KR100524692B1 - Polyester, process for the production of the same, resin or rubber compositions containing the same, and moldings of the compositions - Google Patents

Abstract

It is a polyester obtained by condensation polymerization of the polyhydric carboxylic acid component which has aromatic dihydric carboxylic acid as a main component, and the polyhydric alcohol component which has a disturbance glycol as a main component, and has a hydroxyl value of 30 mgKOH / g, and a weight average molecular weight (Mw) is preferable. Preferably 1,000-500,000 polyester. This polyester is suitable for the modification of a resinous or rubbery polymer.

Description

      Polyester, a manufacturing method thereof, a resin or rubber composition containing the same and a molded article of the composition {POLYESTER, PROCESS FOR THE PRODUCTION OF THE SAME, RESIN OR RUBBER COMPOSITIONS CONTAINING THE SAME, AND MOLDINGS OF THE COMPOSITIONS}

The present invention is excellent in compatibility with a dendritic or rubbery polymer, polyester useful for improving the coating property and adhesion of the polymer by adding to a dendritic or rubbery polymer, and a method for producing the same, and a resinous or rubbery polymer And a composition containing the polyester and a molded article of the composition.

Olefin-based rubbers such as olefin resins such as polypropylene and ethylene-propylene copolymer rubbers are widely used because they have excellent physical properties and are relatively inexpensive. However, since there is no polar group in the molecule, there is a disadvantage in that adhesion between the coating film and the adhesive layer is low and practical adhesive strength is difficult to be obtained.

In view of the above disadvantages of olefinic resins, terminal diol compounds of polyether esters obtained by ring-opening polymerization of ethylene glycol with lactones such as polycarbonate diol (JP-A-6-172596) and ε-caprolactone A method of modifying the surface of an olefin resin by adding a modifier such as -116472 has been proposed. However, the method of using these modifiers does not have sufficient compatibility with an olefin resin and a modifier, and also the improvement of paintability is not enough.

In addition, to the above disadvantages of the olefinic rubber, a method of adding polyhydroxypolybutadiene hydrogenated with a double bond of 98% or more (JP-A 57-6462), polyhydroxypolyolefin, etc. A method of adding a hydrocarbon-based polymer having a hydroxyl group (Japanese Patent Application Laid-Open No. Hei 19797534), a method of adding a low molecular polyisoprene in which at least 50% of a double bond is hydrogenated (Japanese Patent Application Laid-Open No. Hei 2-69545) has been proposed. have. However, these methods have the disadvantage that adhesiveness with paint is not enough.

Therefore, in recent years, the present inventors have found that a polyester having a hydroxyl value of 30 mgKOH / g or more composed of a polyhydric carboxylic acid component and a polyhydric alcohol component mainly containing dimer acid of polymerized fatty acid is an olefin resin or the like. It was found that the compatibility with the dendritic polymer was excellent and the coating property could be greatly improved, and a patent application was filed (Japanese Patent Application No. 7-51955). However, polyesters mainly composed of dimer acid of polymerized fatty acids are generally liquid, so that from the field of kneading in a solid state, they have a high softening point and are excellent in compatibility with resins and paintability while being handled in a solid state. Or modifiers of rubbery polymers are desired.

Disclosure of the Invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polyester suitable for improving the paintability and adhesion of a dendritic or rubbery polymer when added to a dendritic or rubbery polymer, and having a high softening point and excellent workability and a method for producing the same. There is.

Another object of the present invention is to provide a molded article of a dendritic or rubbery polymer having improved paintability and adhesion, and a dendritic or rubbery polymer composition used for producing such a molded article.

According to the present invention, an aromatic divalent carboxylic acid or a functional derivative thereof comprises a polyvalent carboxylic acid component comprising 50-100% by weight,

HOCH ₂ -C (R ¹ R ² ) -CH ₂ OH

The hydroxyl value obtained by condensation polymerization with a polyhydric alcohol component in which hindered glycol represented by (wherein R ¹ and R ² represents an alkyl group having 2 to 10 carbon atoms) occupies 40-100% by weight is 30 mgKOH / A modifier for dendritic or rubbery polymers having a polyester of at least g as an active ingredient is provided.

According to the present invention, there is provided a polymer composition comprising a dendritic or rubbery polymer and 0.01-50 parts by weight of the modifier for dendritic or rubbery polymer relative to 100 parts by weight of the dendritic or rubbery polymer.

Moreover, according to this invention, the polyhydric carboxylic acid component which an aromatic divalent carboxylic acid or its functional derivative occupies 50-100 weight%, and General formula (1)

(Formula 1)

HOCH ₂ -C (R ¹ R ² ) -CH ₂ OH

(In formula, R <^1> and R <^2> represents a C2-C10 alkyl group.) It is polyester obtained by condensation polymerization with the polyhydric alcohol component which occupies 40-100 weight% of impaired glycol, and a hydroxyl value is 60 mgKOH / A polyester is provided which is at least g and has a weight average molecular weight (Mw) of 4,000-100,000.

Moreover, according to this invention, the polyhydric carboxylic acid component which an aromatic divalent carboxylic acid or its functional derivative occupies 50-100 weight%, and General formula (1)

(Formula 1)

HOCH ₂ -C (R ¹ R ² ) -CH ₂ OH

(In the formula, R ¹ and R ² represent an alkyl group having 2 to 10 carbon atoms.) A polyester obtained by condensation of a polyhydric alcohol component comprising 40-100% by weight of an impaired glycol, wherein the hydroxyl value is 30 mgKOH / g or more. And the weight average molecular weight (Mw) is 1,000-500,000, and the average number of hydroxyl groups per molecule m is 5 or more, which is defined by the following formula m = (hydroxy group x weight average molecular weight) / (56.1 × 1,000). Polyester to be provided is provided.

Moreover, according to this invention, in the manufacturing method of the polyester which consists of polycondensing a polyhydric carboxylic acid component and a polyhydric alcohol component, aromatic dihydric carboxylic acid or its functional derivative is 50 of polyhydric carboxylic acid. Occupies -100% by weight, and formula (1)

(Formula 1)

HOCH ₂ -C (R ¹ R ² ) -CH ₂ OH

(In formula, R <^1> and R <^2> represents a C2-C10 alkyl group.) The trouble glycol occupies 40-100 weight% of a polyhydric alcohol, and the said aromatic dihydric carboxylic acid component or its functionalities In addition to the derivatives and the impaired glycols, based on the total weight of the polyhydric carboxylic acid component and the polyhydric alcohol component, in 0.1-60% by weight of the trivalent or higher carboxylic acid and its functional derivative and the trivalent or higher alcohol Provided is a method for producing a polyester, wherein the selected at least one trivalent or higher monomer is polycondensed.

Moreover, according to this invention, the molded object which is a molded object of the said polymer composition, and the coating film is formed in the surface is provided.

Best Mode for Carrying Out the Invention

Polyester

The polyester of the present invention comprises a polyhydric carboxylic acid component having an aromatic divalent carboxylic acid or a functional derivative thereof as a main component, and the general formula (1)

(Formula 1)

HOCH ₂ -C (R ¹ R ² ) -CH ₂ OH

(In formula, R <^1> and R <^2> represents an alkyl group and the sum of carbon number of R <^1> and R <^2> is an integer of 3-20.) It is obtained by polycondensing the polyhydric alcohol component which has a disturbance glycol as a main component.

As for the polyhydric carboxylic acid component used by this invention, aromatic dihydric carboxylic acid or its functional derivative occupies 50-100 weight%.

As the aromatic divalent carboxylic acid component, one having an aromatic ring is generally used as a basic skeleton, but is independently aromatic in the form of biphenyl, p-terephenyl, diphenylmethane, triphenylmethane, stilbene, etc. It may have two to three rings in the skeleton, or may be a condensed two to three aromatic rings such as naphthalene, anthracene and phenanthrene, or a five-membered group to an aromatic ring such as indene or tetralin. The other six-membered carbocyclic ring may have a condensed ring. Carbon number of an aromatic ring is generally 8-30, Preferably it is 8-20, More preferably, it is the range of 8-15.

Examples of the functional derivative of the aromatic divalent carboxylic acid include acid halides, acid anhydrides, and esters. Among these, aromatic divalent carboxylic acid esters are preferable, and methyl of aromatic divalent carboxylic acid is preferable. Especially preferred are esters of lower alkyl having 1 to 6 carbon atoms, such as ethyl, propyl, isopropyl, butyl, amyl, hexyl.

The substitution position of the two carboxyl groups is not particularly limited as long as it does not inhibit the polycondensation reaction with the polyhydric alcohol component.

An aromatic divalent carboxylic acid may have a substituent as long as it is a range which does not inhibit the polycondensation reaction with polyhydric carboxyl components other than the said two carboxyl groups. Examples of the substituent include tertiary amino groups substituted with alkyl (lower term means a carbon number in the range of 1-6. The same below) alkyl such as methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, etc .; Nitro group; Cyano group; Carbamoyl groups; Halogen atoms such as fluorine and chlorine; Lower alkyl groups such as methyl, ethyl, propyl, isopropyl and the like; Lower alkoxy groups such as methoxy, ethoxy and the like; And halogenated lower alkyl groups such as trifluoromethyl.

