JP2001064567A - Resin composition for matte coating material and coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition exhibiting excellent matte effects and suitable of a coating material and to provide a matte coating material capable of giving a coating film excellent in chemical resistance and waterability. SOLUTION: The objective resin composition comprises [I] an organic solvent-soluble copolymer (A) obtained by polymerizing (a) 30-60 wt.% of a styrenic monomer, (b) 5-70 wt.% of an alkyl methacrylate monomer bearing a 2C or lower alkyl group in an ester moiety, (c) 0-65 wt.% of an ehylenically unsaturated monomer other than (a) and (b) aforementioned and [II] a non- water-dispersible resin (D) comprising an organic-soluble copolymer (B) obtained by copolymerizing ethylenically unsaturated monomers substantially free from a styrenic monomer having incorporated therein an organic solvent-insoluble crosslinked copolymer particle (C). Another objective coating comprises the resin composition and a polyisocyanate as a curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for a matte paint and a paint.

[0002]

2. Description of the Related Art Many methods have been proposed for matting a coating film. For example, it is said that an inorganic powder such as silica powder or an organic powder such as polyethylene powder, which is generally called a matting agent, is added, and irregularities are generated on the coating film surface to scatter light reflection to obtain a matting effect. Things.

[0003] However, these methods using a matting agent are inferior in the stability of the coating due to the sedimentation of the matting agent, fail to obtain a uniform matte coating film, and are inferior in coating durability such as weather resistance. There's a problem. In order to solve this problem, a resin composition or the like manufactured by using a special polymerization method without adding a matting agent (see, for example, JP-A-3-81371 and JP-A-6-287235) has been proposed. Proposed. However, there is a problem that the matting property of the coating film is not satisfactory, and the durability of the coating film such as water resistance is poor.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition which is excellent in matting properties and is suitable for a paint.

[0005] Another object of the present invention is to provide, in addition to the above effects,
An object of the present invention is to provide a resin composition having excellent weather resistance of a coating film and suitable for a paint.

Another object of the present invention is to provide a matting paint having excellent chemical resistance and water resistance of a coating film.

[0007]

According to the present invention, there is provided [I] (a)
30 to 60% by weight of a styrene monomer, (b) 5 to 70% by weight of an alkyl methacrylate monomer having an ester-bonded alkyl group having 2 or less carbon atoms, and (c) the ( a) A copolymer (A) soluble in an organic solvent obtained by polymerizing 0 to 65% by weight of an ethylenically unsaturated monomer other than (b) and [II] a styrene monomer Non-aqueous solution containing a copolymer (B) soluble in an organic solvent obtained by copolymerizing an ethylenically unsaturated monomer which is not contained in the polymer, and a copolymer crosslinked particle (C) insoluble in the organic solvent. The present invention relates to a resin composition for a matting paint containing a dispersion type resin (D).

The present invention also relates to a paint obtained by blending a curing agent with the above-mentioned resin composition for a matte paint.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer (A) soluble in an organic solvent according to the present invention comprises (a) a styrene monomer, and (b) an ester-bonded alkyl group having 2 or less carbon atoms. Alkyl methacrylate alkyl ester and (c)
It is obtained by polymerizing an ethylenically unsaturated monomer other than (a) and (b).

(A) Examples of the styrene monomer include styrene, vinyltoluene, α-methylstyrene,
Chlorostyrene and the like. These monomers are used alone or in combination of two or more.

(B) Examples of the alkyl methacrylate monomer in which the ester-bonded alkyl group is an alkyl group having 2 or less carbon atoms include, for example, methyl methacrylate, ethyl methacrylate and the like. These monomers are used alone or in combination of two or more.

(C) Examples of the ethylenically unsaturated monomer other than the above (a) and (b) include the following (b)
Other (meth) acrylic acid derivatives, unsaturated acids, and vinyl compounds.

As the (meth) acrylic acid derivative, alkyl (meth) acrylates other than the above (b),
Hydroxyalkyl (meth) acrylate, mono (meth) acrylate of trihydric or higher polyhydric alcohol, (meth) acrylamide and derivatives thereof, (meth) acrylic acid derivative having oxirane group, hindered amino group A (meth) acrylate having a benzotriazole group, a (meth) acrylate having a benzotriazole group,
(Meth) acrylonitrile and the like.

