JPH044272A - Covering composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is used for the protection of polyolefin resins, such as polypropylene homopolymers, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, etc., or for cosmetic purposes. More specifically, regarding the coating composition used, an isocyanate compound is blended with a specific (meth)acrylic monomer, a copolymer of chlorinated polybutadiene and chlorinated polyolefin, and a polyolefin resin sheet or film is produced. And paint the molded product with Wanko and finish to give it an appearance.

The present invention relates to a coating composition that provides a coating film with excellent adhesion, weather resistance, moisture resistance, solvent resistance, etc.

[Conventional technology]

Polyolefin resins have excellent properties such as chemical resistance, ozone resistance, heat resistance, water resistance, and good electrical properties, and are lightweight and inexpensive, so they are used as industrial materials such as home appliances and automobile parts. It is widely used as a material, and is one of the materials whose use is most expected to grow in the future. However, despite having these characteristics, when it comes to automobile parts, for example, the use of various plastics is being used to reduce weight from the perspective of energy conservation, and the amount of plastic used is increasing year by year. remains in some parts. One of the reasons preventing its widespread use is that polyolefin resins are nonpolar and crystalline, making painting and adhesion extremely difficult. Conventionally, adhesion has been improved by activating the surface of polyolefin resin molded products through plasma treatment or gas flame treatment, but these methods require complicated processes and require large equipment costs and time losses. However, it has the disadvantage that the surface treatment effect varies due to the complexity of the shape of the molded product and the effects of pigments and additives in the resin. Therefore, various primer compositions such as those used in polypropylene bumper coating for automobiles have recently been proposed as coating methods without pretreatment, but these involve the complexity of a two-coat finish. Coating compositions for one-coat finishing include chlorinated polyolefins and cyclized rubbers that have strong adhesion to polyolefin resins, but are weather and moisture resistant.

It has poor solvent resistance and does not show sufficient coating performance.

In order to compensate for these drawbacks, attempts have been made to mix chlorinated polyolefins with acrylic resins and alkyd resins, which have good paint properties, but originally acrylic resins and alkyd resins are not compatible with chlorinated polyolefins. It has poor solubility, which causes problems such as a decrease in the gloss of the coating film and a significant loss of appearance. In order to improve these drawbacks, coating compositions obtained by copolymerizing acrylic monomers and chlorinated polyolefins as seen in JP-A-58-71966 and JP-A-59-27968 have been developed. Resin compositions for coatings comprising a chlorinated polyolefin-modified acrylic graft copolymer obtained by copolymerizing an acrylic monomer having a hydroxyl group with a chlorinated polyolefin, and an isocyanate compound as essential components; The main components are hydroxyl group-containing acrylic-modified chlorinated polyolefin and isocyanate compounds, which are copolymerized with hydroxyl group-containing acrylic monomers in the presence of chlorinated polyolefin and liquid rubber, as seen in No. 62-95372. Adhesive resin compositions consisting of the following have been proposed. However, in these compositions, chlorinated polyolefin, liquid rubber, and acrylic resin are essentially incompatible with each other, so even if they are copolymerized, cloudiness and two-layer separation may occur. occurs, making it impossible to obtain a homogeneous and transparent solution. When a paint resin that is cloudy or has separated into two layers is made into a paint, sufficient pigment dispersion cannot be obtained, the gloss of the paint film is poor, and the storage stability of the paint is also poor. Moreover, when used as an adhesive, sufficient adhesive performance cannot be obtained.

[Problem to be solved by the invention]

In order to solve the above-mentioned problems, the present inventors have developed a copolymer made by copolymerizing an acrylic monomer having a hydroxyl group with the king of chlorinated polydienes and chlorinated polyolefins to form a uniform and transparent liquid. It was discovered that a coating composition prepared by further blending this copolymer with an isocyanate compound exhibits excellent adhesion to polyolefin resins and provides a tough and glossy coating film.
Already proposed in 18434.

However, although this method is sufficiently effective for polyolefin resin materials used in home appliances, etc., it is necessary for coating materials used outdoors such as automobiles and motorcycles.
Gasoline resistance under severe conditions was somewhat insufficient.

[Means to solve the problem]

Therefore, as a result of further investigation, the present inventors found a specific (
A coating composition in which a meth)acrylic monomer, a specific chlorinated polydiene, and a specific chlorinated polyolefin are copolymerized in a limited weight ratio range, and an isocyanate compound is blended into the resulting copolymer and cured. It was discovered that the gasoline resistance of the product was further improved than that of the previous invention (Japanese Unexamined Patent Publication No. 62-18434), and the present invention was completed.

