JPH10265684A - Polymer polyol/tackifier/nitrogenous compound modifier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer modifier which, when added to a resinous or rubbery polymer, can give a polymer composition capable of being vulcanized at an easily controlled vulcanization rate and giving a molding having excellent coatability by mixing a polymer polyol with a tackifier and a nitrogenous compound. SOLUTION: This modifier is obtained by mixing 100 pts.wt. polymer polyol with 1-200 pts.wt. tackifier and 0.1-100 pts.wt. nitrogenous compound. The modifier in an amount to give 0.01-50 pts.wt. polymer polyol is mixed with 100 pts.wt. resinous or rubbery polymer. The polymer polyol used is desirably a polyester polyol having at least one hydroxyl group in the molecular chain, a molecular weight of 1,000-500,000 and a hydroxyl value of 30 mgK0H/g or above. The tackifier is suitably a resin which is compatible or partially compatible with the base polymer and having a softening point of 40-100 deg.C. The nitrogenous compound is desirably an amine compound, especially an imidazoline compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a modifier for a resinous or rubbery polymer containing a polymer polyol, a tackifier and a nitrogen-containing compound, a polymer composition containing the modifier, and the polymer composition. The present invention relates to a polymer molded article obtained by molding a product and a coated polymer molded article obtained by coating the surface of the polymer molded article.

[0002]

2. Description of the Related Art As is well known, olefin resins such as polypropylene and olefin rubbers such as ethylene-propylene-diene copolymer rubber (EPDM) have been used widely because they have excellent properties and are relatively inexpensive. Has been
Because there is no polar group in the molecule, when a coating is applied, there is a problem that practical coatability such as coating adhesion strength, coating water resistance and coating solvent resistance cannot be obtained. . JP-A-4-
JP-A-272948 discloses an olefin-based resin molded article having improved coatability by combining an organotin and / or a tertiary amine compound with a copolymer of ethylene and a hydroxyl group-containing unsaturated compound. Without a pretreatment such as primers and the like, a sufficient effect has not been obtained. Also, JP-A-6-145436 and JP-A-6-145.
No. 440 discloses a technique for improving paintability by combining a modified olefin resin graft-modified with an unsaturated hydroxy compound with a tin compound or a tertiary amine which promotes a reaction between a hydroxyl group and an isocyanate. But,
These techniques are still not satisfactory. Further, JP-A-7-108835 discloses that an intermediate layer in which an organic peroxide and a primary amine or an imidazole compound are combined with an epoxy group-containing acrylic elastomer is provided between an EPDM substrate and a urethane layer. , EP
Although a technique for improving the adhesiveness between the DM base material and the urethane layer is disclosed, the effect is not sufficient for the trouble of providing the intermediate layer. JP-A-8-150684 discloses that, in order to improve the adhesion between the EPDM rubber and the urethane layer, a tin-based compound and / or A technique is disclosed in which a catalyst such as a tertiary amine compound that promotes a reaction with an isocyanate group in a urethane layer may be added, but these effects are not specifically disclosed. Japanese Patent Publication No. 60-34582 discloses a technique for improving the adhesion to a urethane resin by blending a functional hydrocarbon polymer containing a saturated aliphatic ring having a structure similar to that of a tackifier with EPDM rubber. Japanese Patent Application Laid-Open No. 6-306223 discloses a technique for improving the coating property by adding an aromatic modified terpene resin as a tackifier to an olefin resin, but both of these techniques are insufficient in terms of effect. is there. Japanese Patent Application Laid-Open No. 6-306223 discloses a technique of adding a phenolic resin as a polar resin-based tackifier. However, in consideration of a decrease in physical properties, the effect of modification is still insufficient. Absent. In addition, in rubber applications requiring vulcanization, there is still a problem that if an excessive amount of a nitrogen-containing compound is added, the vulcanization time becomes extremely short, and it is difficult to control the production.

[0003]

DISCLOSURE OF THE INVENTION The present invention can improve the coating properties of a resinous or rubbery polymer, such as its coating adhesion strength, coating water resistance, and coating solvent resistance.
In addition, the present invention provides a polymer modifier which is easy to control the vulcanization rate when vulcanizing and has excellent controllability in production, and a polymer composition containing the polymer modifier and having excellent coatability. It is an object of the present invention to provide a polymer molded article and a coated polymer molded article.

[0004]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that a composition containing a polymer polyol, a tackifier and a nitrogen-containing compound is excellent in improving the coatability of a resinous or rubbery polymer. It is easy to control the vulcanization rate and finds it very useful as a modifier,
The present invention has been completed. That is, the nitrogen-containing compound used in the present invention promotes the reaction between the hydroxyl group of the polymer polyol added to the resinous or rubbery polymer composition and the reactive group in the paint, for example, the isocyanate group in the urethane paint, to form a molded article. It has the function of increasing the adhesion strength between the film and the coating. Then, by combining with the tackifier used in the present invention, the wettability of the surface is improved, the effect is exhibited with a small amount of addition, and the coatability such as the adhesion strength to the coating film is improved without changing the vulcanization rate. Can be done. The present invention
A polymer polyol, a modifier for a resinous or rubbery polymer containing a tackifier and a nitrogen-containing compound, and further, a polymer composition containing the modifier in a resinous or rubbery polymer, The present invention also relates to a polymer molded article obtained by molding the polymer composition and a coated polymer molded article obtained by coating the surface of the polymer molded article.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The nitrogen-containing compound used in the present invention is not particularly limited as long as it has at least one nitrogen atom in the molecule. Either may be used. The amine compound may be primary, secondary, or tertiary, but preferably
It is a secondary amine compound.

[0006] The tertiary amine compound is not particularly limited as long as it has at least one tertiary amine structure in the molecule. Even if the tertiary amine structure is located in a chain structure, it is located in a ring structure. You may. A compound having a tertiary amine structure in a ring structure is preferable, and an imidazoline compound is particularly preferable. Compounds having a tertiary amine structure in a chain structure include triethylamine, N, N-dimethylpropylamine, N, N-diethylpropylamine, tetramethylethylenediamine, tetraethylethylenediamine, N-ethyl-N-methylbutylamine, tetraethylaminediamine. Aliphatic amines such as guanidine; N, N-diethylethanolamine, N, N-dimethylethanolamine, N
-Methyl-N- (dimethylaminopropyl) aminoethanol, N-butyldiethanolamine, triethanolamine, tris (2-hydroxypropyl) amine,
Aliphatic amino alcohols such as N, N-bis (2-hydroxyethyl) laurylamine; and aromatic amines such as N, N-diethylbenzylamine and N, N-dimethylaniline. Compounds having a tertiary amine structure in the ring structure include pyridine derivatives such as N, N-diethylaminopyridine and 4-ethyl-2,6-dimethylpyridine; 2-undecylimidazole,
Imidazole derivatives such as mercaptobenzimidazole; imidazoline compounds; tetrakis (N-methyl-
2,2,6,6-tetramethyl-4-piperidine)-
Piperidine derivatives such as 1,2,3,4-butanetetracarboxylate; tetrazole derivatives such as tetrazole and penttetrazole; 2-methyltriethylenediamine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1 , 5-diazabicyclo [4.3.0] -5
Crosslinking compounds such as -nonene, 6-dibutylamino-1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] -octane;
6-dibutylamino-1,8-diazabicyclo [5.
4.0] -7-undecene phenol salt, 6-dibutylamino-1,8-diazabicyclo [5.4.0] -7
-Weak acid salts such as undecene octanoate.

The imidazoline compound is not particularly limited as long as it is an organic compound having an imidazoline ring.
Preferably, it is an N-substituted imidazoline compound, for example, represented by the following formula (1).

Embedded image R ¹ is a hydrogen atom or a hydrocarbon group. The number of carbon atoms of the hydrocarbon group is not particularly limited, but is usually a lower hydrocarbon group having 1 to 6 carbon atoms, preferably a straight-chain or branched-chain methyl group, ethyl group, propyl group, butyl group. , A lower alkyl group such as a pentyl group and a hexyl group. R ² represents a hydrogen atom or an organic residue, preferably an organic residue, more preferably a hydrocarbon group. The carbon number of the organic residue may be appropriately selected according to the purpose of use, but usually from 1 to 200, preferably from 5 to 150, more preferably from 10 to 50, the effect of improving the paintability is high, and bending It is suitable because the decrease in elastic modulus is small. The organic residue may be either linear or branched, saturated or unsaturated having 1 to 5 double bonds, and may have a partial ring structure. n is an integer of 1 or more, preferably 1
To 3, more preferably 1. X is a hydrocarbon group which may contain a hetero atom, and the number of carbon atoms can be appropriately selected according to the purpose of use. The hetero atom is not particularly limited, and includes an oxygen atom and a nitrogen atom. Examples of the hydrocarbon group which may include a hetero atom include an alkyl group, a hydroxyalkyl group, an aminoalkyl group, and a polyaminoalkylene group represented by the following formula (2). _{- [CH 2 CH 2 NH]} mR 3 (2) ( wherein, R ³ is a hydrogen atom or an alkyl group having a carbon number 1 to 20, m is an integer of from 1 to 10.)

Specific examples of preferred imidazoline compounds include 2-heptadecenyl-1-ethylimidazoline, 2-heptadecenyl-1- (4-hydroxybutyl) imidazoline and 2-heptadecenyl-1- (2-
(Hydroxyethyl) imidazoline, 2-heptadecenyl-1- (2-aminoethyl) imidazoline, 2-dodecyl-1- (2-hydroxyethyl) imidazoline, 2-
Octyl-1- (2-aminoethyl) imidazoline, 2
-Pentadecenyl-1- (2-hydroxyethyl) imidazoline, 2-octadecyl-1-ethylimidazoline, condensates of dimer acid with polyethylene polyamines such as triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

Such an imidazoline compound can be easily synthesized by, for example, dehydrating and condensing an organic carboxylic acid and an aminoalkylamine compound.

