JPH08134400A - Coating resin composition and coating - Google Patents

Abstract

PURPOSE: To obtain a coating resin composition excellent in coatability, storage stability, coating film adhesiveness, chemical resistance, gasoline resistance, weatherability and appearance, and useful as a coating for hard-to-coat plastics, comprising a specific modified chlorinated polyolefin copolymer and a polyester polyol. CONSTITUTION: This composition comprises (A) a vinyl-modified chlorinated polyolefin copolymer produced by copolymerizing a double bond-bearing monomer mixture composed of a compound of the formula (X is a copolymerizable double bond-bearing group; Y is a hydrolyzable group or halogen; R is an inert organic group; (m) is 0-2; (n) is 1-3; (m+n)=3), OH-contg. monomer and carboxyl-contg. monomer in the presence of a chlorinated polyolefin resin <=50wt.% in chlorine content, and (B) a straight chain OH-terminated saturated aliphatic polyester polyol (pref. having alicyclic structure) at the weight ratio A/B of (100:5) to (100:20).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for paints and paints. In particular, the present invention is a coating which can be directly applied to difficult-to-paint plastics, and which can provide a coating having excellent performance such as adhesion, storage stability of varnish, chemical resistance, gasoline resistance, weather resistance, and appearance. TECHNICAL FIELD The present invention relates to a resin composition and a paint.

[0002]

2. Description of the Related Art In recent years, synthetic resins such as polyolefin have been widely used in place of metal for the purpose of weight reduction, rust prevention and other purposes in automobiles, home electric appliances and various other industrial fields. In this case, since the surface of the molded product is usually coated, it is required that the surface of the molded product has good coatability. However, a coating film applied to a plastic molded article made of polyolefin such as polyethylene or polypropylene is inferior in adhesiveness, solvent resistance or the like, or as a result of trying to secure adhesiveness, PVC plasticizer migration resistance, alcohol resistance It is inferior to other performances such as sex. Therefore, in order to improve the coating properties such as adhesion to plastic molded articles made of polyolefin, storage stability of varnish, migration resistance to PVC plasticizer, solvent resistance, and weather resistance, many attempts have been proposed in the past. ing. For example, there is a method of improving the adhesion by subjecting the surface of these molded products to a degreasing treatment, a chromic acid treatment or the like. Further, there is a method of applying a chlorinated polyolefin or a polyolefin modified with maleic acid or an anhydride thereof on the surface of the molded product in a solution state or a dispersed state and performing a primer treatment, and then applying a paint having excellent coating performance. (For example, JP-A-58-83042, JP-A-58-118809, and JP-A-59-3083).
No. 0, etc.).

On the other hand, as a coating composition for improving the adhesion of a coating film to a polyolefin molded product, an epoxy resin, a curing agent for epoxy resin and an epoxy or polyolefin copolymer having a functional group reactive with an epoxy group are used. System compositions have been proposed (see, for example, JP-A-56-72053, JP-A-56-50971 and JP-A-58-101122). Also,
An acrylic modified chlorinated polyolefin resin composition comprising an acrylic resin and a chlorinated polyolefin has been proposed (for example, JP-A-58-183718, JP-A-58-194959, and JP-A-59-30830). (See gazette, etc.).

[0004]

However, the above-mentioned surface treatment method cannot sufficiently improve coating film performance such as adhesion. In addition, in the method of applying a primer treatment,
Depending on the type of chlorinated polyolefin and modified polyolefin, there are those that can obtain a coating film with excellent adhesion,
There are drawbacks in that the operation of applying the primer is complicated, that the primer treatment requires a lot of time and labor, and that the coating cost rises. Furthermore, it is hard to say that the above-mentioned epoxy composition has sufficient adhesion to a plastic molded product such as polyolefin. Further, the acrylic modified chlorinated polyolefin composition,
Adhesion is affected by the amount of chlorinated polyolefin, it is necessary to increase the amount of chlorinated polyolefin in order to obtain sufficient adhesion, for this reason storage stability of the varnish, weather resistance, chemical resistance, There is a drawback in that it is difficult to simultaneously improve performance such as gasoline resistance. The present invention
It solves the above-mentioned drawbacks and can be directly applied to the surface of a molded product without surface treatment, and the adhesion of coating film, stability of varnish, chemical resistance, gasoline resistance, weather resistance, appearance, etc. The present invention provides a resin composition for paints and a paint that produces a paint film excellent in performance.