As a preferable specific example of an aromatic divalent carboxylic acid and its functional derivative (henceforth aromatic divalent carboxylic acid and its functional derivative are called "aromatic divalent carboxylic acid monomer"), a terephthalic acid, an isophthalic acid, Naphthalene-2,6-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, ester derivatives thereof, and the like. Among these, terephthalic acid, isophthalic acid and these lower alkyl esters are particularly preferable.

These aromatic divalent carboxylic acid monomers can be used individually or in combination of 2 types or more, respectively.

The proportion of the aromatic divalent carboxylic acid monomer is appropriately selected depending on the purpose of use, but is preferably 50-100% by weight, preferably 70-100% by weight, more preferably 80-100% by weight of the total polyvalent carboxylic acid component. Range. In this range, the softening point is high and suitable.

As the remainder other than the aromatic divalent carboxylic acid monomer in the polyhydric carboxylic acid component, other divalent carboxylic acid monomers (other divalent carboxylic acids or functional derivatives thereof) and 3 used in general polyester synthesis are used. Or more carboxylic acid monomers (trivalent or more carboxylic acids or functional derivatives thereof) can be used without particular limitation.

As "other divalent carboxylic acid monomers", for example, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, pimelic acid, methylmalonic acid, dimethylmalonic acid, sublinic acid, azeraic acid, seba Diacid, brasyl acid, 1,2-cyclohexane, diacid, 1,3-cyclohexane, diacid, 1,4-cyclohexane, diacid, polyalkenylsuccinic acid, dimer acid of polymerized fatty acid (hereinafter, "dimer Acid ”, other divalent carboxylic acids such as hydrogenated dimer acid; And lower alkyl esters thereof. These other divalent carboxylic acid monomers can be used individually or in combination of 2 or more types, respectively.

Examples of the trivalent or higher carboxylic acid monomer include trivalent or higher carboxylic acids such as trimellitic acid, tricarbaric acid, camphoronic acid, trimesic acid, and trimeric acid of polymerized fatty acids, lower alkyl esters thereof, and the like. Can be mentioned.

In the present invention, as the carboxylic acid component, formic acid, acetic acid, butyric acid, 2-methylpropanoic acid, gil acetic acid, isooctyl acid, isononanoic acid, lauric acid, micro You may use together monohydric carboxylic acid, such as a list acid, a palmitic acid, a stearic acid, an isostearic acid, an arakic acid, a linoleic acid, an oleic acid, an oleic acid, and a tolu fatty acid, and ester of these monovalent carboxylic acids. The allowable amount thereof is generally 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less in all the carboxylic acid components.

The polyhydric carboxylic acid component used for this invention contains an obstacle glycol monomer as a main component.

As an obstacle glycol, General formula (1)

(Formula 1)

HOCH ₂ -C (R ¹ R ² ) -CH ₂ OH

What is indicated by is used. Here, R ¹ and R ² each independently represent an alkyl group. Carbon number of an alkyl group becomes like this. Preferably it is the 2-6 range. Moreover, the sum of carbon number of R <^1> and R <^2> is 2-50 normally, Preferably it is 3-20, More preferably, it is 3-10. When carbon number of an alkyl group is this range, it is especially excellent in compatibility with rubber | gum and resin, and coating property, and is suitable. Examples of the alkyl group include ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. Among these, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group are preferable, and ethyl group, propyl Group, butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like are particularly preferable.

Preferred obstacle glycols include, for example, 2,2-dipropyl-1,3-propanediol, 2,2-diisopropyl-1,3-propanediol, 2,2-dibutyl-1,3-propane Diol, 2,2-diisobutyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-propyl-2-pentyl-1,3-propanediol, and the like. Among these, 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 and 2-propyl-2-pentyl-1,3-propanediol are particularly preferred.

These obstacle glycols can be used individually or in combination of 2 types or more, respectively. The amount of the impaired glycol in the polyhydric alcohol component is appropriately selected depending on the purpose of use, but is in the range of 40-100% by weight, preferably 55-100% by weight, more preferably 70-100% by weight of the total amount of polyhydric alcohol component. . If the amount of the obstacle glycol is too small, the compatibility and the paintability of the resin and the rubber deteriorate, which is not preferable.

As the polyhydric alcohol component, it is possible to use other dihydric alcohols and / or trivalent or more alcohols in combination with the obstacle glycol. Examples of the dihydric alcohol include alkanediol, cycloalkanediol, aromatic diol, oligooxyalkylene glycol, polyoxyalkylene glycol, obstacle glycol, and the like. Among these, alkanediol, cycloalkanediol, etc. are preferable, and these dihydric alcohol can be used individually or in combination of 2 or more types, respectively.

As the alkanediol, for example, ethylene glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol , 1,9-nonanediol, and the like.

Among these, alkanediols having 4 to 9 carbon atoms, such as 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, and 1,9-nonanediol are preferable. Do.

Examples of the cycloalkane diol include cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclooctane-1, 4-diol, 2, 6-norbornane diol, etc. are mentioned.

Examples of the aromatic diols include p-xylenediol, 4,4'-methylenediphenyl, 4,4'-dihydroxybiphenyl, 2,5-naphthalenediol, and the like.

As oligooxyalkylene glycol and polyoxyalkylene glycol, what superposed | polymerized the known or mixture of alkylene oxides, such as ethylene oxide, a propylene oxide, butylene oxide, by a well-known method can be used, for example, , Formula 2

HO-((CH ₂ ) _a -CHR ³ O) _b -H

Is displayed. Here, R <^3> represents a hydrogen atom or lower alkyl groups, such as a methyl group and an ethyl group, Preferably it is a hydrogen atom or a methyl group. a represents the integer of 1-6, Preferably it is an integer of 1-4. b represents the integer of 2-100, Preferably it is 2-50, More preferably, it is an integer of 2-25.

Specifically, Oligooxyalkylene glycol, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol; Polyoxyalkylene glycol, such as polyethyleneglycol, polypropylene glycol, polyethylenepropylene glycol, polypropylene glycol, etc. are mentioned.

The trivalent or higher alcohol is not particularly limited as long as it has three or more hydroxyl groups.

As a specific example of a trivalent or more alcohol, Glycerol compounds, such as glycerol, diglycerol, polyglycerol; Sugars such as sorbitol, glucose, mannitol, sucrose, and glucose; Ditrimethylol propane, dipentaerythritol, etc. are mentioned.

Trihydric or higher alcohols,

HOCH ₂ -C (R ⁴ R ⁵ ) -CH ₂ OH

The trivalent or higher impaired glycol represented by can be used. In the formula, each of R ⁴ and R ⁵ independently represents an alkyl group having an alkyl group or a hydroxyl group, and at least one of R ⁴ and R ⁵ is an alkyl group having a hydroxyl group. Here, the carbon number of the alkyl group is not particularly limited, but is generally 1-50, preferably 1-20, more preferably 2-10. Specific examples of the three or more obstacle glycols include trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, and the like. These trivalent or more alcohol components can be used individually or in combination of 2 types or more, respectively.

In the present invention, as the alcohol component, for example, methanol, ethanol, isopropanol, butanol, t-butanol, neopentyl alcohol, 3-methyl-3-pentanol, 3 within a range that does not impair the effects of the invention. Monohydric alcohols such as -ethyl-3-pentanol, 2,3,3-trimethyl-2-butanol, 1-decanol, and nonyl alcohol may be used. This allowable amount is generally 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less in the total alcohol component.

In addition to the aromatic dihydric carboxylic acid monomer and the obstacle glycol, it is preferable to use at least one kind of trivalent or higher monomer selected from trivalent or higher carboxylic acids, functional derivatives thereof, and trivalent or higher alcohols in combination. Not only can the molecular weight and hydroxyl value of the polyester which uses a trivalent or more monomer together be raised sufficiently, but also it can highly balance the compatibility and paintability with resin. The amount of the trivalent or higher monomer is appropriately selected according to the purpose of use, but the total monomer amount in combination of the polyhydric carboxylic acid component and the polyhydric alcohol component is generally 0.1-60% by weight, preferably 0.1-40% by weight, more preferably Is in the range of 1-30% by weight.

When polycondensation of the monomer component, the total number [X] of the alcoholic hydroxyl groups in the total monomers in which the total polyhydric carboxylic acid component and the total alcohol component are combined is carried out under more than the total number [Y] of the carboxylic acid reactive groups. It is preferable because it raises the molecular weight of polyester and also raises a hydroxyl value. The ratio of the total number [X] of the alcoholic hydroxyl group to the total number [Y] of the carboxylic acid reactive group is an equivalent ratio of [X] / [Y], and is generally 1.02 or more, preferably 1.03-3.5, more preferably, It is in the range of 1.04-2.5. Here, as a carboxylic acid reactive group, the carboxylic acid functional group which forms an ester bond is shown, A carboxyl group, ester group, an acid anhydride, etc. are mentioned generally.