The organic carboxylic acid is represented, for example, by the following formula (3). R ^2- (COOH) n (3) (wherein, R ² and n are the same as those in the formula (1).) When n is 1, a preferred organic residue of R ² is Examples include an alkyl group, an alkenyl group, an alkadienyl group, an alkatrienyl group and an alkatetraenyl group.

Specific examples of the alkyl group include linear or branched decyl, undecyl, dodecyl,
Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl,
Hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacosyl group and the like, among which linear or branched dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl And eicosyl groups are preferred. The position and number of the side chains having a branched chain are not particularly limited as long as they do not inhibit the reaction with the aminoalkylamine compound.

Specific examples of the alkenyl group include a linear or branched decenyl group, an undecenyl group, a dodecenyl group,
Tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, eicosenyl group, heneicosenyl group, docosenyl group, tricosenyl group, tetracosenyl group, pentacosenyl group, hexacosenyl group, heptacosenyl group, octacosenyl group, octacosenyl group, octacosenyl group And triacenyl groups, among which linear or branched dodecenyl groups, tridecenyl groups, tetradecenyl groups, pentadecenyl groups, hexadecenyl groups, heptadecenyl groups, octadecenyl groups, nonadecenyl groups, and eicosenyl groups are preferred. The position and number of the side chain and the position of the unsaturated bond in the case of having a branched chain are not particularly limited as long as they do not inhibit the reaction with the aminoalkylamine compound.

Specific examples of the alkadienyl group include linear or branched decadienyl groups, undecadienyl groups, dodecadienyl groups, tridecadienyl groups, tetradecadienyl groups, pentadecadienyl groups, hexadecadienyl groups, and heptadecadienyl groups. An enyl group, an octadecadienyl group, a nonadecadienyl group, an eicosadienyl group, a henecosadienyl group, a docosadienyl group, a tricosadienyl group,
Tetracosadienyl group, pentacosadienyl group, hexacosadienyl group, heptacosadienyl group, octacosadienyl group, nonacosadienyl group, triacosadienyl group and the like, among which straight-chain or branched Dodecadienyl group of the chain, tridecadienyl group, tetradecadienyl group, pentadecadienyl group, hexadecadienyl group,
Heptadecadienyl, octadecadienenyl, nonadecadienenyl, and eicosadienyl are preferred. In the case of having a branched chain, the position and number of the side chain and the position of the unsaturated bond are not particularly limited as long as they do not inhibit the reaction with the aminoalkylamine compound.

Specific examples of the alkatrienyl group include straight-chain or branched-chain decatrienyl groups, undecatrienyl groups, dodecatrienyl groups, tridecatrienyl groups, tetradecatrienyl groups, pentadecatrienyl groups, Decatrienyl group, heptadecatrienyl group, octadecatrienyl group, nonadecatrienyl group, eicosatrienyl group, heneicosatrienyl group, docosatrienyl group, tricosatrienyl group, tetracosatrienyl group, pentaco Satrienyl group, hexacosatrienyl group, heptacosatrienyl group, octacosatrienyl group, nonacosatrienyl group, triacosatrienyl group and the like, among which straight-chain or branched-chain dodecatrienyl group , Tridecatrienyl group, tetradecatrienyl group, pentadecato Enyl, hex tetradecatrienyl group, hepta tetradecatrienyl group, octadecatrienyl group, nona tetradecatrienyl group, eicosatrienoic enyl group. In the case of having a branched chain, the position and number of the side chain and the position of the unsaturated bond are not particularly limited as long as they do not inhibit the reaction with the aminoalkylamine compound.

Specific examples of the alkatetraenyl group include:
Straight or branched chain decatetraenyl group, undecatetraenyl group, dodecatetraenyl group, tridecatetraenyl group, tetradecatetraenyl group, pentadecatetraenyl group, hexadecatetraenyl group, heptadecatetraenyl Group, octadecatetraenyl group, nonadecatetraenyl group, eicosatetraenyl group, heneicosatetraenyl group, docosatetraenyl group, tricosatetraenyl group, tetracosatetraenyl group, pentacosatetraenyl group, Hexacosatetraenyl group, heptacosatetraenyl group, octacosatetraenyl group, nonacosatetraenyl group, triacosatetraenyl group and the like, among which straight-chain or branched-chain dodecatetraenyl group, trideca Tetraenyl group, tetradecatetraenyl group, pentadecate Raeniru group, hexadecanol tetra enyl heptadecaethyleneoxycetanol tetra enyl, octadecatetraenoic enyl, nonadecamethylene tetra enyl, eicosatetraenoic enyl group. In the case of having a branched chain, the position and number of the side chain and the position of the unsaturated bond are not particularly limited as long as they do not inhibit the reaction with the aminoalkylamine compound.

The organic carboxylic acid may have a substituent as long as it does not inhibit the reaction with the aminoalkylamine compound. Examples of such a substituent include methyl, ethyl, propyl, Tertiary amino groups substituted with alkyl such as butyl, amyl, hexyl and the like;
A nitro group; a cyano group; a carbamoyl group; a halogen atom such as fluorine and chlorine; an alkyl group such as methyl, ethyl, propyl, and isopropyl; an alkoxy group such as methoxy and ethoxy; and a halogenated alkyl group such as trifluoromethyl. And the like. Further, the organic carboxylic acid may be a derivative such as an acid halide, an acid anhydride or an ester thereof, and among them, an ester is preferable. The esterification product is not particularly limited, but usually an alkyl ester is used, and lower esters such as methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, amyl ester and hexyl ester are used.

Specific examples of preferred compounds of the organic carboxylic acid include substituted or unsubstituted saturated monocarboxylic acids such as lauric acid, palmitic acid, stearic acid, behenic acid, melicic acid, isopalmitic acid, isostearic acid, and isoarachinic acid. Unsaturated monocarboxylic acids such as 10-undecenoic acid, erucic acid, linoleic acid, eleostearic acid, linolenic acid, and arachidonic acid; lanolin fatty acids, tallow fatty acids, fish fatty acids, soybean fatty acids, coconut fatty acids
Natural fatty acids such as tall oil fatty acids and hydrogenated products thereof; higher fatty acids and the like are examples of n = 1 in the above formula (3). Specific examples of preferred compounds of the formula (3) wherein n = 2 or more include sebacic acid,
Saturated dicarboxylic acids such as brassic acid; dimer acids, trimer acids obtained by polymerizing higher fatty acids such as oleic acid, linoleic acid, ricinoleic acid, and eleostearic acid; and hydrogen-bonding of carbon-carbon unsaturated bonds remaining in these polymerized fatty acids. Additions may be given. Among these, higher fatty acids are preferred, and saturated monocarboxylic acids are particularly preferred.

The aminoalkylamine compound is represented, for example, by the following formula (4). ^{_{H 2 N (CHR 1) 2}} NH-X (4) ( wherein, R ¹ and X are the same as those in (1)) when X is an alkyl group, carbon number 1 to 20, preferably Is 1 to 6, more preferably 1 to 3, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group,
Examples thereof include an isopentyl group, an n-hexyl group, an isohexyl group, an octyl group, a tetradecyl group, and a hexadecyl group, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferred.

When X is a hydroxyalkyl group, it has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
Examples include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group, and a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group are preferred.

When X is an aminoalkyl group, the number of carbon atoms is 1
To 20, preferably 1 to 10, more preferably 1 to 3, and specific examples include aminomethyl, aminoethyl, aminopropyl, aminobutyl, aminopentyl, aminohexyl, and ethylaminoethyl. Groups, a dodecylaminoethyl group and a butylaminoethyl group, preferably an aminomethyl group, an aminoethyl group or an aminopropyl group.

When X is a polyaminoalkylene group, it has 2 to 20, preferably 2 to 15, more preferably 2 carbon atoms.
To 8, and as specific examples, a diethylenediamine group,
Triethylenetriamine group, tetraethylenetetramine group, pentaethylenepentamine group, N-ethyldiethylenediamine group, N-dodecyldiethylenediamine group and the like, preferably diethylenediamine group, triethylenetriamine group, tetraethylenetetramine group is there.

The aminoalkylamine compound may have a substituent as long as it does not inhibit the reaction with the organic carboxylic acid. Examples of such a substituent include methyl, ethyl, propyl, butyl, Tertiary amino groups substituted with alkyl such as amyl, hexyl, etc .; nitro groups; cyano groups; carbamoyl groups; halogen atoms such as fluorine and chlorine; alkyl groups such as methyl, ethyl, propyl and isopropyl; Examples include an alkoxy group such as ethoxy, and a halogenated alkyl group such as trifluoromethyl.

Specific examples of preferred aminoalkylamine compounds include ethylaminoethylamine, propylaminoethylamine, ethanolaminoethylamine, propanolaminoethylamine, butanolaminoethylamine, pentanolaminoethylamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine,
Nonaethylenedecamine, di-1,2-propanetriamine and the like can be mentioned.

The proportion of the aminoalkylamine compound to be used is appropriately selected depending on the number of carboxyl groups of the organic carboxylic acid. Preferably n-5 nmol, more preferably n-2.
5 nmol. In the present invention, when the amount of the aminoalkylamine compound used is less than n mol, unreacted carboxyl groups remain, but there is no particular problem as long as the object of the present invention is not impaired.

