JPH059428A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating composition which is very practicable and is further in compatibility of a chlorinated polyolefin with an acryl or vinyl copolymer, adhesion to a polyolefin substrate, intercoat adhesion and solvent resistance in use as a primer and weather resistance and chemical resistance in use as a topcoating material. CONSTITUTION:A coating composition comprising as an essential film-forming component, a graft copolymer obtained by copolymerizing a specified chlorinated polyolefin with a hydroxylated vinyl monomer, an unsaturated carboxylic acid, and another vinyl monomer copolymerizable therewith and optionaly a polyester resin containing a copolymerizable, ethylenically unsaturated bonds in the presence of an organic solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful coating composition. More specifically, it is obtained by copolymerizing chlorinated polyolefin with hydroxyl group-containing vinyl monomers, unsaturated carboxylic acids and other copolymerizable vinyl monomers other than the above in the presence of an organic solvent. The graft copolymer (A) thus obtained is contained as an essential film-forming component and, if necessary, an ultraviolet absorber and / or an antioxidant is also contained. The present invention relates to a coating composition having excellent adhesion and weather resistance.

[0002]

2. Description of the Related Art Up to now, paints made of alkyd resin, acrylic resin, epoxy resin, etc. have been used. However, paints made of conventional alkyd resin, acrylic resin, epoxy resin, etc. have polarities. It has almost no adhesiveness to various molded products made of small, so-called crystalline polyolefins.

Therefore, in coating such a polyolefin-based substrate, a maleic anhydride modified product of atactic polypropylene or an ethylene-propylene copolymer modified maleic anhydride is used as a primer. It has been proposed that all of these have good adhesion to such a substrate, but poor interlayer adhesion to the top coat, and
When it is used as a clear paint, the coating film becomes cloudy, and when it is applied as an enamel paint containing a pigment, it is remarkably inferior in pigment dispersion and lacks stability of the paint. There was a problem.

There is also known a method in which an acrylic resin or the like is applied to the top coat by using chlorinated polyolefin itself as a primer. However, such a method involves inter-layer adhesion with the top coat, solvent resistance and long-term use. There is a drawback in that the durable adhesion over a period of time decreases.

Further, although it is known to use chlorinated polyolefin itself as a top coat, the hardness, solvent resistance and weather resistance of the coating film are remarkably deteriorated, and therefore it is also not practical. is there.

For the polyolefin substrate,
Chlorinated polyolefins and acrylic copolymers are used as coating compositions in the form of maintaining long-term adhesion or interlayer adhesion with a top coat and further improving coating film performance such as solvent resistance and hardness. Although a resin composition composed of (1) and (2) is effective, the following problems are involved in the case of a composition formed by blending such an acrylic copolymer and a chlorinated polyolefin.

That is, when the chlorination rate is 50% by weight or more, the compatibility between the chlorinated polyolefin and the acrylic copolymer is improved, but the adhesion and solvent resistance of the formed coating film are deteriorated. Therefore, it can be said that practical application is difficult.

On the other hand, in order to improve the adhesiveness,
It is possible to use a chlorinated polyolefin having a chlorination rate of 50% or less, for example, a chlorination rate of around 35%, but in other aspects, compatibility with an acrylic copolymer is lacking, or a coating material is used. The stability of is also extremely poor, and it is extremely difficult to put it to practical use.

[0009]

As described above, since the chlorinated polyolefin itself has no adhesiveness at all, as long as the prior art is followed, a coating composition that can be practically used is inevitable. The reality is that we can't find out.

[0010] In view of the above situation, however, the present inventors have earnestly started research to find a coating composition that can be put to practical use. Therefore, the problem to be solved by the present invention is to impart paintability, to various surface treatments, to which no coating is applied, such as films, sheets or molded articles, so-called untreated polyolefin-based materials. It has a function as a primer for the material, and at the same time, can adopt a one-coat method.
An object of the present invention is to provide a very useful coating composition having good adhesion and weather resistance.

