JPH0559327A - Composition for paint - Google Patents

Abstract

PURPOSE:To obtain the subject composition having primer function, exhibiting excellent adhesivity, flexibility, solvent resistance and weather resistance and useful for molding etc., by compounding a specific graft copolymer, a polyether, etc., an ultraviolet absorber, etc., and a polyisocyanate compound. CONSTITUTION:The objective composition is produced by compounding (A) a graft polymer produced e.g. by polymerizing a chlorinated polyolefin having a chlorination ratio of <=50% with (i) 5-30wt.% of a vinyl monomer containing hydroxyl group, (ii) 0.1-3wt.% of an unsaturated carboxylic acid, (iii) 0-10wt.% of a polyester resin containing copolymerizable unsaturated group and (iv) 50-94.9wt.% of other copolymerizable vinyl monomer (the sum of the monomers is 100wt.% and the weight ratio of the chlorinated polyolefin to the monomer mixture is 10/90 to 90/10 in terms of solid components) in the presence of an organic solvent, (B) a polyether, etc., (C) an ultraviolet absorber and/or an antioxidant and (D) a polyisocyanate compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful coating composition. More specifically, a specific graft copolymer obtained by polymerizing a specific monomer mixture with a chlorinated polyolefin is added to a linear or branched polyether and / or polyester polyol, respectively. The present invention relates to an extremely highly practical coating composition which comprises (B), an ultraviolet absorber and / or an antioxidant (C), and a polyisocyanate compound (D).

The object of the present invention is to provide a film which has not been subjected to any surface treatment to impart paintability,
It has a function as a primer for so-called untreated polyolefin-based materials such as sheets or molded products, and at the same time can operate a one-coat method, in particular, adhesion, flexibility, solvent resistance and weather resistance. To provide a good coating composition.

[0003]

2. Description of the Related Art Conventional paints made of alkyd, acrylic and epoxy resins have almost no adhesiveness to various molded products made of crystalline polyolefin having a small polarity. For coating on such a polyolefin-based substrate, it has been proposed to use, as a primer, a modified product of atactic polypropylene with maleic anhydride, or a modified product of ethylene-propylene copolymer with maleic anhydride. However, all of these have good adhesion to such a substrate, but have poor interlayer adhesion to the top coat, and when used as a clear coating, the coating film becomes cloudy, while, on the other hand, the pigment When applied as an enamel paint containing the above, there is a problem that the pigment dispersion is extremely inferior and the paint stability is poor. Was Tsu.

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

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

As a coating composition which retains long-term adhesion to a polyolefin substrate or interlayer adhesion to a top coat and has improved coating film performance such as solvent resistance and hardness, chlorine can be used. Although a resin composition comprising a modified polyolefin and an acrylic copolymer is effective, for example, when it is used as a coating for automobile bumpers, it is particularly inferior in impact resistance and flexibility in winter, and cracks or detachment of the coating film. Is likely to occur.

By changing the modifying acrylic resin to a soft one, the impact resistance at low temperature and the flexibility are improved, but there is a drawback that the stain resistance and the solvent resistance are impaired.

[0008]

However, the present inventors have further improved the compatibility between the specific chlorinated polyolefin and the acrylic (co) polymer and, at the same time, have improved the adhesion to the polyolefin-based substrate. In order to improve the interlayer adhesion with the top coat when using the primer specifications, solvent resistance and flexibility, and also improve the weather resistance, chemical resistance and flexibility when using the top coat specifications, As a result of research, a vinyl-based monomer containing a hydroxyl group-containing vinyl monomer and an unsaturated carboxylic acid as essential components,
A so-called acrylic or vinyl-modified chlorinated polyolefin (hereinafter referred to as "acryl or vinyl-modified chlorinated polyolefin" obtained by polymerizing a chlorinated polyolefin having a chlorination rate of 50% or less and obtained by grafting a vinyl-based monomer onto the chlorinated polyolefin. This is also referred to as a graft copolymer.)), A coating film obtained by blending a specific polyester- and / or polyether polyol and then curing with polyisocyanate is excellent in flexibility and solvent resistance. In addition, they have found that the adhesion to polyolefin is also good, and have completed the present invention.