That is, the present invention uses a (meth)acrylic monomer (1) containing 30 to 90 wt% of cyclohexyl (meth)acrylate, 5 to 40 w (%) of a hydroxyl group-containing (meth)acrylic monomer, and a chlorine-containing Chlorinated polybutadiene (II) chlorinated with a chlorine content in the range of 5 to 50 wt% and chlorinated polyolefin (m) chlorinated with a chlorine content in the range of 5 to 50 wt%, (1) / (II ) / (
III) A coating composition characterized in that the main binder is a copolymer obtained by copolymerizing at a weight ratio of 30 to 8,515 to 5,015 to 50, and an isocyanate compound is blended therein as a curing agent.

Cyclohexyl (meth)acrylate used in the present invention is a component for smoothly carrying out the copolymerization reaction and improving properties such as solvent resistance, weather resistance, and hardness of the coating film. 30-95v in system monomer (I)
It is necessary to contain 1%. If the amount is less than 30 wt%, gelation occurs during the copolymerization reaction when a methacrylate having a short-chain alkyl group such as methyl methacrylate is used in combination, making it impossible to carry out the reaction smoothly. Further, when a methacrylate having a long-chain alkyl group such as lauryl methacrylate is used in combination, the copolymerization reaction is carried out smoothly, but the gasoline resistance of the coating film deteriorates. If it is 95 wt% or more, the amount of the hydroxyl group-containing (meth)acrylate monomer is limited, so the crosslinking density of the cured coating film due to crosslinking with the isocyanate compound becomes low, and the physical properties of the coating film deteriorate.

That is, the amount of cyclohexyl methacrylate in the (meth)acrylic monomer (1) is 30 to 9, in order to carry out the copolymerization reaction and to obtain good physical properties of the coating film.
It is necessary to contain 5 wt%.

The (meth)acrylic monomer having a hydroxyl group used in the present invention is a component that chemically reacts with an isocyanate compound as a curing agent to form a cured coating film. 5 to 5 in monomer (I)
It is necessary to contain 40 wt%, and preferably the hydroxyl group content in the copolymer is 0.6 to 4. It is necessary to distribute it within the range of h1% (based on solid content).

If the hydroxyl group content in the copolymer is less than 0.6 wt %, the physical properties of the cured coating film, such as solvent resistance, weather resistance, and hardness, will deteriorate. If it exceeds 4.0 wt%, the solution of the copolymer becomes opaque or separates into two layers, resulting in a decrease in the gloss of the coating film.

Furthermore, the adhesion to polyolefin resins becomes poor. Examples of the (meth)acrylic monomer having a hydroxyl group include 2-hydroxylethyl (meth)acrylate, 2-hydroxylpropyl (meth)acrylate,
2-hydroxyl isopropyl (meth)acrylate,
-2-hydroxylbutyl (meth)acrylate, 2
- (Poly)caprolactone modified (poly)caprolactone esterified with hydroxylethyl (meth)acrylate (
There are meta)acrylates, etc. Further, (meth)acrylic monomers other than cyclohexyl (meth)acrylate and hydroxyl group-containing (meth)acrylate monomers may be mixed and used. As the (meth)acrylic monomer used in this case, for example, (meth)
Acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate.

n-Butyl (meth)acrylate, 2-ethylhexyl (
meth)acrylate, lauryl(meth)acrylate,
Examples include glycidyl (meth)acrylate.

The chlorinated polybutadiene (III) used in the present invention is a copolymer of (meth)acrylic monomer (I), chlorinated polybutadiene (n), and chlorinated polyolefin l) in order to impart flexibility to the coating film. It is an essential component in order to obtain a homogeneous and transparent reaction solution. That is, JP-A-5
Copolymers of acrylic monomers and chlorinated polyolefins, such as those found in JP-A No. 8-71966 and JP-A-59-27968, do not form homogeneous and transparent solutions, but separate and become cloudy. Chlorinated polybutadiene (II) as in the invention
), a homogeneous and transparent solution is obtained, and a tough and glossy coating film is also provided. The effect of the presence of chlorinated polybutadiene is thought to be due to the fact that chlorinated polybutadiene is a substance that exhibits compatibility with both chlorinated polyolefins and (meth)acrylic polymers at an appropriate degree of chlorination. It will be done.

