JP2002069135A - Acrylic copolymer, resin composition for coating and coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for coating and a coating material which have a good adhesion to the various material surfaces and which can form a coating film excellent in the glossy feeling, smoothness and alcohol resistance and also which have an excellent waterproofness. SOLUTION: The acrylic polymer of which the acid value is 0.1 to 100 mg KOH/g, the hydroxy group value is 2 to 400 mg KOH/g and the weight average molecular weight is 3,000 to 100,000 is obtained by the copolymerization of (a) 1,4-cyclohexanedimethanol mono(meth)acrylate of 1 to 80 pts.wt., (b) a polymerizable unsaturated monomer having an acid functional group of 0.1 to 10 pts.wt. and (c) other polymerizable unsaturated monomer of 10 to 98.9 pts.wt. (a total 100 pts.wt. of components (a) to (c)). The resin composition for coating and the coating material use the copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition which can be suitably used for coating metals, plastics, wood surfaces and the like, a paint using the same, and an acrylic resin used for the coating resin composition and the paint. The present invention relates to a system copolymer. The coating resin composition and the paint of the present invention,
Excellent gloss, smoothness, alcohol resistance, etc.

[0002]

2. Description of the Related Art Conventionally, as a two-pack polyol resin paint for a metal steel plate or a plastic outer plate, those using an acrylic polyol, a polyester polyol, an oil-modified alkyd polyol, etc. are known.

[0003] Resin coatings using polyester polyols or oil-modified alkyd polyols have good solvent dilutability and sprayability, and the resulting coating films have good gloss and durability. However, there are drawbacks such as initial drying properties, chemical resistance, and contamination due to the penetration of dust and the like during outdoor exposure.

On the other hand, acrylic copolymers are widely used for applications such as paints, inks, adhesives, and synthetic leathers because of their excellent weather resistance, flexibility, strength, adhesiveness, and the like.
In particular, in the application of paints, acrylic copolymers of various compositions suitable for each required performance are used for coating various materials in the fields of automobiles, home appliances, building materials and the like.

For example, in order to improve the drying property, a hydroxyl group to be introduced into an acrylic copolymer is converted into a highly reactive 4-hydroxybutyl (meth) acrylate, (meth) acrylate of polytetramethylene glycol, or 2 -Hydroxyethyl acrylate (2-HEA), 2-hydroxyethyl methacrylate (2-HEMA), etc.
-A method using a caprolactone addition reaction product or the like has been proposed (Japanese Patent Publication No. 3-7433, Japanese Patent Application Laid-Open No. 61-43).
623, JP-A-2-305873, etc.). However, when these are also used in large amounts, for example, sufficient hardness cannot be obtained due to the flexibility of the side chain, the molecular weight between crosslinks becomes too large and the strength is reduced, and the water resistance and weather resistance are significantly increased due to the polyester structure. There are problems such as damage,
None of them satisfy the required performance.

Therefore, a composition containing an acrylic copolymer using 1,4-cyclohexanedimethanol mono (meth) acrylate as a hydroxyl group-containing monomer is excellent in abrasion resistance and chemical resistance, and at the same time, A resin composition for coatings having excellent flexibility has been proposed (International Publication Number: WO95 / 35334). However, since this acrylic copolymer does not use a polymerizable unsaturated monomer having an acidic functional group as a copolymerization component, for example, a paint is prepared in combination with an isocyanate compound, applied to a substrate, and dried. However, there is a problem that a desired crosslinked coating film cannot be obtained because drying is slow and a desired hardness cannot be obtained, and the required performance has not been satisfied.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and adheres well to metals, plastics, wood surfaces, and the like, and can be suitably used for coating. A coating resin composition and a coating capable of forming a coating film having excellent gloss, smoothness, and alcohol resistance and having excellent water resistance, and an acrylic copolymer used for the coating resin composition and the coating. The purpose is to provide.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, 1,4-cyclohexanedimethanol mono (meth) acrylate (a)
And a polymerizable unsaturated monomer (b) having an acidic functional group as an essential component, and other polymerizable unsaturated monomers (c) in combination with each other to polymerize these three components at a specific ratio. It has been found that the acrylic copolymer (A) obtained by the above has an extremely excellent effect, and in particular, the acrylic copolymer (A)
And a coating resin composition and a coating composition using an organic isocyanate compound (B) as a curing agent have excellent gloss and weather resistance, and have excellent balance between dryness and smoothness. Thus, the present invention has been completed.