[0011]

[Means for Solving the Problems] Therefore, as a result of intensive studies, the inventors of the present invention focused on the problems to be solved by the above-mentioned invention, and as a result, found that the specific chlorinated polyolefin was , Further improve the compatibility with acrylic (co) polymers, and at the same time, adhere to polyolefin base materials, interlayer adhesion with the topcoat used for primer specifications, solvent resistance, topcoat specifications In order to mitigate and improve the weather resistance and chemical resistance, the hydroxyl group-containing vinyl monomers represented by β-hydroxyalkyl (meth) acrylate and unsaturated carboxylic acids are essential components. A chlorinated polyolefin obtained by copolymerizing vinyl-based monomers with a specific chlorinated polyolefin having a chlorination rate of 50% or less. The present invention has been completed by finding that acrylic- or vinyl-modified chlorinated polyolefin in a form grafted with vinyl monomers is remarkably excellent in compatibility and also has good adhesion. Came to.

That is, according to the present invention, a hydroxyl group-containing vinyl monomer (a-) represented by hydroxyalkyl (meth) acrylate is used for chlorinated polyolefin having a chlorination rate of 50% or less as one of the essential constituents. 1 to 2 to 30% by weight, unsaturated carboxylic acids (a-2) to 0.1 to 5% by weight, and copolymerizable unsaturated group-containing polyester resin (a-3) to 0 to 10% by weight. % And 50 of other vinyl monomers (a-4) copolymerizable with these (a-1), (a-2) and (a-3).
˜97.9% by weight of these (a-1),
The total amount of the compounds (a-2), (a-3) and (a-4) is set to 100% by weight, and
The solid content weight ratio of the chlorinated polyolefin and the mixture of the various monomers (monomer mixture) is 10: 9.
The number average molecular weight obtained by polymerizing in the presence of an organic solvent at a ratio of 0 to 90:10 is 3,000.
0 to 5 parts by weight of the ultraviolet absorber and / or antioxidant (B) is further added to 100 parts by weight of the solid content of the graft copolymer (A) of 0 to 40,000, if necessary. The polyisocyanate compound (C) also has an OH / NCO equivalent ratio of 2 with respect to the graft copolymer (A).
An object of the present invention is to provide a coating composition which is compounded so as to be 1/1 to 1/2.

Here, the above-mentioned chlorinated polyolefin has a chlorination rate of 50% or less, preferably 10 to 50%.
40% of polyolefin is designated, and if only representative examples of such polyolefin are given, ethylene, propylene, 1-
Butene, 3-methyl-1-butene or 3-methyl-1
-Α-olefin homopolymers or copolymers such as heptene;

Or ethylene-vinyl acetate copolymers,
Various copolymers of α-olefins and other vinyl monomers such as ethylene-butadiene copolymers or ethylene-acrylic acid ester copolymers, and therefore, as the chlorinated polyolefin, Particularly, only representative examples are chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, chlorinated ethylene-vinyl acetate copolymer and the like.

With respect to the chlorination rate of the chlorinated polyolefin, when the chlorination rate exceeds 50%, the adhesion to the polyolefin-based substrate is deteriorated. It should be done in consideration of various coating film performances such as flexibility, flexibility and hardness, preferably 10 to 40%, more preferably
It should be 15-35%, but in this way a resin composition with the most balanced coating performances is obtained.

Next, only specific examples of the hydroxyl group-containing vinyl monomers (a-1) will be given below. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di 2-hydroxyethyl fumarate or mono-2-hydroxyethyl-monobutyl fumarate.

When the amount of the hydroxyl group-containing vinyl monomer (a-1) to be used is less than 2% by weight, the polyisocyanate has an inter-layer adhesion property with the top coat in the primer specification. When combined with, the curability, solvent resistance, chemical resistance, etc. tend to be inadequate. On the other hand, when it exceeds 30% by weight, the adhesion to polyolefin materials and the water resistance of the film tend to decrease. Therefore, 2 to 30% by weight of the total monomer weight,
Preferably, the range of 5 to 25% by weight is suitable.

