JPH09137116A - Primer composition and molded article having primer layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which increases the adhesiveness of a paint to such a substrate with a weak polarity as rubber without a pre-treatment by composing it to include a specific oil soluble polyester, a vulcanizable rubber, vulcanizing agent and organic solvent. SOLUTION: This composition is composed to include an oil soluble polyester which has 3 or more polar groups having H atom and heteroatom in the molecule, a weight average molecular weight of 1,000-1,000,000 and preferably the sum of an acid value and a hydroxyl value of 10-200mg/KOH (e.g. a polyester obtained from a polymerizable fatty acid containing 8.0% monomer acid, 75.0% dimer acid and 17.0% trimer acid, 2-ethyl-2-butyl-1,3-propanediol and trimethylolpropane) and a vulcanizable rubber (e.g. an ethylene-propyrene- ethylidenenorbornene copolymer) and a vulcanizing agent (e.g. S) and an organic solvent (e.g. xylene).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a primer composition, and more particularly to a primer composition containing an oil-soluble polyester that exhibits good adhesion to substrates such as synthetic resins and rubbers. Furthermore, the present invention relates to a molded article having a layer of the primer composition formed on the surface of a substrate, and a coated molded article having a coating film formed on the primer layer surface of such a molded article.

[0002]

2. Description of the Related Art As is well known, hydrocarbon polymer resins such as polyolefins and ethylene-propylene rubbers are widely used because they have excellent physical properties and are relatively inexpensive. Since there is no polar group, there is a problem that the adhesion of the coating film is low and practical adhesive strength cannot be obtained. Furthermore, the hydrocarbon polymers themselves,
It is known that the adhesion of a hydrocarbon polymer to a metal, other resin or rubber is difficult for the same reason.

Conventionally, in order to overcome such drawbacks, (1) the surface is polished with sandpaper, (2) UV irradiation is performed, (3) chemical treatment with phosphoric acid or aldehydes,
(4) A method such as treatment with a primer such as a mixture of chlorinated polypropylene and ethylenediamine is known, but the adhesion or adhesiveness of the paint is not always sufficient in spite of problems in working environment and complicated working process. I couldn't say that. In addition, Japanese Patent Publication No. 60-23779,
Although a technique relating to a primer composition comprising hydrogenated polyhydroxypolybutadiene and an ethylene-propylene-based copolymer is disclosed, it is not sufficient in terms of an anchor effect with a rubber matrix, and in particular, peel strength is not always sufficient. There wasn't.

Conventionally, as such a primer, for example, a primer composition containing a styrene / butadiene block copolymer graft-copolymerized with an α, β-unsaturated vinyl monomer having a hydroxyl group as a main component (Japanese Patent Application Laid-Open No. HEI 9-242242) 2-1
No. 10168), and a primer composition mainly composed of a styrene / isoprene block copolymer graft-copolymerized with a monoolefin dicarboxylic acid (JP-A-4-264174). However, in a primer composition containing these modified block copolymers as a main component, a pretreatment such as steam cleaning using a chlorine-based solvent such as trichloroethane is applied to the base material before being applied on the base material. There is a need for improvement from the standpoint of global environmental protection in recent years.

As a primer composition which does not require pretreatment with a chlorine-based solvent, for example, a block copolymer of styrene / isoprene / styrene obtained by graft copolymerizing an ethylenically unsaturated monomer having a hydroxyl group is used. A primer composition containing a main component is known (Japanese Patent Laid-Open No. 6-
329977). However, this composition has problems such as insufficient anchoring effect to the substrate and insufficient adhesion to the substrate.

[0006]

The object of the present invention is to provide a base material made of a material having a small polarity such as a resin or a rubber made of a hydrocarbon polymer without subjecting its surface to a special pretreatment. It is to provide a primer composition capable of forming a primer layer having excellent adhesion to a substrate and capable of forming a coating film having excellent adhesion on the surface by coating. . Further, another object is to provide a molded product capable of forming a coating film having excellent adhesion on the surface thereof by coating, and a coated product of such a molded product.

[0007]

According to the present invention, at least 3 polar groups containing a hydrogen atom and a hetero atom are contained in a molecule.
Having a weight average molecular weight of 1,000 to 1,000,0
No. 00 oil-soluble polyester, a vulcanizable rubber, a vulcanizing agent, and an organic solvent are provided. According to the present invention, there is further provided a molded body comprising a base material and a primer layer formed on the surface of the base material and comprising the primer composition. According to the present invention, there is further provided a coated molded article comprising a substrate, a primer layer formed on the surface of the substrate and comprising the primer composition, and a coating film formed on the surface of the primer layer. To be done.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Polyester The polyester used in the present invention is characterized by having at least three polar groups containing a hydrogen atom and a hetero atom in the molecule. The polar group is not particularly limited as long as it has at least one hydrogen atom and at least one hetero atom. Heteroatoms include any of the 2nd to 4th periods of the periodic table and the 5th group or the 6th group.
Examples thereof include atoms belonging to Group B, and specific examples thereof include an oxygen atom, a nitrogen atom and a sulfur atom, and an oxygen atom is preferable. Examples of the polar group having a hydrogen atom and a hetero atom include a hydroxyl group, a carboxyl group, an amino group, and a thiol group. Among these, a hydroxyl group and a carboxyl group are preferable, and a hydroxyl group is particularly preferable.

It is necessary that at least three such polar groups containing hydrogen atoms and hetero atoms are present in the polyester molecule, and if the number is less than 3, the adhesiveness to paints and the like will be reduced, which is not preferable. The maximum value of the polar group content may be appropriately selected within the range in which the polyester does not become oil-soluble,
There is no particular limitation. Oil-soluble is a property that does not dissolve in water. If the polyester used is not oil-soluble, the effect of anchoring with the base material is poor, and the adhesion is insufficient, which is not preferable.

When the polar group containing a hydrogen atom and a hetero atom is a hydroxyl group or a carboxyl group, its content in the polyester can be represented by a hydroxyl value or an acid value,
The value can be appropriately selected depending on the molecular weight of the polyester, but the sum of the hydroxyl value and the acid value is usually 10 to 200 mg.
KOH / g, preferably 20-150 mg KOH / g,
More preferably, it is in the range of 40 to 120 mgKOH / g.

