composition was measured according to ASTM-D-1238 at a temperature of 230, a load of 2,160 g, and a residual heat time of 6 minutes.
  • the flexural modulus of the molded article of the polymer composition was measured at 23 ° C on a test specimen (6 X 12.5 X 125 mm) manufactured by injection molding in accordance with JIS-K-7203. The speed was 3 mmZmin.
  • the impact strength of the molded article of the polymer composition was measured at 130 ° C by inserting a notch into a test piece (6 X 12.5 X 63.5 mm) manufactured by injection molding according to JI SK-7110. .
  • Injection-molded test specimens 50 X 5 OX 5 mm are washed with a neutral detergent, washed with water and dried, then directly coated with one-component urethane paint (thickness 30 tm) and baked at 80: for 40 minutes. I did.
  • a test piece with a cross-cut on the surface of the baked coating film was prepared, and an adhesive tape (Nichiban Cellophane) was stuck on the cross-cut, and this was quickly applied. Then, it was peeled off by pulling it in the direction of 90 degrees, and the number of grids remaining without being peeled out of 100 grids was counted. The higher the value, the better the adhesion of the synthetic resin paint.
  • test piece having a width of 3 Omm and a length of 15 mm was cut out so that the cross section was equally exposed, and it contained 10% by volume of ethyl alcohol.
  • the samples were immersed in gasoline No. 23 and the time until the coating film was partially peeled was measured (unit: minute). The higher the value, the better the solvent resistance.
  • Polyester B was prepared in the same manner as in Example 1 using the respective monomers and catalyst amounts shown in Table 1. ⁇ K and a ⁇ e were synthesized. Table 1 shows the evaluation results of the properties of each polyester.
  • Example e Reester monomer component, amount used (
  • polyester M The mixture was stirred while introducing nitrogen gas, and reacted at 200 ° C. for 4.0 hours while removing water and unreacted monomers generated during the reaction. Thereafter, the pressure of the system was gradually reduced, and after 0.5 hour, the pressure was reduced to 5 mmHg or less, and the reaction was continued for a further 3.0 hours while dehydrating to obtain polyester M.
  • Table 2 shows the evaluation results of the properties of Polyester M.
  • the molecular weight of the polyester produced using the polyacid is higher than the molecular weight of the polyester produced using a conventionally known polycondensation catalyst.
  • a conventionally known polycondensation catalyst For example, when 4-methylhexahydrophthalic anhydride and neopentyldaricol are polycondensed using 12-gust (VI) phosphoric acid n-hydrate as a polycondensation catalyst (Examples 1 and 12)
  • VI tandust
  • Example 2 the weight average molecular weights of the polyesters were 24, 150 and 23, respectively.
  • the number average molecular weights are 670 and 13,240 and 13,090, respectively.
  • the weight average molecular weights of titanium tetraisopropoxide (Comparative Example 1) and monobutyltin oxide (Comparative Example 2) were 5, 5, respectively, as the polycondensation catalyst.
  • number average molecular weights are only 1,380 and 970 respectively.
  • polycondensation of 4-methylhexahydrophthalic anhydride and 1,4-cyclohexanedimethanol using 12-tandust (VI) gayric acid 26 hydrate as a polycondensation catalyst (Example The weight average molecular weight of the polyester of 5) is 11,000 and the number average molecular weight is 6,290.
  • monobutyltin oxide was used as the polycondensation catalyst (Comparative Example 3)
  • the weight average molecular weight was only 3,530 and the number average molecular weight was only 1,280.
  • the weight average molecular weight of the polyester of (Example 8) is 22,050, and the number average molecular weight is 11,610.
  • the weight average molecular weight was only 3,030 and the number average molecular weight was only 1,030.