[0005]

The present invention has a chlorine content of 5
In the presence of 0% by weight or less of a chlorinated polyolefin resin, the compound of the general formula (I)

Embedded image (In the formula, X is a group having a copolymerizable double bond, Y is a hydrolyzable group or a halogen atom,
R is an inactive organic group, m is the number of bonds of R is 0, 1 or 2, n is the number of bonds of Y is 1, 2 or 3, and m + n
Is selected so as to be 3), a polymerizable monomer having an unsaturated double bond containing a polymerizable monomer having a hydroxyl group and a polymerizable monomer having a hydroxyl group. A vinyl-modified chlorinated polyolefin-based polymer obtained by polymerizing a monomer mixture, and a resin composition for coating containing a linear saturated aliphatic polyester polyol having a hydroxyl group at the terminal, and this coating resin The present invention relates to a coating material obtained by combining a composition and a curing agent.

Examples of the chlorinated polyolefin resin used in the present invention include polyethylene resin having a chlorine content of 50% by weight or less, polypropylene resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and the like. If the chlorine content exceeds 50% by weight, the adhesion to the polyolefin-based substrate will decrease. The determination of the chlorine content is made taking into account various coating performances. From the viewpoint of the balance of coating film performance, it is preferably 20% by weight or more, and more preferably 20 to 35% by weight.

The polymerizable monomer composition which is polymerized in the presence of the chlorinated polyolefin resin is an unsaturated organosilane compound represented by the general formula (I), a polymerizable monomer having a hydroxyl group and a carboxyl group. A polymerizable monomer having is included as an essential component. The unsaturated organosilane compound is
The adhesiveness of the coating film and the storage stability of the varnish can be improved. The unsaturated organosilane compound is preferably added in an amount of 0.1 to 3% by weight, and more preferably 0.3 to 2% by weight, based on the total amount of the polymerizable monomer composition.
If it is less than 0.1% by weight, the above-mentioned improvement effect is small, and if it exceeds 3% by weight, the hydrolyzable group is hydrolyzed during the polymerization to cause a crosslinking reaction, which tends to cause gelation during the polymerization.

In the above general formula (I), X is a group having a copolymerizable double bond, and examples thereof include an alkenyl group such as vinyl group, allyl group and butenyl group, cyclohexenyl group, cyclopentadienyl group, Cycloalkenyl groups such as cyclohexadienyl group, unsaturated acyloxyalkyl groups such as γ-methacryloxypropyl group, unsaturated acyloxyalkoxy groups such as γ-methacryloxyethylpropyl ether group,

[Chemical 4] Etc. Among these, preferred ones are unsaturated acyloxyalkyl groups such as γ-methacryloxypropyl group or γ
An unsaturated acyloxyalkoxy group such as a methacryloxyethylpropyl ether group.

Y is a hydrolyzable group or a halogen atom, and among them, chlorine, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, an oximo group having 1 to 14 carbon atoms, and the like. Preferably, specifically, a methoxy group,
Alkoxy group such as ethoxy group and butoxy group, acyloxy group such as formyloxy group, acetoxy group and propyleneoxy group,

Embedded image A group that forms a hydroxyl group by hydrolysis such as an oximo group.

[Chemical 6] Alkylamino groups such as and arylamino groups are preferred. Y may be the same or different when n is 2 or 3. R is an inert monovalent organic group, preferably a hydrocarbon group having 1 to 18 carbon atoms, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a tetradecyl group or an octadecyl group. And aryl groups such as phenyl group and tolyl group, and aralkyl groups such as benzyl group.