The polycondensation reaction may be carried out according to a general method, for example, the reaction temperature is preferably performed at 100-300 ° C, preferably 150-280 ° C, and particularly preferably in the presence of an inert gas. If necessary, a water-insoluble organic solvent azeotropic with water such as toluene and xylene may be used, or the reaction is subjected to reduced pressure (generally 0.1-500 mmHg, preferably 1-200 mmHg, more preferably 10-100 mmHg). You may carry out at.

In the case of esterification condensation polymerization, an esterification catalyst is generally used. As esterification catalyst, For example, Brenstead acid, such as paratoluenesulfonic acid, a sulfuric acid, phosphoric acid polymerization; Organometallic compounds such as calcium acetate, zinc acetate, manganese acetate, zinc stearate, alkyl tin oxide, dialkyl tin oxide, titanium alkoxide; Metal compounds such as tin oxide, antimony oxide, titanium oxide and vanadium oxide; The organometallic compound of group IV of a periodic table is preferable from the viewpoint of the oxidation stability of obtained polyester.

The polyester of this invention is characterized by the high hydroxyl value of this. These hydroxyl values are in the range of 30 mgKOH / g or more, preferably 40-250 mgKOH / g, more preferably 60-200 mgKOH / g. In the case where the hydroxyl value is within this range, the coating property and adhesion are particularly excellent and preferable.

The molecular weight of polyester is suitably selected according to the intended use. Polystyrene reduced weight average molecular weight (Mw), as measured by gel permeation chromatography (GPC), generally in the range of 1,000-500,000, preferably 2,000-300,000, and more preferably 4,000-200,000. If the polyester molecular weight is too small, the adhesion strength of the coating material formed on the surface of the molded article is lowered. On the contrary, if the polyester molecular weight is excessively large, the polyester molecules are difficult to move to the surface of the polymer molded article. Not.

Suitable polyesters that can be used to modify the dendritic polymer have a weight average molecular weight (Mw) of generally 4,000-100,000, preferably 5,000-50,000, more preferably 6,000-40,000, and a hydroxyl value of 60 or more, preferably. Preferably 65-200, more preferably 70-150.

Further, preferred polyesters that can be used for the modification of the rubbery polymer have a weight average molecular weight (Mw) of generally 1,000-500,000, preferably 2,000-300,000, and a hydroxyl value of at least 30 mgKOH / g, preferably 40 -250 mgKOH / g, and also the following formula

m = (hydroxyl × weight average molecular weight) / (56.1 × 1000)

The average hydroxyl number m per molecule represented by is in the range of 5 or more, generally 20-200, preferably 30-150, more preferably 40-100.

The softening point of the polyester is generally excellent in operability when it is in the range of 30 ° C or higher, preferably 30-300 ° C, more preferably 60-200 ° C, most preferably 80-150 ° C.

The polyester of the present invention is preferred because it is oil-soluble and excellent in compatibility with a dendritic or rubbery polymer. The usefulness means that the light transmittance of the polyester solution measured as follows is 70% or more, Preferably it is 80% or more. More preferable light transmittance is 85% or more.

5 g of polyester is put into 95 g of toluene, and it melt | dissolves stirring at 80 degreeC for 1 hour in nitrogen atmosphere, and then cools to room temperature (20 degreeC). This toluene dilution liquid was left to stand in a 20 degreeC constant temperature room for 24 hours, and then stirred again, and the transmittance | permeability is measured by a turbidimeter ("ANA-14S" by Tokyo Photoelectric Co., Ltd.). Tungsten incandescent lamps 6V and 6A are used as light sources, and 20 mm square glass cells are used as cells. The transmittance | permeability of toluene itself used for dilution shall be 100%, and the state which closed the shutter shall be 0%.

Resin / Rubber Modifiers

The modifier of the present invention used for modifying the dendritic polymer or the rubbery polymer may be a polyester as the active ingredient, and, if necessary, a compounding agent generally used as a modifier for the general dendritic or rubbery polymer may be added. Do.

As a compounding agent, Various stabilizers; Natural and synthetic polymer compounds described in Japanese Patent Application Laid-Open No. 7-268046; Fiber reinforcing materials described in Japanese Patent Application Laid-Open No. 7-268046; Iron, chromium, nickel, cobalt or alloys thereof, or oxides thereof; Dimethyl phthalate, diethyl phthalate, dihexyl phthalate, butyl lauryl phthalate, di (2-ethylhexyl) phthalate, dilauryl phthalate, di-n-octyl phthalate, di-n-butyl adipate, diisooctyl adipate, Plasticizers such as di-2-ethylhexyl-4-thioazate, diethyl sebacate, di-n-butyl maleate, diethyl maleate; Ethane oxide, zinc oxide (zinc oxide), lead white, podium, cuprous oxide, yellow iron oxide, iron black, cadmium yellow, molybdenum red, silver wine, sulfur lead Inorganic pigments such as chromium oxide, ultramarine blue, carbon black, barium sulfate, alumina white, white carbon, iron red, thioindigo red, phthalocyanine blue, quinacridone red, quinocphthalo yellow, condensed azo Coloring agents such as organic pigments such as yellow and ultramarine; Dispersants such as calcium stearate and magnesium stearate; Waxes such as polyethylene wax and polypropylene wax; Conductivity giving agents such as ferrite and kerotene black; Antistatic agents such as various surfactants; blowing agent; Crosslinking agents; Nucleating agent; Flame retardant: Various additives, such as oil, are mentioned.

As various stabilizers in the said compounding agent, For example, Antioxidants, such as a phenol type and a sulfur type; Ultraviolet absorbers such as an obstacle amine, benzotriazole and benzoate crab; Etc. can be mentioned.

As the phenolic antioxidant, conventionally known ones can be used, for example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, Japanese Patent Application Laid-Open No. 63-179953, such as 2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenylacrylate; An acrylate compound described in -168643 publication; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 4,4'-butylene-bis (6-t-butyl-m-cresol), 4, 4-thiobis (3-methyl-6-t-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis (2- (3- (3-t -Butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1, 1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,8-tris (3,5-di-t-butyl-4-hydroxy Benzyl) benzene, tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate) methane, triethyleneglycolbis (3- (3-t-butyl Alkyl-substituted phenol compounds such as -4-hydroxy-5-methylphenyl) propionate) and triperol; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6- (4-hydroxy-3,5 -Dimethylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6- (4-hydroxy-3-methyl-5-t-butylanilino) -2,4-bis -Octylthio-1,3,5-triazine, 2-octylthio-4,6-bis (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine, etc. Triazine compounds of; Etc. can be mentioned.

As a sulfur type antioxidant, For example, dilauryl, 3,3'- thiodipropionate, dimyristyl, 3,3'- thiodipropionate, distearyl, 3,3'- thiodi Propionate, laurylstearyl 3,3'-thiodipropionate, pentaerythritol tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl ) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like.

As an obstacle amine ultraviolet absorber, it is 2,2,6,6- tetramethyl-4- piperidyl benzoate, bis (2,2,6,6- tetramethyl-4- piperidyl) seba, for example. Kate, bis (1,2,2, 6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalo Nate, 4- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- (3- (3,5-di-t-butyl-4- And compounds such as hydroxyphenyl) propionyloxy) ethyl-2,2,6,6-tetramethylpiperidine.

As a benzotriazole type ultraviolet absorber, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (3-t- butyl- 2-hydroxy-5-methylphenyl) -5-chlorobenzo Triazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzo And compounds such as triazoles.

As a benzoate type ultraviolet absorber, a 2, 4- di-t- butylphenyl-3, 5-di-t- butyl- 4-hydroxy benzoate, hexadecyl-3, 5- di-t-, for example And compounds such as butyl-4-hydroxybenzoate.

These various stabilizers can be used individually or in combination of 2 or more types, respectively, The compounding quantity is suitably determined in the range which does not impair the effect of this invention.

Dendritic polymer

There is no restriction | limiting in particular as a dendritic polymer which can be modified by the modifier of this invention, A general thermosetting resin and a thermoplastic resin are used, and a suitable thing is a thermoplastic resin. Examples of thermosetting resins include phenol resins, cresol resins, urea resins, melamine resins, alkyd resins, furan resins, unsaturated polyester resins, epoxy resins, urethane resins, and the like, and preferably, unsaturated polyester resins, Epoxy resins and urethane resins. Examples of thermoplastic resins include olefin resins, styrene resins, acrylic resins, phenylene ether resins, ester resins, polycarbonate resins, and general-purpose engineering plastics. Among these, hydrocarbon-based thermoplastic resins such as olefin resins and styrene resins can be cited. In particular, when the olefin resin is used, the improvement effect is most remarkable.

