JP2002201236A - Resin for coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for coating materials which can be applied to a hardly coatable plastic without needing a step of pretreatment, primer coating, or the like, can form a coating film excellent in solvent resistance, oil resistance, adhesive properties, etc., and is excellent in storage stability. SOLUTION: The resin for coating materials is obtained by copolymerizing (A) a chlorinated polyolefin having a chlorine content of 50 mass% or lower and (B) a vinyl monomer mixture in a mass ratio of (A)/(B) of (0.5/99.5)-(90/10). The vinyl monomer mixture (B) comprises (I) 2-30 mass% vinyl monomer, (II) 30-97.9 mass% (meth)acrylic ester, and (III) 0.1-68 mass% other vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for coatings for plastics which can be directly applied to hard-to-coat plastics and has greatly improved long-term storage stability, appearance, adhesion, coating film performance and the like.

[0002]

2. Description of the Related Art In recent years, the use of plastic materials for industrial materials has been expanding more and more, and among them, polyolefin resins such as polyethylene and polypropylene are used in automobile parts characterized by moldability, weight reduction, low cost, recyclability and the like. The usage amount for applications, home appliances, etc. is increasing. However, polyolefin resins generally have high crystallinity and low polarity, so that paints, printing inks, adhesives, and the like may be difficult to adhere to.

[0003] In order to improve the adhesion, some pretreatment has been conventionally carried out. Specifically, a physical treatment such as polishing, a chemical treatment such as a mixed solution of chromic acid and a solvent, and other methods such as plasma or corona discharge are used. Processing and the like. However, these pretreatment steps require equipment,
Depending on the shape of the object to be coated, it may not be possible to uniformly treat the object, or the cost may be increased.

[0004] Various primers having good adhesion to polyolefin-based substrates have been proposed, but the coating properties such as interlayer adhesion to a top coat and weather resistance may be insufficient.

[0005] As coating resin compositions having improved coating properties such as adhesion to polyolefin materials and solvent resistance, for example, chlorinated polyolefins and acrylic resins as described in JP-B-63-24628 are known. There is a resin composition comprising a base copolymer.

However, when such a resin composition is used, when using exterior parts such as a bumper, splashes of engine oil and the like accompanying the maintenance work of a car adhere, and when using for home electric appliances, humans are used. Resistance to sweat or cooking oil, that is, oil resistance may be insufficient. That is, when the amount of the chlorinated polyolefin is increased in consideration of the adhesion, the oil resistance may be poor, and the appearance tends to be reduced.

In order to improve these, for example,
By using a specific unsaturated organic silane compound as disclosed in Japanese Patent No. 21948, adhesion and solvent resistance are balanced in a specific chlorinated polyolefin amount range. However, considering oil resistance by the method described in the publication, it is most effective to increase the content of a specific unsaturated organic silane compound. Due to having, the resin gelled during production, or even if the resin was obtained, paints using such a resin may have insufficient storage stability at high temperatures such as in summer, Practical use may be difficult.

[0008]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention relates to a non-paintable plastic, such as a polyolefin resin such as polyethylene or polypropylene, or a nylon resin, which has poor adhesion of a coating film and is difficult to apply. Can be applied without the need for pre-treatment or primer coating
It is another object of the present invention to provide a coating resin composition which can form a coating film having various excellent properties such as solvent resistance, oil resistance, and adhesion, and has excellent storage stability.

[0009]

According to the present invention, there is provided a chlorinated polyolefin having a chlorine content of 50% by mass or less (A) and a vinyl monomer mixture (B).
Is a resin for paint obtained by polymerizing a chlorinated polyolefin (A) and a vinyl monomer mixture (B), and the mass ratio (A) / (B) of the chlorinated polyolefin (A) is 0.5 / 99.5 or more. 90/10 or less, vinyl monomer mixture (B)
100% by mass is a vinyl monomer (I) having a structure represented by at least one of the following general formulas (1) and (2):
30% by mass and 30 to 97.9% by mass of (meth) acrylate (II) having a structure represented by the following general formula (3)
And 0.1 to 68% by mass of a vinyl monomer (III) polymerizable with at least one of the vinyl monomer (I) and the (meth) acrylate (II). A resin is provided.