The molecular weight of the polyester is 1,000 to 1,000 in terms of polystyrene-converted weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).
1,000,000, preferably 2,000-500,
000, more preferably 3,000 to 100,000. Even if the molecular weight of polyester is too small or too large, the anchor effect to the substrate is not sufficient, and the adhesion and peel strength are poor, which is not preferable.

The method for producing the polyester used in the present invention is not particularly limited. For example, (A) a divalent higher carboxylic acid component, (B) a divalent alcohol component and (C) a trivalent or higher carboxylic acid component. , At least one trivalent or higher polyvalent component selected from trivalent or higher alcohols and epoxy compounds having two or more epoxy groups,
1 component of (C) is added to the total amount of both (A) and (B) components.
It can be obtained by polycondensation at a ratio of -80 mol%.

As the divalent higher carboxylic acid (A), those having 8 or more carbon atoms, preferably 10 to 200 carbon atoms, more preferably 20 to 80 carbon atoms are used. When the number of carbon atoms in the carboxylic acid is within this range, the anchor effect with the substrate and the adhesion strength are sufficiently high, which is preferable.

Such divalent higher carboxylic acid is, for example,
It may be linear, branched, cyclic or aromatic, and specific examples thereof include suberic acid, azelaic acid, terephthalic acid, isophthalic acid, methylisophthalic acid, sebacic acid, brassic acid, polyalkylene. Succinic acid,
Examples thereof include dimer acid of polymerized fatty acid, and among these, at least one selected from dimer acid of polyalkylene succinic acid and polymerized fatty acid is preferable,
Dimer acid of polymerized fatty acid is particularly preferable.

The polymerized fatty acid is obtained by polymerizing a higher fatty acid, and usually has 8 to 24 carbon atoms, preferably 16 to 2 carbon atoms.
It is a generic term for polymerized acids obtained by polymerizing an aliphatic having 0 saturated or at least one unsaturated bond or an aliphatic ester derivative thereof. Commercially available polymerized fatty acids are those obtained by polymerizing oleic acid, linoleic acid, ricinoleic acid, eleostearic acid, etc., containing dimer acid as the main component, and polymer acid and monomer acid of trimer acid or more as sub-components. Is what you are doing. The structural analysis of polymerized fatty acids is described in D.S. H. McMahon et al. (J. Am. Oil. Chem. Soc., 5
1 , 522 (1974)). The polymerization product can be separated into polymerized fatty acids having different contents of each component by a distillation method or a solvent extraction method. Further, hydrogenated polymerized fatty acids having good thermal oxidation stability can be obtained by hydrogenating the unsaturated carbon-carbon bonds remaining in these polymerized fatty acids. In the present invention, unpurified polymerized fatty acid, purified polymerized fatty acid or hydrogenated polymerized fatty acid can also be used, and preferably purified polymerized fatty acid containing 60% by weight or more of a dimer acid component or a hydride thereof is used.

Polyalkylene succinic acid has the general formula (1) (R ¹ in the formula is a polymer chain of lower alkylene.)
It is represented by R ¹ is a polymer chain of lower alkylene, and preferably the lower alkylene is at least one selected from ethylene, propylene and butylene. The degree of polymerization of polyalkylene succinic acid is preferably 10 to 300.
Range.

The dihydric alcohol (B) is not particularly limited as long as it is commonly used in polyester synthesis reactions, and examples thereof include alkane diols, cycloalkane diols, polyoxyalkylene glycols and ester diols. And hindered glycols. Among these, alkanediols,
Polyoxyalkylene diols and hindered glycols are preferable, and alkane diols and hindered glycols are particularly preferable. These can be used alone or in combination of two or more.

Examples of the alkanediols include 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, 1,6-hexanediol, 3-methyl-1,5-pentanediol,
Alkanediols having 6 to 9 carbon atoms such as 1,8-octanediol and 1,9-nonanediol are preferable.

Cycloalkanediols include cyclopentane-1,2-diol, cyclohexane-1,
2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-
Examples include 1,4-dimethanol and cyclooctane-1,4-diol.

The polyoxyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol and dipropylene obtained by polymerizing alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide alone or in a mixture by a known method. glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polybutylene glycol and the like, for example, the general formula (2) HO - ((CH 2) m -CHR 2 O) n -H (2) Is represented by. Here, R ² represents a hydrogen atom or a lower alkyl group such as a methyl group or an ethyl group, and preferably a hydrogen atom. m represents an integer of 1 to 6, and preferably an integer of 1 to 4. n represents an integer of 2 to 1,000, preferably 5 to 500, more preferably 10 to 10.
It is an integer of 0.

The ester diols include, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, which are disclosed in JP-A-6-116372.
Lactones such as δ-valerolactone and ethylene glycol, diethylene glycol, triethylene glycol,
Opening products of (poly) alkylene glycol such as tetraethylene glycol and the like, for example, represented by the general formula ^{(3) HO- (R 3 -COO} -G) p -H (3). Here, R ³ represents an alkylene group, and usually has 2 to 6 carbon atoms. p represents an integer of 2 to 1,000, preferably 5 to 500, and more preferably 1
It is an integer of 0 to 100. G ^{_{is, - (CH 2 CHR 4 O}} )
_In the formula, q is an integer of 1 to 4, and R ⁴ is a hydrogen atom or a lower alkyl group such as a methyl group and an ethyl group.

Examples of the hindered glycols include those represented by the general formula (4) HOCH ₂ —C (R ⁵ R ⁶ ) —CH ₂ OH (4). Here, R ⁵ and R ⁶ represent an alkyl group. The carbon number 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 such hindered glycols include 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-diisobutyl-1,3-propanediol, 2-methyl-2-dodecyl -1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-propyl-2-pentyl-1,3
-Propanediol and the like.

In the present invention, in addition to the divalent higher carboxylic acid component (A) and the dihydric alcohol component (B), two or more trivalent or more carboxylic acids, trivalent or more alcohols, and epoxy groups are used. At least one (C) selected from the epoxy compounds having is used.

The trivalent or higher carboxylic acid is not particularly limited as long as it has three or more carboxyl groups, but a trivalent carboxylic acid is usually used. Specific examples of trivalent or higher carboxylic acids include, for example, trimellitic acid, tricarballylic acid, camphoronic acid, trimesic acid,
Examples include polymerized fatty acid trimer acid. Of these, trimesic acid and polymerized fatty acid trimeric acid are preferable, and polymerized fatty acid trimeric acid is particularly preferable.