  • Example 12 Polycondensation of 4-methylhexahydrophthalic anhydride and 2-ethyl-2-butyl-1,1,3-propanediol using 12-tandust (VI) caffeic acid n-hydrate as polycondensation catalyst
  • Example 12 Although the weight average molecular weight of the polyester was 11,940, polycondensation was similarly performed by adding a polyhydric alcohol containing an ether bond (dipentyl erythritol) to these monomer components (Example 13, 14, 16-18), the weight average molecular weight of polyester increases to 20, 230-22, 120. Examples 23 and 24 and Comparative Example 10-12
  • ethylene-propylene-based copolymerized oo rubber compositions (Examples 23 and 24) were prepared according to the compounding recipe shown in Table 4.
  • An epoxy adhesive was applied to the surface of a vulcanized rubber sheet obtained by vulcanizing these rubber compositions at 160 ° C for .15 minutes to a thickness of 300 m (dry film thickness). The peel strength was measured using the test piece. The results are shown in Table 4. Table 4 Examples Comparative examples
  • Vulcanization system (parts by weight)
  • Example 25 a polymer composition of an ethylene-propylene copolymer rubber and a polypropylene resin (Examples 25 and 26) was prepared in accordance with the formulation shown in Table 5.
  • a polymer composition containing no polyester (Comparative Example 13) was also prepared.
  • Each polymer composition is molded by injection molding, a primer is applied to its surface, and then a polyurethane paint is applied to a thickness of 45 / zm (dry film thickness) to prepare a test piece. An eye test and a solvent resistance test were performed. The results are shown in Table 5
  • the molded product of the polymer composition containing the polyester modifier of the present invention is a polyester modifier. It can be seen that the adhesion strength between the surface of the polymer molded article and the coating film is higher than that of the molded article of the polymer composition containing no. In addition, as shown in Comparative Example 17 in Table 7 below, the adhesion strength between the surface of the polymer molded body and the coating film is higher than that of the molded body of the polymer composition containing the conventional polyester. I understand.
  • Vulcanization system (parts by weight)
  • the molded body of the polymer containing the polyester modifier of the present invention has a higher adhesive strength between the surface of the polymer molded body and the adhesive layer than the polymer molded body containing the conventional polyester. It turns out that it is high. Further, in Examples 27 to 29, it can be seen that sufficient adhesion strength can be obtained even though the amount of the polyester modifier is smaller than that in Examples 23 and 24. Examples 30 to 34 and Comparative Examples 16, 17
  • each raw material was mixed with a helical mixer, and then melt-kneaded with a twin-screw extruder set at 220 ° C. Then, a polymer composition (Examples 30 to 34) was prepared. For comparison, a polymer composition containing no polyester (Comparative Example 16) and a polymer composition containing polyester i (Comparative Example 17) were prepared.
  • test piece used for the coating film peel strength test was prepared as follows. Primer (manufactured by Nippon Bee Chemical Co., Ltd., trade name: RB-197) is applied to a test piece (50 x 80 mm, thickness: 3 lmm) by injection molding so as to have a film thickness of 10 m.
  • Microace P4 Talc manufactured by Nippon Talc, average particle size 1.5 m * 11 Index when the flexural modulus of the polymer molded article of Comparative Example 16 (without polyester) is 100
  • the polymer molded article containing the polyester modifier of the present invention has a higher adhesion strength between the surface of the polymer molded article and the coating film than the conventional polymer molded article containing polyester.
  • the polymer molded article of the present invention has a good balance between the flexural modulus and the I ZOD impact strength in high numerical values.
  • a conventional resin modifier is added to a resin, the above two physical properties deteriorate.
  • the flexural modulus can be almost maintained, but the index of the I ZOD impact strength is reduced to 52.2.
  • the bending elastic modulus and the I ZOD impact strength of the polymer molded product showed almost the same values as those of the polymer molded product without adding polyester.
  • the polyester of the present invention is blended with a polymer such as polyolefin as a polymer modifier to greatly improve the adhesion of paints such as acrylate or methacrylate, urethane, acrylic Z urethane, polyester, epoxy, etc. it can.
  • the polymer modifier also has the effect of modifying the adhesiveness of the emulsion adhesive and the printability of aqueous ink, and can broadly improve the surface properties of the resinous or rubbery polymer.