[0009]

[Means for Solving the Problems] That is, the present invention relates to a chlorinated polyolefin having a chlorination rate of 50% or less, which is one of the essential constituents, and a hydroxyl group represented by hydroxyalkyl (meth) acrylate. 5 to 30 wt% of the contained vinyl monomer (a), 0.1 to 3 wt% of the unsaturated carboxylic acid (b), and 0 to 10 wt% of the polyester resin (c) having a copolymerizable unsaturated group. %When,
50 to 94.9% by weight of the other vinyl-based monomers (d) copolymerizable with the above (a), (b) and (c) are added to the above (a) and (b). ), (C) and (d) so that the total amount of each monomer mixture is 100% by weight, and the solid content weight ratio of the chlorinated polyolefin to the monomer mixture is 10:90 to. 90:10
In the presence of an organic solvent so that the number average molecular weight is 3,000 to 4,000.
With respect to 100 parts by weight of the solid content of the graft copolymer (A) of 0,

Each of them has a hydroxyl value of 50 to 200 and is 5 to 50 of a linear or branched polyester- and / or polyether polyol (B).
Parts by weight, UV absorber and / or antioxidant (C)
Of 0 to 5 parts by weight of the polyisocyanate compound (D) with respect to the hydroxyl groups of the graft copolymer (A) and the polyol (B) in an OH / NCO equivalent ratio of 2 /.
The present invention provides a coating composition having extremely high practicability, which is formed by blending so as to be 1 to 1/2.

Here, the above-mentioned chlorinated polyolefin has a chlorination rate of 50% or less, preferably 10 to
40% of the polyolefin is referred to, and a typical example of such a polyolefin is a single weight of α-olefin such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-heptene. A copolymer or a copolymer; or a copolymer of an ethylene-vinyl acetate copolymer, an ethylene-butadiene copolymer, an ethylene-acrylic ester copolymer such as an α-olefin and another vinyl-based monomer. Yes,

Therefore, typical examples of the chlorinated polyolefin include chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer and chlorinated ethylene-vinyl acetate copolymer.

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. , Flexibility and hardness should be taken into consideration in consideration of various coating film performance, preferably 10 to 40%, more preferably 1
It should be 5 to 35%, and in this way the resin composition with the most balanced coating performance is obtained.

The above-mentioned hydroxyl group-containing vinyl monomer (a)
Among them, particularly representative ones are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy. Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-
Chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate or mono-
2-hydroxyethyl-monobutyl fumarate and the like.

When the amount of the hydroxyl group-containing vinyl monomer (a) used is less than 5% by weight, solvent resistance and chemical resistance when combined with polyisocyanate become insufficient, while If it is more than 30% by weight, the adhesion with the polyolefin material will decrease, so
5 to 30% by weight of the total weight of monomers, preferably 5 to 25
The range of weight% is suitable.

[0016] Further, typical examples of the unsaturated carboxylic acid (b) include maleic anhydride, fumaric acid,
Examples thereof include itaconic acid, citraconic acid, (meth) acrylic acid, and the like.

When the amount of the unsaturated carboxylic acid (b) used is less than 0.1% by weight, the curability when combined with polyisocyanate becomes insufficient, while When it is more than 3% by weight,
Since the pot life when combined with polyisocyanate is shortened, it is appropriate to be within the range of 0.1 to 3% by weight, preferably 0.2 to 2% by weight, based on the total amount of the monomers.

Further, the above-mentioned polyester resin (c) having an unsaturated group capable of copolymerization is not limited to pigments having a small oil absorption amount such as acid value titanium and red peony, and in particular, quinacridone type and phthalocyanine type. It is used when it is desired to improve the dispersibility of a pigment having a relatively large oil absorption, such as an organic pigment such as an azo-based or azo-based pigment, or a so-called poor dispersibility such as carbon black. It can be said that the polyester resin (c) does not significantly contribute to the coating film performance itself.

The polyester resin (c) is an alkyd resin modified with oil or fatty acid, or
Although not modified by these, any of so-called oil-free alkyd resins may be used, in the present invention, among these alkyd resins, in particular,
A type having an unsaturated bond copolymerizable with each vinyl monomer is suitable.