The trihydric or higher alcohol is not particularly limited as long as it has three or more hydroxyl groups. Specific examples of trihydric or higher alcohols include, for example,
Examples include glycerol, diglycerol, polyglycerol, sorbitol, glucose, mannitol, sucrose, glucose and the like.

As the trihydric or higher alcohol, a trihydric or higher hindered alcohol represented by the general formula (5) HOCH ₂ —C (R ⁷ R ⁸ ) —CH ₂ OH (5) can be used. . In the formula, R ⁷ and R ⁸ represent an alkyl group,
At least one of R ⁷ and R ⁸ is an alkyl group having a hydroxyl group. Here, the carbon number of the alkyl group is not particularly limited, but is usually 1 to 50, preferably 1 to 20.
The number is more preferably 2 to 10. Specific examples of such trihydric or higher-valent hindered alcohols include trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, and the like.

These trihydric or higher alcohols may be used alone or in admixture of two or more, and the trihydric or higher alcohol component contains at least 10 mol% of the trihydric or higher hindered alcohol. , Preferably 2
0-100 mol%, more preferably 30-100 mol%
Those containing are preferable.

The epoxy compound having two or more epoxy groups is not particularly limited as long as it is a compound having at least two epoxy groups in the molecule, and examples thereof include dimer acid glycidyl ester of polymerized fatty acid and glycidyl ether of bisphenol A. , Glycidyl ether of bisphenol F, glycidyl ether of aliphatic dibasic acid, and the like.

The component (C) can be used either alone or as a mixture of two or more thereof, and the amounts of the components used are the divalent carboxylic acid component (A) and the divalent alcohol component (B). 1) to 80 mol%, preferably 5 to 60 mol%, and more preferably 10 to 40 mol%, based on the total amount of). If the amount of component (C) used is too small, the hydroxyl value or acid value will not be sufficient, and if it is too large, control of the polycondensation reaction will be difficult, and neither is preferred.

The dicarboxylic higher carboxylic acid (A) is contained in the carboxylic acid component as long as the object of the present invention is not impaired.
And a carboxylic acid component having three or more valences (C), other carboxylic acids such as succinic acid, glutaric acid, adipic acid,
Divalent lower carboxylic acids such as maleic acid, itaconic acid, pimelic acid, methylmalonic acid, dimethylmalonic acid; 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 arachidic acid, linoleic acid, oleic acid, and elaidic acid, and other alcohols in addition to the divalent alcohol component (B) and the trivalent or higher alcohol component (C) in the alcohol component, For example, methanol, ethanol, isopropanol, butanol, neopentyl alcohol, 3-methyl-3-pentanol,
A monohydric alcohol such as 3-ethyl-3-pentanol, 2,3,3-trimethyl-2-butanol, 1-decanol or nonyl alcohol may be used in combination. Generally, the permissible amount is 30 mol% or less in the total carboxylic acid component or total alcohol component, respectively.

The ratio of the carboxylic acid component and the alcohol component may be appropriately selected according to the desired molecular weight or hydroxyl value (or acid value) of the polyester.
The OH / COOH (equivalent) ratio is usually 1.1 to 3.0, preferably 1.15 to 2.5, and more preferably 1.2 to.
In the range of 2.0, or the COOH / OH (equivalent) ratio is 1.1 to 3.0, preferably 1.15 to 2.5, and more preferably 1.2 to 2.0.

The polyester used in the present invention can be obtained by polycondensation reaction of the above-mentioned component (A), component (B), component (C) and other optional carboxylic acid and alcohol components. The polycondensation reaction may be carried out according to a conventional method, for example, at a reaction temperature of 100 to 300 ° C, preferably 150 to 280 ° C, and particularly preferably in the presence of an inert gas. If necessary, a water-insoluble organic solvent that is azeotropic with water such as toluene or xylene may be used, or the reaction may be performed under reduced pressure. Further, at the time of esterification polycondensation reaction, usually, as an esterification catalyst, paratoluenesulfonic acid, sulfuric acid, boron trifluoride complex, phosphoric acid, hydrochloric acid, potassium acetate, zinc stearate,
Various metal oxides such as zinc, titanium, tin and alkyltin oxide, and titanium oxide are used.
From the viewpoint of oxidation resistance stability of the obtained polyester, it is preferable to use a metal oxide.

Primer Composition A primer composition containing the polyester of the present invention as an active ingredient contains a vulcanizable rubber, a vulcanizing agent and an organic solvent together with the above oil-soluble polyester. The organic solvent is not particularly limited as long as it is used in a usual primer composition, and is appropriately selected depending on the types of polyester and rubber used. Specific examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; hexane,
Aliphatic hydrocarbons such as heptane, octane and decane;
Cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane,
Alicyclic hydrocarbons such as trimethylcyclopentane and cyclooctane; alcohols such as ethanol and isopropyl alcohol; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Among these, aromatic hydrocarbons, alicyclic hydrocarbons, esters, ketones and the like are preferable, and aromatic hydrocarbons are particularly preferable.

These organic solvents are used alone or in combination of two or more, and the amount thereof is usually 10 to 10,000 per 100 parts by weight of polyester.
The proportion is 0 parts by weight, preferably 50 to 5,000 parts by weight, more preferably 100 to 1,000 parts by weight. When the amount of the organic solvent used is in the above range, workability and coating film stability are excellent and suitable.

A vulcanizable rubber and a vulcanizing agent are added to the primer composition of the present invention in order to improve the adhesion to the substrate and the adhesion of the paint or ink. The rubber is not particularly limited, and those generally used in the rubber industry can be used. Specifically, for example, natural rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, butadiene-isoprene copolymer rubber, styrene-
Butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, acrylonitrile-butadiene copolymer rubber, chloroprene rubber and other conjugated diene polymer rubber; chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber and other modified polyethylene rubber; α-olefin Examples of the copolymer rubber include silicone rubber. Among these, the main chain has a small amount of carbon-carbon double bonds,
For example, a rubber component having an iodine value of 100 or less, preferably 1 to 50, more preferably 5 to 35 is suitable. Among these, modified polyethylene rubber, α-olefin-based copolymer rubber, silicone rubber and the like, particularly α-olefin-based copolymer rubber, are preferable because the modifying effect of the present invention is remarkably exhibited.