Specific examples of the unsaturated organic silane compound represented by the general formula (I) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane and vinyltri (2-
(Methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri (2-methoxyethoxy) silane, γ-acryloxypropyltrimethoxysilane, vinyltri Chlorosilane, γ-methacryloxylaurylpropoxydimethoxysilane, γ-methacryloxyhexyltriethoxysilane, vinyldimethylmethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxyethylmethoxyethoxybutoxysilane, γ-acryloxyoctylbutoxysilane. Methoxysilane, γ-acryloxybutyl methoxydibutoxysilane, and the like.

Y in the unsaturated organic silane compound represented by the general formula (I) reacts with the water used in the starting materials and the polymerization solvent to be hydrolyzed or substituted to form a hydroxyl group or a group having a hydroxyl group. It is considered that the functional groups such as hydroxyl groups undergo a crosslinking reaction during the polymerization reaction and / or when the coating material is dried.

As the polymerizable monomer having a hydroxyl group, 2-hydroxyethyl acrylate and 2-acrylic acid acrylate are used.
2-Hydroxyalkyl acrylates such as hydroxypropyl, lactone-modified 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, lactone-modified 2-hydroxyethyl methacrylate, lactone-modified products thereof, and methacrylic acid. Two
-Hydroxyalkyl or a lactone-modified product thereof is preferred. The polymerizable monomer having a hydroxyl group is preferably added in an amount of 1 to 25% by weight, more preferably 3 to 10% by weight, based on the total amount of the polymerizable monomer mixture, from the viewpoint of adhesion.

As the polymerizable monomer having a carboxyl group, acrylic acid, methacrylic acid, maleic acid,
Unsaturated acids such as fumaric acid, unsaturated dibasic acids, their acid anhydrides and the like are preferred. Carboxyl groups may be included as acid anhydride groups. The polymerizable monomer having a carboxyl group is preferably added in an amount of 0.1 to 4% by weight, more preferably 0.5 to 2% by weight, based on the total amount of the polymerizable monomer mixture, from the viewpoint of storage stability.

The polymerizable monomer blended in the above-mentioned polymerizable monomer blend is, in addition to the polymerizable monomers used as the above-mentioned essential components, the general formula (II)

[Chemical 7] (However, in the formula, R ′ is a hydrogen atom or a lower alkyl group, R ″ is a divalent organic group, and l is 0 or 1.)
A monomer represented by: methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, alkyl acrylate such as cyclohexyl acrylate, or cycloalkyl acrylate, Methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methacrylic acid alkyl ester such as cyclohexyl methacrylate or cycloalkyl ester methacrylic acid, aminomethyl methacrylate,
Aminoalkyl methacrylates such as N-methylaminomethyl methacrylate and N, N-diethylaminoethyl methacrylate, aminomethyl acrylate, aminomethyl acrylate, N-methylaminomethyl acrylate, aminoalkyl acrylates such as N, N-diethylaminoethyl acrylate , Glycidyl methacrylate, glycidyl acrylate, methacrylamide,
Styrene monomers such as acrylamide, styrene, vinyltoluene, α-methylstyrene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl derivatives such as isopropenyl acetate, and unsaturated dibasic acid dimethyl such as maleic acid and fumaric acid. Diesters such as ester and diethyl ester can be used.

In the above general formula (II), R ″ is a divalent organic group, and the number of carbon atoms is preferably 1 to 1
8, more preferably 2 to 12, an alkylene group or the general formula (III)

Embedded image (In the formula, Z and Z'are the same or different alkylene groups having 2 or more carbon atoms, and m is a repeating number and is an integer of 1 or more). Examples of the monomer represented by the general formula (II) include tricyclodecyl acrylate, tricyclodecyl methacrylate, tricyclodecyloxyethyl acrylate, tricyclodecyloxyethyl methacrylate, tricyclodecyloxypropyl acrylate and tricyclodecyl. Examples include tricyclodecyloxyalkyl acrylates or methacrylates such as siloxypropylmethacrylate, acrylates or methacrylates of polyalkylene glycol tricyclodecylmonoether such as acrylates or methacrylates of diethylene glycol tricyclodecyl monoether.