The unsaturated carboxylic acids (a-
As only 2), only representative ones are exemplified, and various unsaturated dicarboxylic acids such as maleic anhydride, fumaric acid, itaconic acid or citraconic acid, or various unsaturated dicarboxylic acids such as (meth) acrylic acid are used. Saturated monocarboxylic acids can be used.

The unsaturated carboxylic acid (a-
As for the amount of 2) used, if the compound is less than 0.1% by weight, the curability tends to be insufficient when combined with the polyisocyanate compound (C). If the amount is too large, the water resistance of the resulting coating tends to decrease, and the pot life when combined with the polyisocyanate compound (C) tends to decrease, so that the total amount of the monomer is 0.1-5. weight%,
Preferably, the range of 0.5 to 2% by weight is suitable.

Further, the above-mentioned polyester resin (a-3) having a copolymerizable ethylenically unsaturated double bond (hereinafter, abbreviated as an unsaturated group) is a so-called acid value titanium or valve pattern, so-called Not to mention pigments with small oil absorption,
Particularly, it is used when it is desired to improve the dispersibility of organic pigments such as quinacridone type, phthalocyanine type or azo type, and pigments such as carbon black having poor dispersibility and relatively large oil absorption. In that sense, it can be said that the polyester resin (a-3) does not contribute so much to the coating film performance itself.

Examples of the resin (a-3) include alkyd resins modified with oils or fatty acids; or with these oils or fatty acids,
Any of the so-called oil-free alkyd resins which are not modified can be used, but in the present invention, among these various alkyd resins, particularly unsaturated copolymerizable with various vinyl monomers, unsaturated. The use of the type having groups is suitable.

Examples of the polyester resin include various saturated fatty acids such as octylic acid, lauric acid, stearic acid or "persatic acid" (branched aliphatic monocarboxylic acid manufactured by Shell Co. of the Netherlands); oleic acid, linoleic acid. Various unsaturated fatty acids such as acids, linoleic acid, eleostearic acid or ricinoleic acid;

"Pamoline 200 or 300"
(Synthetic fatty acids manufactured by Hercules, USA), Chinese laurel oil (fatty acid), linseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil (fatty acid), cottonseed oil (fatty acid),
Various (semi) drying oils (fatty acids) such as soybean oil (fatty acids), olive oil (fatty acids), sahlawa oil (fatty acids), castor oil (fatty acids) or rice bran oil (fatty acids);

Also, various non-drying oils (fatty acids) such as hydrogenated coconut oil (fatty acid) coconut oil (fatty acid) or palm oil (fatty acid), etc., one of these oils or fatty acids Alternatively, with or without a mixture of two or more,

Various polyvalent compounds such as ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, neopentyl glycol, 1,6-hexanediol, 1,2,6-hexanetriol, pentaerythritol or sorbitol. One or more alcohols,

Benzoic acid, p-tert-butylbenzoic acid, (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid, tetrahydro (anhydrous) phthalic acid, phthalic acid, tetrachloro (anhydrous) phthalic acid, hexachloro (anhydrous) phthalic acid Acid, tetrabromo (anhydrous) phthalic acid, trimellitic acid,
"Himitric acid" [Hitachi Chemical Co., Ltd. product], (anhydrous) succinic acid, (anhydrous) maleic acid or (anhydrous) itaconic acid; or fumaric acid, adipic acid, sebacic acid or citric acid, One or more kinds of various carboxylic acids can be prepared by a conventional method.

Furthermore, if necessary, "Kurdura E"
Monoepoxy compounds such as glycidyl esters of various fatty acids such as (Ciel's product); "Epiclon
200 or 400 "," Epicoat 828 or 1001 ", or various polyepoxy compounds; Diisocyanates;

Further, various adducts obtained by addition reaction of these various diisocyanates listed above with various polyhydric alcohols listed above and water; or various burettes; or , 1 type or 2 or more types of polyisocyanates having an isocyanuric ring, which are obtained by (co) polymerization of various diisocyanates with each other, by substituting a part of the above polyhydric alcohols or carboxylic acids, A compound obtained by the reaction is suitable.