Examples of the alkyl (meth) acrylate other than the above (b) include methyl acrylate, ethyl acrylate and (meth) acryl in which the alkyl group having an ester bond is an alkyl group having 3 or more carbon atoms. Acid alkyl esters, for example, propyl (meth) acrylate,
Isopropyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, (meth)
T-butyl acrylate, pentyl (meth) acrylate,
Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate , Decyl (meth) acrylate, (meth)
Undecyl acrylate, dodecyl (meth) acrylate and the like.

Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-iso-propyl (meth) acrylate, 4-hydroxybutyl meth) acrylate,
2-hydroxy-iso-butyl (meth) acrylate,
5-hydroxypentyl (meth) acrylate, (meth)
2-hydroxy-iso-pentyl acrylate, 6-hydroxyhexyl (meth) acrylate, and the like. In addition, these hydroxyalkyl (meth) acrylates and additional compounds such as ε-caprolactone and γ-valerolactone can also be used as the ethylenically unsaturated monomer of the component (c).

Tri- or higher polyhydric alcohol mono (meth)
Examples of the trihydric or higher polyhydric alcohol in the acrylate include glycerin and trimethylolpropane, and examples of the (meth) acrylamide derivative include N-methylol (meth) acrylamide and its alkyl ether. Compounds and the like, and as the (meth) acrylic acid derivative having an oxirane group,
For example, glycidyl methacrylate and the like can be mentioned.

Examples of the unsaturated acid include (meth) acrylic acid, maleic acid, fumaric acid and the like. Examples of the vinyl compound include vinyl acetate and vinyl chloride.

These monomers are used alone or in combination of two or more. Preferred combinations of the monomer as the component (c) include, for example, (1) methyl acrylate, ethyl acrylate, and (meth) acrylic acid in which the alkyl group having an ester bond is an alkyl group having 3 or more carbon atoms. Alkyl esters, (meth) acrylamides and derivatives thereof, (meth) acrylic acid derivatives having an oxirane group, (meth) acrylates having a hindered amino group, (meth) acrylates having a benzotriazole group, ( A monomer selected from the group consisting of (meth) acrylonitrile and vinyl compounds, preferably 2
0-85% by weight, more preferably 25-70% by weight,
(2) hydroxyalkyl (meth) acrylate or mono (meth) acrylate of a trihydric or higher polyhydric alcohol, preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and (3) unsaturated Acid preferably 5
To 20% by weight, more preferably 10 to 15% by weight.

The mixing ratio of the component (a) is based on the copolymer (A)
30 to 60% by weight based on the total amount of monomers used for the polymerization of
, And preferably 35 to 55% by weight. If the mixing ratio is less than 30% by weight, the matting effect can hardly be expected, and if it exceeds 60% by weight, the matting effect cannot be expected similarly.

The mixing ratio of the component (b) is as follows.
Is 5 to 70% by weight, preferably 10 to 50% by weight, based on the total amount of the monomers used for the polymerization. If the mixing ratio is less than 5% by weight, the matting effect can hardly be expected, and if it exceeds 70% by weight, the matting effect cannot be expected.

The mixing ratio of the component (c) is as follows:
0 to 65% by weight, and preferably 5 to 40% by weight, based on the total amount of the monomers used for the polymerization. If it exceeds 65% by weight, the matting effect cannot be expected. Also,
The use of hydroxyalkyl (meth) acrylate or mono (meth) acrylate of trihydric or higher polyhydric alcohol among the components (c) is preferable because the coating properties such as water resistance and weather resistance are improved. . At this time, the mixing ratio of the hydroxyalkyl (meth) acrylate or the mono (meth) acrylate of the trihydric or higher polyhydric alcohol is such that the copolymer (A) has a hydroxyl value of 5 to 150 mgK.
OH / g is preferable, and the mixing ratio is preferably 10 to 10
The mixing ratio is preferably 0 mgKOH / g, more preferably 20 to 70 mgKOH. If the hydroxyl value is less than 5 mgKOH / g, the weather resistance tends to be poor, and the hydroxyl value is 150 mgKOH / g.
If it exceeds 300, the water resistance of the coating film tends to be poor. Also,
When an unsaturated acid is used in the component (c), the pot life and curability of the obtained composition can be controlled.
The mixing ratio of the unsaturated acid is such that the acid value of the copolymer (A) is 0.0
It is preferably adjusted to 1 to 20 mgKOH / g, more preferably to 0.1 to 10 mgKOH / g, and still more preferably to 0.5 to 7 mgKOH / g. Acid value is 0.01mgKO
If it is less than H / g, the curability tends to be poor, and the acid value is 20 m
If it exceeds gKOH / g, the pot life tends to be short.