[0025] The reaction temperature is 100 to 250 ° C, preferably 150 to 230 ° C. The reaction pressure is preferably under reduced pressure, and the degree of reduced pressure is usually 1 to 50 mmHg, preferably 10 to 30 mmHg. The reaction time varies depending on the reaction temperature, the degree of pressure reduction and the raw materials used, but is usually 24 hours or less, generally 3 to 8 hours. If necessary, an appropriate amount of an organic solvent such as toluene or xylene may be added as a reflux solvent. As a catalyst, Periodic Table II or IV
Metals of the genus, oxides, hydroxides, chlorides of these metals,
A carbonate or an organic carboxylate, or the like;
You may add 0.0001-0.1 mol with respect to mol. The obtained product may be optionally isolated by removing the solvent used in the reaction, unreacted aminoalkylamine compound, and the like, for example, by vacuum distillation.

Each of these nitrogen-containing compounds is used alone or in combination of two or more.
Usually, it is in the range of 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight. If the content of the nitrogen-containing compound is too large, it adversely affects vulcanized scorch and bleed.

The polymer polyol used in the present invention is not particularly limited as long as it has at least one hydroxyl group in the molecular chain. For example, (1) Living anion of conjugated alkadiene such as butadiene, isoprene and piperylene Hydroxyl group, epoxy group,
Polymer polyols capped with phenolic hydroxyl groups (USP 4,417,029, USP 4,75
(2) Polymer polyols obtained by radically polymerizing conjugated alkadienes such as butadiene, isoprene and piperylene in the presence of hydrogen peroxide (see JP-A-51-71391). (3) Polymer polyol obtained by hydrogenating the hydroxyl group-containing diene-based polymer according to (1) and (2) with a Ni / Al-based or ruthenium catalyst; (4) Hydroxyl-containing unsaturated such as ethylene and hydroxyethyl methacrylate A polymer polyol copolymerized with a compound (Japanese Unexamined Patent Publication No.
(5) Polymer polyols obtained by heat-adding a hydroxyl group-containing unsaturated compound such as hydroxyethyl methacrylate to an olefin polymer in the presence of an organic peroxide (JP-A-7-62173). (6) a polymer polyol obtained by reacting a dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or transesterifying with a carbonic acid diester; (7) a ring-opening polymerization of a lactone such as ε-caprolactone. Polymer polyol to be obtained; (8)
Polymer polyols obtained by dehydration-condensation polymerization of dicarboxylic acids with glycols and polyhydric alcohols are used.

Preferred examples of the polymer polyol include polybutadiene containing hydroxyl groups at both ends and hydrogenated products thereof, polyisoprene containing hydroxyl groups at both ends and hydrogenated products thereof, polyolefin polyols and hydrogenated products thereof, hydroxyl-pendant polybutadienes and hydrogenated polybutadienes thereof. Product, hydroxyl group pendant polyisoprene and hydrogenated product thereof, polycaprolactone polyol and hydrogenated product thereof, modified polyolefin grafted with hydroxyalkyl acrylate and hydrogenated product thereof, hydroxyl group-containing styrene-butadiene copolymer and hydrogenated product thereof A hydroxyl-containing styrene-butadiene block copolymer and its hydrogenated product, a hydroxyl-containing styrene-isoprene copolymer and its hydrogenated product, a hydroxyl-containing styrene-isoprene block copolymer and Hydrogenated maleic anhydride-added polyolefin amino alcohol adducts, polyester polyols obtained by dehydration polycondensation of polyhydric carboxylic acids and polyhydric alcohols, and the like, in particular, polyhydric carboxylic acids and polyhydric alcohols Polyester polyols obtained by dehydration condensation polymerization are preferred.

The polyhydric alcohol component of the polyester polyol used in the present invention is not particularly limited as long as it is a dihydric or higher alcoholic monomer and is used in ordinary polyester synthesis. A mixture of a monomer or a dihydric alcohol monomer and a trihydric or higher alcohol monomer can be used. In the present invention, it is preferable to use one containing at least one kind of hindered alcohol monomer or oligooxyalkylene glycol in the polyhydric alcohol component, and its content is usually 10% by weight or more in the total polyhydric alcohol component. , Preferably at least 20% by weight, more preferably at least 40% by weight.

Examples of the dihydric alcohol monomer include alkanediols, cycloalkanediols,
Aromatic diols, oligooxyalkylene glycols and polyoxyalkylene glycols, polyester diols, hindered glycols and the like are used. Among these, alkanediols, cycloalkanediols, oligooxyalkylene glycols, polyoxyalkylene glycols, hindered glycols, and the like are preferable, and oligooxyalkylene glycols and hindered glycols are particularly preferable.

Examples of the alkanediols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. Diol, 1,8-octanediol, 1,9-
Nonanediol and the like. Among these,
When the number of carbon atoms in the main chain of 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol is 6 to
Nine alkanediols are preferred. Examples of cycloalkanediols include, for example, cyclopentane-
Examples thereof include 1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclooctane-1,4-diol, and 2,5-norbornanediol.

The aromatic diols include, for example, p
-Xylene diol, 4,4'-methylene diphenol, 4,4'-dihydroxybiphenyl, 2,5-naphthalenediol and the like.

The oligooxyalkylene glycols and polyoxyalkylene glycols include, for example, those obtained by polymerizing alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide alone or in a mixture by a known method. And those represented by the following general formula (1) can be used. _{HO - ((CH 2) a} -CHR 3 O) b -H (5) wherein, R ³ is a lower alkyl group having 1 to 6 carbon atoms, such as hydrogen atom or a methyl group, an ethyl group, preferably It is a hydrogen atom or a methyl group. a represents an integer of 1 to 6, and is preferably an integer of 1 to 4. b is 2 to 100
And preferably 2 to 50, more preferably 2
Is an integer of 〜25. Specifically, oligooxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol; polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, and polybutylene glycol; No.

Examples of the polyester diols include lactones such as β-butyrolactone, γ-butyrolactone, and δ-valerolactone disclosed in JP-A-6-116372, and ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and the like. And a ring-opened product with an oligooxyalkylene glycol or a polyoxyalkylene glycol, for example, those represented by the following general formula (6) can be used. ^{OH- (R 4 -COO-G)} p -H (6) wherein, R ⁴ represents an alkylene group, typically, the number of carbon atoms is 2 to 6. p shows the integer of 2-1000, Preferably it is 5-500, More preferably, it is the integer of 10-100. G is - (CH ₂ CHR ⁵ O) shows the q group, in this formula, q is an integer of 1 to 4, R ⁵ is a hydrogen atom or a methyl group, a lower alkyl having 1 to 6 carbon atoms such as ethyl group Represents a group.

The hindered glycol is not particularly limited as long as it has two hydroxyl groups in the molecule and the β-position carbon atom of the hydroxyl group does not have a hydrogen atom. And those represented by the following general formula (7) can be used. _{^{HOCH 2 -C (R 6 R 7}} ) -CH 2 OH (7) wherein, R ^6, R ⁷ represents an alkyl group independently. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 to 50, preferably 1 to 20, and more preferably 2
10 to 10. Specific examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group , Dodecyl group, tridecyl group, pentadecyl group, octadecyl group, eicosyl group and the like,
Among them, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like are preferable, and ethyl group is preferable. , Propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl and the like. Specific examples of hindered glycols include, for example, 2,2-dimethyl-1,3-propanediol,
2,2-diethyl-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, -Methyl-2-dodecyl-1,3-propanediol, 2-butyl-2-
Ethyl-1,3-propanediol, 2-propyl-2
-Pentyl-1,3-propanediol and the like, and among these, 2,2-diethyl-1,3-propanediol, 2,2-dipropyl-1,3-propanediol, 2,2-dibutyl- 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-propyl-2-pentyl-1,3-propanediol, and the like are preferable, and 2,2-diethyl-1,3 is particularly preferable.
-Propanediol, 2-butyl-2-ethyl-1,3
-Propanediol is preferred.

The trivalent or higher alcoholic monomer is not particularly limited as long as it has three or more hydroxyl groups. For example, a trivalent or higher valent hindered alcohol represented by the following general formula (8): General formula (9)
Glycerol compounds such as glycerol, diglycerol, and polyglycerol; saccharides such as sorbitol, glucose, mannitol, sucrose, and glucose; and an epoxy group in the molecule.
Epoxy compounds having more than one epoxy compound can also be used. Among them, hindered alcohols having a valence of 3 or more represented by the general formula (8) and those having a valence of 4 or more represented by the general formula (9) are preferable.

The hindered alcohols having 3 or more valences are particularly limited as long as they have 3 or more hydroxyl groups in the molecule and the carbon atom at the β-position of the hydroxyl group does not have a hydrogen atom. However, for example, those represented by the following general formula (4) can be used. _{^{HOCH 2 -C (R 8 R 9}} ) R 8 of -CH ₂ OH (8) wherein, R ⁹ is independently an alkyl group having an alkyl group or a hydroxyl group, R ^8, R
^At least one of ⁹ is an alkyl group having a hydroxyl group. Here, the number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 to 50, preferably 1 to 20, and more preferably 2 to 10. Specific examples of the alkyl group include
This is the same as that described in relation to the general formula (7). Specific examples of such trivalent or higher hindered alcohols include:
For example, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and the like can be mentioned, and trimethylolpropane and pentaerythritol are particularly preferable.