At this time, as the alkyd resin, a so-called saturated fatty acid or non-drying oil (fatty acid) modified type having no copolymerizable unsaturated group at all or a small amount of the unsaturated group, or, For the type of oil-free alkyd resin that has not been modified with oils or fatty acids, the copolymerizable unsaturated bond that should be the grafting point for various other vinyl monomers is replaced with (anhydrous) maleic acid or fumaric acid. Needless to say, it is necessary to introduce an unsaturated dicarboxylic acid such as an acid into the alkyd resin.

The alkyd resin thus obtained is used in the range of 0 to 10% by weight.
When it is used in an excessively large amount exceeding 10% by weight, solvent resistance and stain resistance are inevitably deteriorated, which is not preferable.

Furthermore, each of the above described
As only other typical vinyl monomers copolymerizable with (a-1), (a-2) and (a-3), only typical ones are exemplified by methyl (meth) acrylate, ethyl ( (Meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) Various (meth) acrylates such as acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate or alkoxyalkyl (meth) acrylate. Kind;

Diesters of various unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with monohydric alcohols; vinyl acetate, vinyl benzoate or "Veova" (vinyl ester manufactured by Ciel) Various vinyl esters such as; "Biscoat BF, B
FM, 3F or 3FM ”[fluorine-containing acrylic monomers manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth) acrylate, diperfluorocyclohexyl fumarate or Ni-propylperfluorooctanesulfonamidoethyl ( Various fluorine-containing compounds such as (per) fluoroalkyl group-containing vinyl esters, vinyl ethers, (meth) acrylates or unsaturated carboxylic acid esters such as (meth) acrylates;

Alternatively, there are various cyano group-containing vinyl monomers such as (meth) acrylonitrile, and various halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride.

When the above-mentioned various monomers (mixtures) listed above are copolymerized with the above-mentioned chlorinated polyolefin, these chlorinated polyolefins and monomers (mixtures) are to be copolymerized. Usage ratio with is 10:90
It is suitable to be within the range of the solid content weight ratio of ˜90: 10, preferably 15:85 to 60:40.

By such copolymerization, vinyl monomer components such as hydroxyl group-containing vinyl monomers (a-1) represented by β-hydroxyalkyl (meth) acrylate are grafted onto the chlorinated polyolefin component. As a result, a novel acryl- or vinyl-modified chlorinated polyolefin having good compatibility is obtained. As a method of such graft copolymerization, usually, a polymerization temperature of 60 to 100 ° C. is used. It is preferable to carry out solution polymerization using various known and conventional radical-generating polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile.

At this time, when the ratio of the chlorinated polyolefin to the monomers (mixtures) is more than 10:90 in terms of solid content weight ratio, and the amount of the chlorinated polyolefin decreases, the It is not preferable because the adhesion to the polyolefin-based substrate will be decreased. On the other hand, when it exceeds 90:10 and the amount of the chlorinated polyolefin increases too much, the solvent resistance of the obtained coating film becomes
It is not preferable because it will be significantly reduced.

Here, examples of the above-mentioned organic solvent include toluene and xylene, which are known as good solvents for chlorinated polyolefins. In addition to these, butyl acetate and butanol are also included.
It can be used as long as the solubility is not impaired.

The graft copolymer thus obtained has a number average molecular weight (Mn) of 3,000 to 4 at first.
It is necessary to be in the range of 10,000, preferably in the range of 5,000 to 30,000.

For those having a molecular weight lower than 3,000,
By all means, the mechanical strength is not enough, while 4
With a molecular weight higher than 50,000,
In any case, it is difficult to obtain a sufficient spray workability, which is not preferable.

The above-mentioned ultraviolet absorber is a component used when it is necessary to further enhance the durability of the composition of the present invention, and it may be added and mixed in each case. In this case, the acrylic- or vinyl-modified copolymer (A) may be used in an amount of up to 5 parts by weight based on 100 parts by weight of the solid content.