That is, the present invention relates to 1,4-cyclohexanedimethanol mono (meth) acrylate (a)
0 parts by mass, 0.1 to 10 parts by mass of a polymerizable unsaturated monomer having an acidic functional group (b), and 10 to 98.9 parts by mass of another polymerizable unsaturated monomer (c) [ , Component (a), component (b) and component (c) total 100 parts by mass. Having an acid value of 0.1 to 10
0 mgKOH / g and a hydroxyl value of 2 to 40.
It is an acrylic copolymer having a weight-average molecular weight in the range of 0 mgKOH / g and 3,000 to 100,000.

[0010] The present invention further provides a resin composition for coating comprising the acrylic copolymer (A) of the present invention and an organic isocyanate compound (B) as a curing agent; It contains paint.

In this specification, "(meth) acrylate" means "acrylate and / or methacrylate", and "(meth) acrylic acid" means "acrylic acid and / or methacrylic acid".

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below.

The acrylic copolymer (A) of the present invention comprises:
Copolymerization of 1,4-cyclohexanedimethanol mono (meth) acrylate (a), a polymerizable unsaturated monomer (b) having an acidic functional group, and another polymerizable unsaturated monomer (c) Consisting of

In the present invention, 1,4-cyclohexanedimethanol mono (meth) acrylate (a) is a component necessary for improving the gloss, smoothness, weather resistance and the like of the coating film. The amount of 1,4-cyclohexanedimethanol mono (meth) acrylate (a) is 1 to 80 parts by mass based on 100 parts by mass of the total of components (a) to (c). When this amount is at least 1 part by mass, the glossiness will be good. If it is at most 80 parts by mass, excellent performance in weather resistance, usable time and water resistance will be obtained. This amount is more preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass.

In the present invention, the polymerizable unsaturated monomer (b) having an acidic functional group is an internal catalyst for the reaction between the hydroxyl group of the acrylic copolymer (A) and the isocyanate group of the organic isocyanate compound (B). Act as Examples of the polymerizable unsaturated monomer (b) having an acidic functional group include:
Carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and maleic anhydride; sulfones such as vinyl sulfonic acid, styrene sulfonic acid and sulfoethyl (meth) acrylate Acid group-containing unsaturated monomer; 2- (meth) acryloyloxyethyl acid phosphate, 2-
(Meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloro-
Acidic phosphate ester-based unsaturated monomers such as propyl acid phosphate and 2- (meth) acryloyloxyethylphenylphosphoric acid; and the like. These can be used alone or in combination of two or more.

The amount of the polymerizable unsaturated monomer (b) having an acidic functional group is 0.1 to 10 parts by mass based on 100 parts by mass of the total of the components (a) to (c). If this amount is at least 0.1% by mass, the reactivity with the curing agent will be good. When the amount is 10 parts by mass or less, performance excellent in usable time and moisture resistance can be obtained. This amount is further preferably 0.2 to 8 parts by mass, more preferably 0.3 to 5 parts by mass.

In the present invention, the other polymerizable unsaturated monomer (c) does not impair the properties of the acrylic copolymer (A) caused by the components (a) and (b) as described above. It is used in a range. Specifically, the amount of the other polymerizable unsaturated monomer (c) is 10 to 9 based on a total of 100 parts by mass of the components (a) to (c).
It is 8.9 parts by mass. This amount is more preferably from 32 to 96.8 parts by mass, more preferably from 45 to 94.7 parts by mass.