As the alcohol having a valency of 4 or more, a linear or branched —C _n H _2n OH group (n
Is an integer of 0 to 5) and contains 2 or more carbon atoms. The carbon number is not particularly limited,
Usually, it is in the range of 4 to 30, preferably 6 to 20. Further, n is preferably 0 to 2, particularly preferably 1.
Further, those having no hydrogen atom at the carbon atom at the β-position of the hydroxyl group (hindered type) are particularly preferable. The polyhydric alcohol having 4 or more valences is preferably represented by the following general formula (9)
It is represented by

[0039]

Embedded image

Here, R ¹⁰ and R ¹¹ are selected from the group consisting of H, Cn H _2n OH and a substituted or unsubstituted alkyl group (where n is an integer of 0 to 5; X) is oxy, alkyleneoxy, alkyleneoxyalkylene or alkylene having 1 to 10 carbon atoms which may be substituted by a lower alkyl group. The above n is preferably 0 to 2, particularly preferably 1. R
¹⁰ or the number of carbon atoms in the alkyl group of R ¹¹ is not particularly limited, but is usually 1 to 50, preferably in the range of from 1 to 20, more preferably 2 to 10. Specific examples of the alkyl group are the same as those described in relation to the general formula (7). The number of carbon atoms of the alkyleneoxy, alkyleneoxyalkylene or alkylene of X is usually 1 to 10, preferably 1 to
6, more preferably 2-5, most preferably 2.
Specific examples include, for example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group,
n-amylene group, methyleneoxy group, ethyleneoxy group, propyleneoxy group, isopropyleneoxy group, butyleneoxy group, isobutyleneoxy group, sec-butyleneoxy group, tert-butyleneoxy group, n-amyleneoxy group, methyleneoxymethylene group, Examples include a methyleneoxyethylene group, a methyleneoxypropylene group, a methyleneoxybutylene group, an ethyleneoxyethylene group, and an ethyleneoxypropylene group. Preferably it is a methyleneoxymethylene group.

The compounds included in the above general formula are preferably trimethylolethane, trimethylolpropane, trimethylolbutane, triethanolpropane,
Dehydration condensates of one or more compounds selected from the group consisting of triethanol butane, pentaerythritol and glycerin (except when both are glycerin), such as ditrimethylolethane, Methylol propane, ditrimethylol butane, ditriethanol propane, ditriethanol butane, dipentaerythritol and the like are preferable, ditrimethylol propane, dipentaerythritol is more preferable,
Dipentaerythritol is particularly preferred.

As the polyhydric alcohol component, an epoxy compound having two or more epoxy groups in the molecule can also be used. For example, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, polyethylene glycol diglycidyl ether,
Polypropylene glycol diglycidyl ether, polybutadiene glycol diglycidyl ether, hydroquinone diglycidyl ether, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of alkylene oxide adduct of bisphenol A, Diglycidyl adipate, o-
Examples include diglycidyl phthalate, diglycidyl terephthalate, and diglycidyl dimer.

The polyhydric alcohol component may have, in addition to the hydroxyl group, an unsaturated bond group as long as the polycondensation reaction with the divalent carboxylic acid component is not inhibited, and may have other substituents. May be. Examples of the substituent include a tertiary amino group substituted with a lower alkyl such as methyl, ethyl, propyl, butyl, amyl, hexyl, etc .; a nitro group; a cyano group; a carbamoyl group; a halogen atom such as fluorine and chlorine. A lower alkoxy group such as methoxy and ethoxy; a halogenated lower alkyl group such as trifluoromethyl.

The dihydric alcohol monomer and the trihydric or higher alcohol monomer can be used alone or in combination of two or more. The proportion used is appropriately selected according to the purpose of use, but usually the proportion of dihydric alcohol is usually 30 to 100% by weight, preferably 40 to 95% by weight, more preferably 5 to 100% by weight of the total polyhydric alcohol component.
The content of the trihydric or higher alcohol is usually 0 to 70% by weight, preferably 5 to 60% by weight, and more preferably 10 to 50% by weight.

In the present invention, as the alcohol component, for example, methanol, ethanol, isopropanol, butanol, t
-Butanol, neopentyl alcohol, 3-methyl-
3-pentanol, 3-ethyl-3-pentanol,
Monohydric alcohols such as 2,3,3-trimethyl-2-butanol, 1-decanol and nonyl alcohol may be used in combination. These may have a substituent similarly to the above-mentioned polyhydric alcohol. Each of them can be used alone or in combination of two or more. The allowable amount thereof is usually 20% by weight or less, preferably 15% by weight of the total alcohol component.
% By weight, more preferably 10% by weight or less.

The polyvalent carboxylic acid component of the polyester polyol used in the present invention is not particularly limited, as long as it is a divalent or higher carboxylic acid monomer and is used for ordinary polyester synthesis. Preferably, those containing a divalent carboxylic acid-based monomer as a main component are used.
The divalent carboxylic acid monomer is not particularly limited, and a linear, branched or cyclic aliphatic divalent carboxylic acid or aromatic or heterocyclic divalent carboxylic acid is preferably used. Acids and aromatic divalent carboxylic acids.

Examples of the aliphatic dicarboxylic acid include succinic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and the like.
Itaconic acid, pimelic acid, suberic acid, azelaic acid,
A lower aliphatic divalent carboxylic acid having 1 to 9 carbon atoms such as 1,2-cyclohexane diacid, 1,3-cyclohexane diacid, 1,4-cyclohexane diacid and the like and having 10 or more carbon atoms; Higher aliphatic dicarboxylic acids are used, with higher aliphatic carboxylic acids being preferred. The carbon number is usually 1
The range is from 0 to 200, preferably from 20 to 150, and more preferably from 20 to 100. Specific examples of such higher aliphatic divalent carboxylic acids include sebacic acid, brassic acid, polyalkenyl succinic acid, and dimer acids of polymerized fatty acids. Among them, polyalkenyl succinic acid and dimer acid of polymerized fatty acid are preferable, and dimer acid of polymerized fatty acid is more preferable.

The polyalkenyl succinic acid is represented by the following general formula (10).

Embedded image Here, R ¹² is a polymer chain of lower alkylene having 1 to 6 carbon atoms, and preferably, the lower alkylene is one selected from ethylene, propylene, and butylene. The degree of polymerization preferably ranges from 10 to 300.

As the dimer acid of the polymerized fatty acid, generally, a polymer obtained by polymerizing a fatty acid or a fatty acid ester by a known method is used, and is obtained by hydrogenating carbon-carbon unsaturated bonds remaining in the polymerized fatty acid. There may be. A dimer acid of a higher fatty acid obtained by polymerizing a higher fatty acid or a higher fatty acid ester is preferred. The fatty acid may be saturated or unsaturated, and usually has 8 to 3 carbon atoms.
0, preferably 12 to 24, more preferably 16 to 20
Range. As the fatty acid ester, an alkyl ester of the above fatty acid such as methyl, ethyl, propyl, butyl, amyl and cyclohexyl is used. Preferred polymerized fatty acids include, for example, those obtained by polymerizing unsaturated higher fatty acids such as oleic acid, linoleic acid, ricinoleic acid, and eleostearic acid, and those obtained by polymerizing natural fatty acids such as tall oil and tallow. The structural analysis of polymerized fatty acids is described in D.S. H. (J. Am. Oil. Chem. Soc., 5).
1, 522 (1974)). Polymerized fatty acids are also available as commercial products. A commercially available product is obtained by polymerizing oleic acid, linoleic acid, ricinoleic acid, eriostearic acid, or the like, and has dimer acid as a main component, and a polymer acid and a monomer acid which are at least dimer acid as subcomponents. These can be purified by distillation or solvent extraction,
It may be used after purification or may be used as it is without purification.

As the aromatic divalent carboxylic acid, those having one aromatic ring as a basic skeleton are generally used. Or two or three aromatic rings such as naphthalene, anthracene, and phenanthrene may be condensed. An aromatic ring such as indene or tetralin may have a condensed ring in which another 5- or 6-membered carbon ring is condensed. The number of carbon atoms is usually in the range of 8 to 30, preferably 8 to 20, and more preferably 8 to 15.

Preferred specific examples of the aromatic divalent carboxylic acid monomer include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-1,4-
Examples thereof include dicarboxylic acid and naphthalene-2,3-dicarboxylic acid. Of these, terephthalic acid and isophthalic acid are preferred.

A heterocyclic divalent carboxylic acid is a 5- or 6-membered ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen as a heteroatom constituting the ring or a fused ring thereof. It refers to a compound in which two carboxyl groups are coordinated, and a compound commonly used in general polyester synthesis can be appropriately selected and used according to the purpose of use. As the heterocyclic ring, specifically, pyrrole, pyrazole, pyridine, pyrazine, quinoline, naphthyridine, quinoxaline; thiophene, benzothiophene; furan,
Pyran, isobenzofuran, chromene and the like,
Those containing a nitrogen atom as a hetero atom, such as pyrazole, pyridine and pyrazine, are preferred. The carbon number is usually 8
-30, preferably 8-20, more preferably 8-15
Range. Specific examples of the heterocyclic divalent carboxylic acid monomer include, for example, 2,5-pyrroledicarboxylic acid,
2,3-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, pyrazine-
Examples include 2,3-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2,4-quinolinedicarboxylic acid, 2,7-naphthyridinedicarboxylic acid, 2,3-quinoxalinedicarboxylic acid, and 2,5-thiophenedicarboxylic acid. . Among these, 2,3-pyridinecarboxylic acid, 2,2
Preferred are 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid and the like.

Here, the substitution positions of the two carboxyl groups of the dihydric carboxylic acid may be any positions as long as they do not inhibit the polycondensation reaction with the polyhydric alcohol component.
Further, the divalent carboxylic acid may have, in addition to the above two carboxyl groups, other substituents as long as they do not inhibit the polycondensation reaction with the polyhydric alcohol component. Tertiary amino groups substituted with lower alkyl such as propyl, butyl, amyl, hexyl, etc .; nitro groups; cyano groups; carbamoyl groups; halogen atoms such as fluorine and chlorine;
Lower alkyl groups such as isopropyl; lower alkoxy groups such as methoxy and ethoxy; and halogenated lower alkyl groups such as trifluoromethyl.