Examples of the olefin resins include homopolymers of α-olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylphenene-1, ethylene and propylene, and other α-olefins. Copolymers of two or more kinds of α-olefins, such as a copolymer of; Etc. can be mentioned. Among these, the (co) polymer which has ethylene and propylene as a main component is especially preferable. Examples of the (co) polymer containing propylene as a main component include copolymers made of polypropylene and at least 50% by weight of propylene, preferably at least 70% by weight, more preferably at least 90% by weight and other α-olefins. As the α-olefin to be copolymerized, ethylene is particularly preferable.

As another olefin resin, For example, Graft copolymer modified olefin resin which graft-copolymerized the (alpha), (beta)-unsaturated carboxylic acid, such as acrylic acid, maleic acid, and its anhydride, to the said olefin resin; Block copolymer-modified olefin resins obtained by block copolymerizing α, β-unsaturated carboxylic acids such as acrylic acid, maleic acid and anhydrides thereof in the olefin resin; Α-olefins such as ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer, ethylene crotonic acid copolymer, ethylene maleic acid copolymer, ethylene acrylic acid copolymer, ethylene methyl acrylate copolymer and ethylene vinyl acetate copolymer Copolymers with other copolymerizable monomers; Etc. can be mentioned.

As the styrene resin, for example, polystyrene, impact polystyrene, styrene-acrylonitrile copolymer, styrene-alkyl (meth) acrylate copolymer, ABS resin, MBS resin, AAS resin, styrene-modified polyester, styrene-butadiene Block copolymer resin, styrene-isoprene block copolymer resin, these hydrides, etc. are mentioned.

Rubber polymer

The rubbery polymer modified with the polyester of the present invention is not particularly limited as long as it is generally used. As a rubbery polymer, For example, Natural rubber; Conjugated diene polymer rubbers such as polyisoprene rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, and chloroprene rubber; Aromatic vinyl-conjugated diene random copolymer rubbers such as styrene-butadiene random copolymer rubber, styrene-isoprene random copolymer rubber, and styrene-isoprene-butadiene random copolymer rubber; Aromatic vinyl-conjugated diene block copolymer rubbers and hydrogenated materials thereof; Copolymer rubbers of conjugated dienes such as acrylonitrile-butadiene copolymer rubber and other copolymerizable monomers; Modified polyethylene rubbers such as chlorinated polyethylene rubber and chlorosulfonated polyethylene rubber; Olefin copolymer rubbers and modified compounds thereof, acrylic rubbers, silicone rubbers, fluorine rubbers, and the like, but among them, aromatic vinyl-conjugated diene block copolymer rubbers and their hydrogenated materials, modified polyethylene rubbers, and olefin copolymers. Rubber, a modified product thereof, and silicone rubber are preferable, and olefin copolymer rubber is particularly preferable.

As the olefin copolymer rubber, for example, a polymer containing α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene and 4-methyl-1-pentene Although it will not restrict | limit especially if it is an amorphous polymer, For example, the copolymer rubber of 2 or more types of alpha-olefins, the copolymer rubber of alpha-olefin and another polymerizable monomer, etc. are mentioned. The amount of α-olefin in the copolymer rubber is not particularly limited, but is generally in the range of 50% by weight or more, preferably 60-100% by weight, more preferably 80-100% by weight. Although it does not specifically limit as another polymerizable monomer, For example, a conjugated diene and a nonconjugated diene compound are mentioned, A nonconjugated diene compound is preferable.

Examples of the non-conjugated diene compound include ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, and among these, ethylidene norbornene is preferable. Content in the copolymer of these polymerizable monomers is 40 weight% or less normally, Preferably it is 30 weight% or less, More preferably, it is 20 weight% or less.

Specific examples of the olefin copolymer rubber include ethylene-propylene copolymer rubber, ethylene-butene-1 copolymer rubber, propylene-butene-1 copolymer rubber, ethylene-propylene-conjugated diene copolymer rubber, and isobutylene- Conjugated diene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, and the like. Among them, butyl rubber (IIR) obtained by copolymerizing isoprene with isoprene in 0.5-5 mol%, ethylene and propylene, As the ethylidene norbornene, copolymerized ethylene-propylene-diene copolymerized rubber (EPDM) is preferable.

As an olefin copolymer rubber modified body, what modified the said olefin copolymer rubber with the polar compound is mentioned. Specifically, for example, a polar compound graft obtained by graft polymerization of a chlorinated olefin copolymer rubber, a sulfonated olefin copolymer rubber, and a polar vinyl compound obtained by addition reaction of a polar vinyl compound to an olefin copolymer rubber. Polymers; and the like; Preferably, chlorinated olefin copolymer rubbers; Chloride sulfonates of olefin copolymer rubbers and polar vinyl compound adducts of olefin copolymer rubbers. As a polar vinyl compound, acrylic acid, methacrylic acid, crotonic acid, maleic acid (acid anhydride), acrylic acid ester, vinyl acetate etc. are mentioned, for example.

These dendritic or rubbery polymers can be used individually or in combination of 2 or more types, respectively. The amount of the polyester added to the dendritic or rubbery polymer may be appropriately selected depending on the purpose and purpose, but is generally 0.01-50 parts by weight, preferably 0.1-30 parts by weight based on 100 parts by weight of the dendritic or rubbery polymer. Part, More preferably, it is the range of 1-25 weight part.

Polymer composition

The polymer composition in which the polyester of the present invention is blended with the resinous or rubbery polymer is mixed according to the general method, by combining the inorganic filler and the other compounding agent as necessary, and adding each component simultaneously or separately. It can be obtained by. As a method of separately adding each component, it is a method of (1) mixing a dendritic or rubbery polymer and the modifier for dendritic or rubbery polymers of this invention, and then adding and mixing an inorganic filler and another compounding agent, (2) After adding the dendritic or rubbery polymer or other compounding agent, a method of adding and mixing the modifier for dendritic or rubbery polymer of the present invention may be mentioned, and any method may be employed.

As a mixing method of a polymer composition, it should follow a general method, For example, after mixing using a Henschel mixer etc., it is an extruder, such as a single screw extruder and a twin screw extruder, Bunbury, a burrenda, a pressed mill. And kneading using a calendar, kneader, roll, extruder, multi-axis kneader, double spiral ribbon stirrer and the like.

As the inorganic filler to be blended, for example, calcium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, potassium sulfite, mica, dolomite, silica , Clay, talc, carbon black, zinc oxide, glass fibers, carbon fibers, and the like. Among these, potassium carbonate, talc, carbon black and the like are particularly preferable.

In this invention, the surface-treated inorganic filler is used especially suitably. As a specific example of surface treatment, a conventionally well-known thing may be sufficient, For example, what processed with the silane type and the titanium-type coupling agent, acids, such as a higher fatty acid and an unsaturated organic acid, etc. are mentioned. The particle diameter of the inorganic filler is not particularly limited, but an average particle diameter of generally 5 μm or less is used.

These inorganic fillers can be used individually or in combination of 2 types or more, respectively. The amount to be used is appropriately selected depending on the purpose of use, but is generally in the range of 1-200 parts by weight, preferably 2-100 parts by weight, more preferably 5-50 parts by weight, based on 100 parts by weight of the dendritic or rubbery polymer. .

As a compounding agent other than an inorganic filler, the same thing as the compounding agent of the said modifier for dendritic or rubbery polymers is mentioned. As another compounding agent, various additives, such as a vulcanization accelerator, a vulcanization adjuvant, and a dehydrating agent, can be added to a rubbery polymer individually or in combination, for example. These addition amount is suitably determined within the range which does not impair the effect of this invention.

As a vulcanizing agent, sulfur type vulcanizing agents, such as sulfur, morpholine, and disulfide, peroxide type vulcanizing agents, such as dicumyl peroxide and di-t- butyl peroxy diisopropyl benzene, etc. are mentioned, for example. These vulcanizing agents can be used individually or in mixture of 2 or more types, respectively. The amount of use is generally 0.1-20 parts by weight, preferably 0.5-10 parts by weight, more preferably 1-5 parts by weight with respect to 100 parts by weight of the rubbery polymer.

Examples of the vulcanization accelerators include vulcanization accelerators such as mercaptobenzothiazole, dimethyldithiocarbamic acid zinc, and tetramethyllithium sulfide. These amounts of use are generally 0.1-10 parts by weight, preferably 0.5-5 parts by weight, more preferably 1-3 parts by weight per 100 parts by weight of the rubbery polymer.

Molded body

By molding the polymer composition according to a general method, it is possible to obtain a polymer molded article having improved coating adhesion as well as coating property of the surface of the molded article. As the molding method, for example, any known method such as injection molding, blow molding, extrusion molding, compression molding, rotational molding, or the like may be used, and arbitrary moldings may be used.

Moreover, when manufacturing a vulcanized rubber molded object in this invention, it is possible to manufacture by the method generally performed by the rubber industry. For example, (1) after adding the above-mentioned components other than a vulcanizing agent to a banbury, a blowbender, etc. and knead | mixing at 60 degreeC-150 degreeC for 5 minutes-30 minutes, (2) transferring a kneaded material to a roll, After kneading with addition of a vulcanizing agent, (3) it can be obtained by heating and molding with a molding machine such as an extruder. As the vulcanizing method, a method of pressurizing and heating by a press, a method of heating by heating air in an oven, a method of heating by high frequency (UHF), or the like can be adopted. As heating conditions, 0.05-5 hours at 100-250 degreeC is suitable.