The α-olefin used for producing the α-olefin copolymer rubber is an olefin having a carbon-carbon double bond at a terminal, and specific examples thereof include ethylene and
Propylene, 1-butene, 1-hexene, 3-methyl-
1-butene, 3-methyl-1-pentene, 4-methyl-
1-Pentene and the like, but not limited thereto.

The α-olefin copolymer rubber is not particularly limited as long as it is a rubber-like polymer containing the above α-olefin. For example, a copolymer rubber of two or more types of α-olefin, α-olefin Examples thereof include copolymer rubbers of olefins and other polymerizable monomers. The amount of α-olefin in the copolymer rubber is not particularly limited, but is usually 50 to 100.
%, Preferably 60 to 100% by weight, more preferably 80 to 100% by weight. The other polymerizable monomer is not particularly limited, but examples thereof include conjugated dienes and non-conjugated dienes. As a conjugated diene,
For example, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene,
1,3-hexadiene and the like are mentioned, and among these, 1,3-butadiene and isoprene are preferable. Examples of the non-conjugated diene include ethylidene norbornene, dicyclopentadiene, and 1,4-hexadiene. Among these, ethylidene norbornene and dicyclopentadiene are preferable. The content of these polymerizable monomers in the copolymer is usually 50 to 0% by weight, preferably 40 to 0% by weight, more preferably 20 to 0% by weight.
0% by weight.

Specific examples of the α-olefin copolymer rubber include, for example, two or more α-olefin copolymer rubbers such as ethylene-C 3 or more α-olefin copolymer rubber; ethylene-C 3 or more. Copolymers of two or more α-olefins and non-conjugated dienes such as α-olefin-non-conjugated diene copolymer rubbers; α-olefin-conjugated diene copolymerized rubbers; and their chlorinated products, chlorosulphonated products and maleic anhydride. Examples include modified rubbers such as acid addition products. The non-conjugated diene of the ethylene-C3 or more α-olefin-non-conjugated diene copolymer rubber is the above α
-The thing illustrated about the olefin type copolymer rubber is used. Examples of the α-olefin-conjugated diene copolymer rubber include butyl rubber obtained by copolymerizing 90 to 99.5 wt% of isobutene and 0.5 to 10 wt% of isoprene.

Preferred α-olefin copolymer rubbers are ethylene-propylene copolymer rubber, ethylene-butene-1 copolymer rubber, ethylene-propylene-ethylidene norbornene copolymer rubber, ethylene-propylene-dicyclopentadiene copolymer rubber. And so on. The weight ratio of ethylene and propylene is 90:10 to 20:80.
Particularly preferred are ethylene-propylene copolymer rubbers and ethylene-propylene-nonconjugated diene copolymer rubbers having a non-conjugated diene content of 3 to 15% by weight.

The above-mentioned vulcanizable rubbers can be used alone or in combination of two or more, and the amount thereof is usually 10 to 500 with respect to 100 parts by weight of the polyester of the present invention. Parts by weight, preferably 20-400
Parts by weight, more preferably 50 to 250 parts by weight.

The vulcanizing agent is not particularly limited and may be appropriately selected depending on the kind of vulcanizable rubber compounded in the composition. Specific examples of the vulcanizing agent include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halide such as sulfur monochloride and sulfur dichloride;
Organic peroxides such as benzoyl peroxide, tertiary butyl hydroperoxide, 2,4-dichlorodibenzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane Examples include alkylphenol resins having a methylol group. Among these, sulfur and organic peroxides are preferable.

These vulcanizing agents may be used alone or in combination of two or more. The compounding ratio of the vulcanizing agent is not particularly limited, but is usually 0.1 to 15 parts by weight, preferably 0.3 to 100 parts by weight of the vulcanizable rubber.
It is in the range of 10 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

If desired, a vulcanization accelerator can be added to the primer composition of the present invention. In particular, when sulfur is used as the vulcanizing agent, it is preferable to use a vulcanization accelerator.

Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N
-T-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazoleflufenamide, N, N'-diisopropyl-2-
Sulfenamide vulcanization accelerators such as benzothiazole sulfenamide; guanidine vulcanization accelerators such as diphenylguanidine, dioltotolylguanidine, orthotolylbiguanidine; thiocarbanilide, dioltotolylthiourea, ethylenethiourea, diethyl Thiourea-based vulcanization accelerators such as thiourea and trimethylthiourea; 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole sodium salt,
Thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole cyclohexylamine salt and 2- (2,4-dinitrophenylthio) benzothiazole; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide. , A thiuram-based vulcanization accelerator such as dipentamethylene thiuram tetrasulfide; sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium di-n-butyldithiocarbamate, lead dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc di-n-butyldithiocarbamate, zinc pentamethylenedithiocarbamate, ethylphenyldithiocarbamate Dithiocarbamic acid vulcanization such as tellurium diethyldithiocarbamate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, diethyldiethyldithiocarbamate diethylamine, pentamethylenedithiocarbamate piperidine, methylpentamethylenedithiocarbamate pipecoline Accelerators: Xanthogenic acid-based vulcanization accelerators such as sodium isopropylxanthate, zinc isopropylxanthate, and zinc butylxanthate can be used.

Each of these vulcanization accelerators alone is
Alternatively, two or more kinds can be used in combination. The mixing ratio of these vulcanization accelerators is not particularly limited, but is 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 100 parts by weight of vulcanizable rubber. It is in the range of 0.5 to 5 parts by weight.

A vulcanization aid may be added to the primer composition of the present invention, if necessary. As the vulcanization aid, for example, zinc white, zinc carbonate, magnesium oxide, red lead, white lead, calcium hydroxide, stearic acid, zinc stearate, oleic acid, dibutylammonium oleate, dibutylamine, monoethanolamine, trihydrate. Examples thereof include ethanolamine, and among these, zinc white and stearic acid are particularly preferable.

These vulcanization aids may be used alone or in combination of two or more. The compounding ratio of the vulcanization aid is usually 0.05 to 15 parts by weight, preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the vulcanizable rubber.
The amount is 0 parts by weight, more preferably 0.5 to 5 parts by weight.