Other polymerizable unsaturated monomers (c) include, for example, (meth) acrylate monomers other than component (a), styrene monomers, vinyl derivatives, and two or more unsaturated double bonds. And dialkyl esters of unsaturated dibasic acids.

As the (meth) acrylate monomer,
For example, alkyl (meth) acrylate, cycloalkyl (meth) acrylate, aminoalkyl (meth) acrylate, hydroxyl group-containing alkyl (meth) acrylate and the like can be mentioned. Examples of the alkyl (meth) acrylate include an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. ) Acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and the like. As cycloalkyl (meth) acrylate,
For example, a cycloalkyl (meth) acrylate having 3 to 20 carbon atoms in a cycloalkyl group may be mentioned, and specific examples thereof include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate. Examples of the aminoalkyl (meth) acrylate include an aminoalkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, and specific examples thereof include aminomethyl (meth) acrylate and N-methylaminomethyl ( (Meth) acrylate and N, N-diethylaminoethyl (meth) acrylate. Examples of the hydroxyl group-containing alkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. These compounds can be prepared by esterifying (meth) acrylic acid with a large excess of a diol (eg, 1,4-butanediol, 1,6-hexanediol). Further, lactone adducts thereof (for example, “Placcel F” manufactured by Daicel Chemical Industries, Ltd.)
A "series," Placcel FM "series), propylene oxide-based monomers (for example," Blemmer PP-1000 "," Blemmer PP-8 "manufactured by NOF Corporation)
("Blenmer PP-500"), and (meth) acrylic monomers having a hydroxyl group such as ethylene oxide monomers (for example, "Blenmer PE-90" manufactured by NOF Corporation). Manufacturer name and product name of commercial products). In addition, other (meta)
Examples of the acrylate monomer include glycidyl (meth) acrylate and (meth) acrylamide.

Examples of the styrene monomer include styrene, vinyltoluene, α-methylstyrene and the like. Examples of the vinyl derivative include vinyl chloride, vinylidene chloride, vinyl acetate, and isopropenyl acetate. Examples of the monomer having two or more unsaturated double bonds include divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and polyethylene glycol di (meth).
Examples include acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Examples of the dialkyl ester of an unsaturated dibasic acid include dimethyl maleate, diethyl maleate, dimethyl fumarate and diethyl fumarate.

The above-mentioned various polymerizable unsaturated monomers (c)
Can be used alone or in combination of two or more. In particular, when emphasis is placed on the coating film performance of the paint, an unsaturated monomer having a homopolymer Tg of 0 ° C. or higher, such as methyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, or styrene, is used. Is preferred.

The acrylic copolymer (A) of the present invention contains at least a hydroxyl group of 1,4-cyclohexanedimethanol mono (meth) acrylate (a) in a polymer molecule, and contains another polymerizable unsaturated monomer. When a monomer having a hydroxyl group is used as the body (c), the hydroxyl group is also included in the polymer molecule. The hydroxyl value of the acrylic copolymer (A) of the present invention is in the range of 2 to 400 mgKOH / g. When the hydroxyl value is at least 2 mgKOH / g, the appearance and curability of the coating film will be good. In addition, 400mgK
When it is OH / g or less, excellent performance over the usable time can be obtained. This hydroxyl value is further 10 to 200 mg KO
H / g is preferably in the range of 15 to 150 mgKOH /
g is more preferably in the range. In the present invention, the hydroxyl value of the acrylic copolymer (A) is a value obtained by measuring the number of mg of potassium hydroxide equivalent to the hydroxyl group contained in 1 g of the dried acrylic copolymer (A). .