The divalent carboxylic acids may be derivatives thereof such as acid halides, acid anhydrides and ester compounds. The ester compound is not particularly limited, but usually an alkyl ester is used. As the alkyl ester, for example, methyl ester, ethyl ester,
Lower alkyl esters such as propyl ester, isopropyl ester, butyl ester, amyl ester, and hexyl ester; octyl ester, decyl ester,
Higher alkyl esters such as dodecyl ester, pentadecyl ester and octadecyl ester are mentioned, preferably lower alkyl esters, more preferably methyl esters, ethyl esters, propyl esters, butyl esters and the like. The acid halide is not particularly limited, but usually an acid chloride is used.

The divalent carboxylic acid monomers can be used alone or in combination of two or more. The proportion is appropriately selected according to the purpose of use, but is usually in the range of 50 to 100% by weight, preferably 70 to 100% by weight, more preferably 80 to 100% by weight in the total polycarboxylic acid component. .

The remainder other than the divalent carboxylic acid monomer was
Trivalent or higher carboxylic acids used in general polyester synthesis are used without any particular limitation. The trivalent or higher carboxylic acid may have a substituent similarly to the above divalent carboxylic acid-based monomer, or may be a carboxylic acid derivative. Examples of the trivalent or higher carboxylic acid include trivalent or higher carboxylic acids such as trimellitic acid, tricarballylic acid, camphoronic acid, trimesic acid, and trimer acid in polymerized fatty acids. More than one species can be used in combination.

In the present invention, as the carboxylic acid component, as long as the effects of the present invention are not impaired, formic acid, acetic acid, butyric acid, 2-methylpropanoic acid, valeric acid, isooctylic acid, isononanoic acid, lauric acid , Myristic acid, palmitic acid, stearic acid, isostearic acid,
Monovalent carboxylic acids such as arachiic acid, linoleic acid, oleic acid and elaidic acid may be used in combination. These may have a substituent similarly to the above-mentioned divalent carboxylic acid, and may be carboxylic acid derivatives. Each of them can be used alone or in combination of two or more, and the allowable amount is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less in all carboxylic acid components.

In condensation polymerization of the above monomer components,
Polyester can be obtained under the condition that the total number [X] of alcoholic reactive groups in all monomers obtained by adding the polyvalent carboxylic acid component and the polyhydric alcohol component is larger than the total number [Y] of the carboxylic acid reactive groups. Is suitable for increasing the molecular weight and increasing the hydroxyl value. The ratio of the total number of alcoholic reactive groups [X] to the total number of carboxylic acidic reactive groups [Y] is usually 1.02 or more, preferably 1.03 to 1.0, in an equivalent ratio of [X] / [Y]. 5, more preferably 1.04
-3, most preferably in the range of 1.05-2.5.
Here, the alcoholic reactive group refers to an alcoholic functional group that forms an ester bond, and typically includes a hydroxyl group, and the carboxylic acid reactive group includes a carboxylic acid group that forms an ester bond. And generally includes a carboxyl group and an ester group.

The polycondensation reaction may be carried out according to a conventional method. For example, the reaction temperature is 100 to 300 ° C., preferably 150 to 28.
It is carried out at 0 ° C., particularly preferably in the presence of an inert gas such as nitrogen 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 500 mmH).
g, preferably 1 to 200 mmHg, more preferably 1
0-100 mmHg). At the time of the polycondensation reaction, an esterification catalyst is usually used. As the esterification catalyst, for example, paratoluenesulfonic acid,
Bronsted acids such as sulfuric acid and phosphoric acid; Lewis acids such as boron trifluoride complex, titanium tetrachloride and tin tetrachloride; calcium acetate, zinc acetate, manganese acetate, zinc stearate, alkyltin oxide, titanium alkoxide, etc. Metal oxides such as tin oxide, antimony oxide, titanium oxide, and vanadium oxide; and the like, and in terms of oxidation stability of the obtained polyester, organometallic compounds belonging to Group IV of the periodic table, particularly Monobutyltin oxide and tetra-n-butyl-ortho titanate are preferred.

The molecular weight of the polymer polyol may be appropriately selected according to the purpose of use, and is generally 1,000 to 5 in terms of polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).
00,000, preferably 3,000 to 300,00
0, more preferably in the range of 6,000 to 100,000. When the weight average molecular weight of the polymer polyol is in this range, both the transferability to the surface of the resin or rubber molded article and the anchor effect of the coating film on the polymer layer of the resin or rubber molded article are high, and the adhesion strength of the coating film is high. Can be improved.

The hydroxyl value of the polymer polyol may be appropriately selected according to the purpose of use.
/ G or more, preferably 40 to 250 mgKOH / g, more preferably 50 to 200 mgKOH / g. When the hydroxyl value is within this range, the coatability is particularly excellent and suitable.

When the polymer polyol is oil-soluble, the compatibility with the resin-like or rubber-like polymer is further excellent and is suitable. Here, “oil-soluble” means that the light transmittance of the polymer polyol solution measured as described below is 60% or more. The preferred light transmittance is 80% or more. 5 g of the polymer polyol is put in 95 g of toluene, dissolved under stirring at 80 ° C. for 1 hour under a nitrogen atmosphere, and then cooled to room temperature (20 ° C.). This diluted toluene solution is heated at 20 ° C.
The mixture is allowed to stand in a constant temperature chamber for 24 hours, then stirred again, and the transmittance is measured with a turbidity meter (“ANA-14S” manufactured by Tokyo Koden Co., Ltd.). Tungsten incandescent lamp (6V,
6A), a 20 mm square glass cell is used as the cell. The transmittance is 0% when the shutter is closed, and the transmittance of toluene used for dilution is 100%.

These polymer polyols are used alone or in combination of two or more. The addition amount of the polymer polyol is usually 0.1 to 50 parts by weight, based on 100 parts by weight of the resinous or rubbery polymer of the base material,
Preferably from 0.5 to 30 parts by weight, more preferably from 1 to 2 parts by weight.
The range is 0 parts by weight. When it is in this range, the control of the paintability and the vulcanization rate is highly balanced and suitable.

The tackifier used in the present invention is not particularly limited as long as it is a resin having a softening point of 40 ° C. to 160 ° C. which is compatible or partially compatible with the base material. Specifically, rosin and its derivatives, coumarone-indene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, terpene-phenol resin, terpene resin, alkylphenol resin, C9 petroleum resin, C5 petroleum resin, C5 / C
9 copolymer petroleum resin, DCPD petroleum resin and the like. Since the tackifier is intended to improve the wettability and tack of the surface layer, it is necessary that the tackifier is compatible with the resinous or rubbery polymer used, more preferably partially compatible. For improving the coating property of the olefin polymer, a tackifier that is compatible or partially compatible with the olefin polymer is preferable.Specifically, rosin-modified polyhydric alcohol esters, rosin-modified maleic resins, rosin-modified phenol resins, Rosin derivatives, phenol / formaldehyde resins, terpene / phenol resins, xylene / formaldehyde resins, alkylphenol resins, C5 / C9 copolymer petroleum resins, and DCPD petroleum resins containing a polar group are exemplified.

These tackifiers can be used alone or in combination of two or more. The addition amount is usually 1 to 200 parts by weight per 100 parts by weight of the polymer polyol.
Parts by weight, preferably from 5 to 150 parts by weight, more preferably from 10 to 100 parts by weight. When the amount of the tackifier used is within this range, the effect of improving the coating properties and the properties of the vulcanized rubber are highly balanced and suitable.

Examples of the polymer used as the base in the polymer composition of the present invention include resinous or rubbery polymers such as synthetic resins, rubbers, and urethane foams. Although there is no particular limitation on the synthetic resin, a thermosetting resin or a thermoplastic resin is preferably used, and a thermoplastic resin is more preferably used. As a thermosetting resin, for example,
Phenol resin, cresol resin, urea resin, methamine resin, alkyd resin, furan resin, unsaturated polyester resin, epoxy resin, polyurethane resin and the like are preferable, and unsaturated polyester resin, epoxy resin and polyurethane resin are preferable. As a thermoplastic resin,
For example, olefin-based resins, styrene-based resins, acrylate-based resins, phenylene ether-based resins, ester-based resins, carbonate-based resins, general-purpose engineering plastics, and the like, among which hydrocarbon-based resins such as olefin-based resins and styrene-based resins When a thermoplastic resin, especially an olefin resin, is used, the effect of improvement is high, which is preferable.

Examples of the olefin resin include homopolymers of α-olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1; ethylene and propylene or other α-olefins. −
And copolymers of two or more types of α-olefins, such as copolymers with olefins. Among these,
A (co) polymer containing polyethylene or propylene as a main component is preferable, and a (co) polymer containing propylene as a main component is particularly preferable. Examples of the (co) polymer containing propylene as a main component include a copolymer comprising polypropylene and propylene in an amount of 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more and another α-olefin. And as the α-olefin to be copolymerized,
Particularly, ethylene is preferred.

Other olefin resins include, for example, graft copolymerized modified olefin resins obtained by graft copolymerizing the above olefin resin with α, β-unsaturated carboxylic acid such as acrylic acid, maleic acid and anhydride thereof. A block copolymerized modified olefin resin obtained by block copolymerizing the olefin resin with an α, β-unsaturated carboxylic acid such as acrylic acid, maleic acid and anhydride; ethylene / acrylic acid copolymer, ethylene / methacrylic Α-olefins such as acid copolymer, ethylene / crotonic acid copolymer, ethylene / maleic acid copolymer, ethylene / acrylic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / vinyl acetate copolymer And other copolymerizable monomers; and the like.