By adding a reinforcing agent, the peel strength of the primer composition can be further improved. The reinforcing agent is not particularly limited, but examples thereof include carbon black, silica, calcium carbonate, talc, and clay, and carbon black and silica are preferable.

These reinforcing agents can be used alone or in combination of two or more kinds. The mixing ratio of the reinforcing agent is 100 parts by weight of the vulcanizable rubber,
It is usually 10 to 250 parts by weight, preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight.

Other commonly used compounding agents may be added to the primer composition of the present invention, if necessary. Such compounding agents include, for example, antiaging agents, antioxidants, antiozonants, plasticizers, softeners,
Examples include fillers and colorants.

Examples of antiaging agents, antioxidants, and antiozonants include phenyl-α-naphthylamine,
Phenyl-β-naphthylamine, N, N'-diphenyl-p-phenylenediamine, N, N'-diphenylethylenediamine, N-cyclohexyl-N'-phenyl-
Examples thereof include p-phenylenediamine, N-octyl-N'-phenyl-p-phenylenediamine, p-isopropoxy diphenylamine, di-o-tolylethylenediamine and the like. These are used alone or in combination.

Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dihexyl phthalate, butyl lauryl phthalate, di (2-ethylhexyl) phthalate, dilauryl phthalate, di-2-octyl phthalate, di-n-butyl adipate, diisooctyl. Adipate, octyldecyl adipate, di-2-ethylhexyl-4-thioazelate, diethyl sebacate, di-
Examples thereof include n-butyl malate and diethyl malate. These are used alone or in combination of two or more.

As the filler, aluminum sulfate, barium sulfate, calcium sulfate, calcium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate,
Examples thereof include calcium silicate, magnesium silicate, calcium sulfite, mica, dolomite, zinc oxide, and glass fiber.

As the colorant, titanium oxide, cuprous oxide,
Cadmium yellow, molybdenum red, silver vermilion, yellow lead,
Chromium oxide, navy blue, barium sulfate, alumina white,
Examples include inorganic pigments such as white carbon and organic pigments.

Further, in the primer composition of the present invention, if necessary, a conductivity-imparting agent such as ferrite; an organic active halogen compound such as halogenated succinimide, halogenated isocyanuric acid, and hydantoin halogenated; an antistatic agent, a nucleus. Examples include various additives such as agents, flame retardants, oils, etc. These can be added alone or in combination. The addition amount of these is appropriately determined within a range that does not impair the effects of the present invention.

Substrate The primer composition of the present invention is effective for improving the adhesion of the coating material to the surface of various substrates. As a substrate,
Various synthetic resins, rubber, polyurethane foam and the like can be mentioned, and among these, rubber is preferable. As these base materials, injection molding, hollow molding, extrusion molding, compression molding,
Any molded body molded by a known molding method such as rotational molding is used. Further, it may be a substrate in which a coating layer made of synthetic resin, rubber, foamed polyurethane, or a mixture thereof is formed on the surface of a molded body of metal or other inorganic material.

The rubber constituting the substrate itself or the surface coating layer is not particularly limited, and those generally used in the rubber industry can be used. Specific examples of the rubber include the same as those exemplified for the vulcanizable rubber compounded in the primer composition.
Of these, α-olefin copolymer rubbers are preferably used, and specific examples thereof are also the same as those of the vulcanizable rubber compounded in the primer composition.

The synthetic resin constituting the base material itself or the surface coating layer is not particularly limited, but a thermoplastic resin,
Thermosetting resins and the like can be mentioned, and of these, thermoplastic resins are preferable. As the thermoplastic resin, for example, polyolefin resin, styrene resin, ionomer resin, isobutylene-maleic anhydride copolymer, polymethylmethacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, fluororesin, polyamide, polyphenylene. Examples thereof include ethers, and among these, hydrocarbon-based thermoplastic resins such as polyolefin-based resins and styrene-based resins are particularly preferable.

Examples of the olefin resin include homopolymers of α-olefins such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene; ethylene / propylene copolymers and ethylene / 1-butene. Copolymer, ethylene / propylene / diene copolymer, propylene / 1-butene copolymer, propylene / 4
A copolymer containing an α-olefin component such as a methyl-1-pentene copolymer as a main component and an α-olefin such as acrylic acid or maleic acid or its anhydride,
Graft copolymerization modified olefin copolymer obtained by graft-copolymerizing β-unsaturated polar compound component; α, β such as acrylic acid, maleic acid or anhydride thereof in the polymer containing the α-olefin component as a main component Block copolymer modified olefin copolymer obtained by block copolymerizing an unsaturated polar compound component; further, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / crotonic acid copolymer, ethylene / malein Examples thereof include random copolymers containing an α-olefin component as a main component, such as acid copolymers, ethylene / methyl acrylate copolymers, and ethylene / vinyl acetate copolymers. Further, a small amount of a thermoplastic elastomer such as ethylene-propylene copolymer rubber or ethylene-propylene-diene terpolymer rubber may be blended with these olefin resins.

Examples of the styrene resin include polystyrene, high impact polystyrene, AS resin, ABS resin, AAS resin, ACS resin, MBS resin, styrene-modified polyphenylene ether, resinous block polymer such as styrene-butadiene and styrene-isoprene, and the like. And a partial hydride thereof. Of these, polystyrene, high impact polystyrene and ABS resin are preferable.

The polyurethane foam constituting the substrate itself or the surface coating layer is not particularly limited, and those widely used for industrial and household use can be adopted. The substrate to which the primer composition of the present invention is applied, talc,
Incorporate inorganic fillers such as zinc white, glass fiber, titanium white and calcium carbonate, reinforcing agents, softeners, antioxidants, various stabilizers such as ultraviolet absorbers, hydrochloric acid absorbers, pigments, crosslinking agents, etc. Good.

Specific examples of the molded base material to which the primer composition of the present invention is applied include exterior materials for automobiles such as weather strips and glass runs, waterproof mats, waterproof grommets, golf balls, industrial rolls, and conductive rolls. , Various painted packings, construction weather strips, etc.