When the amount used is more than 5 parts by weight, the effect is increased, but the water resistance is lowered and the cost is often disadvantageous. As the ultraviolet absorber, only typical ones are exemplified, and benzophenone, 2,4-dihydrobenzophenone, 2,2'- or 4,4'-tetrahydroxybenzofenone, 2-hydroxy-4-. Methoxybenzophenone, 2,2'-dihydroxy-4,
4'-dimethoxybenzophenone, 2,2'-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-humanoxy-4-methoxy-5-
Sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2
-Hydroxy-4- (2-hydroxy-3-methyl-acryloxyisopropoxybenzophenone;

2- (2'-hydroxy-5'-methyl-
Phenyl) -benzotriazole, 2- (2-hydroxy-3,5-di-tert-amyl-phenyl) -2H
-Benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3', 5 '
-Di-tert-butyl-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3 ',
5'-di-tert-butyl-phenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-isoamyl-phenyl) benzotriazole, (2-hydroxy-5-tert-
Butylphenyl) benzotriazole, phenyl salicylate-4-tert-butyl-phenyl salicylate, p-octyl-phenyl salicylate;

Ethyl-2-cyano-3,3'-diphenyl-acrylate, 2-ethylhexyl-2-cyano-
3,3'-diphenyl-acrylate; hydroxy-5
-Methoxy-acetophenone, 2-hydroxy-naphthophenone; 2-ethoxyethyl-p-methoxycinnamate; nickel-bisoctylphenyl sulfide;
4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis- (2,2,6,6, -tetramethyl-4-piperidyl) sebacate or "tinupin 2
92 "(product of Ciba-Geigy, Germany)
These may be used alone or in combination of two or more.

In order to further increase the effectiveness or usefulness, "Sumilyzer BHT" [Sumitomo Chemical Co., Ltd.]
Product], “Cynox BCS” [Product of Shiraishi Calcium Co., Ltd.], “Irganox 1010 or 1
076 "(product of Ciba-Geigy)," Noclizer "
Various known and conventional antioxidants such as "TNP" (product of Ouchi Shinko Co., Ltd.) or "antioxidant KB" (product of Bayer AG, Germany) can also be used in combination.

The above-mentioned polyisocyanate compound (C) is a component used when it is necessary to further improve the durability and solvent resistance of the composition of the present invention, and is added in each case. It may be mixed, but in that case, the equivalent ratio of OH / NCO to the graft copolymer (A) is 2/1 to 1/2,
The ratio is preferably 1.5 / 1 to 1 / 1.5, and more preferably 1/1.

As the compound (C), only typical ones are shown. Various aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate or diphenylmethane diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate or trimethyl. Various aliphatic diisocyanates such as hexamethylene diisocyanate; or isophorone diisocyanate, methylcyclohexane-2,4- (or 2,6-) diisocyanate,
Diisocyanates such as various alicyclic diisocyanates such as 4,4′-methylenebis (cyclohexyl isocyanate) or 1,3-di (isocyanatomethyl) cyclohexane,

Alternatively, these various diisocyanates, the polyhydric alcohols, low molecular weight polyester resins (including oil-modified resins) having a functional group capable of reacting with an isocyanate group, acryl- or vinyl-based copolymers. Coalescence or adducts with water, etc .; furthermore, burettes, etc., or (co) polymers of the various diisocyanates listed above (including oligomers).
And so on.

The thus-obtained coating composition of the present invention has excellent adhesiveness in a broad sense such as long-term adhesiveness and interlayer adhesion to the top coat, and also has excellent solvent resistance. It provides a cured coating film with various coating performances, and can be widely applied to various polyolefin-based materials or substrates such as various molded products such as films and sheets. For example, polyolefin molded products May be used as a primer in painting,

Further, it may be used as a top coat for various structures or structures, and may also be used as a binder for printing ink.
Above all, various molded products made of polyolefin,
It is useful for structures or structures.