The raw material for the chlorinated polybutadiene of the present invention is to combine butadiene with specific catalysts such as anionic polymerization using metal sodium or organic sodium catalysts, Ziegler-type coordination anionic polymerization, cationic polymerization using Friedel-Crafts catalysts, and radical polymerization. It is a liquid polybutadiene obtained by solution polymerization using a polymerization method, and includes those having a hydroxyl group or a carboxyl group at the end. The number average molecular weight of liquid polybutadiene is preferably 500 to IO,000, and when copolymerized using chlorinated polybutadiene obtained by chlorinating liquid polybutadiene with a number average molecular weight of less than 500,
Physical properties of the coating film, such as solvent resistance, moisture resistance, and weather resistance, deteriorate. In addition, when liquid polybutadiene with a number average molecular weight of 10.000 or more is used, the viscosity of the copolymer may become too high,
Since the liquid becomes opaque, good painting workability and coating film appearance cannot be obtained.

The chlorine content of chlorinated polybutadiene is 5 to 50 wt%
It is preferable to use it within the range of . If the chlorine content is too low, the appearance of the coating film will deteriorate and there is a risk of gelation during the copolymerization reaction. If the chlorine content is too high, the compatibility with the chlorinated polyolefin (m) will deteriorate, so a good coating film appearance will not be obtained, and the reactivity with the (meth)acrylic monomer (1) will also decrease. .

Chlorination of polybutadiene can be easily carried out using conventional reaction methods. For example, liquid polybutadiene is dissolved in a chlorinated solvent such as carbon tetrachloride, and chlorine gas is blown at a temperature range from room temperature to 120°C under pressure or normal pressure without a catalyst, in the presence of a catalyst, or under ultraviolet irradiation. This is done by putting the

The chlorinated polyolefin (m) used in the present invention is a component for imparting adhesion to polyolefin resins, and is preferably used with a chlorine content in the range of 5 to 50W1%. If the chlorine content is too low, the state of the solution at low temperatures and the appearance of the coating film will deteriorate. If the chlorine content is too high, the adhesion to the polyolefin resin will decrease.

Crystalline polyolefins are used as raw materials for chlorinated polyolefins.
Examples include lopylene, non-grade polypropylene, polybutene-1, polypentene-1,4-methylpentene-1, low density or high density polyethylene, ethylene-propylene copolymer, and ethylene-propylene-diene copolymer.

Also (meth)acrylic acid to these olefins.

Maleic acid, maleic anhydride, citraconic acid.

Citraconic anhydride, fumaric acid, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride,
Modified polyolefins into which α,β-unsaturated carboxylic acids and acid anhydrides such as the following are introduced can also be used. Examples of the polymerization initiator used in the modification reaction include G-1ert-
There are peroxides such as butylmiperoxide, dikuzine rubberoxide, benzoyl peroxide, and azonitrile such as azobisisobutyronitrile.

Polyolefin with α, β-unsaturated carboxylic acid or
By modifying the copolymer with the acid anhydride, the pigment dispersibility of the copolymer becomes even better. That is, a modified polyolefin modified to have a saponification value in the range of 6 to 60 is preferable; if the saponification value is less than 6, the contribution to pigment dispersibility will be poor, and if the saponification value is 60 or more, After the pigment is dispersed, the paint may gel or its adhesion to olefin resin may decrease.

The chlorination of polyolefin can be carried out in the same manner as the chlorination of polybutadiene described above, but the chlorination reaction temperature is 50°C.
The temperature range is preferably from 120°C to 120°C, and the chlorination must be carried out in the presence of a catalyst or under irradiation with ultraviolet light. In addition, a method for oxidizing chlorinated polyolefin by simultaneously blowing at least one or more selected from air, oxygen, and ozone during chlorine injection into polyolefin is a method for oxidizing the copolymer into a more uniform and transparent solution. It is an effective means to achieve this goal.

(meth)acrylic monomer (1), chlorinated polybutadiene (n) and chlorinated polyolefin (I) according to the present invention
Copolymerization II) is carried out by solution polymerization. The solvent used is preferably an aromatic hydrocarbon solvent such as toluene or xylene, and ester solvents, ketone solvents,
Alcohol solvents, chlorinated solvents, aliphatic hydrocarbon solvents.

There is no problem in using cycloaliphatic hydrocarbon solvents together.

As a polymerization initiator, benzoyl peroxide, G-1
Peroxides such as eft-butyl peroxide and azo and tolyles such as azobisisobutyronitrile can be used. Quinones such as hydroquinone may be used as a polymerization terminator.