[0010]

Embedded image

(Wherein, R ¹ represents hydrogen or a methyl group; R ² represents a linear or branched alkylene group having 2 to 10 carbon atoms; R ³ may be substituted with a halogen atom. A linear or branched alkyl group having 1 or more carbon atoms,
Represents a cycloalkyl group or an aryl group. )

[0012]

Embedded image

(Wherein, R ⁴ represents hydrogen or a methyl group; R ⁵ represents a linear or branched alkylene group having 2 to 4 carbon atoms; R ⁶ may be substituted with a halogen atom. Represents a linear or branched alkyl group, cycloalkyl group or aryl group having 1 or more carbon atoms; n is an integer of 2 or more.)

[0014]

Embedded image

(In the formula, R ⁷ represents hydrogen or a methyl group; R ⁸ represents a linear or branched alkyl group or a cycloalkyl group having at least one carbon atom which may be substituted with a halogen atom.)

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a paint composition is prepared by polymerizing a vinyl monomer mixture containing a (meth) acrylic monomer at a specific ratio in the presence of a chlorinated polyolefin having a specific chlorination rate. Manufacture resin. The paint prepared using the resin obtained in this manner can be applied to difficult-to-paint plastics without the need for steps such as pretreatment and primer coating. Further, the obtained coating film has excellent properties such as solvent resistance, oil resistance, and adhesion. Furthermore, the coating resin of the present invention has excellent storage stability.

Although the above reason is not clear, it is presumed that the chlorinated polyolefin is present in the resin in a stable state by the above-mentioned production method.

[0018] The hard-to-coat plastics are plastics such as polyolefin resins such as polyethylene and polypropylene, and polyamide resins, which are difficult to apply due to poor adhesion of the coating film.

Hereinafter, a preferred embodiment of the present invention will be described.

The chlorine content of the chlorinated polyolefin (A) used in the present invention is preferably 50% by mass or less, and more preferably 40% by mass or less, from the viewpoint of realizing good adhesion to hard-to-paint plastics. .

The chlorinated polyolefin (A) is obtained by chlorinating a polyolefin such as polyethylene or polypropylene by a known method, and various commercially available products can be used. For example, Supercron L (chlorinated polyolefin manufactured by Nippon Paper Industries; chlorine content: 27.5%), Supercron 832L (chlorinated polyolefin manufactured by Nippon Paper Industries; chlorine content: 27%), Supercron 822 ( Nippon Paper Industries' modified chlorinated polyolefin; chlorine content 2
4.5%), Supercron 803 MW (modified chlorinated polyolefin manufactured by Nippon Paper Industries Co., Ltd .; chlorine content 29.
5%), Supercron 814H (modified chlorinated polyolefin manufactured by Nippon Paper Co., Ltd .; chlorine content: 41%), hardlen 14LLB (chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd .; chlorine content: 27%), hardlen B- 13 (modified chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd .; chlorine content: 16%).

The chlorinated polyolefin (A) can be used alone or in combination of two or more kinds. The amount of the chlorinated polyolefin (A) is the same as the vinyl monomer mixture (B) and the mass ratio (A) /
In (B), 0.5 / 99.5 or more is preferable, and 3/97
The above is more preferable, and the ratio is more preferably 5/95 or more. Moreover, 90/10 or less is preferable, 80/20 or less is more preferable, and 60/40 is still more preferable. Mass ratio (A) /
If (B) is at least 0.5 / 99.5, the resulting paint will have good adhesion to difficult-to-paint plastics,
If the ratio is 90/10 or less, the solvent resistance and the coating film hardness of the obtained coating film are improved.

The vinyl monomer mixture (B) contains a vinyl monomer (I) having a structure represented by the general formula (1) and / or (2). These monomers are vinyl monomers having an alkoxy group, a cycloalkoxy group, or a phenoxy group at a terminal.

Examples thereof include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, normal butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, tert-butoxyethyl (meth) acrylate, and cyclohexyloxy (meth) acrylate. ) Acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, Blenmer PME-100, Blenmer PME-200 (trade names manufactured by NOF Corporation; methoxypolyethylene glycol) Mono (meth) acrylate), Blemmer 50PO
EP-800B (trade name, manufactured by NOF CORPORATION; polyethylene glycol polypropylene glycol monooctanol ether methacrylate), Blemmer 20ANEP
-600 (trade name, manufactured by NOF CORPORATION; nonylphenol poly (ethylene glycol-polypropylene glycol) adduct acrylate) and the like. These monomers are components effective for improving basic performance for forming a coating film, that is, oil resistance, adhesion and the like.