Examples of the styrene resin include polystyrene, high impact polystyrene, styrene-acrylonitrile copolymer, styrene-alkyl (meth) acrylate copolymer, ABS resin, MBS resin, AAS resin,
Examples include styrene-modified polyphenylene ether, styrene-butadiene block copolymer resin, styrene-isoprene block copolymer resin, and hydrides thereof.

Examples of the rubber include, without particular limitation, natural rubber; conjugated diene polymer rubber such as polyisoprene rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, and chloroprene rubber; styrene-butadiene random copolymer rubber; Aromatic vinyl-conjugated diene random copolymer rubber such as styrene-isoprene random copolymer rubber, styrene-isoprene-butadiene random copolymer rubber; aromatic vinyl-conjugated diene block copolymer rubber and its hydrogenated product; acrylonitrile A copolymer rubber of a conjugated diene such as a butadiene copolymer rubber and another copolymerizable monomer; a chlorinated polyethylene rubber,
Modified polyethylene rubber such as chlorosulfonated polyethylene rubber; olefin-based copolymer rubber and its modified products;
And silicone rubber. Among them, aromatic vinyl-conjugated diene block copolymer rubber and hydrogenated product, modified polyethylene rubber, olefin-based copolymer rubber and its modified product, silicone rubber and the like are preferable, and olefin-based copolymer rubber is preferred. Particularly preferred.

The olefin copolymer rubber includes, for example, a copolymer rubber obtained by copolymerizing two or more of the α-olefins exemplified for the olefin resin, and an α-olefin and other copolymerizable monomers. And a copolymer rubber obtained by copolymerizing the above. Specifically, for example, ethylene / propylene copolymer rubber, ethylene / butene-1
Copolymer rubber of ethylene and other α-olefin such as copolymer rubber; isobutene (90 to 99.5% by weight)
Α such as isoprene (10-0.5% by weight) copolymer rubber
-Copolymer rubber of olefin and diene monomer; ethylene and other α-olefin and diene monomer such as ethylene / propylene / dicyclopentadiene copolymer rubber, ethylene / propylene / ethylidene norbornene copolymer rubber Copolymer rubber; and the like.

Examples of the modified olefin copolymer rubber include those obtained by modifying the olefin copolymer rubber with a polar compound. Specifically, for example, a chlorinated olefin copolymer rubber, a chlorosulfonated olefin copolymer rubber, a polar vinyl compound adduct obtained by adding a polar vinyl compound to an olefin copolymer rubber,
Examples include a polar compound graft polymer obtained by graft-polymerizing a polar vinyl compound to an olefin copolymer rubber,
Preferred are chlorinated olefin copolymer rubbers, chlorosulfonated olefin copolymer rubbers, and polar vinyl compound adducts of olefin copolymer rubbers. Examples of the polar vinyl compound include acrylic acid, methacrylic acid, crotonic acid, maleic acid, methyl acrylate, and vinyl acetate.

These resinous or rubbery polymers can be used alone or in combination of two or more. The ratio between the resinous or rubbery polymer and the polymer modifier of the present invention is appropriately selected depending on the purpose of use, but the polymer polyol in the polymer modifier is 100 parts by weight of the resinous or rubbery polymer. 0.01-50
Parts by weight, preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight.

In the polymer composition of the present invention, if necessary, a vulcanizing system such as a stabilizer, an inorganic filler, a vulcanizing agent, a vulcanization accelerator, a vulcanizing activator, a dehydrating agent such as calcium oxide, and the like. Other additives commonly used in the resin industry can be added.

As the stabilizer, for example, phenol type,
Antioxidants such as phosphorus and sulfur; ultraviolet absorbers such as hindered amine, benzotriazole and benzoate; and the like. Among these, the addition of a phosphorus-based antioxidant is preferred, and the phosphorus-based antioxidant is used alone or in combination with a phosphorus-based antioxidant and another stabilizer (other antioxidant and / or ultraviolet absorber). .

As the phenolic antioxidant, those conventionally known can be used. For example, 2-t-butyl-6-
(3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-
JP-A-63-179953 and JP-A-Heisei 1-79 such as 2-hydroxyphenyl) ethyl) phenyl acrylate.
Acrylate compounds described in JP-B-168463; 2,6-di-t-butyl-4-methylphenol;
2,6-di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-
Bis (4-methyl-6-t-butylphenol), 4,
4′-butylidene-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-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tetrakis (methylene-3- (3 ′, 5′-
Di-t-butyl-4'-hydroxyphenyl) propionate) methane, triethylene glycol bis (3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionate), alkyl-substituted phenolic compounds such as tocopherol; 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-
Triazine-based compounds such as octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine; and the like.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, and tris (2, 4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-)
Methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide, 10- (3,5
-Di-t-butyl-4-hydroxybenzyl) -9,1
0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10
Monophosphite compounds such as -dihydro-9-oxa-10-phosphaphenanthrene; 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl phosphite); 4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite), 4,4'-isopropylidene-bis (diphenylmonoalkyl (C12-C15) phosphite),
1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, tetrakis (2,4-di-t-butylphenyl) -4,4 ′
-Biphenylenediphosphite, cyclic neopentanetetraylbis (octadecylphosphite), cyclic neopentanetetraylbis (isodecylphosphite), cyclic neopentanetetraylbis (nonylphenylphosphite), cyclic neo Pentanetetraylbis (2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis (2,4-dimethylphenylphosphite),
Diphosphite compounds such as cyclic neopentanetetraylbis (2,6-di-t-butylphenylphosphite) and cyclic neopentanetetraylbis (2,4,6-tri-t-butylphenylphosphite) And the like. Among these, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-diphenyl) -T-butylphenylphosphite), cyclic neopentanetetraylbis (2,6-di-t-butylphenylphosphite), cyclic neopentanetetraylbis (2,4,6-
Tri-t-butylphenylphosphite) and the like are particularly preferred.

Examples of the sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 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.

Examples of the hindered amine ultraviolet absorber include, for example, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( 1,
2,2,6,6-pentamethyl-4-piperidyl) -2
-(3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy)
Ethyl) -2,2,6,6-tetramethylpiperidine and the like.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (3-t-butyl-2-).
(Hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole,
Compounds such as 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole are exemplified.

Examples of the benzoate-based ultraviolet absorber include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate. The compound of.

These stabilizers are used alone or in combination of two or more. The amount of these stabilizers is appropriately selected according to the purpose of use,
Usually 0.02 to 100 parts by weight of polymer polyol
To 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.5 part by weight.

Examples of the inorganic filler to be blended include calcium oxide, magnesium oxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, magnesium carbonate, calcium silicate, magnesium silicate, calcium carbonate, calcium titanate, barium sulfate, Magnesium sulfate, calcium sulfite, talc, clay,
Glass, mica, dolomite, basic calcium carbonate,
Examples thereof include zinc oxide, silica, carbon black, and glass fiber, and preferably, calcium carbonate, barium sulfate, mica, talc, and carbon black.

In the present invention, a surface-treated inorganic filler is particularly preferably used. Specific examples of the surface treatment may be those conventionally known, and include, for example, those treated with an acid such as a silane-based or titanium-based coupling agent, a higher fatty acid or an unsaturated fatty acid. The particle size of the inorganic filler is not particularly limited, but those having an average particle size of usually 5 μm or less are used.

These inorganic fillers can be used alone or in combination of two or more. The amount of the inorganic filler used is appropriately selected according to the purpose of use, but is usually 1 to 50 parts by weight, preferably 2 to 40 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the resinous or rubbery polymer. -30 parts by weight.

The vulcanizing agent is not particularly restricted but includes, for example, powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur,
Sulfur such as highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; dicumyl peroxide; organic peroxides such as di-t-butyl peroxide; p-quinone dioxime; Quinone dioximes such as dibenzoylquinone dioxime; organic polyamine compounds such as triethylenetetramine, hexamethylenediaminecarbamate, and 4,4'-methylenebis-o-chloroaniline;
And alkylphenol resins having a methylol group; among these, sulfur is preferred, and powdered sulfur is particularly preferred. Each of these vulcanizing agents, alone,
Alternatively, two or more kinds are used in combination.

The vulcanizing agent is usually added in an amount of 0.1 to 15 parts by weight, based on 100 parts by weight of the polymer as the base material.
Preferably 0.3 to 10 parts by weight, more preferably 0.1 to 10 parts by weight.
It is in the range of 5 to 5 parts by weight. When the compounding ratio of the vulcanizing agent is in this range, it is particularly preferable because it has excellent tensile strength and abrasion resistance as well as excellent properties such as heat generation and residual strain.

Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide and N-cyclohexyl-2-benzothiazolesulfenamide.
-Sulfenamide vulcanization accelerators such as -t-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N, N'-diisopropyl-2-benzothiazolesulfenamide Guanidine-based vulcanization accelerators such as diphenylguanidine, diortitolylguanidine, ortho-tolylbiguanidine; thiourea-based vulcanization accelerators such as thiocarbanilide, diortotolylthiourea, ethylenethiourea, diethylthiourea, trimethylthiourea;
-Mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt, 2
-Mercaptobenzothiazole sodium salt, 2-mercaptobenzothiazole cyclohexylamine salt,
Thiazole vulcanization accelerators such as (2,4-dinitrophenylthio) benzothiazole; thiurams such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide and dipentamethylenethiuram tetrasulfide Vulcanization accelerators: sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium di-n-butyldithiocarbamate, lead dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, pentamethylene Zinc dithiocarbamate, zinc ethylphenyldithiocarbamate, tellurium diethyldithiocarbamate, dimethyldithiocarbamate Dithiocarbamic acid-based vulcanization accelerators such as selenium acid selenium, selenium diethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, diethylamine diethyldithiocarbamate, piperidine pentamethylenedithiocarbamate, and pipecoline methylpentamethylenedithiocarbamate; sodium isopropylxanthogenate , Xanthogen acid-based vulcanization accelerators such as zinc isopropylxanthate and zinc butylxanthogenate; and vulcanization accelerators.