As a method for polymerizing the copolymer (A), for example, a usual radical polymerization method can be used, and the method is not particularly limited. As a method of performing polymerization using a radical polymerization method, for example, the components (a), (b) and (c) and a polymerization catalyst (polymerization initiator) are mixed in an organic solvent,
A method of heating at 1 ° C. for 1 to 10 hours can be used. Examples of the organic solvent used in the radical polymerization method include aromatic hydrocarbons such as toluene and xylene, and aromatic hydrocarbons such as Solvesso 100 and Solvesso 150 (trade name of Edanon, a mixed solvent of aromatic hydrocarbons). Hydrogen mixed solvent, pentane, hexane, heptane, octane, aliphatic hydrocarbons such as decane, cyclohexane,
Cycloaliphatic hydrocarbons such as methylcyclohexane and ethylcyclohexane, esters such as ethyl acetate, butyl acetate and cellosolve, ketones such as methyl ethyl ketone and methyl isobutyl ketone, 1-butanol, 2-butanol, 1-propanol and 2 -Alcohols such as propanol and butyl cellosolve. Also,
Mineral spirit, mineral thinner, petroleum spirit, white spirit, mineral terpene, etc., which are mixed solvents of aliphatic hydrocarbons, can also be used.

These organic solvents can be used alone or in combination of two or more.

Examples of the polymerization initiator used for the polymerization of the copolymer (A) include organic peroxides and azo compounds. Examples of the organic peroxide include isobutyl peroxide, lauroyl peroxide, 3,5,5-
Trimethylhexanoyl peroxide, octanoyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butyl Peroxy)-
3,3,5-trimethylcyclohexane, 3,3,5-
Trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, diisobutylperoxydicarbonate, 2-diethylhexylperoxydicarbonate, 2,5-dimethyl-2,5-bis (2-
Ethylhexanoylperoxy) hexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis ( t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-
Butyl peroxy-2-ethylhexanoate, 1,
1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, and the like. Can be Examples of the azo compound include 2,2'-azobis-isobutyronitrile, dimethylazodiisobutyrate, 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (2 -Methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate, 1 , 1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,2,4-
Trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane) and the like.

These polymerization initiators can be used alone or in combination of two or more.

The amount of the polymerization initiator to be used is determined according to the desired molecular weight of the copolymer (A), but is usually based on the total amount of the monomers used for the polymerization of the copolymer (A). On the other hand, the content is preferably 0.1 to 10.0% by weight.

If necessary, the molecular weight may be adjusted using a chain transfer agent. Examples of the chain transfer agent include n-dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and the like.

The weight average molecular weight of the copolymer (A) in the present invention (value measured by GPC and converted to standard polystyrene,
The same applies hereinafter), preferably from 10,000 to 400,000, more preferably from 20,000 to 200,000. When the weight average molecular weight is less than 10,000, weather resistance and chemical resistance tend to decrease, and
If it exceeds 000, the viscosity of the resin becomes high, and it tends to be practically difficult to prepare a paint.

The non-aqueous dispersion type resin (D) in the present invention comprises:
An organic solvent-soluble copolymer (B) obtained by copolymerizing an ethylenically unsaturated monomer substantially free of a styrene-based monomer is mixed with an organic solvent-insoluble copolymer crosslinked particle (C ).

The copolymer (B) soluble in an organic solvent can be obtained by copolymerizing two or more ethylenically unsaturated monomers substantially free of styrene-based monomers. The styrene-based monomer may be contained if it is 5% by weight or less based on the total amount of the ethylenically unsaturated monomer to be copolymerized. As the ethylenically unsaturated monomer to be copolymerized, an ethylenically unsaturated monomer other than the styrene-based monomer that can be used for the synthesis of the copolymer (A) is appropriately selected and used. be able to. The combination and the mixing ratio of the ethylenically unsaturated monomer to be copolymerized are not particularly limited as long as the obtained copolymer is a combination and the mixing ratio at which the obtained copolymer is soluble in an organic solvent. Usually, it is used in an amount of 40% by weight or more based on the total amount of the ethylenically unsaturated monomer copolymerizing the alkyl (meth) acrylate in which the alkyl group having an ester bond is an alkyl group having 4 or more carbon atoms. preferable. If the styrene-based monomer is added in an amount exceeding 5% by weight, the matting properties of the paint are inferior, and the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms is less than 40% by weight. And the solubility of the copolymer (B) in an organic solvent tends to decrease.

