WO1999051660A1 - Polyester, process for producing the same, and application thereof as polymer modifier - Google Patents

Abstract

A polyester which has a hydroxyl value of 5 to 200 mg-KOH/g and a weight-average molecular weight of 10,000 to 500,000 and is obtained by the polycondensation of one or more polycarboxylic acids comprising at least one member selected among alicyclic dicarboxylic acids having a molecular structure in which the two carboxyl groups are respectively bonded to two adjacent carbon atoms and functional derivatives thereof with one or more polyhydric alcohols comprising an alkanediol having a molecular structure in which the two hydroxyl groups are respectively bonded to two carbon atoms separated by a carbon atom having no hydrogen atom. This polyester is produced using a heteropolyacid as a polycondensation catalyst. It is useful as a surface modifier for polymers such as an olefin polymer.

Description

 Description 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.

 More specifically, 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. Background technology

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. As a method of improving such a defect, 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. In addition, 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

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 Disclosure of the invention

 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.

 As a result of intensive studies, 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. However, in the past, 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. We have found that it is possible to efficiently synthesize 100,000 or more. Furthermore, when this was blended with ethylene-propylene rubber, it was found that the adhesion of the urethane-based coating film formed on the surface of the vulcanized sheet of the rubber was significantly improved, and based on these findings, the present invention was carried out. Was completed. Thus, according to the present invention, 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〇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. There is provided a polyester comprising an alkanediol having a molecular structure in which a carbon atom to which a hydrogen atom is not bonded is interposed.

Further, according to the present invention, it 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. Provided is 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.

 Further, according to the present invention, there is provided a polymer modifier composition comprising, as an active ingredient, a polyester obtained from the above polycarboxylic acid (A) and polyhydric alcohol (B). You.

 Further, according to the present invention, there is provided a polymer composition comprising a polymer and the above-mentioned modifier composition for a polymer.

 Further, according to the present invention, a molded article obtained by molding the polymer composition is provided.

BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail.

 (1) Polyester

 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. At least one selected from an alicyclic dicarboxylic acid having a molecular structure and a functional derivative thereof, wherein the polyhydric alcohol (B) has two carbon atoms each having a hydroxyl group bonded thereto. It contains an alkanediol having a molecular structure in which a carbon atom to which a hydrogen atom is not bonded is interposed.

 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.

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. When the hydroxyl value is within this range, the coatability of a molded product obtained from a polymer composition prepared by blending the polyester with another polymer is remarkably improved. Furthermore, 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.

 When the polyester is oil-soluble, it generally has better compatibility with many polymers to be modified, including polyolefin, and is suitable. Here, “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.

 Polycarboxylic acid (A)

 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.

Specific examples of the saturated alicyclic dicarboxylic acid include hexahydrophthalic acid (1,2-cyclohexane'diacid), 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, and 2,2-methylhexahydrophthalic acid. Specific examples of 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. Specific examples of the saturated alicyclic dicarboxylic anhydride 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. Specific examples of the alicyclic dicarboxylic acid ester 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. Specific examples of the alicyclic dicarboxylate 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.

 Among the above alicyclic dicarboxylic acids and functional derivatives thereof, hexahydrophthalic acid, 3-methylhexahydrofuric acid, 4-methylhexahydrofuric acid, 2,3-norpolnanodiacid, Preference is given to xahydrohydrofuric anhydride, 3-methylhexahydrofuric anhydride, 4-methylhexahydrofuric anhydride and 2,3-norbornane diacid anhydride. In particular, it is obtained when 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.

In the 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). Examples of 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. Specific examples of such 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.

 Other optional 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.

 Further, the 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.

 Furthermore, 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.

 Specific examples of the 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.

 Polyhydric alcohol (B)

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”). Usually, 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. Specific examples of the alkyl group 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. Of these, 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. Specific examples of such 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. Among them, 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.

These hindered glycols can be used alone or in combination of two or more. 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. Of polyhydric alcohols (ie, other dihydric alcohols and trihydric or higher polyhydric alcohols) can be used together. 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).

 Other 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 dimethanol, hydrogenated bisphenol A and adamantinediol; Diethylene glycol, triethylene glycol, tetraethylene dalichol, dipropylene glycol, tripropylene glycol and other oligooxyalkylene dallycols, and other diols having an ether bond in the molecule; p-xylene diol, 4, 4- Diethylene component of methylene diphenol and diol component of propylene glycol adduct, ethylene oxide of bisphenol A and / or diol component of propylene glycol adduct, ethylene of biphenol And aromatic diols such as oxides and diol components of Z or propylene glycol adducts. Of these, cycloalkanediol is preferred, and 1,4-cyclohexanedimethanol is particularly preferred.

 Examples of the 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.

Among the polyhydric alcohols used in combination, tetrahydric or higher alcohols having an ether bond in the molecule, such as dipentaerythritol and ditrimethylolpropane, are particularly preferred. Preferred. As 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 When a mixture with a polyhydric alcohol having 4 or more is used, 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.

 Furthermore, 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.

 (2) Polyester production method

 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.