These vulcanization accelerators can be used alone,
Alternatively, two or more kinds are used in combination. The compounding ratio of the vulcanization accelerator is generally 0.1 to 15 parts by weight, preferably 0.3 to 15 parts by weight, based on 100 parts by weight of the polymer as the base material.
10 parts by weight, more preferably 0.5 to 5 parts by weight.

The vulcanization activator is not particularly limited, but higher fatty acids such as stearic acid and zinc oxide can be used. As the zinc oxide, for example, it is preferable to use one having a high surface activity and a particle size of 5 μm or less. As such a specific example, the particle size is, for example,
Active zinc white of 0.05 to 0.2 μm and zinc white of 0.3 to 1 μm can be exemplified. Also, zinc oxide
A surface-treated material with an amine-based dispersant or wetting agent can be used.

These vulcanization activators can be used alone or in combination of two or more.
The mixing ratio of the vulcanization activator is appropriately selected depending on the type of the vulcanization activator, but is usually 0.05 to 20 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer as the base material.
It is 1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight.

The polymer composition may be mixed according to a conventional method. The above components are mixed using, for example, a Henschel mixer, and then mixed with an extruder such as a single-screw extruder or a twin-screw extruder; Kneading using a brabender, plastmill, kneader, roll, extruder, multi-axis kneader, double helical ribbon stirrer, and the like. The kneaded polymer composition is usually handled in a pellet form.

By molding the polymer composition according to a conventional method, it is possible to obtain a polymer molded article having improved coatability on the surface of the molded article. As a molding method, for example,
Any known method such as injection molding, hollow molding, extrusion molding, compression molding, rotational molding and the like may be used, and an arbitrary molded body can be obtained.

By coating (coating) the surface of the above-mentioned polymer molded product, a resin-coated molded product having excellent coating film strength and solvent resistance can be obtained.

The paint to be applied is not particularly limited as long as it is a paint generally used in industry. For example, a solvent type thermoplastic (meth) acrylic type paint, a solvent type thermosetting (meth) type
Acrylic paints, polyurethane paints, acrylic urethane paints, silicon-modified urethane paints, melamine paints, epoxy paints, acrylic-modified alkyd paints,
Amine alkyd paints, alkyd melamine paints,
Examples thereof include polyether melamine-based paints and polyester melamine-based paints. Among these, polyurethane-based paints, acrylic urethane-based paints, epoxy-based paints, alkyd melamine-based paints, polyether melamine-based paints, and the like are preferred, and polyurethane-based paints, polyether melamine-based paints, and polyester melamine-based paints are particularly preferred.

The paint is applied directly on the surface of the polymer molded body or, if necessary, by a degreasing treatment such as washing with warm water.
Alternatively, it can be performed after the primer treatment.
The method of applying the paint may be in accordance with a conventional method, for example,
Methods such as electrostatic coating, spraying (air spray) coating, brush coating, and coating with a roller are used. The application of the paint may be performed by a method of applying an undercoat and then applying an overcoat. After applying the paint, a method of heating and curing with nichrome wire, infrared ray, high frequency (UHF), etc. is adopted.
It is appropriately selected depending on the shape, the properties of the paint used, and the like.

The polymer composition of the present invention contains a vulcanization system,
When applying a paint to the molded article and curing by heating, the paint may be applied to the vulcanized molded article and cured by heating, or the paint may be applied after being formed into an unvulcanized molded article by an extruder or a press, Vulcanization and curing of the paint may be performed simultaneously.

The thickness of the paint is appropriately selected according to the purpose of use, but is usually 1 to 1,000 μm after drying.
Preferably 5-500 μm, more preferably 10-20
The range is 0 μm.

Since the coated molded article of the present invention has its coating film firmly adhered thereto, various industrial parts such as automobile bumpers, mat guards, side moldings, wheel caps, spoilers, seal sponges, glass run, etc. Industrial rubber products such as automotive exterior parts, instrument panels, lever knobs, lining and other automotive interior parts, hoses, tubes, belts, various rolls, O-rings, waterproof sheets, waterproof grommet, rubber parts for various seals , Roofing materials, building materials such as wall materials, electric wire cables, footwear, pots, vacuum cleaners, washing machines, refrigerators, lighting equipment, AV equipment, OA equipment and other electrical equipment parts, sports equipment such as golf balls for practice, color boxes Use for painted items such as daily necessities such as storage cases, storage cases, and medical tools Applications it is necessary to lower the sliding resistance by computing, urethane or epoxy adhesive or the like other materials and the adhesive to be able to like widely used applications to be used by using the.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Parts and percentages in these examples are on a weight basis unless otherwise specified.

(1) Weight Average Molecular Weight The weight average molecular weight of the polymer polyol was calculated as a standard polystyrene equivalent in accordance with the GPC method. (2) Hydroxyl Value and Acid Value The hydroxyl value and the acid value of the polymer polyol were measured according to the following described in “Standard Oil and Fat Analysis Test Method” (Japan Oil Chemical Association). Hydroxyl value 2,4,9,2-83 Acid value 2,4,1-83 (3) Adhesion test of coating film on rubber surface Gauze is stuck on the coating film surface with an instant adhesive to form a 1 cm wide strip. After piercing the rubber and gauze ends 200mm
The film was pulled in the direction of 180 ° at a speed of / min, and its maximum peel strength (kgf / cm) was measured. (4) Adhesion test of coating film on resin surface According to the cross-cut test method described in JIS K5400, a cross-cut test piece was prepared, and cellophane (Nichiban) was placed on the cross-cut. After sticking, it is quickly pulled in the direction of 90 ° to be peeled off.
Among them, the number of grids not peeled was measured. (5) Solvent resistance test A sample cut out equally to a size of 20 × 30 mm from a painted product was immersed in gasohol (gasoline containing 10% by volume of ethyl alcohol) at 23 ° C. until the coating film was partially peeled. Was measured. (6) Vulcanization rate According to JIS K6300-1944, the vulcanization rate of Tc (5) was measured at 160 ° C. using a disc rheometer (ASTO-100, manufactured by Toyo Seiki Seisaku-sho, Ltd.).

Production Example 1 (Polymer polyol A) 166.1 g of terephthalic acid, 2,2-dipropyl 167.6 g of -1,3-propanediol, 65.4 g of ditrimethylolpropane and manganese acetate hydrate 0.2 as a catalyst
4 g and antimony trioxide 0.29 g were charged. (OH / COOH equivalent ratio = 1.56) While stirring while introducing nitrogen gas to remove water and unreacted diol generated during the reaction, the temperature was reduced from 200 ° C to 2 ° C.
The temperature was raised to 40 ° C. over 6 hours. Then 240 ° C
The reaction was continued for 3 hours while dehydrating under reduced pressure of 50 mmHg. The obtained polymer polyol A had a weight average molecular weight of 12,450, an acid value of 0.15 mgKOH / g,
The hydroxyl value was 135 mgKOH / g, and the light transmittance was 92%.

Production Example 2 (Polymer polyol B) 132.9 g of terephthalic acid and 33.2 g of isophthalic acid were placed in a 500-cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water separator, and a nitrogen gas inlet tube. , 2-butyl-2-ethyl-1,3-propanediol 186.1
g, 32.7 g of dipentaerythritol and 0.20 g of monobutyltin oxide as a catalyst. (OH / COOH equivalent ratio = 1.54) While stirring while introducing nitrogen gas to remove water and unreacted diol generated during the reaction, the temperature was lowered from 200 ° C. to 2 ° C.
The temperature was raised to 40 ° C. over 6 hours. Then 240 ° C
The reaction was continued for 3 hours while dehydrating under reduced pressure of 50 mmHg. The obtained polymer polyol B had a weight average molecular weight of 19,200, an acid value of 0.15 mgKOH / g,
The hydroxyl value was 116 mgKOH / g, and the light transmittance was 93%.

Production Example 3 (Polymer polyol C) 358.8 g of terephthalic acid, 2-butyl-2 -Ethyl-1,3-
260.1 g of propanediol, 80.4 of glycerol
g and monobutyltin oxide as catalyst 0.20 g
Was charged. (OH / COOH equivalent ratio = 1.35) While stirring while introducing nitrogen gas, while removing water and unreacted diol generated during the reaction, the temperature was lowered from 200 ° C. to 2 ° C.
The temperature was raised to 40 ° C. over 6 hours. Then 240 ° C
The reaction was continued for 3 hours while dehydrating under reduced pressure of 50 mmHg. The obtained polymer polyol C had a weight average molecular weight of 12,410, an acid value of 0.15 mgKOH / g,
The hydroxyl value was 105 mgKOH / g, and the light transmittance was 89%.

Production Example 4 (Polymer Polyol D) 1302.2 g of terephthalic acid, 2-ethyl-2 -Butyl-1,3
1361.7 g of propanediol, 128.5 g of pentaerythritol and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.32) 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 diol generated during the reaction. After that, while dehydrating at 240 ° C, 5
The reaction was continued for an hour, and finally, the reaction was continued for 3 hours under a reduced pressure of 50 mmHg. The obtained polymer polyol D had a weight average molecular weight of 6,840, an acid value of 0.3 mgKOH / g, a hydroxyl value of 95.3 mgKOH / g, and a light transmittance of 96%.