When a hydroxyalkyl (meth) acrylate or a mono (meth) acrylate of a trihydric or higher polyhydric alcohol is used as one of the monomers for polymerizing the copolymer (B), the weather resistance is improved. It is preferable because the coating properties such as properties are improved. At this time, the mixing ratio of the hydroxyalkyl (meth) acrylate or the mono (meth) acrylate of the trihydric or higher polyhydric alcohol is such that the hydroxyl value of the copolymer (B) is 5 to 150 mgKOH / g. Preferably 10 to 100 mg KOH
/ G is more preferably 20 to 20 g / g.
More preferably, it is blended so as to be 70 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, the weather resistance tends to be poor. If the hydroxyl value exceeds 150 mgKOH / g, the water resistance of the coating film tends to be poor.

When an unsaturated acid is used as one of the monomers for polymerizing the copolymer (B), the pot life and curability of the obtained composition can be controlled.
The mixing ratio of the unsaturated acid is such that the acid value of the copolymer (B) is 0.0
It is preferable to mix it so as to be 1 to 20 mgKOH / g, more preferably 0.1 to 10 mgKOH / g, and more preferably 0.5 to 7 mgKOH / g. preferable. If the acid value is less than 0.01 mgKOH / g, the curability tends to be poor, and if the acid value exceeds 20 mgKOH / g, the pot life tends to be short.

Preferred examples of the combination of the ethylenically unsaturated monomers for synthesizing the copolymer (B) include, for example, (1) an ester bond with respect to 100 parts by weight of the total amount of the monomers. (Meth) acrylic acid alkyl ester wherein the alkyl group is an alkyl group having 4 or more carbon atoms
9 parts by weight, preferably 50 to 80 parts by weight, (2) hydroxyalkyl (meth) acrylate or mono (meth) acrylate of a trihydric or higher polyhydric alcohol 1 to 35 parts by weight, preferably 2 to 15 parts by weight Parts by weight, (3) 0 to 5 parts by weight of an unsaturated acid, preferably 0.1 to 2 parts by weight, and (4) an alkyl group having an ester bond has 3 carbon atoms.
The following alkyl groups (meth) acrylic acid alkyl esters, (meth) acrylic acid amides and derivatives thereof, (meth) acrylic acid derivatives having an oxirane group, (meth) acrylic acid esters having a hindered amino group, benzotriazole Those containing 0 to 59 parts by weight, preferably 10 to 40 parts by weight of a monomer selected from the group consisting of a (meth) acrylic ester having a group, (meth) acrylonitrile and a vinyl compound are exemplified.

In order to synthesize the copolymer (B), various known polymerization methods can be used. However, radical solution polymerization is simple, and the resulting solution of the copolymer (B) is prepared by the following method. Can be directly used in the step of synthesizing the crosslinked copolymer (C) insoluble in the organic solvent described above.

The organic solvent used for the polymerization reaction for synthesizing the copolymer (B) is not particularly limited. For example, the organic solvent used for synthesizing the copolymer (A) described above may be used. Can be used.

The polymerization initiator used for the radical polymerization of the copolymer (B) and the amount used are the same as the polymerization initiator used for the synthesis of the copolymer (A) and the amount used.

If necessary, the molecular weight may be adjusted using the above-mentioned chain transfer agent which can be used for the synthesis of the copolymer (A).

[0038] The weight average molecular weight of the copolymer (B) in the present invention is preferably from 10,000 to 400,000, more preferably from 40,000 to 200,000. If the weight average molecular weight is less than 10,000, the dispersion stability of the crosslinked copolymer particles (C) tends to decrease. If the weight average molecular weight exceeds 400,000, the resin becomes highly viscous and practically difficult to form a coating. There is a tendency.

As the crosslinked copolymer-insoluble particles (C) in the present invention, for example, crosslinked particles obtained by crosslinking a copolymer of an ethylenically unsaturated monomer insoluble in an organic solvent are preferable. It is. Examples of the ethylenically unsaturated monomer used for synthesizing the copolymer crosslinked particles (C) include, for example,
Styrene-based monomers, (meth) acrylic acid derivative unsaturated acids, vinyl-based compounds and the like exemplified as monomers usable for the synthesis of the copolymer (A), and as essential components,
Use is made of an ethylenically unsaturated monomer having a reactive functional group necessary for a crosslinking reaction performed simultaneously with or after the copolymerization reaction.