Among these, at least one selected from the monomers represented by the general formula (II), alkyl acrylates, cycloalkyl acrylates, methacrylic acid alkyl esters and methacrylic acid cycloalkyl esters. It is preferable to use the polymerizable monomer of since it is excellent in coating film characteristics such as adhesion of the coating film, alcohol resistance, and vinyl chloride plasticizer migration resistance. These are 50 to 98.8% by weight, and further 68% in the total amount of the polymerizable monomer blend.
It is preferable to add 99.8% by weight because the balance of the above characteristics is excellent.

In this case, the polymerizable monomer blend is
(A) 0.1 to 3% by weight of the unsaturated organosilane compound represented by the general formula (I), (b) 1 to 25% by weight of a polymerizable monomer having a hydroxyl group, and (c) a polymerizable group having a carboxyl group. 0.1 to 4% by weight of a monomer, and (d) a monomer represented by the general formula (II), an alkyl acrylate ester, a cycloalkyl acrylate ester, an alkyl methacrylate ester and a cycloalkyl methacrylate ester. At least one or more polymerizable monomers 6 selected from esters
It is more preferable to add 8 to 98.8% by weight so that the total amount becomes 100% by weight.

In the above-mentioned polymerizable monomer composition, as other polymerizable monomers, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol dimethacrylate, Polyethylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, etc. Polymer, polyvinyl alcohol di-, tri-, tetra- or pentaacrylate or It can also be incorporated a small amount of such similar methacrylate. These are preferably added in an amount of 1% by weight or less based on the total amount of the polymerizable monomer mixture. If it is too large, gelation tends to occur during polymerization. When a polymerizable monomer having a functional group such as a glycidyl group or an amino group is used in the above-mentioned polymerizable monomer composition, the amount is 5% by weight or less based on the total amount of the polymerizable monomer composition. Preference is given to using.

The mixing ratio of the chlorinated polyolefin resin (the former) and the polymerizable monomer mixture (the latter) is preferably 3/97 to 20/80 in the former / the latter. If this weight ratio exceeds 20/80, the weather resistance, gasoline resistance, and storage stability of the varnish will tend to decrease, and if the weight ratio is less than 3/97, the adhesion to the polyolefin substrate will tend to decrease. This weight ratio is 5 / 95-15 /
More preferably, it is 85.

Polymerization of the polymerizable monomer composition in the presence of the chlorinated polyolefin resin is carried out by a known radical polymerization method, and the method is not particularly limited. In this case, as the organic solvent, an aromatic solvent such as toluene and xylene, a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an ester solvent such as ethyl acetate and butyl acetate, and a chlorine solvent such as carbon tetrachloride are used. It Further, in the polymerization, as the polymerization initiator, benzoyl peroxide, dicumyl peroxide, organic peroxides such as dibutyl peroxide, azobis-isobutyronitrile, azobis compounds such as azobis valeronitrile is used. It The polymerizable monomer composition,
It is preferable that the monomers to be blended are mixed and used in advance, but they may be added separately during the polymerization, or the mixture may be divided and added.

The resulting vinyl-modified chlorinated polyolefin polymer is blended with a linear saturated aliphatic polyester polyol having a hydroxyl group at the terminal. As this saturated aliphatic polyester polyol, a polyester polyol obtained from a condensation reaction of an aliphatic or alicyclic polybasic acid component and an aliphatic or alicyclic polyhydric alcohol component is used. The polybasic acid component, for example, adipic acid, azelaic acid, sebacic acid, aliphatic polybasic acids such as dodecanedioic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid and their anhydrides, There are alicyclic polybasic acids such as methylhexahydrophthalic acid and their anhydrides. Examples of the aliphatic or alicyclic polyhydric alcohol component include ethylene glycol, diethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, cyclohexanedimethanol and the like. There are glycols and alcohols. As the saturated aliphatic polyester used in the present invention, those having an alicyclic structure and containing neither a branched structure nor an aromatic ring structure are preferable because they give good coating properties. Further, those having a number average molecular weight of 500 or less, more preferably 150 to 400, are preferable because they give good coating properties.