These vinyl monomers (I) can be used alone or in combination of two or more. The proportion of the vinyl monomers (B) used is preferably 2% by mass or more, and more preferably 7% by mass. % Or more is more preferable. Moreover, 30 mass% or less is preferable, and 20 mass% or less is more preferable. When the content is 2% by mass or more, the oil resistance and the adhesion to the substrate are good, and when the content is 30% by mass or less, the water resistance is good.

The vinyl monomer mixture (B) contains a (meth) acrylate (II) having a structure represented by the general formula (3). (Meth) acrylic acid ester (I
I) is a component effective for improving basic performance for forming a coating film, namely, coating workability, drying property, hardness, solvent resistance, weather resistance, water resistance and the like.

Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl. (Meta)
Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecyl (meth) acrylate, etc., and alkyl groups in particular in terms of weather resistance and coating film hardness. Is a straight-chain or branched alkyl group having 4 or less carbon atoms,
Those having a cycloalkyl group composed of not more than one are preferred.

These (meth) acrylates (I)
I) can be used singly or in combination of two or more, and the usage ratio to the whole vinyl monomer mixture (B) is preferably 30% by mass or more, more preferably 40% by mass or more. Moreover, 97.9 mass% or less is preferable,
90 mass% or less is more preferable. When it is 30% by mass or more, the drying property and hardness are good, and when it is 97.9% by mass or less, the coating workability and the solvent resistance become good.

Other copolymerizable vinyl monomers (III) used in the vinyl monomer mixture (B) include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (Meth) acrylate, polypropylene glycol mono (meth) acrylate, "Placcel FM or FA"
Various (meth) acrylates such as [Product name of Daicel Chemical Co., Ltd .; caprolactone-added monomer] may be mentioned.

Further, unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid and fumaric acid;
Phosphorus-containing (meth) acrylate compounds such as (meth) acryloxyethyl phosphate; heterocyclic-containing (meth) acrylate compounds such as tetrahydrofurfuryl (meth) acrylate; polymerizable unsaturated nitriles such as (meth) acrylonitrile; Polymerizable amides such as (meth) acrylamide, N-methylol (meth) acrylamide, butoxy (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
Dialkylaminoethyl (meth) acrylates such as acrylate, epoxy group-containing (meth) acrylate compounds such as glycidyl (meth) acrylate, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane And polyfunctional (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1,4-butanediol di (meth). Acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane trimethacrylate, and the like. Other compounds include styrene,
Styrene derivatives such as α-methylstyrene, p-tert-butylstyrene, vinyltoluene, unsaturated carboxylic esters such as diethyl maleate, dibutyl maleate, dibutyl fumarate, diethyl itaconate, dibutyl itaconate, vinyl acetate, propion Vinyl esters such as vinyl acrylate; and fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate.

These vinyl monomers (III) are:
One or two or more can be used in combination,
The proportion of the vinyl monomer mixture (B) used is as follows:
0.1 mass% or more is preferable, 68 mass% or less is preferable, and 50 mass% or less is more preferable.

When a monomer having a hydroxyl group or a carboxylic acid group in the molecule is used, the resulting polymer has a hydroxyl value and an acid value of 150, respectively, in consideration of water resistance and the like.
It is preferable that the concentration be not more than mgKOH / g.
More preferably, it is 50 mgKOH / g or less.

When a monomer having a crosslinkable group such as an unsaturated organic silane compound or a polyfunctional (meth) acrylate compound is used, gelation during the polymerization reaction can be prevented, and the obtained polymer can be stabilized. In consideration of the properties, it is preferable that the content is 5% by mass or less based on the total amount of the chlorinated polyolefin mixture (A) and the vinyl monomer mixture (B).

A coating resin obtained by polymerizing a chlorinated polyolefin (A) having a chlorine content of 50% by mass or less and a vinyl monomer mixture (B) can be produced according to a known method. Production by polymerizing a vinyl monomer mixture (B) in the presence of a chlorinated polyolefin (A) and a polymerization initiator because phase separation is difficult and good temporal stability can be realized. Is preferred.

For example, using a radical polymerization initiator,
To 180 ° C., more preferably 75 to 120 ° C., for 6 to 12 hours, and the resulting polymer has a number average molecular weight of 1,000.
The range of ~ 30000 is preferred. Number average molecular weight is 100
If it is 0 or more, the oil resistance and solvent resistance of the obtained coating film will be good, and if it is 30000 or less, the appearance of the obtained coating film will be good.