The copolymerization method involves diluting chlorinated polybutadiene (■) and chlorinated polyolefin (m) appropriately with a solvent and mixing them.
The basic process is to add a polymerization initiator, heat it, and gradually add (meth)acrylic monomer (I) while reacting. There is no problem even if the mixture is mixed, a polymerization initiator is added, and then heated and reacted.

(meth)acrylic monomer (I), chlorinated polybutadiene (II) and chlorinated polyolefin (
The blending ratio when copolymerizing m) can be determined as appropriate depending on the desired surface hardness, abrasion resistance, surface gloss, etc. of the coating film, but too much or too little will result in a well-balanced result. A coating film cannot be obtained. That is, (I) / (II) /
(III) It is preferable to copolymerize in a weight ratio range of -30 to 8,515 to 5,015 to 50.

Also, the amount of isocyanate compound added is (1) and (1)
It is appropriate that 1 to 2 moles of isocyanate groups are used per mole of hydroxyl groups in the copolymer obtained by copolymerizing and (In).

Examples of the isocyanate compound of the curing agent used in the present invention include diisocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, and isophorone diisocyanate. More preferred is a method in which it is modified into an isocyanate derivative such as a propane adduct. Also, as a curing accelerator, octenoic acid is used.

There are organometallic compounds such as dibutyltin dilaurate, and zinc naphthenate and cobalt naphthenate, which are internal curing agents for oxidatively polymerized resins, and these can be added to promote the curing reaction.

[Made by for〕

The coating composition according to the present invention may be used as a coating as it is, or may be used as a paint by adding a solvent, a pigment, or other additives. The composition itself exhibits well-balanced coating film properties, but if necessary, alkyd resins, acrylic resins, acrylic polyols, polyester resins, polyester polyols, polyether resins, polyether polyols, polyurethane resins, There is no problem even if a chlorinated polyolefin resin or the like is further added.

The coating composition according to the present invention is applied to a polyolefin resin sheet or molded article and dried at a temperature between room temperature and 150°C to obtain a cured coating film with a one-coat finish. The resulting paint film has excellent adhesion and provides a much tougher and glossier paint film than other one-coat finishing paints used for similar purposes. This coating composition is superior in weather resistance, moisture resistance, water resistance, cracking resistance, etc. than the coating composition already proposed in JP-A No. 62-18434.

The composition of the present invention can be used not only for polyolefin resins but also for
It can also be applied to other base materials such as plastics, wood, concrete, and metal, and can also be used as a primer.

Existing paints such as urethane resin paints, melamine resin paints, alkyd resin paints, etc. are suitable as the top coat paint to be removed.

[Examples and effects of the invention]

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Prototype example-1 Nippon Soda Polybutadiene B-300 (1 (Liquid polybutadiene made by Nippon Soda (Kiki), number average molecular weight 3000) 500
g was put into a glass-lined reaction vessel, and 81 carbon tetrachloride was added and uniformly dissolved. Air was completely purged with nitrogen gas, and chlorine gas was introduced from the bottom of the reaction vessel while maintaining the temperature at 50° C. and irradiating ultraviolet rays. Two samples with chlorine content of 30W1% and 35W+% were taken out, carbon tetrachloride was distilled off, and replaced with toluene until the nonvolatile content was 50W1%.
Two types of toluene solutions of chlorinated polybutadiene were obtained.

Prototype Example-2 500 g of isotactic polypropylene with a number average molecular weight of 5.000 was placed in a glass-lined reaction vessel, 81 carbon tetrachloride was added, and the mixture was sufficiently dissolved at a temperature of 110°C and a pressure of 2 kg/cIl. Afterwards, chlorine gas was introduced from the bottom of the reaction vessel while irradiating it with ultraviolet rays. Chlorine content is 2
Two samples of 7wt% and 30wt% were taken out, carbon tetrachloride was distilled off, and replaced with toluene to obtain two types of toluene solutions of chlorinated polypropylene with a nonvolatile content of 3Qw4%.

Prototype Example-3 500 g of isotactic polypropylene with a number average molecular weight of 15.000 was put into a glass-lined reaction vessel, 81 carbon tetrachloride was added, and it was sufficiently dissolved at a temperature of 110°C and a pressure of 2 kg/cd. After that, chlorine gas and air were introduced from the bottom of the reactor while irradiating it with ultraviolet light. A sample was taken out with a chlorine content of 30WI%, carbon tetrachloride was distilled off, and the sample was replaced with toluene to obtain a toluene solution of chlorinated polypropylene with a nonvolatile content of 3Qwt%.