 Dicarboxylic acids and polyhydric alcohols having a molecular structure in which carboxyl groups are bonded to adjacent carbon atoms using catalysts such as conventionally known brenstead acid, organometallic compounds, and metal oxides When polycondensation is carried out, side reactions such as an elimination reaction are very likely to occur, which makes it difficult to obtain a high molecular weight polymer. In addition, when 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. However, when 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.

 Polycarboxylic acid (a)

Adjacent to each other contained in the polycarboxylic acid (a) used in the production method of the present invention 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.

 Among the 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. In addition to 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.

 Other 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.

Examples of 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.

 Examples of 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.

 Further, 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.

 In the present invention, other than the polyvalent carboxylic acid (a), 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. Can be

 Polyhydric alcohol (b)

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. Among them, 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.

 Specific examples of the hindered glycol 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.

 Specific examples of alkane diols other than hindered glycol, cycloalkane diols, diols having an ether bond in the molecule, aromatic diols and trivalent or higher alcohols include the above-mentioned polyester (1) and polyhydric alcohol (B). Examples of the above are given.

 As described above, 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. Further, 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).)

 In the present invention, 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).

 Heteropoly acid

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. There are no particular restrictions on the type or structure. Examples of 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.

 Specific examples of 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.

 Among these, 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. Examples of the salt of the heteropolyacid include an acid metal salt and an acid salt. Examples of 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. Examples of the acidic sodium salts include ammonium salts with amines and ammonia, and phosphonium salts. Can be mentioned.

 Further, as the heteropolyacid used in the present invention, those having water of crystallization in the molecule can also be used.

 When the heteropolyacid used in the present invention is 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.

 Other 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.

 Polycondensation reaction

 In the method for producing a polyester of the present invention, 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

-It is preferable to carry out the reaction under the condition that the total number of alcoholic reactive groups (X) and the total number of carboxylic acid reactive groups (Y) in the component are in an appropriate ratio, in order to increase the molecular weight of the polyester. is there. 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. In particular, in order to obtain a high molecular weight and high hydroxyl value polyester useful as a modifier, the equivalent ratio of (X) / (Y) is usually 1.00 or more, preferably 1.01 to 3.5. It is preferably in the range of 1.03 to 2.5. Here, the alcoholic reactive group is an alcoholic functional group that forms an ester bond, and usually includes a hydroxyl group. In addition, 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〇H / g or less. The hydroxyl value of the polyester is usually 5 to 20 OmgKOH / g, preferably 10 to: L5 OmgKOHZg. Further, the glass transition temperature (Tg) of the polyester is not particularly limited, but is usually 10 to 30 O, preferably 30 to 200.

 (3) Polymer modifier composition

 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. Can be The concentration of the polyester in the polymer modifier is usually 1 to 90% by weight, preferably 5 to 70% by weight. (4) Polymer composition

 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.

 When a mixture of the olefin copolymer rubber and the olefin resin is used as the polymer, the amount of the polyester used is appropriately selected depending on the blending amount of the olefin polymer rubber and the olefin resin.

 More specifically, 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 α-olefin and a copolymer rubber thereof with a copolymerizable monomer or a copolymer rubber of two or more α-olefins. Usually, 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 α-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 α-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 dennorpolene, 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.

 Specific examples of the olefin copolymer rubber 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. Among them, isobutylene-isoprene copolymer rubber (IIR) and ethylene-propylene-ethylidene norportene copolymer rubber (EPDM) are preferred. These can be used alone or in combination of two or more.

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. Examples of the olefin resin include α-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 α-olefins, such as other copolymers with α-olefins. Among these, 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. As a polymer containing propylene as a main component, a copolymer composed of at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight of polypropylene and propylene and other α-olefins Among the one-year-old olefins that copolymerize, Ethylene is preferred.

 Other olefinic resins include, for example, graft copolymerization of a, β-unsaturated sulfonic acid such as acrylic acid or maleic acid and its anhydride onto a homopolymer or copolymer of α-leufin. Graft copolymerized modified olefin resin; block copolymer obtained by block copolymerization of β-unsaturated carboxylic acid such as acrylic acid or maleic acid and its anhydride with the above-mentioned α-olefin homopolymer or copolymer. 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.

 By blending the polymer modifier composition of the present invention with other polymers other than the above-mentioned polyolefins and the like, it is also possible to improve the paintability of the paint on the surface of the polymer molded product. Other 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.

 In the 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. Examples of the 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.

 (4) Molded body

 The molded article of the present invention is obtained by molding the above-mentioned polymer composition by an ordinary method. As a molding method, for example, any known method such as injection molding, blow molding, extrusion molding, compression molding, and rotational molding may be used.

 By coating the surface of the molded article of the present invention with an appropriate paint, a good coating can be formed. Examples of 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.

 Hereinafter, the present invention will be described with reference to examples. The present invention is not limited to these examples. Parts and percentages in the examples are on a weight basis unless otherwise specified. The characteristics of the polyester, the polymer composition containing the polyester, and the characteristics of the molded product in the examples were evaluated by the following test methods.

 (1) Molecular weight

 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.

 (2) hydroxyl value and acid value (mgKOH / g)

 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).