The polymerization method is not particularly limited, such as emulsion polymerization, suspension polymerization, bulk polymerization, etc., but solution polymerization using an organic solvent is advantageous in terms of productivity and workability. Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene, swazol # 1000 (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso # 150 (trade name, manufactured by Exxon Chemical Co., Ltd.), and methyl ethyl ketone. Ketones such as methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, DBE (trade name of DuPont), n-butanol, isopropyl alcohol; Alcohols such as cyclohexanol and the like, glycol solvents such as ethylene glycol monobutyl ether and propylene glycol monomethyl ether, and aliphatic hydrocarbons such as mineral terpen and Isopar E (trade name of Exxon Chemical Co., Ltd.) There are Considering the stability aromatic hydrocarbons scan is preferred.

As the radical polymerization initiator, 2
Azo compounds such as 2'-azobisisobutyronitrile and 2,2'-azobismethylonitrile, tertiary butyl hydroperoxide, lauroyl peroxide, benzoyl peroxide, ditertiary butyl peroxide, tertiary butyl Peroxides such as peroctoate and tertiary butyl peroxyisopropyl carbonate are exemplified.

The resin composition for a coating composition of the present invention comprises: a glitter such as aluminum paste and mica; a coloring agent such as titanium oxide, carbon black and quinacridone; a non-acrylic resin such as an alkyd resin, an epoxy resin and a cellulose resin. An auxiliary additive such as a surface conditioner, an ultraviolet absorber, an antioxidant, a curing catalyst, a pigment sedimentation inhibitor and the like are selected as needed and added by a general compounding method to form a paint.

When the coating resin of the present invention contains a hydroxyl group, the melamine resin or the isocyanate compound is mixed as a crosslinking agent component to improve the coating properties such as solvent resistance, water resistance and weather resistance. Can be achieved.

Specific examples of the melamine resin include n-butylated melamine resin and methylated melamine resin.

Further, specific examples of the isocyanate may be a polyisocyanate compound having a free isocyanate group or a blocked isocyanate compound. Specifically, aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4- (or 2,6-) diisocyanate, and 4,4'-methylenebis (cyclohexyl isocyanate) , Cycloaliphatic diisocyanates such as 1,3 di (isocyanatomethyl) -cyclohexane, aromatic diisocyanates such as tolylene diisocyanate and xylene diisocyanate, these organic diisocyanates themselves, or excess and large amounts of these organic diisocyanates. Examples thereof include an adduct with a polyhydric alcohol or water, a polymer of each of the above organic diisocyanates, and an isocyanate / buret body.

The isocyanate compound is NCO / OH = 0.1 / 1 in equivalent ratio with the hydroxyl group-containing component in the coating resin.
It is preferably used in the range of 3/1.

The method for forming a coating film using the coating resin of the present invention is carried out by a known and commonly used method. In general, after dilution with an appropriate organic solvent, spray coating is performed by a spray gun in a dry film thickness range of about 10 to 80 μm.

[0044]

The present invention will be described in more detail with reference to the following examples. The parts and percentages are based on mass. Unless otherwise specified, commercially available high-purity reagents and the like were used.

(Method of analyzing characteristics of coating resin) (a) Number average molecular weight: After adjusting the coating resin to have a solution concentration of 0.4% with tetrahydrofuran, TOS
O company columns (GE4000HXL and G2000H
XL) into a gel permeation chromatography apparatus manufactured by TOSO (injection volume: 100 μl), and subjected to gel permeation chromatography under various conditions (flow rate: 1 ml / min (eluent: tetrahydrofuran), column temperature: 40 ° C.). And the number average molecular weight based on polystyrene.

(A) Acid value: The paint resin was dried to obtain a solid content of the paint resin. The number of mg of potassium hydroxide required to neutralize 1 g of this solid content was measured, and the acid value (mgK
OH / g).

(C) Gardner viscosity: measured at 25 ° C. using a Gardner-Holdt foam viscometer.

(D) Storage stability (varnish stability): 50
Each coating resin obtained in the production example was stored in a heat-insulating container at a temperature of ℃, and the state of the solution after three months was observed. ：: good, △: slightly separated,
×: Evaluation was made in three stages of complete separation into two layers.

(Method for Evaluating Performance of Coating Material) The performance of the coating film was evaluated by the following method.