Production Example 5 (Polymer polyol E) 358.8 g of terephthalic acid, 2-ethyl-2 -Butyl-1,3-
278.2 g of propanediol, 45.2 g of neopentyl glycol, 73.8 g of pentaerythritol and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.50) 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 diol generated during the reaction. After that, while dehydrating at 240 ° C, 5
The reaction was continued for an hour, and finally, the reaction was continued for 3 hours under a reduced pressure of 50 mmHg. The obtained polymer polyol E had a weight average molecular weight of 12,300, an acid value of 0.3 mg KOH / g, a hydroxyl value of 116 mg KOH / g, and a light transmittance of 87%.

Production Example 6 (Polymer Polyol F) In a four-necked 1000-cc flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, polymerized fatty acid Haridima 250 (manufactured by Harima Kasei; dimer) Acid 7
9.0%, trimer acid 18.0%, monomeric acid 3.0
%, Acid value 193) 420 g, 2,2-diethyl-1,3
113.4 g of propanediol, 41.4 g of pentaerythritol and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.40) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 100 ° C. Subsequently, the temperature was raised from 100 ° C. to 240 ° C. over 6 hours while removing water and unreacted diol generated during the reaction. Then, while dehydrating at 240 ° C, 1
The reaction was continued for 0 hour, and finally,
A time reaction was performed. The obtained polymer polyol F had a weight average molecular weight of 21,500 and an acid value of 0.2 mgKOH /
g, hydroxyl value 89.5 mgKOH / g, light transmittance 98%
Met.

Production Example 7 (Polymer Polyol G) A polymerized fatty acid Hariddimer 250 (manufactured by Harima Chemicals; Dimer) was placed in a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube. Acid 7
9.0%, trimer acid 18.0%, monomeric acid 3.0
%, Acid value 193) 420 g, 2-butyl-2-ethyl-
116.5 g of 1,3-propanediol, 69.6 g of diethylene glycol, 44.3 g of pentaerythritol
And 0.17 g of tetra-n-butyl-ortho titanate as a catalyst. (OH / COOH equivalent ratio = 1.50) The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 100 ° C. Subsequently, the temperature was raised from 100 ° C. to 240 ° C. over 6 hours while removing water and unreacted diol generated during the reaction. Then, while dehydrating at 240 ° C, 1
The reaction was continued for 0 hour, and finally,
A time reaction was performed. The obtained polymer polyol G had a weight average molecular weight of 13,700 and an acid value of 0.1 mg KOH /
g, hydroxyl value 96.1 mgKOH / g, light transmittance 92%
Met.

Production Example 8 (Nitrogen-containing compound) 360 g of isostearic acid (Mw = 284) and tetraethylenepentamine (Hereinafter abbreviated as TEPA, Mw = 189)
240 g was charged. At this time, the molar ratio between TEPA and isostearic acid was 1: 1. Next, this was sealed, and a reaction was performed at a pressure of 400 mmHg and a temperature of about 150 ° C. for 3 hours. Subsequently, the reaction system was heated, and a reaction was performed at a pressure of 30 mmHg and a temperature of 200 ° C. for 8 hours. During this time, the acid number dropped to 1.2. Subsequently, heating was stopped and the reaction mixture was cooled. Taking an infrared spectrum and nuclear magnetic resonance spectrum of the reaction product was identified, (N-H stretching vibration of 3300 cm ^-1) aminoethyl group, 2 absorption and ring imine band imidazoline ring (1660 cm ^-1 And the presence of a methine group at position 2 on the imidazoline ring. The structural formula of this imidazoline compound is as follows. Further, the composition of the reaction product was analyzed by liquid chromatography (reverse phase distribution mode). As a result, the proportion of the imidazoline compound was 86%. This compound is hereinafter referred to as imidazoline A.

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Production Example 9 (Nitrogen-containing compound) 360 g of oleic acid (Mw = 282) and 2-hydroxyethyl were placed in a 1-liter four-necked flask equipped with a stirrer, thermometer, sample extraction tube, condenser and pressure gauge. Aminoethylamine (hereinafter abbreviated as HEAEA, Mw
= 104) 133 g were charged. At this time, the molar ratio between HEAEA and oleic acid was 1: 1. Next, this was sealed, and a reaction was performed at a pressure of 400 mmHg and a temperature of about 150 ° C. for 3 hours. Subsequently, the temperature of the reaction system was increased to a pressure of 30 mmHg.
g, and the reaction was carried out at a temperature of 200 ° C. for 8 hours. During this time, the acid number dropped to 1.2. Subsequently, heating was stopped and the reaction mixture was cooled. Taking an infrared spectrum and nuclear magnetic resonance spectrum of the reaction product was identified, (O-H stretching vibration of 3450 cm ^-1) hydroxyethyl group, 2 absorption and ring imine band imidazoline ring (1660 cm ^-1 And the presence of a methine group at position 2 on the imidazoline ring. The structural formula of this imidazoline compound is as follows. Also,
When the composition of the reaction product was analyzed by liquid chromatography (reverse phase distribution mode), the proportion of the imidazoline compound was 96%. This compound is referred to as imidazoline B
Call.

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Examples 1-3, Comparative Example 1, Reference Examples 1-2 Using the polymer polyols A, B and D produced above,
Rubber compositions were prepared according to the formulation shown in Table 1 (Examples 1 to 3). In addition, what did not add a modifier (polymer polyol / tackifier / nitrogen-containing compound) was also prepared for comparison (Comparative Example 1 and Reference Examples 1 and 2). After kneading each component other than the nitrogen-containing compound, sulfur and the vulcanization accelerator with a 0.8 liter Banbury mixer at 60 ° C. for 5 minutes, the modifier, sulfur and the vulcanization accelerator are removed with a 6-inch roll to remove the nitrogen-containing compound. And kneaded at 60 ° C. The sheet-shaped unvulcanized rubber was taken out from the roll, and extruded into a flat plate by a 20φ extruder. The surface of the rubber molded product was coated with a urethane paint for glass run of Comparative Example 1 described in JP-A-7-150074 using a spatula so as to have a thickness of 100 μm.
, And vulcanization and curing were performed simultaneously for 12 minutes to prepare a test piece. An adhesion test of the coating film of the obtained coated product was performed, and the vulcanization rate was measured. The results are shown in Table 1.

[Table 1]

Examples 4-6, Comparative Example 2, Reference Examples 3-4 Using the polymer polyols C, E and F produced above,
Rubber compounds were prepared according to the compounding recipe shown in Table 2 (Examples 4 to 6). In addition, what did not add a modifier (polymer polyol / tackifier / nitrogen-containing compound) was also prepared for comparison (Comparative Example 2, Reference Examples 3 and 4). After kneading the components other than the modifier, sulfur and the vulcanization accelerator with a 0.8 liter Banbury mixer at 60 ° C. for 5 minutes, the modifier, sulfur and the vulcanization accelerator were added by a 6-inch roll, and the mixture was heated to 60 ° C. And kneaded. The sheet-shaped unvulcanized rubber was taken out from the roll and vulcanized at 160 ° C. for 15 minutes at 100 kg / cm ² using a press to obtain a 150 × 80 × 2 mm vulcanized rubber sheet. A vulcanized rubber sheet is cut into 75 × 40 × 2 mm, and an epoxy adhesive (manufactured by Konishi Co., Ltd., Bond MO
S1010) is applied to a thickness of 300 μm,
The test piece was dried at 60 ° C. for 2 hours and then left standing for 96 hours. An adhesion test of the coating film of the obtained coated product was performed, and the vulcanization rate was measured. The results are shown in Table 2.

[Table 2]

Examples 7 and 8, Comparative Example 3 and Reference Example 5 Each raw material was mixed in a Henschel mixer in the composition shown in Table 3 and then melt-kneaded by a twin-screw extruder set at 220 ° C., and pelletized to obtain a resin. A composition was made. A test piece used for a coating film adhesion test was prepared as follows. Specimens by injection molding (50 × 80 mm, thickness 3.
1 mm), a primer (trade name: RB-197, manufactured by Nippon B.P.Chemical Co., Ltd.) is applied to a thickness of 10 μm, dried at 80 ° C. for 10 minutes, and then a urethane-based metallic paint (Nippon B.P. (Trade name: RB-212) and urethane clear paint (trade name: RB-28, manufactured by Nippon Beep Chemical Co., Ltd.)
8) was prepared based on the specifications of Nippon B.P. Chemical Co., Ltd., and applied so that the film thickness became 20 μm and 25 μm.
It was dried at 0 ° C. for 45 minutes and then left for 24 hours to obtain a test piece. Using this test piece, an adhesion test and a solvent resistance test of the coating film were performed. The results are shown in Table 3.

[Table 3]

From the results shown in Tables 1 to 3, it is understood that when the polymer composition containing the modifier of the present invention is used, a coated molded article having excellent adhesion and solvent resistance of the coating film can be obtained. . Further, from the results in Tables 1 and 2, it is understood that the use of the modifier of the present invention makes it easy to control the vulcanization rate and has a great advantage in production.

[0114]

According to the present invention, there is provided a novel polymer modifier capable of sufficiently improving the coatability of a resin having a low polarity such as polypropylene or a highly saturated hydrocarbon rubber. Further, the modifier of the present invention has an effect of improving adhesiveness and printability in addition to the above-mentioned use for improving the coating property, and can widely improve the surface characteristics of a resinous or rubbery polymer.

Claims (4)

[Claims] 1. A modifier for a resinous or rubbery polymer, comprising a polymer polyol, a tackifier and a nitrogen-containing compound. 2. A polymer composition comprising the resinous or rubbery polymer and the modifier according to claim 1. 3. A polymer molded article obtained by molding the polymer composition according to claim 2. 4. A coated polymer molded article obtained by coating the surface of the polymer molded article according to claim 3.