Prototype Example-4 500 g of maleic anhydride-modified polypropylene with a number average molecular weight of 15.000 and a saponification value of 26 was chlorinated in the same manner as in Prototype Example-2 to produce a product with a chlorine content of 25 wt% and a non-volatile content of 30W1%. A toluene solution of maleic anhydride-modified chlorinated polypropylene was obtained.

Example-1 The chlorinated polybutadiene obtained in Prototype Example-1 (chlorine content: 30w!%, nonvolatile content: 50wt) was placed in a flask equipped with a stirrer, a thermometer, and a cooling tube for refluxing the monomer.
%) 100g, chlorinated polypropylene obtained in Prototype Example-2 (chlorine content 27wt%, non-volatile content 30W1%)
500g of toluene, 100g of toluene, and 25g of benzoyl peroxide were added, and the mixture was stirred at 85°C for 30 minutes. Next, 119 g of cyclohexyl methacrylate,
A mixture of 81 g of methyl methacrylate, 40 g of lauryl methacrylate, 3 g of methacrylic acid, and 57 g of 2-hydroxyethyl acrylate was added over about 3 hours, and after further copolymerization reaction for about 8 hours, 250 g of toluene was added.
The copolymerization reaction was stopped. The obtained copolymer was a homogeneous, transparent, and viscous liquid with a nonvolatile content of 40.
It was 1wt%. Next, 100 g of this copolymer and 26 g of titanium dioxide were pigment-dispersed in a sand mill for 3 hours, and then 8.7 g of an isocyanate curing agent Desmodur N3390 (manufactured by Bayer AG, hexamethylene diisocyanate type, isocyanurate) was added, and an Nα4 food cup was added. The viscosity was adjusted with toluene so that the temperature was 13 to 15 seconds/20°C, and the mixture was spray-painted onto a polypropylene plate TX-933A (manufactured by Mitsubishi Yuka Co., Ltd.). After drying at room temperature for about 15 minutes, it was force-dried at 80° C. for 30 minutes, and after being allowed to stand indoors for one week, the coating film was tested. The results are shown in Table-1.

Example-2 Chlorinated polybutadiene obtained in Prototype Example-1 (chlorine content 3
5wt%, nonvolatile content 50wt%) 100g, chlorinated polypropylene obtained in Prototype Example-2 (chlorine content 3Qvj
%, nonvolatile content 30W1%) 500 g, ) toluene 350 g, benzoyl peroxide 25 g, cyclohexyl methacrylate) 243 g, and 2-hydroxyethyl acrylate 57 g, Example-1
A copolymerization reaction was carried out according to the reaction method of . The obtained copolymer is a homogeneous, transparent and viscous liquid, with a non-volatile content of 4.
It was 0.2W1%.

Next, 100 g of this copolymer and 26 g of titanium dioxide.

Isocyanate curing agent Desmodur N339Q.

At a blending ratio of 8.7 g, paint preparation and coating film testing were conducted in the same manner as in Example-1. The results are shown in Table-1.

Example-3 Chlorinated polybutadiene obtained in Prototype Example-1 (chlorine content 3
5wt%, nonvolatile content 5Qwt%) 200g, chlorinated polypropylene obtained in Prototype Example-3 (chlorine content 30wf)
%, non-volatile content 30W1%) 500g, toluene 300g, benzoyl peroxide 25g, cyclohexyl methacrylate 160g, ethyl acrylate 25g, 2-hydroxyethyl methacrylate 5g
A copolymerization reaction was carried out according to the reaction method of Example-1 at a blending ratio of . The obtained copolymer was a homogeneous, transparent, and viscous liquid, and the nonvolatile content was 40.3 wj%. Next, 100 g of this copolymer, 26 g of titanium dioxide, and an isocyanate curing agent Desmodur N 3390. 8.7
A coating material was prepared and a coating film test was conducted in the same manner as in Example-1 using a blending ratio of 100 g. The results are shown in Table-1.

Example-4 Chlorinated polybutadiene obtained in Prototype Example-1 (chlorine content 3
0wt%, nonvolatile content 50wt%) 300g, maleic anhydride-modified chlorinated polypropylene obtained in Prototype Example-4 (
Chlorine content 25W1%, non-volatile content 30wt%) 50
0g, ) toluene 250g, hensyl peroxide 25g, cyclohexyl methacrylate 90g,
A copolymerization reaction was carried out according to the reaction method of Example 1, using a blending ratio of 45 g of methyl methacrylate and 5 g of 2-hydroxyl methacrylate. The obtained copolymer was a homogeneous, transparent, and viscous liquid with a nonvolatile content of 40.2w.
It was t%. Next, 1.0 Og of this copolymer, 26 g of titanium dioxide, and an isocyanate curing agent Desmodur Z4 were added.
370 (manufactured by Bayer, isophorone diisocyanate type, isocyanurate type) 14.6 g, curing accelerator di-n-butyltin dilaure-1-0.08 g in a blending ratio,
Paint preparation and coating film testing were conducted in the same manner as in Example-1. The results are shown in Table-1.