Examples of the monomer having a reactive functional group for crosslinking reaction include a combination of an unsaturated acid and a glycidyl group-containing (meth) acrylic acid ester, a (meth) acrylic acid hydroxyalkyl ester or a trivalent or higher polyvalent. Examples include a combination of a mono (meth) acrylate of alcohol and a (meth) acrylate containing an isocyanato group, and a hydrolyzable silyl group-containing (meth) acrylate. Among them, the above-mentioned unsaturated acid monomers can be used. Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate. Can be used. As the (meth) acrylic acid hydroxyalkyl ester or the mono (meth) acrylic acid ester of a trihydric or higher polyhydric alcohol, those described above can be used, and as the isocyanato group-containing (meth) acrylic acid ester, For example, isocyanatoethyl (meth) acrylate and the like can be used. Examples of the hydrolyzable silyl group-containing (meth) acrylate include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and the like.

The proportion of the monomer having a reactive functional group is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the monomers used for synthesizing the crosslinked copolymer particles (C). , 0.1 to 2 parts by weight is more preferred. 0.01
If the amount is less than 10 parts by weight, the matting property tends to be poor.
If the amount is more than 10 parts by weight, the viscosity tends to increase during the synthesis and the gel tends to be formed. In addition, the compounding ratio here is a compounding ratio of a monomer that can actually participate in a crosslinking reaction, for example,
In the case of a reaction between a carboxyl group and a glycidyl group, it refers to the amount of a combination of a carboxyl group-containing monomer and a glycidyl group-containing monomer that can react with each other in an equivalent ratio of 1: 1. Alternatively, it does not contain a glycidyl group-containing monomer.

As the monomer used for synthesizing the crosslinked copolymer particles (C), it is preferable to use a combination in which the copolymer of the monomer is insoluble in an organic solvent. For example, a (meth) acrylic acid alkyl ester in which the alkyl group having an ester bond is an alkyl group having a carbon number of 3 or less is converted into 100 parts by weight of the total amount of monomers used for the synthesis of the copolymer crosslinked particles (C). Of these, it is preferable to use at least 40 parts by weight, more preferably at least 60 parts by weight. When the amount is less than 40 parts by weight, the copolymer particles and the crosslinked particles thereof are easily dissolved in a solvent, and the stability of the composition tends to be poor.

Among the monomers used for the synthesis of the crosslinked copolymer particles (C), hydroxyalkyl (meth) acrylate or mono (meth) acrylate of a trihydric or higher polyhydric alcohol may be used. It is preferable to use it because the coating properties such as weather resistance are improved. In this case, the mixing ratio of the hydroxyalkyl (meth) acrylate or the mono (meth) acrylate of the trihydric or higher polyhydric alcohol is such that the hydroxyl value of the crosslinked copolymer particles (C) is 5 to 150 m.
gKOH / g.
It is more preferably adjusted to 100 mgKOH / g, and further preferably adjusted to 20 to 70 mgKOH / g. If the hydroxyl value is less than 5 mg KOH / g, the weather resistance tends to be poor, and the hydroxyl value is 150 mg KOH / g.
If it exceeds H / g, the water resistance of the coating film tends to be poor. Combination of hydroxyalkyl (meth) acrylate or mono (meth) acrylate of trihydric or higher polyhydric alcohol and isocyanato group-containing (meth) acrylate as a monomer having a reactive functional group for crosslinking reaction When is used, the hydroxyl group in the total amount of the monomer /
An excessive amount of hydroxyalkyl (meth) acrylate or mono (meth) acrylate of trihydric or higher polyhydric alcohol is used so that the equivalent ratio of the isocyanate group is greater than 1, and the copolymer crosslinked particles (C) It is preferable that the hydroxyl value be in the above range.

When an unsaturated acid is used in the monomer used for synthesizing the copolymer crosslinked particles (C), the copolymer is used for controlling the pot life and curability of the obtained composition. The acid value of the crosslinked particles (C) is 0.01 to 20 mgKOH / g
Is preferably used in an amount of 0.1 to 10 mgK.
OH / g is more preferably used.
More preferably, it is used in an amount of と 7 mgKOH / g. If the acid value is less than 0.01 mgKOH / g, the curability of the composition tends to be poor, and if the acid value exceeds 20 mgKOH / g, the pot life tends to be short. When a combination of an unsaturated acid and a glycidyl group-containing (meth) acrylate is used as a monomer having a reactive functional group for a crosslinking reaction, the equivalent ratio of carboxyl group / glycidyl group in the total amount of monomers is It is preferable to use an excess amount of unsaturated acid so as to be larger than 1, so that the acid value of the crosslinked copolymer particles (C) falls within the above range.