 Hydroxyl value 2,4,9,2-83

 Acid value 2, 4, 1-83

 (3) Gardner hue

The hue of the polyester was measured by the Gardner colorimeter method.

 (4) Softening point C)

The softening point of polyester is measured according to the ring and ball method specified in JIS K2531. Was.

 (5) Light transmittance (%)

 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.

 (6) Melt index (Ml)

 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.

 (7) Flexural modulus (MPa)

 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.

(8) I ZOD impact strength (KJZm ² )

 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. .

 (9) Adhesiveness of adhesive layer on polymer molded body surface (peel strength test)

Gauze was adhered to the surface of the polymer molded body coated with the adhesive with an instantaneous adhesive, and then a rectangular test piece having a width of 1 cm was formed by punching. Part of the gauze at the end of the test piece was peeled off, and the polymer molded body and the end of the gauze were peeled off by pulling in 180 degrees at a speed of 20 OmmZ, and the maximum peel strength was measured (unit: kg) fZcm). Number is W

 twenty one

The larger, the better the adhesion between the adhesive and the polymer surface.

 (10) Adhesion of the coating film on the surface of the molded polymer (cross cut test)

 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.

 According to the cross-cut test method specified in JIS K5400, 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.

 (1 1) Adhesion of coating film on polymer molded body surface (solvent resistance test)

 From the polymer molded body having a baked urethane coating film prepared by the method described in (10) above, a 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.

 Example 1 (Synthesis of Polyester A)

 A 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube was charged with 150 g of 4-methylhexahydrofluoric anhydride, 95.8 g of neopentyl glycol, 12 Tandust (VI) 0.12 g of phosphoric acid n-hydrate was charged. The mixture was stirred at 180 ° C. for 6 hours while stirring while introducing nitrogen gas to remove water and unreacted monomers generated during the reaction. Thereafter, the pressure of the system was gradually reduced, and after 1.5 hours, the reaction pressure was reduced to ImmHg or less, and the reaction was continued for a further 3 hours while dehydrating, to obtain a polyester A. Table 1 shows the evaluation results of the properties of Polyester A.

Examples 2 to: L 1 and Comparative Examples 1 to 5 (Synthesis of Polyesters B to K and a to e) 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 (

'Carpho' acid

 4 Cyl phenol phthalate 150.0 150.0 170.0 250.0 130.0 150.0

 Acid anhydride

 Phthalic anhydride 150.0

1,2-SiC D-hexan'carbone 150.0 Acid anhydride

 2,3-Norpho's Renansi'Cal'on

 Acid anhydride

 C 14-Arke :: Rucocarboxylic anhydride

Bivalent alcohol

 To neo. Ethylene glycol 95.8 95.8 96.4 108.2 104.4 ethylene glycol 75.3

 Shi Metchi-Le Hair Tan 247.5

 1,4-cyclohexene methanol 115.0

 'Ethylene glycol' catalyst, consumption (g)

 12 tanks strike (VI) phosphoric acid 0.12 0.12 0.24 0.12 0.13 0.08 hydrate

 12 Tank 'strike (VI) Caic acid 0.12 0.12

 26 hydrate

 Mono tylus' oxide

 C. Rattoluenesulfonic acid polyester properties.

Weight average molecular weight (Mw) 24, 150 23,670 32, 300 13,750 11,000 12,940 20,720 22,050 Number average molecular weight (Mn) 13,240 13,090 14,360 8,680 6,290 6,210 12,170 11,610 Molecular weight distribution (Mw / Mn) 1.82 1.81 2.25 1.58 1.75 2.08 1.7 1.9 Force '-Donna-Hue 3 3 3 2 2 2 2 3

Continued

W

 twenty four

 Example 12 (Synthesis of Polyester L)

 In a 2 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen gas inlet tube, 80.0 g of 4-methylhexahydrophthalic anhydride, 2-ethyl-2-butyl- 800,3 g of 1,3-propanediol and 0.81 g of 12-tandust (VI) gay acid hydrate were charged. (OHVZAV 1.05)

 The mixture was stirred while introducing nitrogen gas, and reacted at 180 ° C for 4.5 hours while removing water and unreacted monomers generated during the reaction. Thereafter, the pressure of the system was gradually decreased, and after 0.5 hour, the pressure was reduced to 5 mmHg or less, and the reaction was continued for another 3 hours while dehydrating to obtain a polyester F. Table 2 shows the evaluation results of the properties of Polyester F.

 Example 13 (Synthesis of Polyester M)

 In a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, add 40.0 g of 4-methylhexahydrofluoric anhydride, 20.0 g of 2-ethyl-2-butyl-1 370.1 g of, 3-propanediol, 47.7 g of dipentaerythritol and 0.41 g of 12 tandust (VI) silicate n-hydrate were charged. (0 HV / AV = 1.05)

 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.