In the present invention, the vinyl-modified chlorinated polyolefin polymer (former) and the linear saturated polyester polyol having a hydroxyl group at the terminal (latter).
The blending ratio with and is, by weight, the former / the latter = 100/5 to 10
It is preferably blended so as to be 0/20. If the latter exceeds 20 in this weight ratio, the coating film hardness tends to decrease, and if the latter is less than 5 in this weight ratio, the adhesion and appearance tend to decrease. This weight ratio is 100 / 8-1
A value of 00/15 is more preferable because the coating film characteristics are well balanced. The formulation thus obtained is
It is dissolved in an appropriate organic solvent to obtain a resin composition for paint.
As the organic solvent, those exemplified as the organic solvent at the time of polymerization can be used.

The coating composition of the present invention comprises the resin composition for coating composition and a curing agent in combination. Examples of the curing agent include amino resins, blocked polyisocyanates, polyisocyanates and the like. As the amino resin, those obtained by addition-condensing an amino compound such as benzoguanamine, urea, melamine and an aldehyde such as formaldehyde, and an etherified amino resin obtained by reacting these with a lower alcohol such as methanol, butanol, isobutanol, etc. Since it is possible to bake the paint at a relatively low temperature and it is easy to obtain a smooth coating film without cissing,
Most preferably, an n-butyl etherified melamine resin is used. As the blocked polyisocyanate, polyisocyanates such as isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and xylylene diisocyanate are blocked with phenol, ethyl acetoacetate, cyclohexanol, ε-caprolactam, acetoxime, diisobutylketoxime and the like. There are things.

The amino resin and the blocked polyisocyanate are usually used alone as a curing agent.
These curing agents can be used in combination depending on the desired physical properties of the coating film. Here, the amino resin is preferably used in an amount of 15 to 40 parts by weight based on 100 parts by weight of the vinyl-modified chlorinated polyolefin polymer and the linear saturated aliphatic polyester polyol having a hydroxyl group at the terminal. . In addition, the blocked polyisocyanate is
The equivalent ratio (OH / N) between the hydroxyl group of the vinyl-modified chlorinated polyolefin polymer and the linear saturated aliphatic polyester polyol having a hydroxyl group at the terminal (the former) and the isocyanato group of the blocked polyisocyanate (the latter).
CO) is preferably 1 / 0.5 to 1 / 1.5, and particularly preferably blended so as to be 1/1. When the amino resin and the blocked polyisocyanate are used in combination, the vinyl-modified chlorinated polyolefin polymer and the linear saturated aliphatic polyester polyol having a hydroxyl group at the terminal are used in an amount of 100 parts by weight, It is preferable to use 15 to 40 parts by weight of the amino resin and 1 to 20 parts by weight of the blocked polyisocyanate.

As the polyisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate and the like, burettes formed from 3 mol of hexamethylene diisocyanate and 1 mol of water, and isophorone diisocyanate containing an isocyanurate ring can be used. Polymers such as monomers, etc., in which two or more isocyanate groups remain, which are formed by the reaction of these isocyanates with a polyhydric alcohol such as propanediol, hexanediol, polyethylene glycol, trimethylolpropane, pentaerythritol, etc. From the viewpoint of toxicity and dryness, a polyisocyanate having a high molecular weight is preferable. Where polyisocyanate is
The hydroxyl group of the vinyl-modified chlorinated polyolefin-based polymer and the linear saturated aliphatic polyester polyol having a hydroxyl group at the terminal, and the isocyanate group of the polyisocyanate are 1 / 0.5 to OH / NCO (equivalent ratio). 1 /
It is preferably 1.5, and particularly preferably 1/1.

The resin composition for paints and paints according to the present invention are prepared by dispersing inorganic pigments such as titanium white and carbon black, and organic pigments such as phthalocyanine-based and azo-based pigments by a usual pigment dispersion method. Can be made into paint. In addition, aluminum paste, plasticizer, coating film strengthening resin,
It may contain various additives such as a dispersant, a coating surface modifier, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant and a crosslinking reaction accelerator.