Preferred examples of the combination of ethylenically unsaturated monomers for synthesizing the copolymer crosslinked particles (C) include, for example, based on 100 parts by weight of the total amount of the monomers.
(1) 40 to 90 parts by weight, preferably 50 to 80 parts by weight of an alkyl (meth) acrylate in which the alkyl group having an ester bond is an alkyl group having 3 or less carbon atoms;
(2) Combination of ethylenically unsaturated monomers for crosslinking reaction 0.01 to 10 parts by weight, preferably 0.1 to 2 parts by weight, (3) hydroxyalkyl (meth) acrylate or trivalent or more 1 to 35 parts by weight, preferably 2 to 20 parts by weight, of mono (meth) acrylic acid ester of polyhydric alcohol, (4) 0.1 to 3 parts by weight of unsaturated acid, preferably 0.5 to 2 parts by weight, and (5) (meth) acrylic acid alkyl esters, (meth) acrylic acid amides and derivatives thereof, and (meth) acrylic acid having a hindered amino group, wherein the alkyl group having an ester bond is an alkyl group having 4 or more carbon atoms 0 to 40 parts by weight of a monomer selected from the group consisting of an ester, a (meth) acrylate having a benzotriazole group, a (meth) acrylonitrile and a vinyl compound, preferably Ku include those containing 5 to 20 parts by weight.

As a method for synthesizing the copolymer crosslinked particles (C) using an ethylenically unsaturated monomer, for example, a copolymer is synthesized by a usual radical polymerization method, and simultaneously with the synthesis of the copolymer. Or a method of performing a crosslinking reaction after the synthesis of the copolymer. As a method of synthesizing the copolymer crosslinked particles (C) using a radical polymerization method, for example, the ethylenically unsaturated monomer mixture and a polymerization initiator are mixed in an organic solvent, and the mixture is mixed at 60 to 150 ° C. It is heated for 1 to 20 hours, preferably 80 to 130 ° C. for 2 to 10 hours to copolymerize to form a copolymer particle insoluble in the solvent,
0 to 150 ° C for 1 to 20 hours, preferably 120 to 15
A method of keeping the temperature at 0 ° C. for 2 to 10 hours to crosslink the inside of the copolymer particles can be used.

The organic solvent used in the polymerization reaction and the cross-linking reaction for synthesizing the copolymer cross-linked particles (C) is not particularly limited. The organic solvents used can be used.

The polymerization initiator used in the synthesis of the copolymer crosslinked particles (B) and the amount used are the same as the polymerization initiator used in the synthesis of the copolymer (A) and the amount used. is there.

The non-aqueous dispersion type resin (D) in the present invention comprises:
For example, the copolymer crosslinked particles (B) may be prepared by dispersing the copolymer crosslinked particles (B) in a solution of the copolymer (B). The method prepared by synthesizing C) is preferred.

The mixing ratio of the copolymer (B) and the copolymer crosslinked particles (C) in the non-aqueous dispersion type resin (D) in the present invention is such that the copolymer (B) and the copolymer crosslinked particles (C )) With the total amount of the components being 100 parts by weight, the blending amount of the copolymer (B) is 5
To 70 parts by weight, the blending amount of the copolymer crosslinked particles (C) is 30
Preferably, the blending amount of the copolymer (B) is 15 to 60 parts by weight, and the blending ratio of the copolymer crosslinked particles (C) is 40 to 85 parts by weight. If the blending amount of the copolymer crosslinked particles (C) is less than 30 parts by weight, the matting property tends to be poor, and if it exceeds 95 parts by weight, the dispersion stability of the copolymer crosslinked particles (C) tends to be poor. . Further, for the purpose of improving the dispersion stability, it is possible to graft the copolymer (B) and the crosslinked copolymer particles (C).

The average particle size of the crosslinked copolymer particles (C) (for example, a value obtained by measuring with an N4 type submicron particle analyzer manufactured by Coulter Co., Ltd. at a temperature of 20 ° C. in an INTENSITY mode, the same applies hereinafter) is about 100-1500n
m, more preferably about 300 to 1000 nm. If it is too small, the viscosity of the resin solution tends to be high, and if it is too large, the particles tend to swell or aggregate during storage, resulting in poor stability. The average particle diameter is adjusted by selecting the organic solvent, the molecular weight of the copolymer (B), the blending ratio of the copolymer (B) and the copolymer crosslinked particles (C), and the solubility parameter (SP value). Is done.