The acid value of the acrylic copolymer (A) of the present invention is in the range of 0.1 to 100 mg / KOH. When the acid value is at least 0.1 mgKOH / g, the drying property and the reactivity will be good. Further, when the amount is 100 mgKOH / g or less, performance excellent in usable time, moisture resistance and smoothness can be obtained. This acid value is further from 0.5 to 80 m
g / KOH, preferably 1 to 30 mg / KOH.
Is more preferable. In the present invention, the acid value of the acrylic copolymer (A) is determined by mg of potassium hydroxide required to neutralize 1 g of the dried acrylic copolymer (A).
It is a value obtained by measuring the number.

The weight average molecular weight of the acrylic copolymer (A) of the present invention is from 3,000 to 100,000. When the weight average molecular weight is 3,000 or more, the blocking resistance and the coating film strength are improved. Also, 100,000
When it is below, the viscosity of the resin is in an appropriate range, the workability is good, and an excellent appearance of the coating film is obtained. In the present invention, the weight average molecular weight of the acrylic copolymer (A) is:
A solution of the acrylic copolymer (A) in tetrahydrofuran (0.4% by mass) was prepared, and a column manufactured by TOSO (GE
100 μl of the above solution was injected into a gel permeation chromatography apparatus manufactured by TOSO equipped with 4000 HXL and G2000HXL), and the flow rate was 1 m.
1 / min, eluent tetrahydrofuran, column temperature 40
It is a value measured by gel permeation chromatography under the condition of ° C. and converted into standard polystyrene.

The acrylic copolymer (A) of the present invention comprises:
1,4-cyclohexanedimethanol mono (meth) acrylate (a), a polymerizable unsaturated monomer (b) having an acidic functional group, and another polymerizable unsaturated monomer (c) It is obtained by copolymerization using a ratio. In addition, the ratio of each component (a) to component (c) used for the polymerization is usually
It becomes almost equal to the ratio in the repeating unit constituting the molecule of the acrylic copolymer (A) as it is.

As the polymerization method, various conventionally known polymerization methods such as a solution polymerization method can be used. Further, high-temperature pressure polymerization in which polymerization is performed under pressure can also be used.

When the solution polymerization method is employed, usable solvents include, for example, toluene, xylene and other aromatic solvents having a high boiling point; ester solvents such as ethyl acetate, butyl acetate and cellosolve acetate; methyl ethyl ketone and methyl isobutyl. Ketone solvents such as ketones; alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol and isobutyl alcohol; These can be used alone or in combination of two or more.

As a polymerization initiator for obtaining the acrylic copolymer (A), a usual radical polymerization initiator can be used, and for example, an organic peroxide, an azo compound or the like can be used. . As the organic peroxide, for example,
t-butyl peroxy 2-ethylhexanoate, benzoyl peroxide, dicumyl peroxide, dibutyl peroxide, and the like. As the azo compound, for example, 2,2′-azobisisobutyronitrile,
2,2'-azobis (2-methylbutyronitrile), 2,2
2′-azobis (2,4-dimethylvaleronitrile) and the like. These can be used alone or in combination of two or more. In addition, a chain transfer agent can be optionally used. Examples of the chain transfer agent include 2
-Mercaptoethanol, n-dodecyl mercaptan,
t-dodecyl mercaptan and the like. These are 1
The species can be used alone or in combination of two or more.

The reaction temperature during the polymerization is usually from room temperature to 200
° C, preferably within the range of 40 to 170 ° C. When the temperature is in the range of room temperature to 200 ° C., the amount of residual monomer at the end of polymerization is small, and the reaction proceeds favorably.

Further, the acrylic copolymer (A) of the present invention
Has an acidic group as a functional group, and can be converted into an aqueous resin using water as a medium by neutralizing with an amine.

The coating resin composition of the present invention contains the acrylic copolymer (A) of the present invention and an organic isocyanate compound (B) as a curing agent. Such a coating resin composition is included.

The organic isocyanate compound (B) is usually a compound containing two or more isocyanate groups in the molecule, and includes, for example, aromatic, aliphatic or alicyclic isocyanate compounds and polyisocyanate compounds. It is. Further, it may be a urethane adduct, a burette, an isocyanate, or the like, and is not particularly limited in these respects.