 Example 14 (Synthesis of Polyester N)

In a 2 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen gas inlet tube, 100-0.0 g of 4-methylhexahydrophthalic anhydride, 2-0.02-g 85.0 g of butyl_1,3-propanediol, 85.0 g of 1,4-cyclohexanedimethanol, 79.5 g of dipentyl erythryl) and 12 tandast (VI) Gay acid n-hydrate 1 4 lg was charged. (OHVZAV = l.05) The reaction was carried out at 200 ° C for 4.5 hours while stirring while introducing nitrogen gas to remove water and unreacted monomers generated during the reaction. Thereafter, the pressure of the system was gradually decreased, and after 0.5 hour, the pressure was reduced to 5 mmHg or less, and the reaction was continued for 3 hours while performing dehydration to obtain polyester N. Table 2 shows the evaluation results of the properties of Polyester N. W 51

 twenty five

 Example 15 (Synthesis of Polyester P)

 In a 2 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, add 100.0 g of 4-methylhexahydrofluoric anhydride, 1000.0 g, 2-ethyl 2- 807.5 g of butyl-1,3-propanediol, 130 g of 1,4-cyclohexanedimethanol, erythri dipentyl! 79.5 g of cellulose and 0.14 g of 12 tandust (VI) phosphate n-hydrate were charged. (OHVZAV::!. 05) Stirring was performed while introducing nitrogen gas, and the mixture was reacted at 200 for 4.5 hours while removing water and unreacted monomers generated during the reaction. Thereafter, the pressure of the system was gradually reduced, and after 5 hours, the pressure was reduced to 5 mmHg or less, and the reaction was continued for 3.5 hours while dehydrating, to obtain polyester P. Table 2 shows the evaluation results of the properties of Polyester P.

 Example 16 (Synthesis of Polyester Q)

 In a 1 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, add 80.0 g of 4-methylhexahydrofuric anhydride to 2-ethyl_2_butyl_1 558.8 g of 3,3-propanediol, 166.4 g of 1,4-cyclohexanedimethanol, 61.8 g of dipentyl erythritol and 12 tandust

(V I) 0.81 g of gay acid n-hydrate was charged. (〇HVZAV = 1.05) The mixture was stirred at 200 ° C for 4.5 hours while stirring while introducing nitrogen gas to remove water and unreacted monomers generated during the reaction. Thereafter, the pressure of the system was gradually decreased, and after 0.5 hour, the pressure was reduced to 5 mmHg or less. The reaction was continued for another 4.0 hours while dehydrating, and polyester Q was obtained. Table 2 shows the evaluation results of the properties of Polyester Q.

 Example 1 (Synthesis of Polyester R)

 In a 2 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, add 80.0 g of 4-methylhexahydrofluoric anhydride, 2-ethyl-2-butyl-1, 68-2 g of 3-propanediol, 49.5 g of neopentyl glycol, 60.8 g of dipentaerythritol and 0.8 lg of 12-ngst (VI) silicate n-hydrate were charged. (OHVZAV-1. 05)

Stirring was performed while introducing nitrogen gas, and the reaction was carried out at 200 for 4.0 hours while removing water and unreacted monomers generated during the reaction. Then, the pressure of the system was gradually reduced, and after 0.5 hours, the pressure was reduced to 5 mmHg or less. Then, polyester R was obtained. Table 2 shows the evaluation results of the properties of Polyester R. Example 18 (Synthesis of Polyester S)

 In a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, 40.0 g of 4-methylhexahydrofluoric anhydride, 20.0 g of 2-ethyl-2-butyl-1 , 3-propanediol 279.4 g, neopentyldaricol 60,1 lg, dipentyl erythritol 30.9 g, and 12 tungsto (VI) carboxylic acid n-hydrate 0.4 lg were charged. (〇HVZAV = 1.05)

 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 5 hours, the pressure was reduced to 5 mmHg or less. The reaction was continued for 3.5 hours while dehydrating, and polyester S was obtained. Table 2 shows the evaluation results of the properties of Polyester S.

 Comparative Example 6 (Synthesis of polyester f)

 In a 2 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, 80.0 g of 4-methylhexahydrofluoric anhydride, 2-ethyl-2-butyl-1 , 3-propanediol (800.3 g) and monobutyltin sulfide (1.60 g) were charged. (OHVZAV = l. 05)

 The mixture was stirred while introducing nitrogen gas, and reacted at 200 ° C. for 4.5 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 another 0.3 hours while dehydrating, to obtain a polyester f. Table 2 shows the evaluation results of the properties of Polyester f.

 Comparative Example 7 (Synthesis of polyester g)

 In a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen gas inlet tube, add 30.0 g of 1,4-cyclohexanedicarboxylic acid, 2-ethyl-1-butyl-1,3-butyl-1,4-cyclohexanedicarboxylic acid. 284.6 g of 3-propanediol and 0.30 g of 12 gust (VI) gaynic acid n-hydrate were charged. (OHVZAV = l. 02)

The mixture was stirred while introducing nitrogen gas, and reacted at 200 ° C for 4 hours while removing water and unreacted monomers generated during the reaction. Thereafter, the pressure of the system was gradually reduced, and after 5 hours, the pressure was reduced to 5 mmHg or less, and the reaction was continued while dehydrating for another 3 hours to obtain polyester g. Table 2 shows the evaluation results of the properties of Polyester g. Table 2 Example h ΨΧ V'i