When a hydroxyalkyl (meth) acrylate or a mono (meth) acrylate of a trihydric or higher polyhydric alcohol is used in the synthesis of the copolymer (B) and the crosslinked copolymer particles (C). Is preferably blended such that the hydroxyl value of the non-aqueous dispersion type resin (D) is 5 to 150 mgKOH / g, and 10 to 100 mgKOH.
/ G is more preferably 20 to 20 g / g.
More preferably, it is blended so as to be 70 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, the weather resistance tends to be poor. If the hydroxyl value exceeds 150 mgKOH / g, the water resistance of the coating film tends to be poor. (B)
When an unsaturated acid is used for the synthesis of (C), it is preferable that the acid value of the non-aqueous dispersion type resin (D) is adjusted to be 0.01 to 20 mgKOH / g, and 0.1 to 10 mgKOH / g.
OH / g is more preferably blended,
More preferably, it is blended to be 0.5 to 7 mgKOH. Acid value is 0.01mgKOH / g
If less than 30, the curability tends to be poor, and the acid value is 20 mg KO.
If it exceeds H / g, the pot life tends to be short.

The resin composition for matte coating of the present invention can be obtained by mixing a copolymer (A) soluble in an organic solvent and a non-aqueous dispersion type resin (D). The mixing ratio of the copolymer (A) and the non-aqueous dispersion resin (D) soluble in the organic solvent is such that the total amount of the copolymer (A) and the non-aqueous dispersion resin (D) is 1
As 100 parts by weight, the blending amount of the copolymer (A) is 10 to 9
It is preferably in the range of 0 parts by weight, more preferably 20 to 80 parts by weight, and even more preferably 30 to 70 parts by weight.

The matte paint resin composition of the present invention is usually prepared in a state where a soluble resin component is dissolved in an organic solvent.
Stored and used. Although the amount of the organic solvent is not particularly limited, it is preferably 50 to 1000 parts by weight, and more preferably 80 to 100 parts by weight based on 100 parts by weight of the resin composition for a matte coating composition of the present invention.
800 parts by weight are more preferred.

The above-obtained matte coating resin composition is preferable because a weathering, water and chemical resistance is improved by adding a polyisocyanate as a curing agent.

As the polyisocyanate, 2 in the molecule is used.
Compounds containing more than one isocyanenato group, for example,
Hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, methylcyclohexane diisocyanate, isopropylidene bis (4
-Cyclohexyl isocyanate), aliphatic or alicyclic isocyanates, trimers thereof and the like. Further, these isocyanates and polyhydric alcohol compounds such as propanediol, butanediol, hexanediol, decanediol, dodecanediol, 12-hydroxystearyl alcohol, polyethylene glycol, trimethylolpropane, pentaerythryl, and dimer diol, and water and Can be used as the polyisocyanate.

The compounding amount of the polyisocyanate is preferably such that the total hydroxyl / isocyanato group equivalent ratio of the copolymer (A) and the non-aqueous dispersion type resin (D) is 0.5 to 2.0, More preferably, it is set to 0.8 to 1.2. If it is less than 0.5, a large amount of unreacted polyisocyanate remains in the coating film, so that the properties of the coating film tend to decrease, and if it exceeds 2.0, the water resistance and weather resistance of the coating film tend to decrease. . It is preferable that the matting resin composition of the present invention and the polyisocyanate are mixed and stirred and mixed immediately before coating.

The resin composition for a matte paint in the present invention can be mixed with an inorganic pigment and an organic pigment to form an enamel paint. As the inorganic pigment, for example, titanium white,
Examples of the organic pigment include phthalocyanine blue and azo-based organic pigments.
In addition, extenders such as calcium carbonate and barium sulfate can be added. These are usually used as a main component (copolymer (A)
And a resin solution containing the non-aqueous dispersion type resin (D)). It is also possible to make a clear paint without adding the pigment. As a method for forming an enamel coating, for example, a known method such as a roll, a sand mill, and a disperser can be used. In the case of a non-aqueous resin, a high shearing force is applied when dispersing the pigment when forming an enamel paint, and the resin may be agglomerated. Therefore, an enamel paint may be produced by mixing a coloring seed pen (paste) having good compatibility with the resin composition of the present invention. Furthermore, in order to improve the performance as a paint,
It is also possible to add a pigment dispersant, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer and the like at the time of coating or after coating.