Molded Product In the molded product containing the primer layer of the present invention, the primer composition is applied on the surface of the base material and dried to form the primer layer on the surface of the base material, and then the coating material is applied on the surface. It is manufactured by The coating of the primer composition on the surface of the substrate may be carried out by a conventional method, for example, the primer composition is coated by a method such as brush coating, dipping, spraying, spin coating, or roll coater, and the solvent is volatilized. be able to. The coating may be performed at room temperature. After the coating, the coating is dried by an appropriate method such as natural drying or forced drying by heating to form a coating film.

The coating amount is such that the solvent-free primer layer has a thickness of 0.1 to 100 μm, preferably 0.5 to 50 μm.
m, more preferably 1 to 30 μm,
This is preferable because the adhesion between the rubber base material and the paint is sufficiently high.

The coating applied on the surface of the primer layer is not particularly limited, but examples thereof include solvent-type thermosetting acrylic resin coating, polyurethane resin coating (two-pack type, one-pack type, emulsion type), melamine resin coating, Epoxy resin paints, alkyd melamine resin paints, acrylic modified alkyd resin paints and the like are suitable.

The coating of the coating material on the surface of the primer layer can be carried out by a conventional method, for example, electrostatic coating, spray coating,
A method such as brush painting may be 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 the paint film with nichrome wire, infrared rays, high frequency (UHF), etc. is adopted, but the method is appropriately selected depending on the material and shape of the base material surface, the properties of the paint used, etc. To be done.

The primer composition of the present invention can exhibit a function as a binder when substrates are adhered to each other. For example, the primer composition of the present invention is applied to an ethylene-propylene-based vulcanized rubber base material, and then a soft, semi-rigid urethane foam base material is foamed thereon to form urethane foam and ethylene-propylene-based vulcanization. It is possible to obtain a product having excellent adhesion made of rubber. Examples of the soft urethane foam material include 100 parts by weight of polypropylene glycol-based polyol (molecular weight of about 3000),
It may be composed of 4 parts by weight of water, 0.1 parts by weight of triethylenediamine, 0.4 parts by weight of stannas octoate and 105 parts by weight of toluene diisocyanate.

When a linear polymer polyurethane is used as a paint or an adhesive, the linear polymer polyurethane is dissolved in an organic solvent after applying the primer composition of the present invention to an ethylene-propylene vulcanized rubber substrate. When applied, the adhesion can be improved.

[0069]

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. The vulcanized rubber base material used in the examples was prepared as follows. Ethylene-propylene-ethylidene norbornene copolymer (Ethylidene norbornene content 7%, iodine value 15, manufactured by Japan Synthetic Rubber Co., Ltd .; E
P-103A) 100 parts, carbon black 70 parts, mineral oil 35 parts, zinc white 5 parts, stearic acid 1 part, vulcanization accelerator 2 parts, sulfur 1.5 parts at 160 ° C. for 30 minutes. Sulfurization was performed to obtain a vulcanized rubber base material.

The physical properties were measured by the following methods. (1) Weight average molecular weight The weight average molecular weight of the polyester is determined according to the GPC method.
It was measured as a standard polystyrene equivalent amount. (2) Hydroxyl Value and Acid Value The hydroxyl value and acid value of the polyester were measured according to the following described in "Standard oil and fat analysis test method" (Japan Oil Chemistry Association). Hydroxyl value 2,4,9,2-83 Acid value 2,4,1-83 (3) 180 ° peel strength test The peel strength test was measured according to JIS DO202.
That is, the coating film formed on the surface of the rubber base material is cut into 1 cm width by the cutter blade until the blade reaches the base material.
After peeling off the edge, remove the edge of the peeled coating film by 50c.
The peel strength (kg / cm ² ) was obtained by pulling in the direction of 180 ° at a speed of m / min.

Production Example 1 (Preparation of Polyester A) A 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water diversion tube and a nitrogen gas inlet tube was charged with polymerized fatty acid (acid value 193 mg KOH / g, monomer). Acid 8.0
%, Dimer acid 75.0%, trimer acid 17.0%; Haridimer 200, manufactured by Harima Chemicals) 420.0 g, 2
-Ethyl-2-butyl-1,3-propanediol 1
5.0 g, 94.6 g of trimethylolpropane and 0.26 g of monobutyltin oxide as a catalyst were charged. (COOH / OH = 1.60 (equivalent ratio))

Stirring is carried out while introducing nitrogen gas, and 10
The temperature was raised to 0 ° C. Subsequently, while removing water and unreacted diol generated during the reaction, the temperature is changed from 100 ° C. to 260 ° C.
The temperature was raised to 6 ° C over 6 hours. After that, the reaction was continued for 10 hours while dehydrating at 260 ° C. The resulting polyester A has a weight average molecular weight of 11,700 and an acid value of 0.2 m.
It had a gKOH / g and a hydroxyl value of 82 mgKOH / g.

Production Example 2 (Preparation of Polyester B) A 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a diversion tube and a nitrogen gas inlet tube was charged with polymerized fatty acid (acid value 195 mgKOH / g, monomer). Acid 5.0
%, Dimer acid 75.0%, trimer acid 20.0%; Haridimer 250, manufactured by Harima Kasei Co., Ltd.) 440.0 g, 3
28.1 g of -methyl-1,5-pentanediol, 85.0 g of trimethylolpropane and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / C
OOH = 1.56 (equivalent ratio))

Stirring is carried out while introducing nitrogen gas, and 10
The temperature was raised to 0 ° C. Subsequently, while removing water and unreacted diol generated during the reaction, the temperature is changed from 100 ° C. to 260 ° C.
The temperature was raised to 6 ° C over 6 hours. After that, the reaction was continued for 10 hours while dehydrating at 260 ° C. The resulting polyester B has a weight average molecular weight of 6,800 and an acid value of 0.2 mg.
The KOH / g and the hydroxyl value were 78 mgKOH / g.

Production Example 3 (Preparation of Polyester C) Polymerized fatty acid (acid value 195 mgKOH / g, monomer was added to a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water diversion tube and nitrogen gas inlet tube. Acid 5.0
%, Dimer acid 75.0%, trimer acid 20.0%; Haridimer 250, manufactured by Harima Kasei Co., Ltd.) 460.0 g, pentaerythritol 33.5 g, 2-ethyl-2-butyl-1,3-propanediol 105. 0 g and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH = 1.40 (equivalent ratio))

Stirring is performed while introducing nitrogen gas, and 10
The temperature was raised to 0 ° C. Subsequently, while removing water and unreacted diol generated during the reaction, the temperature is changed from 100 ° C. to 260 ° C.
The temperature was raised to 6 ° C over 6 hours. After that, the reaction was continued for 10 hours while dehydrating at 260 ° C. The resulting polyester C has a weight average molecular weight of 7,300 and an acid value of 0.1 mg.
The KOH / g and the hydroxyl value were 46 mgKOH / g.