12 13 14 15 16 17 R 7 Polyester L M N P n Q f rf Monomer component, amount used (g)

'Carpho' acid

 4-methylhexahydr phthalate 800.0 400.0 1000.0 1000.0 800.0 800.0 400 0 8000

 Acid anhydride

 1,4-cyclohexan'carboic acid---1-300

Bivalent alcohol

 2-ethyl 2-ethyl 1-3-800.3 370.1 855.0 807.5 558.8 684.2 279.4 800.3 284.6 Nishi's

Ether thread ^ "Alcohol

 ** 4 ° 79.5 79.5 61.8 60.8 30.9

Other alcohol

 14-Cyclohexane methanol 85.0 130 166.4

 To neo. N-thyl diol-49.5 60.1--Catalyst, halo used (g)

 12 tanks strike (VI) phosphoric acid 0.14

 η hydrate

 12 Tandust (VI) Keiic acid 0.81 0.41 0.41 0.81 0.81 0.41 0.30 η-hydrate

 Monophthyl oxide 1.60 hostile properties.

Weight average molecular weight (Mw) 11,94022, 11022,08017,55027,89020, 42020,230 9,710 3,960 Number average molecular weight (Mn) 6,982 3,773 3,971 3,553 4,025 4,373 3,883 2,675 1,690 Molecular weight distribution (Mw / Mn) 1.71 5.86 5.56 4.94 6.93 4.67 5.21 3.63 2.35 Hydroxyl value (mgKOH / G) 13 55 58 58 44 51 50 18 76 Force '-Donna-hue 3 2 3 2 2 1 1 7 4 Softening point CC) 76 86 84 80 88 80 79 76 7 Light transmission Rate (%) 100 98 96 95 93 97 96 93 90 Example 19 (Synthesis of Polyester T)

 In a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, add 40.0 g of 4-methylhexahydrofuric anhydride to 15.0 g of 2-methyl-2-butyl-1 , 3_propanediol 147.0 g, and 12 tandust (VI) phosphoric acid n-hydrate 0.12 g were charged. The mixture was stirred while introducing nitrogen gas, and reacted at 180 ° C. for 6 hours while removing water and unreacted monomers generated during the reaction. Thereafter, the pressure of the system was gradually reduced, and after 1.5 hours, the reaction pressure was reduced to ImmHg or less, and the reaction was continued for another 3 hours while dehydrating, to obtain polyester T. Table 3 shows the evaluation results of the properties of Polyester T.

Examples 20 to 22 and Comparative Examples 8 and 9 (Synthesis of polyesters U to W and h and i) Polyesters U to W were prepared in the same manner as in Example 19, using the monomers and catalyst amounts shown in Table 3. And h, i were synthesized. Table 3 shows the evaluation results of the properties of each polyester.

Table 3 m Example Comparison Example

19 20 21 22 8 9 Holes T U V W h i Monomer component> Weight used (g)

カ ル

 4-; (Cylhexahydr phthalate 150 150-150 mono-anhydride

 Hexahit D phthalic acid 150

 Anhydrous

 Phthalic anhydride 150

 Terephthalic acid---1,200

2 {jffi alcohol

 2-ethyl-2-phenyl-1 3-147 139.6 162 119.1 171.6 1 102.2 Fluoranone

Other alcohol

 What. Nantaerythritol-6.28---104.1 Trimethyl-Luff DANO 6.19 Catalyst, amount used (g)

 12 tanks strike (VI) phosphoric acid 0.12 0.12 0.12 0.12 0.12

 η hydrate

 Alkylene oxide '1.20 Holistic properties.

Weight average molecular weight (Mw) 11, 540 10 940 11, 800 19, 150 8 570 43 130 Number average molecular weight (Mn) 6,830 4,220 6,860 6, 140 4,995 9,915 Molecular weight distribution (Mw / Mn) 1.69 259 1.72 3.12 1.72 4.35 Hydroxyl group Value (mgKOH / G) 21 63 33 53 37 50 Softening point (in) 88 93 77 95 83 105 Light transmittance (%) 99 98 99 99 99 88

From the results shown in Tables 1 to 3, the polycondensation catalyst (

It can be seen that 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. 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) In the case of polycondensation using tandust (VI) gayric acid 26 hydrate (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. On the other hand, 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.

720 and 2,230, number average molecular weights are only 1,380 and 970 respectively.

 Similarly, 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. On the other hand, when 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.

 Also, when polycondensation of 1,2-cyclohexanedicarboxylic anhydride and neopentyldaricole is performed using 12-gustust (VI) phosphoric acid n-hydrate as a polycondensation catalyst

The weight average molecular weight of the polyester of (Example 8) is 22,050, and the number average molecular weight is 11,610. On the other hand, when paratoluenesulfonic acid was used as the polycondensation catalyst (Comparative Example 4), the weight average molecular weight was only 3,030 and the number average molecular weight was only 1,030.