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

"Pamoline 200 or 300"
(Synthetic oils and fats 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), soybean oil (fatty acid) Various (semi) drying oils (fatty acids), such as olive oil (fatty acids), sulahua oil (fatty acids), castor oil (fatty acids) or rice bran oil (fatty acids); or hydrogenated coconut oil (fatty acids), coconut oil (Fatty acid) or palm oil (fatty acid), such as various non-drying oils (fatty acids), or one or a mixture of two or more fatty acids, or not used,

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

Benzoic acid, pt-butylbenzoic acid, (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid, tetrahydro (anhydrous) phthalic acid, phthalic acid, tetrachloro (anhydrous) phthalic acid, hexachloro (anhydrous) phthalic acid , Tetrabromo (anhydrous) phthalic acid, trimellitic acid, "Himitic acid" [Hitachi Chemical Co., Ltd. product], (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, adipic acid, sebacine An acid or one or more kinds of carboxylic acids such as silicic acid are prepared by a conventional method.

Further, if necessary, "Kurdura E"
(Ciel's product), monoepoxy compound such as glycidyl ester of fatty acid, "Epiclone 200 or 400", "Epicote 828 or 100"
1 "such as polyepoxy compound,

Alternatively, diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or 4,4'-methylenebis (cyclohexyl isocyanate); addition reaction of each of these diisocyanates with the above polyhydric alcohols, water, etc. Polyisocyanates obtained by

Alternatively, one or more polyisocyanates having an isocyanuric ring, which are obtained by (co) polymerization of diisocyanates with each other, may be used in place of one part of the polyhydric alcohols or carboxylic acids described above to carry out a conventional method. Therefore, those obtained by the reaction are suitable.

At this time, as the above-mentioned alkyd resin, a saturated fatty acid or a non-drying oil (fatty acid) modified type which has no copolymerizable unsaturated bond at all or has little unsaturated bond, or For the type of oil-free alkyd resin that is not modified with oil or fatty acid, the copolymerizable unsaturated bond to be the grafting point from other various vinyl monomers,
Needless to say, it is necessary to introduce the unsaturated carboxylic acid such as (anhydrous) maleic acid or fumaric acid into the alkyd resin.

Then, the alkyd resin thus obtained is 0 to 1 as the polyester resin (c).
It is used within the range of 0% by weight, but when it is used in a large amount exceeding 10% by weight, the solvent resistance, stain resistance, etc. become inferior.

Further, the above-mentioned (a), (b) and (c) and other vinyl-based monomers (d) which can be copolymerized.
Of these, particularly representative ones are methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate,
i-Butyl (meth) acrylate, t-butyl (meth)
Of acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate or alkoxyalkyl (meth) acrylate Various (meth) acrylates; unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid, and monohydric alcohols,
Various diesters;

Various vinyl esters such as vinyl acetate, vinyl benzoate or "Veova" (vinyl ester manufactured by Ciel); "Viscoat BF, BFM, 3F or 3FM" [included by Osaka Organic Chemical Co., Ltd.] Fluorine-based acrylic monomer], perfluorocyclohexyl (meth) acrylate, diperfluorocyclohexyl fumarate or vinyl ester containing a (per) fluoroalkyl group such as N-i-propylperfluorooctanesulfonamidoethyl (meth) acrylate, Various fluorine-containing compounds such as vinyl ethers, (meth) acrylates or unsaturated carboxylic acid esters; or olefins such as (meth) acrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride And so on.

When the above-mentioned various monomers (mixtures) are polymerized with the chlorinated polyolefin, the chlorinated polyolefin and the monomer (mixture) are mixed with each other. The use ratio is the former chlorinated polyolefin: the latter monomer (mixture) = 10: 90 to 90: 1.
It is suitable that the solid content weight ratio is 0, preferably 15:85 to 60:40.