Example 1 (Coated film molded product) 100 parts of ethylene-propylene-ethylidene norbornene copolymer (EP-103A), 5 parts of zinc white, 1 part of stearic acid, 100 parts of carbon black, 20 mineral oils
Parts, tetrathiuram disulfide 1 part, 2-mercaptobenzothiazole 1.5 parts and sulfur 2 parts, and
It was made into the compound. A primer composition was prepared by dissolving 3 parts of this formulation and 2 parts of the polyester A prepared in Production Example 1 in 95 parts of xylene. A vulcanized rubber base material is dipped in this primer composition, the solvent is evaporated at room temperature, and then a urethane prepolymer having terminal NCO groups on the surface of the vulcanized rubber base material (Oflex No. 500, Ohashi Chemical Industry Co., Ltd.). Manufactured) and cured at 100 ° C. for 10 minutes. As a result of a 180 ° peel test, the peel strength was 3.8.
kg / cm ² .

Example 2 (Coated film molded product) 100 parts of ethylene-propylene-ethylidene norbornene copolymer (EP-103A), 5 parts of zinc white, 1 part of stearic acid, 50 parts of carbon black, 50 parts of silica.
Parts, 3 parts of dicumyl peroxide and 0.5 parts of sulfur were kneaded to obtain a blend. 4 parts of this formulation and 1 part of polyester B prepared in Production Example 2 were dissolved in 95 parts of xylene to prepare a primer composition. A vulcanized rubber base material is dipped in this primer composition, and the resulting mixture is heated at 180 ° C.
After the primer composition was cured for a minute, the surface of the vulcanized rubber substrate was coated with the urethane prepolymer having the same terminal NCO groups as used in Example 1, and the temperature was maintained at 100 ° C. for 10 minutes.
Cured for minutes. As a result of a 180 ° peel test, the peel strength was 4.0 kg / cm ² .

Example 3 (Coated film molding) Ethylene-propylene-dicyclopentadiene copolymer (dicyclopentadiene content 6%, iodine value 1)
2, Mitsui Petrochemical Co. EPT-1035) 100 parts, zinc white 5 parts, stearic acid 1 part, mineral oil 20 parts, silica 50.
Parts, tetrathiuram disulfide 1 part, 2-mercaptobenzothiazole 1.5 parts and sulfur 2 parts, and
It was made into the compound. A primer composition was prepared by dissolving 3 parts of this composition and 2 parts of the polyester C prepared in Production Example 3 in 95 parts of xylene. A vulcanized rubber substrate was dipped in this primer composition, the solvent was evaporated at room temperature, and then a urethane prepolymer having the same terminal NCO group as that used in Example 1 was formed on the surface of the vulcanized rubber substrate. It was applied and cured at 100 ° C. for 10 minutes. As a result of a 180 ° peel test, the peel strength was 4.4 kg / cm ² .

Comparative Example 1 (Coated Film Molded Body) Ester resin 20 (saturated polyester manufactured by Toyobo Co., Ltd.) was used in place of the polyester A used in Example 1, and xylene / methyl ethyl ketone was used instead of xylene as the organic solvent. A (= 9/1) mixed solvent was used and other operations were performed in the same manner as in Example 1 to prepare a primer composition, a rubber substrate was further coated, and a 180 ° peeling test was performed. The peel strength was 0.6 kg / cm ² .

Comparative Example 2 (Coated Film Molding) Polyester (a hydroxyl group-containing polyolefin resin manufactured by Mitsubishi Chemical Co., Ltd.) was used in place of the polyester B used in Example 2, and other operations were the same as in Example 1. To prepare a primer composition, and then coat the rubber substrate,
A 180 ° peel test was performed. The peel strength is 1.5 kg
/ Cm ² .

As shown in Examples and Comparative Examples, a coated article having a primer layer comprising the primer composition of the present invention formed on the surface of a substrate and having a coating film formed thereon has a conventional primer composition. The peel strength is excellent as compared with the case of using the product (Comparative Examples 1 and 2). in this way,
The primer composition of the present invention is excellent in adhesion to the substrate and is also excellent in adhesion to the coating film formed thereon, even if the surface of the substrate is not subjected to any special pretreatment.

Preferred Embodiments of the Invention The primer composition of the present invention (claims 1 and 2), a molded product having a primer layer comprising the primer composition (claim 3) and a coated product of the molded product (claim 4) The preferred embodiments of are summarized below. (1) The polar group containing a hydrogen atom is selected from a hydroxyl group, a carboxyl group, an amino group and a thiol group, more preferably a hydroxyl group and a carboxyl group, and further preferably a hydroxyl group. (2) The sum of the acid value and the hydroxyl value of the polyester is 10 to 20.
0 mgKOH / g, more preferably 20-150 mgK
OH / g, most preferably 40-120 mg KOH / g
Range. (3) The molecular weight of the polyester is a polystyrene-converted weight average molecular weight (Mw) measured by gel permeation chromatography (GPC), preferably 2,000.
0 to 500,000, more preferably 3,000 to 10
It is in the range of 0000.

(4) The polyester has (A) a divalent higher carboxylic acid component and (B) a divalent alcohol component, and (C) a trivalent or higher carboxylic acid, a trivalent or higher alcohol and two epoxy groups. At least one compound selected from the epoxy compounds having the above (A), in a proportion of 1 to 80 mol% with respect to the total amount of both components (B),
It is obtained by polycondensation of the three components (A), (B) and (C).

(5) The divalent higher carboxylic acid (A) used in the production of the polyester of the above (4) has 8 or more, more preferably 10 to 200, most preferably 20 to 80 carbons. (6) The divalent higher carboxylic acid (A) of the above item (5) is selected from polyalkylene succinic acid and dimer acid of polymerized fatty acid, and more preferably dimer acid of polymerized fatty acid.