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

 Evaluation of polymer composition containing polyester modifier (1)

 Using the above-mentioned polyesters U and W, ethylene-propylene-based copolymerized oo rubber compositions (Examples 23 and 24) were prepared according to the compounding recipe shown in Table 4. For comparison, a rubber composition containing no polyester (Comparative Example 10) and a rubber composition containing each of the above polyesters h and i (Comparative Examples 11, 12) were also prepared. 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

 23 24 10 11 12

Mixing (parts by weight)

 EPDM 1060 * 1 100 100 100 100 100

 Force horn rack (seam 116) * 2 50 50 50 50 50

 Oil (Dynamic Roses 60 60 70 60 60 Zinc flower 5 5 5 5 5

 Stearic acid 1 1 1 1 1

 Heavy calcium carbonate 60 60 60 60 60

Vulcanization system (parts by weight)

 Sulfur (325) 1.00 1.00 1.00 1.00 1.00

 Vulcanization accelerator

 TB * 4 1.00 1.00 1.00 1.00 1.00

 MTBS * 5 1.00 1.00 1.00 1.00 1.00

 TMTD * 6 0.75 0.75 0.75 0.75 0.75

 DPTT * 7 0.50 0.50 0.50 0.50 0.50

E. Riester. U W h i

 Addition amount (parts by weight) 10 10 10 10

Hot lima-molded body properties.

Peel strength (kgf / cm) 1.5 1.7 0.1 1.0 1.0 The components in Table 4 are as follows.

 * 1 Mitsui Petrochemical Co., Ltd .: Ethylene-propylene-gen copolymer rubber

 * 2 Tokai Riki Ippon Co., Ltd .: Carbon black

 * 3 Idemitsu Kosan Co., Ltd .: Process oil

 * 42-Mercaptobenzothiazole

 * 5 Dibenzothiazyl disulfide

 * 6 Tetramethylthiuram disulphide

 * 7 Dipentamethylenethiuramtetrasulfide

 From the results shown in Table 4, the molded article of the polymer containing the polyester of the present invention as a modifier was compared with the molded article of the polymer containing no polyester modifier and the conventional molded article of the polymer containing polyester. It can be seen that the adhesion strength between the polymer molded body surface and the adhesive is high.

 Examples 25, 26 and Comparative Example 13

 Evaluation of polymer composition containing polyester modifier (2)

 Using the polyesters T and V described above, 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. For comparison, 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

Table 5 Example Comparative example

 25 26 13

 Mixing (parts by weight)

 Resin PP * 8 75 75 75 Comb EPR * 9 12 12 15 Inorganic filler * 10 10 10 10 e. Riester TV

 Compounding amount (parts by weight) 3 3

 Solvent resistance (min) 60 60 60 5 5

Crosscut test 100/100 100/100 30/100 The components in Table 5 are as follows.

 * 8 J _ 3050HP: Idemitsu Petrochemical Co., Ltd. polypropylene resin, MFR = 42 * 9 EP 02: Nippon Synthetic Rubber Co., Ltd. ethylene-propylene copolymer rubber,

 MFR = 3.2

 * 10 Microace P4: Talc manufactured by Nippon Talc, average particle size 1.5 urn Based on the results 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.

 Examples 27 to 29 and Comparative Examples 14, 15

 Evaluation of polymer composition containing polyester modifier (3)

Using the above polyesters U, N, and R, rubber compositions (Examples 27 to 29) were prepared according to the formulation shown in Table 6. For comparison, a rubber composition containing no polyester (Comparative Example 14) and a rubber composition containing the above polyester i (Comparative Example 15) were prepared. These rubber compositions were vulcanized at a pressure of 100 kg / cm ² at 160 t: 15 minutes to obtain a vulcanized rubber sheet of 150 × 80 × 2 mm.

Cut the vulcanized rubber sheet into 75 x 80 x 2 mm, apply epoxy adhesive (Pond MOS 1010, manufactured by Konishi Co., Ltd.) on the surface to a thickness of 300 zm, and dry at 60 ° C for 2 hours. Thereafter, the specimen was left for 96 hours to prepare a test piece. A peel strength test of the test piece was performed. The results are shown in Table 6.

Table 6 Examples Comparative examples

 27 28 29 14 15

 Ingredients (parts by weight)

 Com EPDM 1060 * 1 100 100 100 100 100 Power-Horn rack (cyst 116) * 2 50 50 50 50 50 Oil (Mic process with tab) 60 60 60 70 60

 (PW 380) * 3

 Zinc flower 5 5 5 5 5

 Stearic acid 1 1 1 1 1

 Heavy calcium carbonate 60 60 60 60 60

 Vulcanization system (parts by weight)

 Sulfur (325) 1.00 1.00 1.00 1.00 1.00 Vulcanization accelerator

 MTB U 1.00 1.00 1.00 1.00 1.00

MTBS * 5 1.00 1.00 1.00 1.00 1.00

TMTD * 6 0.75 0.75 0.75 0.75 0.75

DPTT * 7 0.50 0.50 0.50 0.50 0.50 E. Riester. U N R i

 Addition amount (parts by weight) 5 5 5 5

 Ho'lima-molded body properties.