Comparative Example-1 Chlorinated polypropylene obtained in Prototype Example-2 (chlorine content 2
7wt%, non-volatile content 30W1%) 4 (Ig, acrylic boriol desmophene A-16 (1 (manufactured by Bayer),
47 g (hydroxyl group content: 1.6%, non-volatile content: 60 wt%) were mixed. The mixed face was opaque and non-uniform, and separated into two layers upon standing. Next, add this mixed face, 26g of titanium dioxide, and the isocyanate hardening agent Desmodur N.
339 (1,9,6g mixing ratio) Paint preparation and coating film test were conducted in the same manner as in Example-1.The results are shown in Table-
Shown in 1.

Comparative Example-2 Chlorinated polypropylene obtained in Prototype Example-2 (chlorine content 2
7W1%, non-volatile content 30wt%) 5 (lGg,
400 g toluene, 2.5 g benzoyl peroxide
g.

Cyclohexyl methacrylate 144g, methyl methacrylate 98g, lauryl methacrylate 48g
, 3 g of methacrylic acid, and 57 g of 2-hydroxyethyl acrylate, a copolymerization reaction was carried out according to the reaction method of Example-1. The obtained copolymer was a non-uniform and opaque viscous liquid, and the nonvolatile content was 40.3 wf%. Next, this copolymer Ing, 26 g of titanium dioxide,
Isocyanate curing agent Desmodur N 3390.
A coating material was prepared and a coating film was tested in the same manner as in Example-1 using a blending ratio of 8.7 g. The results are shown in Table-1.

Comparative Example-3 Chlorinated polybutadiene obtained in Prototype Example-1 (chlorine content 3
0 wt%, nonvolatile content 50 wt%) lDDg, chlorinated polypropylene obtained in Prototype Example-2 (chlorine content 27 w (
%, non-volatile content 3 (lit%) 5 [1 [1 g, toluene 350 g, benzoyl peroxide 2.5 g,
Methyl methacrylate 98g, lauryl methacrylate 145g, 2-hydroxyethyl acrylate 5
A copolymerization reaction was carried out according to the reaction method of Example-1 at a blending ratio of 7 g. The obtained copolymer was a homogeneous, opaque, viscous liquid, and the nonvolatile content was 411.2 wt%.

Next, 100 g of this copolymer.

26 g of titanium dioxide, isocyanate hardener Desmodur N 3390. A coating material was prepared and a coating film was tested in the same manner as in Example-1 using a blending ratio of 8.7 g. The results are shown in Table-1.

Judgment criteria in the table ◎: Good △: Slightly poor xX: Very poor ○: Good quality ×: Poor Test method - Adhesive Make 100 squares on the coated surface at 1 mm intervals to reach the substrate. Apply cellophane adhesive tape 1
It was peeled off in 800 directions and judged based on the extent to which the coating remained.

- An accelerated weathering carbon arc type sunshine weather meter was used. Gloss level is 60° specular reflection.

Whiteness was measured with a Hunter.

・Warm water resistance: Painted board in hot water (pure water) at 40℃ for 120 hours and 24 hours.
After immersion for 0 hours, the state of the coating film was examined.

・Gasoline resistance (rubbing 100 times) Soak absorbent cotton with Nisseki regular gasoline and apply 1 coat to the coated surface.
The coating was rubbed 00 times and the condition of the coating film was examined.

(Immersed for 2 hours) Sukura Sochi (marked with an x) that reached the substrate was placed on the painted surface, and immersed in Nisseki regular gasoline for 2 hours to examine the condition of the paint film.

From the results in Table 1, the resin components of Examples 1, 2, 3, 4 and Comparative Example 3 are as follows:
It is obtained by copolymerizing a (meth)acrylic monomer with chlorinated polybutadiene and chlorinated polypropylene. Comparative Example 4 is a mixture of acrylic resin and chlorinated polypropylene. Comparative Example 2 was obtained by copolymerizing a (meth)acrylic monomer and chlorinated polypropylene. The results in Table 1 are as follows: Examples 1, 2,
It is shown that the compositions of Comparative Examples 3 and 4 and Comparative Example 3 are superior in the gloss of the coating film and the solution state of the varnish compared to Comparative Examples 1 and 2.