In this invention, the polymer coating molded object excellent in coating-film strength and solvent resistance is obtained by coating the surface of the said polymeric molded object.

The paint to be applied is not particularly limited as long as it is a paint used in industrial general. For example, a solvent-type thermoplastic (meth) acrylic paint, a solvent-type thermosetting ((meth) acrylic paint, an acrylic modified alkyd paint, and an epoxy-based paint Paints, acrylic urethane paints, silicone modified urethane paints, polyurethane paints, alkyd melamine paints, polyethermelamine paints, polyester melamine paints, amine alkyd paints, and the like. Acryl urethane paints, polyurethane paints, alkyd melamine paints, polyester melamine paints, and polyethermelamine paints are particularly preferred, and polyurethane paints, polyester melamine paints and polyethermelamine paints.

Coating to the coating molded body can be performed directly on the surface of the polymer molded body or after degreasing treatment such as hot water washing and / or primer treatment, if necessary. As the coating method of the coating material, a general method may be used. For example, methods such as electrostatic coating, air spray coating, hakake coating, roller coating, and the like are used. The application of these paints may be performed by applying the upper side after applying the lower side. As a coating film hardening method after coating application, it selects suitably according to the material, shape of a molded object, the property of a paint, etc., for example, by natural drying, heat hardening, such as nichrome wire, infrared rays, and high frequency (UHF) heating. It hardens | cures and a coating film is formed.

The thickness of the paint can be varied depending on the purpose of use of the molded article, and there is no particular limitation, but in general, after drying, from 1 micron to 500 microns, preferably from 5 microns to 300 microns, and particularly preferably from 10 microns to 200 microns. Range.

Moreover, in this invention, the adhesiveness of the said polymer body surface is improved, and various adhesive agents are applied. Examples of the adhesive used include (water-based and non-aqueous) epoxy adhesives, (water-based and non-aqueous) urethane-based adhesives, (water-based and non-aqueous) acrylic adhesives, cyanoacrylate-based instant adhesives, and the like. Preferably, they are (aqueous, non-aqueous) epoxy clock adhesives, and (water, non-aqueous) urethane adhesives.

As an application means of the adhesive to the molded body, for example, a method such as spatula application, air spray application, Hake application, application by roller, or the like is used. The curing method after application of the adhesive is appropriately selected depending on the material, shape of the molded article, the properties of the paint, and the like. For example, natural drying, drying by heating and drying such as nichrome wire, infrared ray, and high frequency heating is dried. And an adhesive layer is formed.

The thickness of the adhesive layer may vary depending on the purpose of use of the molded article, and there is no particular limitation, but in general, after adhesion, from 1 micron to 2000 microns, preferably from 3 microns to 1000 microns, and particularly preferably from 5 microns to 500 microns Range.

Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. Parts and percentages in these examples are based on weight unless otherwise specified. The properties of the polyester and the properties of the molding quality film are evaluated by the following method.

(1) weight average molecular weight

The weight average molecular weight of polyester was computed as a standard polystyrene conversion amount according to the GPC method.

(2) hydroxyl value and acid value

The hydroxyl value and acid value of polyester were measured according to the following as described in the "standard maintenance analysis method" (Japan Chemical Association).

Hydroxyl 2, 4, 9, 2-83

Acid number 2, 4, 1-83

(3) Softening point

The softening point of polyester was measured in accordance with the round ball method specified in JIS-K2531.

(4) Compatibility with resins and appearance

After molding, the molded body surface was visually observed and evaluated as the following criteria.

A: No delamination is recognized

B: The delamination is recognized

(5) Adhesion of rubber surface

(A) Peel strength

After gauze is adhered to the coating surface with a momentary adhesive, and blanked in a 1 cm width of a single step, the rubber and the ends of the gauze are stretched in the direction of 180 ° at a speed of 200 mm / min, and the maximum peel strength (kgf) / cm) was measured.

(B) Adhesiveness (checkerboard test)

The process is performed in accordance with JIS K5400. 11 cuts are made orthogonal at intervals of 1 mm with a load of 350 kg on the coating surface, and 100 checkerboards are made per 1 cm 2, and a pressure roller of 18 mm in width is pressed under a load of 1300 kg using a pressing roller. Then, a peeling test was carried out to peel at a peel angle of 180 °, and the number of checkerboards not peeled out of the checkerboard 100 was expressed as an adhesion rate (%).

(6) adhesion of the coating film on the resin surface

(A) Adhesiveness (checkerboard test)

In accordance with the test method described in JIS K5400, a test piece with a checkerboard is prepared, and a cellophane (manufactured by Nichi-San) is adhered on the checkerboard, and then it is quickly stretched in the 90 ° direction to peel off, and the checkerboard The number of non-peeling checkerboard eyes in 100 eyes was measured.

(B) solvent resistance

After cutting the sample cut out to 15 x 30 mm in size from the coating molding, it was immersed in 23 degreeC plastic hole (gasoline / ethanol = 90/10 volume ratio), and time (minute) until the coating film partially peeled was measured. .

Preparation Example 1

In a 2000cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a fountain tube and a nitrogen gas introduction tube, 800 g of terephthalic acid, 770 g of 2-butyl-2-ethyl-1,3-propanediol, and petaneryte 72.7 g of lithol and 0.80 g of monobutyltin oxide were added as a catalyst (OH / COOH equivalence ratio = 1.21).

The mixture was stirred while introducing nitrogen gas, and the reaction was carried out at 220 ° C. for 3 hours while removing water generated during the reaction, and then the reaction was continued at 240 ° C. for 6 hours. The reaction was continued at 240 ° C. after dehydration under reduced pressure of 200 mmHg, followed by removal of unreacted diol under reduced pressure of 50 mmHg. The obtained polyester polyol A had a weight average molecular weight of 44,020, an acid value of 0.35 mgKOH / g, a hydroxyl value of 66 mgKOH / g, a hydroxyl number of 52, a softening point of 105 ° C, and a light transmittance of 92% per molecule.

Preparation Example 2

In a 2000cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a fountain tube, and a nitrogen gas introduction tube, 800 g of isophthalic acid, 734.8 g of 2-butyl-2-ethyl-1,3-propanediol, and pentaerythritol 69.4 0.80 g of monobutyltin oxide was added as a g and a catalyst (OH / COOH equivalence ratio = 1.16).

The mixture was stirred while introducing nitrogen gas, and the reaction was continued at 240 ° C. for 3 hours while removing water generated during the reaction, followed by 240 ° C. for 6 hours. The reaction was continued for 2 hours while dehydrating under reduced pressure of 200 mmHg at 240 ° C. and then removing unreacted diol under reduced pressure of 50 mmHg. The obtained polyester polyol B had a weight average molecular weight of 61,600, an acid value of 0.38 mgKOH / g, a hydroxyl value of 38 mgKOH / g, a hydroxyl number of 42, a softening point of 101 ° C, and a light transmittance of 89% per molecule.

Preparation Example 3

In a 3000cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, fountain tube and nitrogen gas introduction tube, 1200 g of terephthalic acid, 1090.2 g of 2-butyl-2-ethyl-1,3-propanediol, and 303.2 g of pentaerythritol And 1.20 g of monobutyltin oxide was added as a catalyst (OH / COOH equivalence ratio = 1.27).

The mixture was stirred while introducing nitrogen gas, and the reaction was continued at 220 ° C. for 3 hours while removing water generated during the reaction for 6 hours at 340 ° C. Thereafter, dehydration was carried out at 240 ° C. under reduced pressure of 300 mmHg, and the reaction was continued for 2 hours while removing unreacted diol under reduced pressure of 50 mmHg. The obtained polyester polyol C had a weight average molecular weight of 40,290, an acid value of 0.25 mgKOH / g, a hydroxyl value of 86 mgKOH / g, a hydroxyl number of 62 per molecule, a softening point of 102 ° C, and a light transmittance of 93%.

Preparation Example 4

In a 2000cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, fountain tube and nitrogen gas introduction tube, 800 g of terephthalic acid, 612.2 g of 2,2-diethyl-1,3-propanediol, 70.7 g of pentaerythritol, and 1.10 g of monobutyltin oxide was added as a catalyst (OH / COOH equivalence ratio = 1.18).

The mixture was stirred while introducing nitrogen gas, and the reaction was continued at 220 ° C. for 3 hours while removing the water generated during the reaction. The reaction was continued at 240 ° C. for 6 hours. Thereafter, dehydration was performed at 240 ° C. under reduced pressure of 200 mmHg, and the reaction was continued for 2 hours while removing unreacted diol under reduced pressure of 50 mmHg. The obtained polyester polyol D had a weight average molecular weight of 49,560, an acid value of 0.45 mgKOH / g, a hydroxyl value of 75 mgKOH / g, a hydroxyl number of 66, a softening point of 107 ° C, and a light transmittance of 90% per molecule.