By such polymerization, various vinyl-based monomer components mainly composed of a hydroxyl group-containing vinyl monomer, an unsaturated carboxylic acid, and other vinyl-based monomers that can be copolymerized are converted into chlorine. A modified chlorinated polyolefin having good compatibility is obtained as a result of being grafted to a modified polyolefin component. As a method for such polymerization, benzoyl peroxide or benzoyl peroxide is usually used at a polymerization temperature of 60 to 100 ° C. Solution polymerization is often performed using a radical-generating polymerization initiator such as azobisisobutyronitrile,

At this time, when the ratio of each of the above-mentioned chlorinated polyolefin and the monomer (mixture) exceeds 10:90 by solid content weight ratio and the amount of chlorinated polyolefin decreases, the polyolefin is In any case, when the amount of chlorinated polyolefin exceeds 90:10 and the amount of chlorinated polyolefin increases, the solvent resistance of the resulting coating film decreases remarkably. Is also not preferable.

Here, as the above-mentioned organic solvent,
Among them, known as a good solvent for chlorinated polyolefin, such as toluene or xylene, but in addition to these, butyl acetate and butanol, etc., within the range that does not impair the solubility, Can be used.

The graft copolymer (A) thus obtained must first have a number average molecular weight (Mn) within the range of 3,000 to 40,000, preferably. The range of 5,000 to 30,000 is suitable.

For those having a molecular weight lower than 3,000,
In terms of mechanical strength, it is not sufficient. On the other hand, if the molecular weight is higher than 40,000, it will be difficult to obtain a sufficient spray workability, which is not preferable.

As the linear or branched polyester- and / or polyether polyol (B) having a hydroxyl value of 50 to 200, polyethylene glycol ether, polypropylene glycol ether, polytetramethylene can be used. Examples thereof include glycol and polycaprolactone polyol, which may be used alone or in combination of two or more kinds.

[0038] The amount and type of use are acrylic resin,
It should be determined by the degree of hardness of the resin skeleton of the polyisocyanate compound, when the glass transition point of the acrylic resin used is low, or when a soft polyisocyanate compound is used, It is better that the amount used is small and the hydroxyl value is high.

The amount used is suitable within the range of 5 to 50 parts by weight with respect to 100 parts by weight of the solid content of the graft copolymer (A). If the amount is less than 5 parts by weight, the flexibility at low temperature is inevitably deteriorated.
When it is used in a large amount exceeding 0 parts by weight, the solvent resistance is inevitably deteriorated.

The polyester- and / or polyether polyol (B) may, of course, be straight-chain or branched, and further, may be straight-chain or branched. You may use together.

The above-mentioned ultraviolet absorber is a component used when it is necessary to further improve the durability of the composition of the present invention, and it may be added and mixed each time. In this case, the modified copolymer (graft 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.

If the amount used exceeds 5 parts by weight, the effect is great, but on the other hand, the water resistance is lowered and the cost is often disadvantageous. If only typical ones of the ultraviolet absorbers are shown,
Benzophenone, 2,4-dihydrobenzophenone,
2,2'- or 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxybenzophenone, 2-hydroxy -4-octoxybenzophenone,
2-hydroxy-4-dodecyloxybenzophenone, 2
-Hydroxy-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-acryloxyisopropoxy) benzophenone; 2- (2'-hydroxy-
5'-methyl-phenyl) -benzotriazole, 2-
(2-Hydroxy-3,5-di-t-amyl-phenyl) -2H-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl-phenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-
Di-t-butyl-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-
t-butyl-phenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-
Isoamyl-phenyl) benzotriazole, (2-hydroxy-5-t-butylphenyl) benzotriazole, phenyl salicylate, 4-t-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 29
2 "(product of Ciba-Geigy Co., Ltd.) and the like, and these may be used alone or in combination of two or more kinds.

In addition, to increase effectiveness, or
"Sumilyzer BHT" [Sumitomo Chemical Co., Ltd. product], "Seanox BCS" [Shiraishi Calcium Co., Ltd. product], "Irganox 1010 or 1"
076 "(product of Ciba-Geigy)," Noclizer "
Well-known conventional antioxidants such as "TNP" (product of Ouchi Shinko Co., Ltd.) or "antioxidant KB" (product of Bayer Co.) can be used in combination.