Specific examples of the organic isocyanate compound (B) include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate,
5-naphthalenediisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane isocyanate,
Tetraalkyldiphenylmethane diisocyanate,
1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, tolidine diisocyanate, cyclohexane
1,4-diisocyanate, xylylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, and the like.

It is also possible to use a burette or isocyanurate, which is a trimer of hexamethylene diisocyanate, or an isocyanate compound mainly containing an adduct of hexamethylene diisocyanate with trimethylolpropane. Commercial products of such isocyanate compounds include Coronate HX, Coronate HK, Coronate HL manufactured by Nippon Polyurethane Co., Ltd., and Sumidur N-75 and Sumidur N-3200 manufactured by Sumitomo Bayer Urethane Co., Ltd. Can be (the above is a trade name). Further, those blocks in which isocyanate is regenerated by heating or the like can also be used.

The above various organic isocyanate compounds can be used alone or in combination of two or more.

Regarding the amount of the organic isocyanate compound (B) used, the amount of the hydroxyl group in the acrylic polyol [that is, the acrylic copolymer (A)] and the amount of the isocyanate group in the organic isocyanate compound (B) are: The amount is preferably such that the equivalent ratio falls within the range of OH / NCO = 10/1 to 0.1 / 1. OH / NCO is 10
When it is at most / 1, the drying property and the coating film hardness will be good. When the ratio is 0.1 / 1 or more, performance excellent in solvent resistance and water resistance can be obtained. This ratio is OH / NCO = 5/1 to
It is more preferably within a range of 0.3 / 1, and OH /
It is particularly preferred that NCO is in the range of 3/1 to 0.5 / 1.

The coating resin composition of the present invention and a coating material using the same may further contain, if necessary, various additives, for example, a known catalyst for accelerating a urethanization reaction between a hydroxyl group and an isocyanate group. Can also be used. Such catalysts include, for example, di-n-dilaurate
Organic tin compounds such as butyl tin, dimethyl tin bis (methyl maleate), dimethyl tin (ethyl maleate), dimethyl tin (butyl maleate), dibutyl tin (butyl maleate), and dibutyl tin (dodecylbenzene sulfonate) A crosslinking reaction accelerator can be used. These can be used alone or in combination of two or more.

As the diluent, the above-mentioned organic solvents and the like can be used as the solvent that can be used when adopting the solution polymerization method. Furthermore, aluminum paste, filler,
It may contain a plasticizer, a pigment dispersion stabilizer, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, crosslinked resin particles as a rheology control agent, and the like. Also, if necessary,
You may contain an inorganic pigment, an organic pigment, etc. Examples of the inorganic pigment include titanium white and carbon black, and examples of the organic pigment include a phthalocyanine pigment and an azo pigment. In order to incorporate these inorganic pigments and organic pigments, a usual pigment dispersion method can be used.

The coating resin composition of the present invention and a coating material using the same may optionally contain another polymer different from the acrylic copolymer (A). As the other polymer, a polymer compatible with the acrylic polymer (A) is preferable. For example, polyacrylic resins such as copolymers of styrene and alkyl acrylate, polyester resins, polyurethane resins,
Examples include polyether resins, polyamide resins, alkyd resins, and the like. These can be used alone or in combination of two or more. The compounding amount of the other polymer may be within a range that does not impair the properties obtained by the acrylic copolymer (A). Generally, the acrylic copolymer (A) and the other polymer have a mass ratio of 10 /
It is preferably in the range of 90 to 100/0.