That is, it can be seen that chlorinated polybutadiene is an extremely useful component for obtaining a uniform and transparent copolymer. Moreover, Examples 1, 2, 3, and 4 contain cyclohexyl (meth)acrylic in the (meth)acrylic monomer component, but Comparative Example 3 does not contain these acrylates. The results in Table 1 show that Examples 1, 2, 3, and 4 are superior in gasoline resistance compared to Comparative Example 3. That is, the present invention is achieved by incorporating cyclohexyl (meth)acrylic into a (meth)acrylic monomer component and copolymerizing it.
It can be seen that the gasoline resistance, which was a drawback of the composition already proposed in 2003, has been improved.

Procedural amendment (voluntary) 1. Indication of the case 1990 Patent Application No. 106925 2. Name of the invention Coating composition 3. Relationship with the person making the amendment Patent applicant address Marunouchi-chome, Chiyoda-ku, Tokyo 4th and 5th name
Name (234) Sanyo Kokusaku Pulp Co., Ltd. 4, Agent Address: 16 Kanda Kita Jorimono-cho, Chiyoda-ku, Tokyo Lot 3rd Floor, Ei Building 5°Claims column of the specification subject to the amendment and detailed description of the invention Contents of amendment in column The following matters in the specification of the application will be corrected.

Record 1. Correct the scope of claims as shown in the attached sheet.

2. The following matters will be corrected in the Detailed Description of the Invention column.

(On page 8, line 10 of the specification) It says "finishing with a dog" Corrected to "one coat finish".

(2) On page 5, lines 3-4 of the specification, the phrase "despite the fact that it is increasing" is corrected to "despite the fact that it is increasing."

(3) Line 166 of the same page It says "no pre-treatment" Corrected to "without pretreatment."

(4) On the last line of page 8 of the specification It says "30-90wt%" Corrected to "30-95w (%)".

(5) Lines 2-3 of page 10 of the specification It says "gasoline resistant" Corrected to "gasoline resistant".

(6) Lines 3-4 of the same page It says "Hydoxyl group" Corrected to "hydroxyl group".

(7) On the last line of the same page It says "allocate" Corrected to "mix".

(8) On page 16, line 7 of the specification It says "hydroxyl group" Corrected to "hydroxyl group".

(9) Lines 8-9 of the same page It says "2-hydroxylethyl" Corrected to "2-hydroxyethyl."

(10) On lines 9 and 10 of the same page, [2-hydroxylpropyl J was corrected to read "2-hydroxypropyl."

(11) On lines 10 and 11 of the same page, "2-hydroxyisopropyl" was corrected to "2-hydroxyisopropyl."

(12) Lines 11-12 of the same page [2-Hydroxylbutyl] Corrected to "2-hydroxybutyl."

(13) Line 133 of the same page [2-hydroxylethyl] Corrected to "2-hydroxyethyl."

(14) Line 144 of the same page "Caprolactone J" Corrected to "Caprolactones".

(15) On page 16, line 8 of the specification Corrected r (III) J to r (II) J.

(16) Line 166 of the same page It says, "Even though it becomes cloudy." "As opposed to becoming cloudy," he corrected.

(17) On page 13, line 10 of the specification It says "as solution polymerization" Corrected to "solution polymerization."

(18) On page 16, line 7 of the specification It says "Penten-1" “Corrected as Penten-IJ.

(19) Specification, page 16, 9-) Corrected "olefin resin" to "polyolefin resin" in line 0.

(20) On page 16, line 1 of the specification It says "cyanates" Corrected to "diisocyanates".

(21) On page 20, line 10 to line 11 of the specification, the word "clacking resistance" was corrected to "gasoline resistance."

(22) On page 16, line 7 of the specification It says "methacrylate" Corrected to "methacrylate."

(23) On page 16, lines 2 and 8 of the specification, the words "(meth)acrylic" were corrected to "(meth)acrylate".

(Attachment) Claims (1) At least 30 to 95 wt% of cyclohexyl (meth)acrylate in the (meth)acrylic monomer,
5 to 4 hydroxyl group-containing (meth)acrylic monomers
(meth)acrylic monomer (1) containing 0W1%,
Chlorinated polybutadiene (II) chlorinated to a chlorine content of 5 to 50 wt% and chlorine content of 5 to 50 w
Chlorinated polyolefin (II
1. A coating composition comprising a copolymer obtained by copolymerizing I) as a main binder and an isocyanate compound as a curing agent.