  • it is also suitable as a compatibilizer between different molecules.
  • the polymer composition blended with the polyester of the present invention as a modifier is useful as a part for electric, electronic, and automobile parts, a packaging material, and a container for beverages, cosmetics, etc. by utilizing the above-mentioned properties.
  • exterior materials such as bumpers, mudguards, weather strips, glass run channels, instrument panels, grommets, airbags, etc.
  • surface modification applications such as automotive materials such as interior materials, sporting goods such as sports shoes and golf poles, seat waterproofing materials, gaskets and sealing materials.

Abstract

L'invention concerne un polyester ayant un indice hydroxyle de 5 à 200 mg-KOH/g et un poids moléculaire moyen en poids compris entre 10 000 et 500 000. Ledit polyester est obtenu par polycondensation de un ou plusieurs acides polycarboxyliques comprenant au moins un élément est choisi parmi des acides dicarboxyliques alicycliques ayant une structure moléculaire dans laquelle les deux groupes carboxyle sont liés respectivement à deux atomes de carbone adjacents et des dérivés fonctionnels dudit produit, avec un ou plusieurs polyols comprenant un alcanediol ayant une structure moléculaire dans laquelle les deux groupes hydroxyle sont respectivement liés à deux atomes de carbone séparés par un atome de carbone exempt d'atome d'hydrogène. On produit ledit polyester en utilisant un hétéropolyacide comme catalyseur de polycondensation. Ledit polyester est utile comme modificateur de surface pour des polymères tel qu'un polymère oléfinique.
PCT/JP1999/001695 1998-03-31 1999-03-31 Polyester, procede de production associe, et son utilisation comme modificateur de polymere WO1999051660A1 (fr)

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WO2003082934A1 (fr) 2002-03-28 2003-10-09 Zeon Corporation Agent de modification de polymeres hydrocarbones, compositions de polymeres hydrocarbones et moulages
JP2004346320A (ja) * 2003-05-19 2004-12-09 Degussa Ag 狭い分子量分布を有するポリエステルベースの分枝状非晶質マクロポリオール
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WO2001040350A1 (fr) * 1999-11-29 2001-06-07 Zeon Corporation Polyester et polymere modificateur dont le polyester constitue l'agent actif
JP2001348474A (ja) * 2000-06-09 2001-12-18 Nippon Zeon Co Ltd ポリエステル系熱可塑性エラストマー組成物、それを含有する樹脂成形体および樹脂成形体の製造方法
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US8044170B2 (en) 2004-06-01 2011-10-25 Basf Aktiengesellschaft Highly functional, highly branched or hyperbranched polyesters, the production thereof and the use of the same
WO2019131413A1 (fr) * 2017-12-26 2019-07-04 Dic株式会社 Composition thermodurcissable, agent de modification de résine thermodurcissable, son produit durci, matériau d'étanchéité de semi-conducteur, préimprégné, carte de circuit et film de dépôt
CN111527152A (zh) * 2017-12-26 2020-08-11 Dic株式会社 热固化性组合物、热固化性树脂改性剂、其固化物、半导体密封材料、预浸料、电路基板和增层膜
JPWO2019131413A1 (ja) * 2017-12-26 2021-01-14 Dic株式会社 熱硬化性組成物、熱硬化性樹脂改質剤、その硬化物、半導体封止材料、プリプレグ、回路基板及びビルドアップフィルム
CN111527152B (zh) * 2017-12-26 2022-04-29 Dic株式会社 热固化性组合物、热固化性树脂改性剂、其固化物、半导体密封材料、预浸料、电路基板和增层膜
JP2019172810A (ja) * 2018-03-28 2019-10-10 東洋紡株式会社 共重合ポリエステル樹脂およびこれを含む粘着剤組成物
JP2019172811A (ja) * 2018-03-28 2019-10-10 東洋紡株式会社 共重合ポリエステル樹脂およびこれを含む粘着剤組成物

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