In order to form a crosslinked coating film using the coating resin composition or coating composition of the present invention, for example, the coating resin composition or coating composition may be applied to a target substrate and crosslinked. Spray coating, brush coating,
Dip coating, roll coating, sink coating and the like can be mentioned. About the temperature and time for crosslinking the coating film, the type and content of the acrylic copolymer (A), the type and the amount of the crosslinking agent,
Optimum conditions vary depending on conditions such as the type and content of the catalyst, the presence / absence, type and amount of the crosslinking promoting catalyst. However, in general, the temperature is preferably in the range of room temperature to 200 ° C., and the time is preferably in the range of 3 seconds to 1 week.

The coating resin composition of the present invention or a paint using the same adheres well to metals, plastics, wood surfaces and the like, and can be suitably used for the coating. For example, for large structures, automobiles It can be used for a wide range of applications such as automobile repair, plastic molded products, and woodworking such as furniture painting.

[0042]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” indicate “parts by mass” and “% by mass”, respectively.

Example 1 In a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, 56.5 parts of toluene and 6.2 parts of isobutyl acetate were charged and heated at 110 ° C.
Heated. Next, at the mixing ratio (parts) shown in Table 1,
Monomer comprising 1,4-cyclohexanedimethanol mono (meth) acrylate (a), a polymerizable unsaturated monomer containing an acidic functional group (b), and another polymerizable unsaturated monomer (c) The mixture and “Kayaester O (trade name)” as a polymerization initiator (manufactured by Kayaku Akzo Co., Ltd.)
t-butylperoxy-2-ethylhexanoate) 1
And a mixture in which 2.7 parts of AIBN (2,2'-azobisisobutyronitrile) were uniformly dissolved were added dropwise over 4 hours while keeping the inside of the flask at the same temperature.

Further, 2 parts of isobutyl acetate was charged into the flask and held for 30 minutes, and 0.2 parts of AIBN was charged into the flask at the same temperature in 30 minutes at intervals of 4 times and held for 1 hour. Finally, 16.3 parts of toluene was added so that the solid content became 55%, and the mixture was cooled to obtain an acrylic copolymer (A). Table 1 also shows the hydroxyl value, acid value, weight average molecular weight, and the like of the obtained acrylic copolymer (A).

<Examples 2 to 5, 8 to 10, Comparative Examples 1 to 5>
5, 7> 1,4-cyclohexanedimethanol mono (meth) acrylate (a), a polymerizable unsaturated monomer containing an acidic functional group (b), and other components at the ratios shown in Tables 1 and 2. Acrylic copolymer (A) was produced in the same manner as in Example 1 except that the ratio of polymerizable unsaturated monomer (c) was changed. Table 1 also shows the hydroxyl value, acid value, weight average molecular weight, and the like of the obtained acrylic copolymer (A).

<Example 6> At the rate shown in Table 1, 1,4-
Cyclohexanedimethanol mono (meth) acrylate (a), a polymerizable unsaturated monomer containing an acidic functional group (b), another polymerizable unsaturated monomer (c), and
An acrylic copolymer (A) was produced in the same manner as in Example 1, except that the ratio of the polymerization initiator was changed and the reaction temperature was changed to 140 ° C. Obtained acrylic copolymer (A)
Table 1 also shows the hydroxyl value, acid value, weight average molecular weight, etc.

Example 7 In a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, 56.5 parts of toluene and 6.2 parts of isobutyl acetate and 1,4-cyclohexanedimethanol were added. Amounts shown in Table 1 of a monomer mixture comprising a mono (meth) acrylate (a), a polymerizable unsaturated monomer containing an acidic functional group (b), and another polymerizable unsaturated monomer (c) Half of (50 copies)
And 0.1 part of “Kayaester O” as a polymerization initiator, and the mixture was heated from room temperature to 80 ° C. over 1 hour, then heated to 90 ° C. over 30 minutes, and further heated in the flask at the same temperature for 1 hour. Hold for hours.