 Peel strength (kgi / cm) 0.7 1.0 1.1 0.1 0.5

* 1 Manufactured by Mitsui Petrochemical Co., Ltd .: ethylene-propylene-one-gen copolymer rubber

* 2 Tokai Carbon: carbon black

 * 3 Idemitsu Kosan Co., Ltd .: Process oil

 * 42-Mercaptobenzothiazole

 * 5 Dibenzothiazyl disulfide

 * 6 Tetramethylthiuram disulfide

 * 7 Dipentamethylenethiuramtetrasulfide

From the results shown in Table 6, 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

 Evaluation of polymer composition containing polyester modifier (4)

 Using the polyesters T, M, P, R, and S in the composition shown in Table 7, 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.

 The 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. After drying for one minute, apply a urethane-based metallic paint (Nippon Bee Chemical Co., trade name: RB-212) and a urethane clear paint (Nippon Bee Chemical Co., trade name: RB-288) to one side of the primer It was prepared according to the specifications specified by the company, applied so as to have a film thickness of 20 m and 25 m, respectively, dried with 8 O: for 45 minutes, and then left for 24 hours to obtain a test piece. The peel strength of the test piece was measured. The results are shown in Table 7.

Example Comparative example

 30 31 32 33 34 16 17 Formulation (parts by weight)

 Resin PP * 8 70 70 70 70 70 73 70 Comb EPR * 9 20 20 20 20 20 20 20 Inorganic filler * 10 7 7 7 7 7 7 7 e. Riester T M P R S i Content (parts by weight) 3 3 3 3 3 3

 Ml 28 27 27 27 26 22 23 Flexural modulus (Mpa) 1,090 1,130 1,150 1,100 1,120 1,170 1,160 Flexural modulus, index * 11 93.2 96.6 98.3 94.0 95.7 100 99.1

IZ0D impact strength (Kl / m ² ) 6.0 6.5 6.5 6.2 6.4 6.7 3.5

IZ0D impact strength, index * 12 89.6 97.0 97.0 92.5 95.5 100 52.2 Solvent resistance (min) 60 く 60 60 60 5 60 60 60 5 5 20 Cross cut test 100/100 100/100 100/100 100/100 90/100 30/100 70/100 * 8 J-305 OHP: Idemitsu Petrochemical Company's polypropylene resin, MFR = 42

* 9 EP 02: ethylene-propylene copolymer rubber manufactured by Nippon Synthetic Rubber Co., Ltd.

 MFR = 3.2

 * 10 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

 * 12 Index when the I ZOD impact strength of the polymer molded article of Comparative Example 16 (without adding polyester) is 100

 From the results shown in Table 7, it can be seen that 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. I understand. Further, 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. When a conventional resin modifier is added to a resin, the above two physical properties deteriorate. For example, in Comparative Example 17, the flexural modulus can be almost maintained, but the index of the I ZOD impact strength is reduced to 52.2. However, in the present invention, in Example 32, 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. Industrial applicability

 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. Furthermore, 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. Furthermore, 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. Yes, especially exterior materials such as bumpers, mudguards, weather strips, glass run channels, instrument panels, grommets, airbags, etc. It is suitable for 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.