Further, of the above-mentioned polyisocyanate compounds (D), only typical ones will be shown. Various aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate or diphenylmethane diisocyanate; Various aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate or trimethylhexamethylene diisocyanate;

Or various fats such as isophorone diisocyanate, methylcyclohexane-2,4- (or 2,6-) diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate) or 1,3-di (isocyanatomethyl) cyclohexane. Diisocyanates such as cyclic diisocyanates;

Alternatively, each of these diisocyanates, the above polyhydric alcohols, low molecular weight polyester resins (including oil-modified types) having a functional group capable of reacting with an isocyanate group, acrylic copolymers ( Including those containing styrene as a comonomer component) or an adduct with water;

Further, there are burettes and (co) polymers (including oligomers) of the above-mentioned diisocyanates. The amount used is such that the OH / NCO equivalent ratio is 2/1 to 1/2, preferably 1.5 / 1 to 1 with respect to the hydroxyl groups of the graft copolymer (A) and the polyol (B). The ratio is within the range of /1.5, more preferably 1/1.

The composition of the present invention thus obtained is, in particular, excellent in adhesiveness in a broad sense such as adhesiveness over a long period of time and interlayer adhesiveness with a top coat, and is also excellent in solvent resistance. It gives a cured coating with performance,

It can be widely applied to various polyolefin materials or substrates such as various molded products such as films and sheets, and may be used as a primer for coating polyolefin molded products, for example.

Further, it may be used as a top coat for various structures or structures, or may be used as a binder for printing inks, but in particular, various molded products made of polyolefin as a material, Useful for structures or structures.

Thus, the coating composition of the present invention comprises ethylene, propylene, 1-butene or 3-methyl-1-.
It can be applied as a paint to molded products, structures, or structures of homopolymers or copolymers of various α-olefins such as heptene, and in particular, it contains a filler such as titanium oxide, talc, or silica. It shows excellent adhesion to molded polyolefin molded products, and can be used as a clear paint or as a pigment or leveling agent.
It goes without saying that it may be used as an enamel paint in a form in which known and commonly used additive components are mixed.

[0053]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified. .

Reference Example 1 (Synthesis Example of Polyester Resin Containing Unsaturated Group) 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, then cooled to 200 ° C., and 824 parts of glycerin and 364.1 parts of phthalic anhydride were added thereto, and 230 ° C.
At room temperature for 10 hours in a nitrogen stream.

The product was diluted with toluene so that the nonvolatile content was 50%, and the Gardner viscosity at 25 ° C. was 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. Hereinafter, this is abbreviated as alkyd resin-1.

Reference Example 2 (Synthesis Example of Polyester Resin Containing Unsaturated Group) In a four-necked flask equipped with a stirrer, a thermometer, an air condenser and a nitrogen introducing tube, 440 parts of isophthalic acid and 177.5 parts of adipic acid were placed. , Neopentyl glycol 3
61 parts, 181.3 parts of trimethylolpropane and 15 parts of maleic anhydride were charged, and 22 parts of
Hold at 0 ℃ for about 10 hours to react, acid value 8
And the OH number is 132, the hydroxyl equivalent is 425, and
A resin having a number average molecular weight of 1,600 was obtained.

Then, this was mixed with toluene: butyl acetate = 5.
Non-volatile content of 60% in a mixed solvent of 0:50 (weight ratio)
When diluted to give a solution of the target resin having a Gardner viscosity of H, an acid value of 4.8, an OH value of 79.2, and a color number of 2.

Reference Example 3 [Preparation Example of Graft Copolymer (A)] In a reactor equipped with a stirrer and a cooler, "Hardlen 14ML" [chlorinated polypropylene manufactured by Toyo Kasei Co., Ltd .; chlorination rate 26] %, Solid content 30%] and 800 parts of toluene were added, and the temperature inside the vessel was adjusted to 80 ° C., 500 parts of methyl methacrylate, 200 parts of isobutyl methacrylate (IBMA), 2 parts of methacrylic acid were added.
-140 parts of hydroxyethyl (2-HEMA) and 10 parts of methacrylic acid, 5 parts of benzoyl peroxide (BPO), azobisisobutyronitrile (A
5 parts of IBN) and 350 parts of butyl acetate were dissolved for 3 hours, and the mixture was kept at the same temperature for 12 hours after the dropping, and the nonvolatile content was 40.2. ,And,
4, a chlorinated polypropylene-modified acrylic resin having a number average molecular weight of 25,000 was obtained.