Preparation Example 5

In a 2000cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, fountain tube and nitrogen gas introduction tube, 800 g of terephthalic acid, 825.9 g of 2-butyl-2-ethyl-1,3-propanediol, 123.8 g of glycerol and a catalyst 0.20 g of monobutyl tin oxide was added (OH / COOH equivalent ratio = 1.44).

While the mixture was stirred while introducing nitrogen gas, the temperature was raised from 220 ° C to 240 ° C over 6 hours while removing water and unreacted diols generated during the reaction. The reaction was then continued for 3 hours while dehydrating at 50C Hg under reduced pressure at 240 ° C. The obtained polyester polyol E had a weight average molecular weight of 13,200, an acid value of 0.35 mgKOH / g, a hydroxyl value of 108 mgKOH / g, a hydroxyl number of 25, a softening point of 85 ° C, and a light transmittance of 95% per molecule.

Example 1-4, Comparative Example 1

Using polyesters A, B, C and E prepared above, rubber compositions were prepared according to the formulation formulation shown in Table 1. Each component other than sulfur and a vulcanization accelerator was kneaded at 60 DEG C for 5 minutes with a 0.81 Bunbury mixer, and then sulfur and a vulcanization accelerator were added with a 6 inch roller and kneaded at 60 DEG C. The sheet-like unvulcanized rubber was taken out from the roller. And comparative example-1 of Unexamined-Japanese-Patent No. 7-150074 on the surface, using the 20-mm (3) extruder (made by Dongyang Chemical Co., Ltd., die temperature 60 degreeC, cylinder temperature 50ψ, rotor rotation speed 40rpm), and extruding it to flat form. Glass coating was applied so as to have a thickness of 100 µm with hair hair. The coated plate was subjected to simultaneous vulcanization of the rubber and softening of the paint in a gear oven at 180 ° C. for 18 minutes to prepare a test piece.

The adhesion strength of the obtained coating product was measured. The test piece was created similarly and evaluated similarly except not using polyester (i) as a comparative example. The results are shown in Table 1.

Example Comparative example Example One 2 3 One 4 Rubber EPDM * 1 Carbon Black (Sist 116) * 2 Oil (Dynamic Process PW380) * 3 Zincation # 1 Stearic Acid Dehydrant (Besta PP) * 4 10014060516 10014060516 10014060516 10014070516 10014060516 Sulfur (325) Vulcanization Accelerator MBT * 5 MBTS * 6 TMTD * 7 DPPTT * 8 1.001.001.000.750.50 1.001,001,000.750.50 1.001.001.000.750.50 1.001.001.000.750.75 1.001.001.000.750.50 Polyester A10 B10 C10 ----- E10 Adhesive Strength (kgf / cm) * 9 1.2A 1.2A 1.1A 0.2B 0.8 A

* 1 3070 made by Samjung Petrochemical Co., Ltd.

* 2 East Sea carbon company

* 3 Manufactured by Gwangkwang Heungsan

* 4 Manufacture of normal lime

* 5 2-mercaptobenzothiazole

* 6 dibenzothiazole disulfide

* 7 tetramethylthiuram disulfide

* 8 dipentamethylene thiuram tetrasulfide

* 9 The peeling condition was observed after the peeling test was performed, and the surface-broken state A was marked as A, and the surface peeled as B.

Example 5-8, Comparative Example 2

Using the polyesters A, B, D and E prepared above, rubber compositions were prepared according to the formulation formulation shown in Table 2. Moreover, the thing which did not add polyester for comparison was prepared (comparative example). Each component other than the sulfur and the vulcanization accelerator was kneaded at 60 DEG C for 5 minutes with a 0.81 Bunbury mixer, and then sulfur and the vulcanization accelerator were added as a 6 inch roller and kneaded at 60 DEG C. The sheet-like unvulcanized rubber was taken out from the roller, and it vulcanized at 160 degreeC x 15 minutes and 100 kg / cm <2> using the press, and obtained the vulcanized rubber sheet of 150x80x2mm.

Cut the vulcanized rubber sheet into 75 × 80 × 2 mm, apply an epoxy adhesive (bond MOS1010 manufactured by Konishi Co., Ltd.) to a thickness of 300 μm, dry it at 60 ° C. for 2 hours, and leave it for 96 hours. Was written.

The peeling strength test of the obtained test piece was done. The results are shown in Table 2.

Example Comparative example Example 5 6 7 2 8 Rubber EPDM 1060 * 9 Carbon Black (Cist 116) * 2 Oil (Dynamic Process PW380) * 3 Zincation # 1 Stearic Acid Heavy Calcium Carbonate 10050605160 10050605160 10050605160 10050705160 10050605160 Sulfur (325) Vulcanization Accelerator MBT * 5 MBTS * 6 TMTD * 7 DPTT * 8 1.001.001.000.750.50 1.001,001,000.750.50 1.001.001.000.750.50 1.001.001.000.750.75 1.001.001.000.750.50 Polyester A10 B10 D10 ----- E10 Adhesion strength (kgf / cm) 1.0 1.1 1.1 0.1 0.4

* 1 3070 manufactured by Samjung Petrochemical

* 2 Donghae carbon company

* 3 Manufacture of Kwangkwang Heungsan

* 4 Manufacture of normal lime

* 5 2-mercaptobenzothiazole

* 6 dibenzothiazole disulfide

* 7 tetramethylthiuram disulfide

* 8 dipentamethylene thiuram tetrasulfide

* 9 Manufactured by Samjeong Petrochemical

Examples 9 and 10 and Comparative Example 3

After mixing each raw material with the Henschel mixer by the formulation shown in Table 3, melt-kneading was carried out by the twin screw extruder set to 220 degreeC, and it pelletized to produce the polymer composition.

And the test piece used for coating-film adhesiveness test was created as follows. A primer (50 * 80mm, 3.1mm thickness) was applied to the test piece by injection molding so that a primer (manufactured by Nippon-Bio Chemical Co., Ltd., brand name: RB-197) was applied to a film thickness of 10 µm, and dried at 80 ° C for 10 minutes, and then the primer surface Urethane-based metal paints (manufactured by Nippon-Bik Chemical Co., Ltd., brand name: RB-212) and urethane-based clear paints (manufactured by Nippon-Bik Chemical Co., Ltd., brand name: RB-288) were prepared based on the designation method of Nippon-Bik Chemical Co., Ltd. It apply | coated so that it might become 20 micrometers and 25 micrometers, respectively, and after drying at 80 degreeC for 45 minutes, it was left to stand for 24 hours and the test piece was obtained.

The adhesion strength of the obtained coating product was measured. The results are shown in Table 3.

Example Comparative example 9 circulation 10 circulation 3 circulation Inorganic inorganic filler PP * 1EPR * 2Talc * 3 751210 PP * 1EPR * 2Talc * 3 751210 PP * 1EPR * 1Talc * 3 751510 Polyester A 3 C 3 - - Checkerboard 100/100 100/100 30/100

* 1 J 3050HP (manufactured by Kwang Petrochemical Co., Ltd.) MFR = 42

* 2 EP02 (made by Nippon Synthetic Rubber) MFR = 3.2

* 3 MicroS P4 (manufactured by Nippon Talc Co., Ltd.), average particle size 1.5 μm

Preparation Example 6

In a 500 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a fountain tube and a nitrogen gas introduction tube, 166.2 g of terephthalic acid, 181.1 g of 2-butyl-2-ethyl-1,3-propanediol, and pentaerythritol 34.2 0.17 g of tetrabutoxy titanate was added as a g and a catalyst (OH / COOH equivalence ratio = 1.50).

The temperature was raised over 160 hours from 160 degreeC to 240 degreeC, stirring, introducing nitrogen gas, and removing the water and unreacted diol produced | generated during reaction. Thereafter, the reaction was continued for 4 hours while dehydration was performed at 240 ° C. under a reduced pressure of 50 mmHg. The obtained polyester F had a weight average molecular weight (Mw) of 7130, an acid value of 0.15 mgKOH / g, a hydroxyl value of 93.5 mgKOH / g, a hydroxyl number of 12 per molecule, and a softening point of 81 ° C.

Preparation Example 7

In a 500cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a fountain tube and a nitrogen gas introduction tube, 194.2 g of dimethyl terephthalate, 170.5 g of 2-butyl-2-ethyl-1,3-propanediol, and pentaerythritol 36.1 g and 0.24 g of manganese acetate tetrahydrate and 0.29 g of antimony trioxide were added as a catalyst (OH / COOH equivalence ratio = 1.38).

The temperature was raised over 160 hours from 160 degreeC to 240 degreeC, stirring, introducing nitrogen gas, and removing methanol and unreacted diol produced | generated during reaction. Thereafter, the reaction was continued for 6 hours while dealcoholization was performed at 240 ° C. × 50 mmHg. The obtained polyester G had a weight average molecular weight (Mw) of 11400, the acid value of 0.15 mgKOH / g, the hydroxyl value of 81.6 mgKOH / g, the number of hydroxyl groups 17 per molecule, and the softening point of 89 ° C.