Thus, the composition of the present invention is a molded product of homopolymers or copolymers of various α-olefins such as ethylene, propylene, 1-butene or 3-methyl-1-heptene, It can be applied as a paint to a structure or a structure, and particularly shows excellent adhesion to a polyolefin molded product containing various fillers such as titanium oxide, talc or silica,
It goes without saying that it may be used as a clear paint or as an enamel paint in the form of being mixed with various known and commonly used additive components such as pigments and leveling agents.

[0051]

EXAMPLES Next, the present invention will be described in detail with reference to Examples and Comparative Examples. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 (Preparation Example of Unsaturated Group-Containing Polyester Resin) In a four-necked flask equipped with a stirrer, a thermometer, an air condenser and a nitrogen introducing tube, 500 parts of linseed oil, 105.8 parts of glycerin and 0.125 parts of litharge was charged, transesterified at 240 ° C. for 1 hour and then cooled to 200 ° C., and 824 parts of glycerin and 364.1 parts of phthalic anhydride were added thereto, and the mixture was heated to 10 ° C. at 230 ° C.
The reaction was carried out in a nitrogen stream for a period of time.

The product thus obtained is then diluted with toluene to a non-volatile content of 50% and the Gardner viscosity is B
-C, acid value 36, number average molecular weight 8,800,
A linseed oil alkyd resin solution having an oil length of 50% was obtained.

Reference Example 2 (Same as above) In a four-necked flask equipped with a stirrer, a thermometer, an air condenser and a nitrogen inlet tube, 440 parts of isophthalic acid, 177.5 parts of adipic acid and 3 parts of neopentyl glycol were added.
61 parts, 181.3 parts of trimethylolpropane and 15 parts of maleic anhydride were charged, and 22 parts of
After reacting at 0 ° C. for about 10 hours, the acid value is 8 and O
A solution of the target resin having an H value of 132, a hydroxyl group equivalent of 425, and a number average molecular weight of 1,600 was obtained.

Then, this was mixed with toluene: butyl acetate = 5.
When the nonvolatile content is diluted to 60% with a mixed solvent of 0:50 (weight ratio), Gardner has a viscosity H and an acid value of 4.8.
The resin solution had an OH value of 79.2 and a color number of 2.

Example 1 In a reactor equipped with a stirrer and a condenser, "Hard Resin 14ML" [chlorinated polypropylene manufactured by Toyo Kasei Co., Ltd .; chlorination rate = 26%, solid content = 30%] was added.
Add 00 parts and 800 parts of toluene and set the internal temperature to 8
The mixture was brought to 0 ° C., to which a mixture consisting of 450 parts of methyl methacrylate, 250 parts of isobutyl methacrylate, 140 parts of 2-hydroxyethyl methacrylate and 10 parts of methacrylic acid, 5 parts of benzoyl peroxide and azobisisomethoxide. 5 parts of butyronitrile and 3 parts of toluene
The dissolved product dissolved in 50 parts was added dropwise over 3 hours, and the reaction was continued by maintaining the same temperature for 12 hours even after the completion of the addition, and the nonvolatile content was 40.2%, and A chlorinated polypropylene-modified acrylic resin having a number average molecular weight of 25,000 was obtained. Hereinafter, this is referred to as a graft copolymer (A
-1) is abbreviated.

Then, 583 parts of this graft copolymer,
30 parts of titanium oxide, 69 parts of talc, 1 part of carbon and 150 parts of xylene were kneaded in a sand mill for 1 hour to obtain various primers.

Thereafter, each primer was evaluated and examined for its adhesion to the polypropylene material and interlayer adhesion between the primer and the top coat. The evaluation results are shown in Table 1. Examples 2 to 4 and Comparative Examples 1 to 6 Using polymerization solvent, initiator, unsaturated group-containing monomer and chlorinated polyolefin as shown in Table 1, and polymerization conditions as shown in the same table. Various chlorinated polyolefin-modified acrylic copolymers were obtained in the same manner as in Example 1 except that the procedure was changed to 1.

Then, 5 of each graft copolymer was prepared.
83 parts, 30 parts of titanium oxide, 69 parts of talc, 1 part of carbon and 150 parts of xylene are sand-milled.
It was kneaded for 1 hour to obtain various primers.