(2) (meth)acrylic monomer (I), chlorinated polybutadiene (II), and chlorinated polyolefin (III) (1) / (II) / (m) = 30 to 8515
The coating composition according to claim 1, which is copolymerized in a weight ratio of 5015 to 50.

(3) The hydroxyl group content of the copolymer obtained by copolymerizing (1), (II), and (III) is 0.6 to 4.
The coating composition according to claim 1 or 2, wherein the coating composition has a content of 9 wt% (based on solid content).

(4) Chlorinated polybutadiene or number average molecular weight 500~
4. A coating composition according to claim 1, obtained by chlorinating 10,000 ml of liquid polybutadiene.

(5) Chlorinated polybutadiene has a number average molecular weight of 500 to
10.000 and which is obtained by chlorinating liquid polybutadiene containing hydroxyl groups and/or carboxyl groups.

(6) Chlorinated polybutadiene is claimed in claim 4 or claim 5.
Claims 1 to 3 are those in which the above chlorinated products are used in combination.
The coating composition according to any one of the preceding items.

(7) Chlorinated polyolefin is polyolefin α,
Claims 1 to 6 obtained by modifying with one or more selected from β-unsaturated carboxylic acids or their acid anhydrides so that the saponification value becomes 6 to 60, and further chlorinating. The coating composition according to any one of the preceding items.

(8) The coating composition according to any one of claims 1 to 7, wherein the chlorinated polyolefin is obtained by oxidizing polyolefin with air/air and/or oxygen and/or ozone during a chlorination reaction. thing.

(9) A (meth)acrylic monomer (I) containing cyclohexyl (meth)acrylate and a hydroxyl group-containing (meth)acrylic monomer, and a chlorinated polybutadiene (
II) and chlorinated polyolefin (III) as the main binder, and an isocyanate compound is added as a curing agent to the copolymer, which adheres to polyolefin molded products and films. A method for producing a coating composition with good properties.

Claims (9)

[Claims] (1) At least 30 to 95 wt% of cycloxyl (meth)acrynolate in the (meth)acrylic monomer,
5 to 4 hydroxyl group-containing (meth)acrylic monomers
A (meth)acrylic monomer (I) containing 0 wt%, a chlorinated polybutadiene (II) chlorinated to a chlorine content of 5 to 50 wt%, and a chlorine content of 5 to 50 wt%.
Chlorinated polyolefin (III
1. A coating composition comprising a copolymer obtained by copolymerizing ) as a main binder and an isocyanate compound as a curing agent. (2) (meth)acrylic monomer (I), chlorinated polybutadiene (II), and chlorinated polyolefin (III) (
I)/(II)/(III)=30~85/5~50/5~
The coating composition according to claim 1, which is copolymerized at a weight ratio of 50%. (3) The hydroxyl group content of the copolymer obtained by copolymerizing (I), (II), and (III) is 0.6 to 4.0wt
% (based on solid content). (4) Chlorinated polybutadiene has a number average molecular weight of 500 to
4. A coating composition according to claim 1, obtained by chlorinating 10,000 ml of liquid polybutadiene. (5) Chlorinated polybutadiene has a number average molecular weight of 500 to
5. The coating composition according to claim 1, which is obtained by chlorinating liquid polybutadiene having a molecular weight of 10,000 and containing hydroxyl groups and/or carboxyl groups. (6) Chlorinated polybutadiene is Claim 4 or Claim 5
Claims 1 to 3 are those in which the above chlorinated products are used in combination.
The coating composition according to any one of the preceding items. (7) Chlorinated polyolefin has polyolefin α,
Claims 1 to 6 obtained by modifying with one or more selected from β-unsaturated carboxylic acids or their acid anhydrides so that the saponification value becomes 6 to 60, and further chlorinating. The coating composition according to any one of the preceding items. (8) The coating composition according to any one of claims 1 to 7, wherein the chlorinated polyolefin is obtained by oxidizing a polyolefin with air and/or oxygen and/or ozone during a chlorination reaction. (9) A (meth)acrylic monomer (I) containing cyclohexyl (meth)acrylate and a hydroxyl group-containing (meth)acrylic monomer, a chlorinated polybutadiene (II), and a chlorinated polyolefin (III) The main binder is a copolymer obtained by copolymerizing , and an isocyanate compound is blended therein as a curing agent. A method for producing a coating composition that has good adhesion to polyolefin molded products and films.