Preparation Example 8

In a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, fountain tube and nitrogen gas introduction tube, 388.4 g of dimethyl isophthalate, 264.6 g of 2,2-diethyl-1,3-propanediol, trimethylolpropane 67.2 g and 0.20 g of monobutyltin oxide were added as a catalyst (OH / COOH equivalence ratio = 1.37).

The temperature was raised over 160 hours from 160 degreeC to 240 degreeC, stirring, introducing nitrogen gas, and removing methanol and unreacted diol produced | generated during reaction. Thereafter, the reaction was continued for 3 hours while dealcoholization was performed at 240 ° C. × 50 mmHg. The obtained polyester H had a weight average molecular weight (Mw) 6830, an acid value of 0.15 mgKOH / g, a hydroxyl value of 83.2 mgKOH / g, a hydroxyl number of 10 and a softening point of 76 ° C per molecule.

Preparation Example 9

In a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, fountain tube and nitrogen gas introduction tube, 291.4 g of terephthalic acid, 213.8 g of 2-butyl-2-ethyl-1,3-propanediol, and 45.3 pentaerythritol 0.20 g of monobutyltin oxide was added as a g and a catalyst (OH / COOH equivalence ratio = 1.32).

The temperature was raised over 160 hours from 160 degreeC to 240 degreeC, stirring, introducing nitrogen gas, and removing the water and unreacted diol produced | generated during reaction. After that, the reaction was continued for 8 hours while dehydration was carried out under a reduced pressure of 240 ° C. × 50 mmHg. Obtained polyester I had a weight average molecular weight (Mw) of 19200, an acid value of 0.15 mgKOH / g, a hydroxyl value of 83.2 mgKOH / g, a hydroxyl number of 29 per molecule, and a softening point of 90 ° C.

Preparation Example 10

In a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, fountain tube, and nitrogen gas introduction tube, 388.4 g of dimethyl terephthalate, 377.2 g of 2-butyl-2-ethyl-1,3-propanediol, and trimethylolpropane 35.0 g and 0.20 g of monobutyltin oxide were added as a catalyst (OH / COOH equivalence ratio = 1.32).

The temperature was raised over 160 hours from 160 degreeC to 240 degreeC, stirring, introducing nitrogen gas, and removing methanol and unreacted diol produced | generated during reaction. Thereafter, the reaction was continued for 2 hours while dealcoholization was performed under a reduced pressure of 240 ° C. × 50 mmHg. Polyester J thus obtained had a weight average molecular weight (Mw) of 5040, an acid value of 0.15 mgKOH / g, a hydroxyl value of 66.2 mgKOH / g, a number of hydroxyl groups of 6 molecules, and a softening point of 71 ° C.

Preparation Example 11

In a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, fountain tube and nitrogen gas introduction tube, 388.4 g of dimethyl isophthalate, 387.1 g of 2,2-diethyl-1,3-propanediol and mono as catalyst 0.20 g of butyltin oxide was added (OH / COOH equivalence ratio = 1.25).

The temperature was raised over 160 hours from 160 degreeC to 240 degreeC, stirring, introducing nitrogen gas, and removing methanol and unreacted diol produced | generated during reaction. Thereafter, the reaction was continued for 2 hours while dealcoholization was performed at 240 ° C. × 50 mmHg. Polyester K thus obtained had a weight average molecular weight (Mw) of 4140, an acid value of 0.15 mgKOH / g, a hydroxyl value of 53.6 mgKOH / g, a hydroxyl number of 4 per molecule, and a softening point of 56 ° C.

Preparation Example 12

In a 500 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a fountain tube, and a nitrogen gas introduction tube, 194.2 g of methyl terephthalate, 225.8 g of 2-butyl-2-ethyl-1,3-propanediol and acetic acid as a catalyst 0.24 g of manganese tetrahydrate and 0.29 g of antimony trioxide were added (OH / COOH equivalence ratio = 1.40).

The temperature was raised over 160 hours from 160 degreeC to 240 degreeC, stirring, introducing nitrogen gas, and removing methanol and unreacted diol produced | generated during reaction. Thereafter, the reaction was continued for 2 hours while dealcoholization was performed under a reduced pressure of 240 ° C. × 50 mmHg. Obtained polyester L had a weight average molecular weight (Mw) of 2100, an acid value of 0.15 mgKOH / g, a hydroxyl value of 103.1 mgKOH / g, and a softening point of 36 ° C.

Production Example 13 (Preparation of Comparative Example Polyester)

In a 500 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a fountain tube and a nitrogen gas introduction tube, 194.2 g of methyl terephthalate, 147.8 g of 1,6-hexanediol, 0.24 g of manganese acetate and tetrahydrate as a catalyst, trioxide 0.29 g of antimony was added (OH / COOH equivalence ratio = 1.25).

The temperature was raised over 160 hours from 160 degreeC to 240 degreeC, stirring, introducing nitrogen gas, and removing methanol and unreacted diol produced | generated during reaction. Thereafter, the reaction was continued for 3 hours while the dealcoholization was performed under a reduced pressure of 240 ° C. × 50 mmHg. The polyester M thus obtained had a weight average molecular weight (Mw) of 4430, an acid value of 0.15 mgKOH / g, a hydroxyl value of 50.6 mgKOH / g, a number of hydroxyl groups per molecule, and a softening point of 66 ° C.

Examples 11-17, Comparative Examples 4 and 5

In the formulations shown in Table 4, each raw material was mixed with a Henschel mixer, followed by melt kneading with a twin screw extruder (ZE40A manufactured by Bellstall; 1340 mm in total length, L / D = 33.5) set at 220 ° C., and pelletized. To prepare a resin composition. Next, each pellet-like resin composition was 150 × 150 mm using an injection molding machine (F85 manufactured by Crock Company) under conditions of a mold temperature of 45 ° C., a nozzle temperature of 210 ° C., an injection pressure of 550 kg / cm 2 and a holding pressure of 450 kg / cm 2. , A test piece having a thickness of 2.4 mm was made. At that time, the delamination of the surface of the injection molded article was observed, the compatibility between the resin and the polyester was evaluated, and the results are shown in Table 4.

Next, a primer (manufactured by Nippon-Bio Chemical, trade name: RB-197) was applied on the surface of the test piece so as to have a film thickness of 10 μm, and dried at 80 ° C. for 10 minutes, and then a urethane-based metal paint (Japan non-Japanese) Chemical company, brand name: RB-212) and urethane clear paint (Japanese non-chemical company, brand name: RB-288) were prepared based on the designation method of the Japanese chemical company, and the film thickness of 20 micrometers, 25 micrometers was respectively The layer was applied in two layers, dried at 80 ° C. for 45 minutes, and left for 24 hours. The coating film characteristics were tested using the obtained test piece, and the result is shown in Table 4.

Example Comparative example 11 12 13 14 15 16 17 4 5 Composition (part) Polypropylene * 1 Talc * 2 Polyester F polyester G polyester H polyester I polyester J polyester K polyester L polyester M 87103 ------- 8710-3 ------ 8710--3 ----- 8710 --- 3 ---- 8710 ---- 3 --- 8710 ----- 3-- 8710 ------ 3- 8710 ------- 3 9010 -------- Compatibility Coating Strength Solvent Resistance (Min) A100> 60 A100> 60 A100> 80 A100> 60 A9040-50 A8030-40 A5010-20 B * 3 * 3 A10 <5

* 1 J-3050HP (manufactured by Kwang Petrochemical Co., Ltd.)

* 2 micro PS P-4 (average particle size 1.5㎛; manufactured by Nippon Talc Co., Ltd.)

* 3 Not measurable

From the results in Table 4, the inventive examples incorporating the polyester FJ of the present invention (Examples 11-15) are excellent in any of the paintability properties such as compatibility with resins, coating film strength and solvent resistance. It can be seen that the paintability and adhesion are further improved when the polyester FI of 70 mgKOH / g or more is used (Example 11-14). On the other hand, the use of polyesters K and L having a low molecular weight or small hydroxyl value results in a small degree of improvement in coating properties (Examples 16-17), and the use of polyester M which does not contain impaired glycol as a component It is understood that the compatibility and adhesiveness of the film are inferior to any of the properties (comparative example 4).

Preparation Example 14

In a 500cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a fountain tube and a nitrogen gas introduction tube, 358.8 g of terephthalic acid, 348.1 g of 2-ethyl-2-butyl-1,3-propanediol and 73.8 pentaerythritol 0.26 g of monobutyltin oxide was added as a g and a catalyst (OH / COOH equivalence ratio = 1.25).

The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Subsequently, the temperature was raised from 180 ° C to 240 ° C over 3 hours while removing water and unreacted diols generated during the reaction. Then, reaction was continued for 5 hours, dehydrating at 240 degreeC, and reaction was performed for 3 hours under reduced pressure of 50 mmHg last. The polyester W thus obtained had a weight average molecular weight (Mw) of 10,200, an acid value of 0.3 mg KOH / g, and a hydroxyl value of 88.9 mg KOH / g.