(A) Appearance: Excellent (◎), good (○), slightly poor (△), poor (×) by visual judgment
It was evaluated on a scale.

(A) Adhesion: Evaluation was made based on the adhesion rate by a cellotape (registered trademark) peel test of a squared pattern (1 mm interval).

(C) Gasoline resistance: Gauze was impregnated with gasoline, and the appearance after rubbing 16 times was visually judged. Excellent (で), good (○), slightly poor (△), poor (×) were evaluated in four stages.

(D) Alcohol resistance: The gauze was impregnated with ethyl alcohol, and the appearance after 16 reciprocal rubbings was visually judged. Excellent (で), good (○), slightly poor (△), poor (×) were evaluated in four stages.

(E) Tallow resistance: 1 g of tallow is weighed, placed on a coated plate, then covered with gauze, covered with tallow, placed in a glass petri dish, covered, and allowed to stand at 80 ° C. for 7 days. The surface condition after washing and drying with a kitchen detergent was visually judged. Excellent (で), good (○), slightly poor (△), poor (×) were evaluated in four stages.

(F) Coating film hardness: The coating film was evaluated for scratches according to JIS K 5400.

Example 1 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with toluene 14
7.2 parts, "Hardlen 14LLB" (chlorinated polyolefin manufactured by Toyo Kasei Kogyo Co., Ltd., chlorine content 27%, solid content 15%, toluene solution) 3.4 parts (chlorinated polyolefin component is 0.5 part) And 0.2 parts of t-butyl peroctoate were charged, and the internal temperature of the flask was raised to 80 ° C.

Further, 3-methoxybutyl acrylate 1
Vinyl type comprising 1.1 parts, 58.7 parts of methyl methacrylate, 9.2 parts of isobutyl methacrylate, 11 parts of tricyclodecyl methacrylate, 8 parts of isobutyl acrylate, 1 part of methacrylic acid and 1 part of 1,3-butylene glycol dimethacrylate Monomer mixture (B-1) 1
00 parts were prepared.

Next, the internal temperature of the flask was maintained at 80 ° C.
After stirring for hours, the above vinyl monomer mixture (B-
99.5 parts of 1) and t-butyl peroctoate 2
A part of the mixed solution was added dropwise over 3 hours. 0.5 / 99.5 for chlorinated polyolefin / vinyl monomer mixture
It is.

After the reaction was allowed to proceed for 2 hours, t-
0.5 parts of butyl peroctoate was added, and the mixture was further kept at 80 ° C. for 2 hours and then cooled to obtain a coating resin (A-1) having a heating residue of 40%. Table 1 shows the characteristic values of the obtained resin.

Examples 2 to 5 As shown in Table 1, chlorinated polyolefin resin Hardlen B-13 (manufactured by Toyo Kasei Kogyo Co., Ltd.) having a chlorine content of 1
6%, solid content 30%), Nippon Paper Industries chlorinated polyolefin resin Supercron 803 MW (chlorine content 2
A chlorinated polyolefin resin Supercron 814H (chlorine content 41%, solid content 60%) manufactured by Nippon Paper Industries Co., Ltd. was used. Further, as a vinyl monomer mixture, (B-2) to (B-5) shown in Table 2
It was used. In addition, Blemmer PME-100 is a methoxypolyethylene glycol monomethacrylate manufactured by NOF Corporation.

The chlorinated polyolefin resin and vinyl monomer mixture were used in the compositions shown in Table 1 except that
In the same manner as the coating resin (A-1), the coating resin (A-
2) to (A-5) were produced. The chlorinated polyolefin / vinyl monomer mixture is as shown in Table 1. Table 1 also shows the characteristic values of the obtained resin.

(Comparative Examples 1 to 7) The coating resin (A-1) was used except that (B-6) to (B-12) shown in Table 3 were used as the vinyl monomer mixture in the composition shown in Table 1. ) To (A-5)
In the same manner as in the above, paint resins (A-6) to (A-12) were produced. Table 1 shows the characteristic values of the obtained resin.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

(Performance Test) Resins for paints (A-1) to (A)
-12) was tested for storage stability.