(7) The dihydric alcohol (B) used in the production of the polyester of the above item (4) is selected from alkanediol, cycloalkanediol, polyoxyalkylene glycol, ester diol and hindered glycol, and more preferably Is alkane diol, polyoxyalkylene glycol, or hindered glycol, more preferably alkane diol or hindered glycol.

(8) The trivalent or higher carboxylic acid (C) used in the production of the polyester of the above (4) is trimellitic acid,
It is selected from among tricarballylic acid, camphoronic acid, trimesic acid and trimeric acid of polymerized fatty acid, more preferably selected from trimesic acid and trimeric acid of polymerized fatty acid, and most preferably trimeric acid of polymerized fatty acid.

(9) The trihydric or higher alcohol (C) used in the production of the polyester of the above item (4) is represented by the following general formula (5).
At least 10 mol%, more preferably 20 to 100 mol%, and most preferably 30 to 100 mol% of a hindered alcohol represented by HOCH in _{^{2 -C (CR 7 R 8)}} -CH 2 OH (5) formula, R ^7, R ⁸ is an alkyl group having an alkyl group or a hydroxyl group, at least one of the two alkyl groups having hydroxyl groups Is.

(10) A dimer acid glycidyl ester of a polymerized fatty acid, wherein the epoxy compound (C) having two or more epoxy groups used in the production of the polyester of the above item (4) is
It is selected from glycidyl ether of bisphenol A, glycidyl ether of bisphenol F and glycidyl ether of aliphatic dibasic acid. (11) The amount of the component (C) used in the production of the polyester of the above (4) is 1 to 80 mol% based on the total amount of the divalent carboxylic acid component (A) and the divalent alcohol component (B) It is more preferably 5 to 60 mol%, still more preferably 10 to 40 mol%.

(12) The organic solvent is at least one selected from aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols and ketones. (13) The amount of the organic solvent is usually 10 to 10,000 parts by weight, preferably 50, relative to 100 parts by weight of polyester.
To 5,000 parts by weight, more preferably 100 to 1,000
0 parts by weight. (14) The vulcanizable rubber is an α-olefin copolymer rubber.

(15) The α-olefin copolymer rubber of the above item (14) is 50 to 100% by weight, more preferably 60.
.About.100 wt.% .Alpha.-olefin and 50 to 0 wt.%, More preferably 40 to 0 wt.% Conjugated and / or non-conjugated dienes. (16) The α-olefin copolymer rubber according to the above (14) and (15) is ethylene-α-olefin copolymer rubber having 3 or more carbon atoms, ethylene-α-olefin-non-conjugated diene copolymer copolymer having 3 or more carbon atoms. It is selected from rubber, α-olefin-conjugated diene copolymer rubber, and chlorinated and chlorosulfonated products thereof.

(17) The amount of vulcanizable rubber is 10 to 500 parts by weight, more preferably 20 to 400 parts by weight, and still more preferably 50 parts by weight based on 100 parts by weight of polyester.
２５０250 parts by weight. (18) The vulcanizing agent is sulfur or organic peroxide. (19) The amount of the vulcanizing agent is 0.1 to 15 parts by weight, and more preferably 0.3 to 1 part by weight with respect to 100 parts by weight of vulcanizable rubber.
It is 0 part by weight, more preferably 0.5 to 5 parts by weight.

(20) The primer composition is used in an amount of 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, still more preferably 0.5 to 100 parts by weight of vulcanizable rubber. ˜5 parts by weight of vulcanization accelerator. (21) 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and still more preferably 0.5 to 100 parts by weight of the vulcanizable rubber.
˜5 parts by weight of a vulcanization aid, more preferably a vulcanization aid selected from zinc white and stearic acid.

(22) The primer composition is further reinforced by 10 to 250 parts by weight, more preferably 20 to 200 parts by weight, further preferably 30 to 150 parts by weight, based on 100 parts by weight of vulcanizable rubber. Agent, more preferably a reinforcing agent selected from carbon black and silica. (23) The base material is made of a rubber material or has a coating layer made of a rubber material.

(24) The rubber material of the above item (23) is 100
Or less, more preferably 1 to 50, further preferably 5 to
It has an iodine value of 35. (25) The rubber material according to the above (23) or (24) is selected from modified polyethylene rubber, α-olefin copolymer rubber and silicone rubber, and more preferably α-olefin copolymer rubber. (26) The thickness of the primer layer is 0.1 to 100 μm, more preferably 0.5 to 50 μm, and further preferably 1 to
30 μm.

(27) The coating film formed on the surface of the primer layer is selected from thermosetting acrylic resin paints, polyurethane resin paints, melamine resin paints, epoxy resin paints, alkyd melamine resin paints and acrylic modified alkyd resin paints. Made of painted paint. (28) A layer of the primer composition is formed on a base material made of an α-olefin copolymer rubber, and a foamed polyurethane base material is further adhered thereon.

[0097]

EFFECT OF THE INVENTION The primer composition of the present invention can greatly improve the adhesiveness between a base material made of synthetic resin, rubber and the like and various coating materials. In particular, even a base material made of a polymer rubber having a small polarity such as polyolefin can improve the adhesiveness with a coating material without special pretreatment. Also,
The primer composition of the present invention has an effect of improving adhesiveness and printability in addition to the above-mentioned use as a coating primer, and can widely improve the surface characteristics of a rubber substrate.

Therefore, the primer composition of the present invention makes use of these characteristics, and is used for exterior materials for automobiles such as weather strips and glass runs, waterproof mats, waterproof grommets, golf balls, industrial rolls, conductive rolls, various types. Suitable for surface modification applications such as painted packing and weather strips for construction.

Claims (4)

[Claims] 1. A weight average molecular weight of 1,0 having at least three polar groups containing a hydrogen atom and a hetero atom in the molecule.
A primer composition comprising from 0 to 1,000,000 oil-soluble polyester, a vulcanizable rubber, a vulcanizing agent and an organic solvent. 2. The primer composition according to claim 1, wherein the sum of the acid value and the hydroxyl value of the polyester is 10 to 200 mgKOH / g. 3. A molded article comprising a base material and a primer layer formed on the surface of the base material and comprising the primer composition according to claim 1. 4. A coated material comprising a base material, a primer layer formed on the surface of the base material and comprising the primer composition according to claim 1 or 2, and a coating film formed on the surface of the primer layer. Molded body.