Preparation Example 15

In a 500cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, fountain tube and nitrogen gas introduction tube, 358.8 g of terephthalic acid, 278.2 g of 2-ethyl-2-butyl-1,3-propanediol, and neopentyl glycol 45.2 73.8 g of pentaerythritol and 0.26 g of monobutyltin oxide were added as a catalyst (OH / COOH equivalence ratio = 1.25).

The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Then, temperature was raised over 180 hours from 180 degreeC to 240 degreeC, removing methanol and unreacted diol produced | generated during reaction. Then, reaction was continued for 5 hours, dehydrating at 240 degreeC, and reaction was performed for 3 hours under reduced pressure of 50 mmHg last. The polyester X thus obtained had a weight average molecular weight (Mw) of 12,300, an acid value of 0.3 mg KOH / g, and a hydroxyl value of 85.3 mg KOH / g.

Preparation Example 16

In a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, fountain tube and nitrogen gas introduction tube, 358.8 g of terephthalic acid, 260.1 g of 2-ethyl-2-butyl-1,3-propanediol, 80.4 g of glycerol, and 0.26 g of monobutyltin oxide was added as a catalyst (OH / COOH equivalence ratio = 1.15).

The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 180 ° C. Then, temperature was raised over 180 hours from 180 degreeC to 240 degreeC, removing methanol and unreacted diol produced | generated during reaction. Then, reaction was continued for 5 hours, dehydrating at 240 degreeC, and reaction was performed for 3 hours under reduced pressure of 50 mmHg last. The polyester Y thus obtained had a weight average molecular weight (Mw) of 12,400, an acid value of 0.3 mg KOH / g, and a hydroxyl value of 98.9 mg KOH / g.

Example 18-20 and Comparative Example 6

Using the polyesters W, X and Y prepared above, a rubber composition was prepared according to the formulation formulation shown in Table 6. Also, for the sake of comparison, no polyester was added (Comparative Example 6). Each component other than the sulfur and the vulcanization accelerator was kneaded at 80 ° C. for 5 minutes with a prabender-type Bunbury mixer, and then sulfur and vulcanization accelerator was added with a 6 inch roller to kneading at 60 ° C. Next, the kneaded material was extruded into a cross-sectional shape having a width of 30 mm and a thickness of 5 mm using an extruder (L / D = 70,75 mmφ), and then vulcanized at 200 ° C. for 5 minutes.

Next, a urethane paint (manufactured by Kansai Paint Co .; trade name Circex 2500;) was applied to the surface of the vulcanized molded body by spraying, baked in a hot air oven at 100 ° C. for 15 minutes, and a checkerboard test and a peeling test were performed. The results are shown in Table 5.

Example Comparative example 18 19 20 6 Composition of rubber (part) EPM * 1 Polyester type Polyester modifier Carbon black * 2 Oil * 3 Zincated stearic acid Sulfur accelerator Mercaptobenzothiazole 92W867.535.0511.52.0 90X1067.535.0511.52.0 90Y1067.535.0511.52.0 100-67.535.0511.52.0 Coating adhesion rate (%) Adhesion strength (kgf / cm) 1001.21 950.78 980.91 Less than 00.1

* 1 Esplen 505A Zhou Chemical Industrial Co., Ltd.

* 2 FEF grade 40-50㎛

* 3 Process oil (PW-380)

When the modifier of the polyester of the present invention is blended into a polymer such as a resinous or rubbery polymer, the coating film, in particular an acrylate or methacrylate type, a urethane type, an acryl / urethane type, a polyester type, with almost no deterioration in the performance of the polymer to be modified. The adhesiveness of the coating film of coating materials and adhesives, such as an epoxy type, can be improved significantly. The polyester modifier also has modification effects such as adhesiveness of emulsion-based adhesives and printability of aqueous ink, and can improve the properties of many dendritic or rubbery polymer surfaces. Moreover, it is also preferable as a use agent between heterogeneous molecules.

The composition of the dendritic or rubbery polymer containing the polyester of the present invention utilizes the above-described properties, and can be used for electric and electronic parts such as cap plugs, ports, refrigerators, lighting equipment, audio equipment, OA appliances, automobile parts, empty boxes, Useful as containers for daily necessities such as storage cases, various film packaging, foods, cosmetics, etc., particularly automobile bumpers, corner bumpers, bumper air dumb skirts, mat guards, side malls, foil caps, spoilers, side malls Suitable for surface modifications such as door mirror bases, weather strips, glass columns, grommets, airbags, interior materials such as interior heating materials, sports goods such as sports shoes and wetsuits, sheet waterproofing materials, gaskets and sealing materials .

Claims (12)

A polyhydric carboxylic acid component in which an aromatic divalent carboxylic acid or a functional derivative thereof occupies 50-100% by weight, (Formula 1) HOCH ₂ -C (R ¹ R ² ) -CH ₂ OH The hydroxyl value is 30 mgKOH / g obtained by polycondensing a polyhydric alcohol component in which hindered glycol represented by (wherein R ¹ and R ² represents an alkyl group having 2 to 10 carbon atoms) accounts for 40-100% by weight. Modifier for dendritic or rubbery polymers having the above polyester as an active ingredient. The modifier for dendritic or rubbery polymer according to claim 1, wherein the weight average molecular weight (Mw) of the polyester is in the range of 1,000-500,000. A polymer composition comprising a dendritic or rubbery polymer and a modifier for dendritic or rubbery polymers according to claim 1 or 0.01 with respect to 100 parts by weight of the dendritic or rubbery polymer. 4. The polymer composition according to claim 3, wherein the hydroxyl value of the polyester, which is an active ingredient of the dendritic or rubbery polymer modifier, is 60 mgKOH / g or more, and the weight average molecular weight (Mw) is 4,000-100,000. The following formula of polyester of Claim 3 which is an active ingredient of the modifier for dendritic or rubbery polymers. m = (hydroxyl × weight average molecular weight) / (56.1 × 1,000) The polymer composition characterized by the above-mentioned, the average number of hydroxyl groups m per molecule is 5 or more.        A polyhydric carboxylic acid component in which an aromatic divalent carboxylic acid or a functional derivative thereof occupies 50-100% by weight, (Formula 1) HOCH ₂ -C (R ¹ R ² ) -CH ₂ OH (In the formula, R ¹ and R ² represent an alkyl group having 2 to 10 carbon atoms.) A polyester obtained by condensation of a polyhydric alcohol component comprising 40-100% by weight of an impaired glycol, and having a hydroxyl value of 60 mgKOH / g or more. And a weight average molecular weight (Mw) is 4,000-100,000. A polyhydric carboxylic acid component in which an aromatic divalent carboxylic acid or a functional derivative thereof occupies 50-100% by weight, (Formula 1) HOCH ₂ -C (R ¹ R ² ) -CH ₂ OH (In the formula, R ¹ and R ² represent an alkyl group having 2 to 10 carbon atoms.) A polyester obtained by condensation of a polyhydric alcohol component comprising 40-100% by weight of an impaired glycol, wherein the hydroxyl value is 30 mgKOH / g or more. And a weight average molecular weight (Mw) is 1,000-500,000, and the average number of hydroxyl groups per molecule, m, defined by the following formula m = (hydroxy group x weight average molecular weight) / (56.1 × 1,000) is 5 or more. Polyester. 8. The polyester according to claim 7, wherein the average number of hydroxyl groups m per molecule is in the range of 40-100. The method according to any one of claims 6 to 8, based on the total weight of the polyhydric carboxyl component and the polyhydric alcohol component in addition to the aromatic divalent carboxylic acid or the functional derivative thereof and the impaired glycol. And 0.1-60% by weight of a trivalent or higher carboxylic acid, a functional derivative thereof, and at least one monomer selected from trivalent or higher alcohols are condensation-polymerized. In the method for producing a polyester formed by polycondensation of a polyvalent carboxylic acid component and a polyhydric alcohol component, an aromatic divalent carboxylic acid or a functional derivative thereof accounts for 50-100% by weight of the polyvalent carboxylic acid component, (Formula 1) HOCH ₂ -C (R ¹ R ² ) -CH ₂ OH (In formula, R <^1> and R <^2> represents a C2-C10 alkyl group.) The impaired glycol occupies 40-100 weight% of a polyhydric-alcohol component, and said aromatic divalent carboxylic acid or its functionality In addition to the derivatives and the impaired glycols, based on the total weight of the polyhydric carboxylic acid component and the polyhydric alcohol component, in 0.1-60% by weight of the trivalent or higher carboxylic acid and its functional derivative and the trivalent or higher alcohol A method for producing a polyester, characterized in that the polycondensation of at least one selected trivalent or more monomers. The polyester production method according to claim 10, wherein the ratio of the total number [X] of hydroxyl groups to the total number [Y] of the carboxylic acid reactor is 1.02 or more in an equivalent ratio of [X] / [Y].  It is a molded object of the polymer composition of any one of Claims 3-5, The surface of this is coated the polymer molded object characterized by the above-mentioned.