Reference Examples 4 to 9 Using a polymerization solvent, an initiator, a polymerizable unsaturated bond-containing monomer and a chlorinated polyolefin as shown in Table 1,
Moreover, various chlorinated polyolefin-modified vinyl copolymers were obtained in the same manner as in Reference Example 3 except that the polymerization conditions were changed as shown in the same table.

Cyclohexyl methacrylate is
Abbreviated as "CHMA".

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

Example 1 225 of the graft copolymer (A) obtained in Reference Example 3
Parts, 82 parts of titanium oxide and 47 parts of xylene were kneaded in a sand mill for 1 hour to obtain white enamel.

Next, to this white enamel,
900 parts (UV absorber made by Ciba Geigy) and 31 parts of "Bernock DN-980" [polyisocyanate compound manufactured by Dainippon Ink and Chemicals, Inc.] were added, and toluene / xylene / acetic acid n was added. -Butyl = 1/1
Diluted to a spray viscosity with a thinner (1/1 by weight), coated, baked for 30 minutes, and evaluated for a coating film when left at room temperature for 1 week.
The results are shown in Table 2.

Examples 2 and 3 and Comparative Examples 1-
3 The coating film performance was evaluated and evaluated in the same manner as in Example 1 except that the blending ratio shown in Table 2 was changed. The results are shown together in the same table.

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

[Table 6]

[0070]

[Table 7]

[0071]

[Table 8]

[0072]

[Table 9]

[0073]

INDUSTRIAL APPLICABILITY As described above, the composition of the present invention has excellent adhesiveness in a wide sense such as long-term adhesiveness and interlayer adhesion to the top coat, and also has solvent resistance. It gives a cured coating film having excellent coating film performance, and can be widely applied to various polyolefin-based materials or base materials such as various molded articles such as films and sheets. It may be used as a primer in coating a molded article, or may be used as a top coat for various structures and structures, and can also be used as a binder for printing ink. It is useful for various molded products, structures or structures made of polyolefin.

Claims (4)

[Claims] 1. A chlorinated polyolefin, a vinyl monomer having a hydroxyl group (a), an unsaturated carboxylic acid (b), and other vinyl monomers (d) copolymerizable with these.
A linear or branched polyether and / or polyester polyol with respect to the graft copolymer (A) obtained by polymerizing a monomer mixture mainly composed of (B), an ultraviolet absorber and /
Alternatively, a coating composition comprising an antioxidant (C) and a polyisocyanate compound (D). 2. The above-mentioned graft copolymer (A) with respect to a chlorinated polyolefin having a chlorination rate of 50% or less,
5 to 30% by weight of the hydroxyl group-containing vinyl monomer (a), 0.1 to 3% by weight of the unsaturated carboxylic acid (b), and 0 to 1 of the polyester resin (c) having a copolymerizable unsaturated group.
0% by weight, 50 to 9 of other vinyl-based monomers (d) copolymerizable with these (a), (b) and (c).
4.9% by weight of these (a), (b),
The total amount of the monomer mixture (c) and (d) is 100% by weight, and the solid content weight ratio of the chlorinated polyolefin to the monomer mixture is 10:90.
The number average molecular weight obtained by polymerization in the presence of an organic solvent at a ratio of about 90:10 is 3,000.
The coating composition according to claim 1, which is in the range of about 40,000. 3. The straight-chain or branched polyester described above.
Ter- and / or polyester polyol (B)
Has a hydroxyl value within the range of 50 to 200. 2. The coating composition according to claim 1, wherein 4. The linear or branched polyether and / or polyester polyol (B) and the ultraviolet absorber, respectively, relative to 100 parts by weight of the solid content of the graft copolymer (A). And / or the mixing ratio of the antioxidant (C) and the polyisocyanate compound (D) is within the range of 5 to 50 parts by weight of the polyether and / or polyester polyol (B), and the ultraviolet light The amount of the absorbent and / or the antioxidant (C) is 0 to 5 parts by weight, and the polyisocyanate compound (D) is further added to the hydroxyl groups of the graft copolymer (A) and the polyol (B). OH
The coating composition according to any one of claims 1 to 3, wherein the equivalent ratio of / NCO is in the range of 2/1 to 1/2.