The coating resins (A-1) to (A-1)
2) using carbon black MA- manufactured by Mitsubishi Chemical Corporation.
100 and BYK-335, a leveling agent manufactured by BYK Japan KK, were blended and dispersed according to the compositions shown in Tables 4 and 5, to prepare a paint for plastics. The obtained paint,
Toluene / xylene / Superzol # 1500 (hydrocarbon high boiling point solvent manufactured by Mitsubishi Nisseki Co., Ltd.) = 20/40/4
It was diluted with a thinner of 0 in a Ford Cup # 4 to 12 seconds. Then, 3 m thick molded from polypropylene resin TX-1810A manufactured by Nippon Polychem Co., Ltd.
m was spray-coated to a dry film thickness of 30 μm. Then, after standing for 20 minutes, it was dried by heating at 80 ° C. for 30 minutes, and the performance of the obtained coated plate was evaluated. Tables 4 and 5 show the obtained results.

The duranate P-301- in Table 4 was used.
75E is an isocyanate resin manufactured by Asahi Kasei Corporation.

[0069]

[Table 4]

[0070]

[Table 5]

As is clear from Tables 4 and 5, the coating resin of the present invention is excellent in storage stability, and the coating film formed by using the coating resin of the present invention has good appearance, adhesion, and resistance. Excellent gasoline, alcohol and tallow resistance.

[0072]

As described above, the coating resin of the present invention has excellent storage stability over a long period of time, and further, the plastic coating prepared using the coating resin is
It has good adhesion to difficult-to-paint plastics and can be applied directly without pre-treatment or primer coating. And it is excellent in paint appearance, and it is made of adhesion, gasoline resistance,
Because it can form a coating film with excellent alcohol resistance, tallow resistance, etc., automotive exterior parts such as bumpers, wheel caps, mudguards, lamp housings, automotive interior parts such as instrument panels and console boxes, and home appliances It can be used for difficult adhesion materials such as polyolefin. Therefore, the coating resin of the present invention greatly contributes to the expansion and development of applications of hard-to-paint plastics.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuhiko Hotta 1-60, Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture F-term in Mitsubishi Rayon Co., Ltd. Product Development Laboratory 4J011 AA05 PA64 PC02 PC08 4J026 AA11 AA12 AA13 AC08 BA05 BA19 BA20 BA25 BA27 BA28 BA29 BA30 BA31 BA32 BA34 BA36 BA39 BA41 BA43 BA50 DB02 DB09 DB12 DB15 GA06 4J027 AC02 AC03 AC04 AC06 BA04 BA05 BA06 BA07 BA08 BA09 BA10 BA12 BA13 BA14 BA20 BA21 BA26 CA04 CB03 CB09 GA03 GA08 GA09 GA10 GA12 GA15 MA06 MA09 MA14 MA15 NA01 NA04 NA12 NA26 PA18 PA19 PB04 PB05 PC08

Claims (2)

[Claims] 1. A coating resin obtained by polymerizing a chlorinated polyolefin (A) having a chlorine content of 50% by mass or less and a vinyl monomer mixture (B), wherein the chlorinated polyolefin (A) and Vinyl monomer mixture (B)
Of (A) / (B) is 0.5 / 99.5 or more and 90
/ 10 or less, and the vinyl monomer mixture (B) 100
2% to 30% by mass of a vinyl monomer (I) having a structure represented by at least one of the following general formulas (1) and (2) and (meth) acryl having a structure represented by the following general formula (3) Acid ester (II) 30 to 97.9% by mass, vinyl monomer (III) polymerizable with at least one of vinyl monomer (I) and (meth) acrylate (II) 0.1 to 68% by mass And a paint resin. Embedded image (Wherein, R ¹ represents hydrogen or a methyl group; R ² represents a linear or branched alkylene group having 2 to 10 carbon atoms;
R ³ represents a linear or branched alkyl group, cycloalkyl group or aryl group having 1 or more carbon atoms which may be substituted with a halogen atom. ) (Wherein R ⁴ represents hydrogen or a methyl group; R ⁵ represents a linear or branched alkylene group having 2 to 4 carbon atoms;
⁶ represents a linear or branched alkyl group, cycloalkyl group or aryl group having 1 or more carbon atoms which may be substituted with a halogen atom; n is an integer of 2 or more. ) (In the formula, R ⁷ represents hydrogen or a methyl group; R ⁸ represents a linear or branched alkyl group or cycloalkyl group having 1 or more carbon atoms which may be substituted with a halogen atom.) 2. The coating resin according to claim 1, which is obtained by polymerizing a vinyl monomer mixture (B) in the presence of a chlorinated polyolefin (A) and a polymerization initiator.