After that, for each primer, a comparative study was made on the adhesion to the polypropylene material and the interlayer adhesion between the primer and the top coat. The evaluation results are shown together in the same table.

Examples 5 to 8 and Comparative Example 7 A coating material was prepared in the same manner as in Example 1 except that the mixing ratios shown in Table 2 were changed, and an ultraviolet absorber and a curing agent were also added. In addition, a polypropylene plate was air-spray coated to a dry film thickness of 30 μm (μm), dried at 80 ° C. for 30 minutes, and further dried at 25 ° C. for 5 days to obtain a coating film. The evaluation results of coating film performance are summarized in the same table.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

The coating composition of the present invention is, in particular, a film, a sheet or a molded product which is not subjected to any surface treatment of various surface treatments which should impart coatability to the substrate. It has a function as a primer for a so-called untreated polyolefin-based material such as the above, and at the same time, can be adopted in a one-coat method, and is excellent in adhesion and weather resistance and is extremely useful.

Claims (5)

[Claims] 1. A chlorinated polyolefin obtained by copolymerizing hydroxyl group-containing vinyl monomers, unsaturated carboxylic acids, and other copolymerizable vinyl monomers other than the above in the presence of an organic solvent. The coating composition, which contains the graft copolymer (A) as an essential film-forming component and, if necessary, also contains an ultraviolet absorber and / or an antioxidant. object. 2. A vinyl monomer having a hydroxyl group, an unsaturated carboxylic acid, a copolymerizable polyester resin having an ethylenically unsaturated double bond, and other vinyl copolymerizable other than the above with respect to a chlorinated polyolefin. A graft copolymer (A) obtained by copolymerizing a monomer and an organic solvent in the presence of an organic solvent is contained as an essential film-forming component, and if necessary, an ultraviolet absorber and / or Alternatively, the coating composition, which also contains an antioxidant (B). 3. A chlorinated polyolefin obtained by copolymerizing a hydroxyl group-containing vinyl monomer, an unsaturated carboxylic acid and other copolymerizable vinyl monomers other than the above in the presence of an organic solvent. The graft copolymer (A) is contained as an essential film-forming component, and further, if necessary, an ultraviolet absorber and / or an antioxidant (B) or a polyisocyanate compound (C). A coating composition, which further comprises: 4. A vinyl monomer having a hydroxyl group, an unsaturated carboxylic acid, a polyester resin having a copolymerizable ethylenically unsaturated double bond, and a vinyl copolymerizable other than the above with respect to a chlorinated polyolefin. A graft copolymer (A) obtained by copolymerizing a monomer and an organic solvent in the presence of an organic solvent is contained as an essential film-forming component, and if necessary, an ultraviolet absorber and / or Or an antioxidant (B) or a polyisocyanate compound (C).
Paint composition. 5. A hydroxyl group-containing vinyl monomer (a-) for a chlorinated polyolefin having a chlorination rate of 50% or less.
2 to 30% by weight of 1) and unsaturated carboxylic acids (a-
Polyester resins (a-3) having an ethylenically unsaturated double bond capable of being copolymerized with 0.1 to 5% by weight of 2).
0 to 10% by weight of (a-1), (a-2)
And 50 to 97.9% by weight of other vinyl monomers (a-4) copolymerizable with (a-3), (a-1), (a-2) and (a-3). ) And (a-4)
Presence of an organic solvent such that the total amount of each compound is 100% by weight, and the solid content weight ratio of the chlorinated polyolefin and each compound is 10:90 to 90:10. Below, with respect to 100 parts by weight of the solid content of the graft copolymer (A) having a number average molecular weight of 3,000 to 40,000 obtained by copolymerization, an ultraviolet absorber and / or an antioxidant (B ) Is added to the graft copolymer (A), and a polyisocyanate compound (C) is added to the graft copolymer (A), if necessary.
A coating composition, which is blended so that an equivalent ratio of OH / NCO is 2/1 to 1/2.