Next, 1,4-cyclohexanedimethanol mono (meth) acrylate (a), a polymerizable unsaturated monomer containing an acidic functional group (b), and other polymerizable unsaturated monomers ( A mixture obtained by uniformly dissolving the remaining half (50 parts) of the monomer mixture consisting of c) and 0.5 part of “Kayaester O” as a polymerization initiator was kept in the flask at the same temperature for 2 hours. It was dropped. afterwards,
Two parts of isobutyl acetate were charged into the flask and maintained for 30 minutes, and 0.2 parts of AIBN were divided into four times at 30 minute intervals and then charged into the flask at the same temperature and maintained for 1 hour. Finally, 16.3 parts of toluene was added so that the solid content became 55%, and the mixture was cooled to obtain an acrylic copolymer (A). Table 1 also shows the hydroxyl value, acid value, weight average molecular weight, and the like of the obtained acrylic copolymer (A).

Comparative Example 6 The amount of toluene in the initial flask was reduced to 36.5 parts, and the amount of toluene for finally adjusting the solid content was correspondingly increased to 36.3 parts.
Further, 1,4-cyclohexanedimethanol mono (meth) acrylate (a), a polymerizable unsaturated monomer containing an acidic functional group (b), and other polymerizable unsaturated monomers at the ratios shown in Table 2 An acrylic copolymer (A) was produced in the same manner as in Example 7, except that the ratio of the monomer (c) was changed. Table 2 also shows the hydroxyl value, the acid value, the weight average molecular weight, and the like of the obtained acrylic copolymer (A).

[0050]

[Table 1]

[0051]

[Table 2] <Example 11> The ratio of the hydroxyl group in the acrylic copolymer (A) to the isocyanate group in the compound relative to 100 parts of the acrylic copolymer (A) (solid content: 55%) obtained in Example 1. Was mixed with Coronate HX (trade name) [organic isocyanate compound manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate content = 21.3% by mass] so that the equivalent ratio was OH / NCO = 1/1. Xylene / toluene / Supersol # 1500 (manufactured by Nisseki Mitsubishi Co., aromatic hydrocarbon mixture) = 40/20/40 (mass ratio) with Ford cup # 4 (JI
According to SK5400. ) For 12 seconds to obtain a paint (or a resin composition for coating).

Next, an ABS resin base material (manufactured by Mitsubishi Rayon, trade name: Diapet ABS3001M, plate thickness: 3 m
m, size 9 cm × 5 cm) was degreased by wiping with gauze impregnated with isopropyl alcohol, and a dried coating film was formed on the surface of the ABS resin base material using a coating spray gun.
Spray the solution of the paint so as to have a thickness of 0 μm.
After drying at 30 ° C. for 30 minutes, a coated plate for evaluation of glossiness, weather resistance, water resistance, alcohol resistance and smoothness was obtained. Table 3 shows the evaluation results.
Are shown together.

<Examples 12 to 20, Comparative Examples 8 to 14> As shown in Tables 3 and 4, the acrylic copolymers (A) obtained in Examples 2 to 10 and Comparative Examples 1 to 7 were used. A coating material (or a resin composition for coating) was produced in the same manner as in Example 11 except that it was blended in the proportions (parts) shown in the same table, and the evaluation coated plate was evaluated in the same manner. The evaluation results of the obtained coated plate are shown in Tables 3 and 4. Examples 12 to 2
0, In Comparative Examples 9 to 14, OH / NCO is all
It is 1/1.

[0054]

[Table 3]

[0055]

[Table 4] The evaluations shown in Tables 3 and 4 were based on the following methods.

(1) Smoothness The state of the coating film was visually evaluated according to the following evaluation criteria. A: The coating film surface is smooth and excellent. ：: Very slight undulation on the coating film surface, but good. △: Slight undulation on the coating film surface, but at practical level. Δ: The surface of the coating film has undulation, is slightly defective, and does not withstand use. ×: The surface of the coating film becomes orange peel and cannot be used.

(2) Gloss The state of the coating film was visually evaluated according to the following evaluation criteria. A: The coating film is glossy and excellent. ：: The coating film was very slightly scattered, but good. △: The coating film is slightly scattered, but at a practical level. Δ: The coating film was scattered and the skin was slightly poor, and was not usable. ×: The coating film surface was scattered and had no luster, and was not usable.