Claims

The scope of the claims 1. Obtained by polycondensing polyhydric carboxylic acid (A) with polyhydric alcohol (B), has a hydroxyl value of 5 to 20 OmgKOHZg and a weight average molecular weight in terms of standard polystyrene of 10,000 to 500,000. A polyester, wherein the polycarboxylic acid (A) is selected from alicyclic dicarboxylic acids having a molecular structure in which a carbonyl group is bonded to two mutually adjacent carbon atoms and functional derivatives thereof Polyhydric alcohol (B) 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, respectively. A polyester characterized by containing an alkyl diol.  2. The polyester according to claim 1, having a weight average molecular weight of 10,000 to 300,000. 3. hydroxyl value from 10 to 1501 1: Rei_11 Bruno _§ Dearu Claims paragraph 1 or polyester second Claims.  4. The alicyclic dicarboxylic acid is selected from 1,2-cyclohexane diacid, 3-methyl-hexahydrophthalic acid, 4-methyl-hexahydrofuric acid, and 2,3_norpolnanane-diacid The polyester according to any one of claims 1 to 3, wherein the polyester is a polyester. 5. The functional derivative of an alicyclic dicarboxylic acid is selected from among alicyclic dicarboxylic acid halides, alicyclic dicarboxylic anhydrides, alicyclic dicarboxylic esters and alicyclic dicarboxylic acid salts. Item 5. The polyester according to any one of Items 1 to 4.  6. The cyclic dicarboxylic acid anhydride is 1,2-cyclohexane diacid anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride and 2, 6. The polyester according to claim 5, wherein the polyester is selected from anhydrides of 3-norpolnanodiacid.  7. The polycarboxylic acid (A) is selected from the group consisting of at least one selected from the alicyclic dicarboxylic acids and functional derivatives thereof, based on the total weight of the polycarboxylic acid (A), from 50 to 100% by weight. % Of the polyester according to any one of claims 1 to 6 8. Polyhydric alcohol (B) has two carbon atoms, each with a hydroxyl group Between claim 1 and claim 2.It is a mixture of an alkanediol having a molecular structure in which a carbon atom to which a hydrogen atom is not bonded is sandwiched, and a tetravalent or higher valent alcohol having an ether bond in the molecule. 8. The polyester according to any one of clauses 7.  9. The polyhydric alcohol (B) according to any one of claims 1 to 8, wherein the alkanediol contains 80 to 100% by weight based on the weight of the total polyhydric alcohol (B). Polyester as described.  10. Multivalent carboxylic acid containing 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 a functional derivative thereof (a) And a polyhydric alcohol (b) in the presence of a heteropolyacid.  11. The claim according to claim 10, wherein said dicarboxylic acid and its functional derivative are at least one selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their functional derivatives. Method for producing polyester.  12. The production of the polyester according to claim 10, wherein the dicarboxylic acid and the functional derivative thereof are at least one selected from alicyclic dicarboxylic acids and functional derivatives of alicyclic dicarboxylic acids. Method.  1 3. The alicyclic dicarboxylic acids are 1,2-cyclohexane 'diacid, 3-methyl-hexahydrophthalic acid, 4-methyl-hexahydrophthalic acid and 2,3-norpornane • The method for producing a polyester according to claim 11 or 12, wherein the polyester is selected from diacids.  14. The description of claims 11 or 12 wherein the functional derivative of the alicyclic dicarboxylic acid is selected from among alicyclic dicarboxylic acid anhydrides, octagens, esters and salts. Method for producing polyester.  15. The alicyclic dicarboxylic anhydrides are 1,2-cyclohexane diacid anhydride, 3-methyl-hexahydrofuric anhydride, 4-methyl-hexahydrofuric anhydride and 2, 3. The method for producing a polyester according to claim 14, wherein the polyester is selected from anhydrides of 3 -norpolnandiacid. 16. The polycarboxylic acid (a) contains at least 80% by weight, based on the weight of the total polycarboxylic acid, of at least one selected from the dicarboxylic acids and functional derivatives thereof. The method for producing a polyester according to any one of claims 10 to 15, wherein 17. The polyhydric alcohol (b) contains an alkane diol having a molecular structure in which a carbon atom to which a hydrogen atom is not bonded is sandwiched between two carbon atoms each having a hydroxyl group bonded thereto. 17. The method for producing a polyester according to any one of Items 10 to 16.  18. The polyhydric alcohol (b) is composed of an alkane diol having a molecular structure in which a carbon atom without a hydrogen atom is sandwiched between two carbon atoms each having a hydroxyl group, 17. The method for producing a polyester according to claim 10, which is a mixture with a tetravalent or higher alcohol having an ether bond.  19. The method for producing a polyester according to claim 17, wherein the polyhydric alcohol (b) contains the alkanediol in an amount of 80 to 100% by weight based on the weight of the total polyhydric alcohol.  20. The method for producing a polyester according to any one of claims 10 to 19, wherein the heteropolyacid is at least one member selected from the group consisting of tandustric acid, tandusticaic acid, molybdophosphoric acid, and molybdogeic acid.  21. The use amount of the heteropolyacid is in the range of 50,000 to 10 ppm with respect to the total weight of the polycarboxylic acid component (a) and the polyhydric alcohol (b). Item 21. The method for producing a polyester according to any one of Items 20 to 20.  22. In the polycondensation reaction, at a reaction temperature of 100 to 300, in the presence of an inert gas, the total number of alcoholic reactive groups (X) and the total number of carboxylic acid reactive groups ( 22. The method for producing a polyester according to any one of claims 10 to 21, wherein the ratio (X) Z (Y) (equivalent ratio) to Y) is 1.0 or more.  23. The polyester has a standard polystyrene equivalent weight average molecular weight of 10,000 to 500,000, an acid value of SmgKOHZg or less, a hydroxyl value of 10 to 200 mgKOH / g, and a glass transition temperature (Tg). The method for producing a polyester according to any one of claims 1 to 22, wherein the number is from 10 to 300. 24. A polymer modifier composition comprising the polyester according to any one of claims 1 to 9 as an active ingredient. 25. The polymer according to claim 24, which is in the form of a powder, particles, pellets, a solution dissolved in an organic solvent, a disperse powder dispersed in a poor solvent, or an emulsion prepared using an emulsifier. Modifier composition for use.  26. The method according to claim 24, wherein the content of the polyester in the polymer modifier composition is 1 to 90% by weight based on the weight of the polymer modifier composition. The polymer modifier composition according to the above item.  27. A polymer composition comprising a polymer and the modifier composition for a polymer according to any one of claims 24 to 26.  28. The polymer composition according to claim 27, wherein the polymer composition contains 0.01 to 50 parts by weight of the polyester based on 100 parts by weight of the polymer.  29. The polymer composition according to claim 27, wherein the polymer is an olefin copolymer rubber or an olefin resin.  30. A molded article obtained by molding the polymer composition according to any one of claims 27 to 29.  31. The molded article according to claim 30, which is coated with a synthetic resin paint containing a thermosetting resin as a main component or an adhesive containing a thermosetting resin as a main component.