The resin composition for coating material and the coating material according to the present invention can be coated by a conventional coating method conventionally used. For coating, an air spray machine, an airless spray machine, an electrostatic coating machine, Immersion, a roll coater, a brush, etc. can be used. The resin composition for paints and paints according to the present invention can be directly applied to polyolefin base materials such as polyolefin-based molded products, sheets and films, and can be used as top clears, enamel paints, metallic paints, primers and the like.

When the amino resin and / or the blocked polyisocyanate is used as a curing agent, the coating material according to the present invention needs to be crosslinked and cured by heating, and generally 1 to 100 at 80 to 180 ° C. It is preferable to heat-cure for a minute. When polyisocyanate is used as a curing agent, a sufficiently cured coating film can be obtained even at room temperature, but a cured coating film is preferably obtained by heating at 50 to 100 ° C for 1 to 60 minutes. The appropriate heating temperature and time are appropriately selected in consideration of the heat distortion temperature of the base material and the like.

[0029]

EXAMPLES Examples of the present invention will be described below. Below, part and%
Indicates parts by weight and% by weight. Examples 1 to 28 (1) Synthesis Examples 1 to 7 In a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, chlorinated polypropylene having the solid content shown in Table 1 and toluene were added in total. The mixture was charged to 134 parts and heated to 110 ° C., and a mixture of the monomers having the composition shown in Table 1 and 1 part of 2,2′-azobisisobutyronitrile was uniformly added dropwise over 2 hours. The temperature was kept at the same temperature for 1 hour. Then, a mixed solution in which 0.2 parts of 2,2′-azobisisobutyronitrile was uniformly dissolved in 20 parts of toluene was added dropwise over 1 hour and then aged for 2 hours. After cooling
The polyester polyols in the amounts shown in Table 1 were added and mixed uniformly, and toluene was added so that the heating residue was 40%.

[0030]

[Table 1]

Comparative Examples 1-28 (1) Synthetic Examples 8-14 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with chlorinated polypropylene and toluene having the solid content shown in Table 2. Was heated to 110 ° C. so that the total amount was 134 parts, and a mixture of the monomers shown in Table 1 and 1 part of 2,2′-azobisisobutyronitrile was uniformly added dropwise over 2 hours. After that, the temperature was kept at the same temperature for 1 hour. Then, a mixed solution in which 0.2 parts of 2,2′-azobisisobutyronitrile was uniformly dissolved in 20 parts of toluene was added dropwise over 1 hour and then aged for 2 hours. After cooling
Toluene was added so that the heating residue was 40%.

[0032]

[Table 2]

Test Method The storage stability of each of the coating resin compositions obtained in Examples 1-28 and the coating resin compositions obtained in Comparative Examples 1-28 was tested. In addition, Examples 1 to 28 and Comparative Example 1
~ 28 using the resin composition for coating materials, the ingredients shown in Tables 3 to 7 are mixed and dispersed by a known method to prepare coating materials.
Toluene / xylene / methyl isobutyl ketone / butyl cellosolve = 10/50/20/20
15 in Ford Cup # 4 with thinner (volume ratio)
After diluting so as to be sec / 20 ° C., a dry film thickness of 30 to 3 is applied to a polypropylene molding plate which is not surface-treated.
It was spray-coated so as to have a thickness of 5 μm and left at room temperature for 10 minutes. Then, it was baked and dried. Here, as a curing agent,
When an amino resin, blocked polyisocyanate or a combination thereof was used, it was baked and dried at 120 ° C. for 30 minutes. When polyisocyanate was used as the curing agent, it was baked and dried at 80 ° C. for 30 minutes. Then, the performance of the obtained coated plate was evaluated. Table 8 to Table 15
The respective results are shown in Examples 1-28 and Comparative Examples 1-28.