(3) Water Resistance After the obtained evaluation coated plate was immersed in ion-exchanged water at 40 ° C. for 240 hours, changes in the coating film were visually evaluated according to the following criteria. ：: The coating film has no change and is excellent. ：: Very good, with traces remaining on the coating film. △: Slight traces remain on the coating film, but at a practical level. Δ: Traces remain on the coating film, are slightly defective, and do not withstand use. ×: Marks are clearly seen on the coating film, or blisters are generated, and the film is not usable.

(4) Alcohol resistance While pressing the gauze impregnated with ethanol against the surface of the coating film, the coating film was rubbed 50 times from one end to the other end, and the change of the coating film was visually observed according to the following criteria. evaluated. ：: There is no change in the coating film and it is excellent. ：: The coating film is slightly whitened, which is good. △: The coating film is slightly whitened, but at a practical level. Δ: The coating film was whitened, slightly defective, and did not stand use. ×: The coating film is affected by ethanol and is not usable.

(5) Usable time of paint The paint containing the curing agent was allowed to stand at room temperature (25 ° C.) for 8 hours, and the difference from the initial viscosity of the paint was measured. A: Excellent without any change in paint viscosity. ：: Good, as the viscosity of the paint is slightly increased. ○ △: The viscosity of the paint slightly increased, but was at a practical level. Δ: The viscosity of the paint was increased, was slightly poor, and was not usable. ×: The viscosity of the coating material was remarkably increased or gelled, and the coating was not usable.

As is clear from the results in Table 3, Example 1
Any of the paints 1 to 20 (or the resin composition for coating)
Also had good smoothness and excellent gloss. In addition, good physical properties of the coating film were obtained and excellent. In contrast, as is clear from the results in Table 4, Comparative Examples 8 to
The 14 paints (or resin compositions for coating) could not satisfy all of the evaluation items.

[0062]

Industrial Applicability The resin composition for coating and the paint using the acrylic copolymer of the present invention adhere well to metals, plastics, wood surfaces, etc., can be suitably used for the coating, and have a glossy feeling. It can form a coating film with excellent smoothness and alcohol resistance, and has excellent water resistance. For large structures, automobiles, automobile repairs, plastic molded products, woodworking such as furniture coating, etc. Can be used for a wide range of applications.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenichi Tomihara 4-160 Sunadabashi, Higashi-ku, Nagoya-shi, Aichi F-term in the Mitsubishi Rayon Co., Ltd. Product Development Laboratory (reference) 4J038 DG191 DG271 DG281 DG291 DG301 NA01 NA04 PC02 PC06 PC08 4J100 AB02Q AJ01R AJ02R AJ08R AJ09R AK32R AL03Q AL04Q AL08P AL08Q AL08R AL09Q AL10Q AP01R BA03P BA29Q BA38H BA56R BA64R BB01R BC04P BC43R CA05 DA01 DA29 DA30 FA03 HA53 HC51 JA01

Claims (3)

[Claims] 1 to 80 parts by mass of 1,4-cyclohexanedimethanol mono (meth) acrylate (a), polymerizable unsaturated monomer having an acidic functional group (b) 0.1 to
10 parts by mass, and other polymerizable unsaturated monomers (c)
10 to 98.9 parts by mass, wherein the total of the components (a), (b) and (c) is 100 parts by mass. Having an acid value in the range of 0.1 to 100 mgKOH / g, a hydroxyl value in the range of 2 to 400 mgKOH / g, and a weight average molecular weight of 3,000 to 100,000. Acrylic copolymer within the range of. 2. A coating resin composition comprising the acrylic copolymer (A) according to claim 1 and an organic isocyanate compound (B) as a curing agent. 3. A paint containing the resin composition for coating according to claim 2.