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

[0037]

[Table 6]

[0038]

[Table 7]

[0039]

[Table 8]

[0040]

[Table 9]

[0041]

[Table 10]

[0042]

[Table 11]

[0043]

[Table 12]

[0044]

[Table 13]

[0045]

[Table 14]

[0046]

[Table 15]

1) Glossiness Measured at a reflection angle of 60 ° according to JIS K-5400. 2) Adhesion Adhesion was measured by a scoring tape test method according to JIS K-5400. 100/100; Good adhesion 51-99 / 100; Poor adhesion 50/100 or less; Poor adhesion 3) Acid resistance 10% H ₂ SO ₄ aqueous solution is dropped on the coating film, and the coating plate is 60 ° C. Heated to room temperature and left for 40 minutes. Then, the surface of the coating film was observed. ○: No trace △: Slight trace ×: Trace 4) Gasoline resistance Gauze was impregnated with commercially available gasoline, and the coating film surface was strongly strengthened to 2
After rubbing 0 times, the surface of the coating film was observed. ⊚: Poor adhesion and no gloss on coating surface ○: Almost no bad adhesion or gloss on coating surface ×: Conspicuous adhesion failure and gloss 5) Water resistance After immersing in 40 ° C warm water for 240 hours, wash with water Then, the coating film surface was observed. ◯: No change Δ: Slightly glossy X: Blistering 6) Weather resistance The gloss retention rate (%) after 1000 hours of sunshine weather meter is shown.

[0048]

EFFECTS OF THE INVENTION The resin composition for paints and paints according to the present invention have excellent adhesion to unpainted plastics such as unpainted polyolefins and can be directly painted without pretreatment or primer coating. . And the coating film appearance,
It has excellent weather resistance, gasoline resistance, water resistance, acid resistance, storage stability of varnish, etc., and can form an excellent coating film that does not deteriorate over a long period of time.

Claims (7)

[Claims] 1. In the presence of a chlorinated polyolefin resin having a chlorine content of 50% by weight or less, the compound represented by the general formula (I): (In the formula, X is a group having a copolymerizable double bond, Y is a hydrolyzable group or a halogen atom,
R is an inactive organic group, m is the number of bonds of R is 0, 1 or 2, n is the number of bonds of Y is 1, 2 or 3, and m + n
Is selected so as to be 3), a polymerizable monomer having an unsaturated double bond containing a polymerizable monomer having a hydroxyl group and a polymerizable monomer having a hydroxyl group. A coating resin composition comprising a vinyl-modified chlorinated polyolefin polymer obtained by polymerizing a monomer mixture and a linear saturated aliphatic polyester polyol having a hydroxyl group at a terminal. 2. The coating resin composition according to claim 1, wherein the linear, saturated aliphatic polyester polyol having a hydroxyl group at the terminal has an alicyclic structure and does not contain a branched structure or an aromatic ring structure. . 3. A polymerizable monomer composition having an unsaturated double bond is used in which (a) 0.1 to 3% by weight of an unsaturated organosilane compound represented by the general formula (I), and (b) a hydroxyl group. 1 to 25% by weight of a polymerizable monomer having (b), (c) 0.1 to 4% by weight of a polymerizable monomer having a carboxyl group, and (d) a general formula (II) (However, in the formula, R ′ is a hydrogen atom or a lower alkyl group, R ″ is a divalent organic group, and l is 0 or 1.)
The total amount of the monomer selected from the group consisting of acrylic acid alkyl ester, acrylic acid cycloalkyl ester, methacrylic acid alkyl ester and methacrylic acid cycloalkyl ester is 68 to 98.8% by weight.
The coating resin composition according to claim 1 or 2, wherein the resin composition is blended so as to have a weight percentage. 4. The compounding ratio of the vinyl-modified chlorinated polyolefin polymer and the linear saturated polyester polyol having a hydroxyl group at the terminal is the former / the latter = 100 /
It is 5-100 / 20, The resin composition for coating materials of Claim 1, 2 or 3. 5. A paint comprising a combination of the resin composition for paint according to claim 1, 2, 3 or 4 and a curing agent. 6. The coating composition according to claim 5, wherein the curing agent is an amino resin and / or a blocked polyisocyanate. 7. The paint according to claim 5, wherein the curing agent is polyisocyanate.