The coating composition of the present invention usually contains an organic solvent. The amount of the organic solvent is preferably 40 to 40% of the total amount of the coating composition so as to obtain a coating composition having a suitable viscosity according to the coating method of the coating composition.
It can be adjusted appropriately in the range of 95% by weight, more preferably 50 to 85% by weight.

The paint of the present invention is prepared according to a usual coating method.
It can be used for coating various substrates and surfaces of articles.
For coating, for example, an air spray machine, an airless spray machine, an electrostatic coater, a dipping, a roll coater, a brush or the like can be used. Examples of the substrate include wood, metal, slate, roof tile, and the like.

When the paint of the present invention is used as a curable paint, it is necessary to cure the coating film.
After the application, it is preferable to leave at room temperature to 300 ° C. for about 1 minute to 10 days.

[0062]

The present invention will be described below in detail with reference to examples. "Parts" means "parts by weight" and "%" means "% by weight".
Is shown.

Production Examples 1-2 Production of copolymer (A) soluble in organic solvent A flask equipped with a thermometer, a stirrer, a nitrogen gas blowing tube and a reflux condenser was charged with 30 parts of xylene and 20 parts of butyl acetate. Was heated to 100 ° C. under a nitrogen stream, and a mixture shown in Table 1 was added dropwise over 2 hours. Then, xylene 2
A mixture of 0 parts and 0.2 parts of azobisisobutyronitrile was added dropwise over 1 hour, and the mixture was further kept warm for 3 hours. Thereafter, the mixture was cooled, and xylene was added so that the heating residue became about 50% to obtain copolymers (A-1 to A-2). Table 1 shows the heating residue of the obtained copolymer solution, and the acid value, hydroxyl value and weight average molecular weight of the copolymer.

[0064]

[Table 1] Azobisisobutyronitrile: 2,2'-azobisisobutyronitrile Production Examples 3 to 5 Production of Copolymer (B) 40 parts of Solvesso 100 were charged into the synthesis apparatus used in Production Examples 1 and 2, The temperature was raised to 110 ° C. under a nitrogen stream, and a mixture having the composition shown in Table 2 was added dropwise over 2 hours. Subsequently, a mixture of 40 parts of Solvesso 100, 0.2 parts of azobisisobutyronitrile, and 0.1 part of t-butylperoxybenzoate was added dropwise over 1 hour, and the mixture was further kept warm for 3 hours. Thereafter, the mixture was cooled and Solvesso 100 was added so that the heating residue was about 48%. The obtained copolymer solution (B-
Table 2 shows the heating residue of 1 to B-3), and the acid value, hydroxyl value and weight average molecular weight of the copolymer.

[0065]

[Table 2] Production Examples 6 to 8 Production of Non-Aqueous Dispersion Type Resin (D) Using the synthesis apparatus used in Production Examples 1 and 2, the copolymers (B) obtained in Production Examples 3 to 5 were blended as shown in Table 3. Solution (B-1)
~ B-3) and 5 parts of xylene, and charged under nitrogen stream.
The temperature was raised to 05 ° C., and the mixture shown in Table 3 was added dropwise over 2 hours. Subsequently, a mixed solution of 30 parts of xylene and 0.2 parts of azobisisobutyronitrile was added dropwise over 1 hour, and the temperature was further maintained for 1 hour. Thereafter, the temperature was raised to 125 ° C. and kept for 2 hours to crosslink the inside of the particles. After cooling, xylene was added so that the heating residue of the obtained dispersion was about 50%. Table 3 shows the heating residue of the obtained dispersion (a solution of the non-aqueous dispersion type resin containing crosslinked copolymer particles), the acid value of the nonaqueous dispersion type resin, the hydroxyl value, and the average particle size of the crosslinked particles.

[0066]

[Table 3] Examples 1-3 and Comparative Examples 1-5 The copolymer solutions A-1 and A-2 obtained in Production Examples 1-2 and the non-aqueous dispersion type resin solution D-1 obtained in Production Examples 6-8. ~ D
-4 was mixed in the mixing ratio shown in Table 4, and a polyisocyanate (Duranate (trade name)) was used as a curing agent so as to be equimolar to the hydroxyl value of the copolymer (A) and the non-aqueous dispersion resin (D). TSA-100, manufactured by Asahi Kasei Corporation)
Thereafter, the mixture was diluted with an Iwata cup using a thinner of xylene / butyl acetate = 7/3 (weight ratio) so as to be 15 seconds (25 ° C.) to prepare a paint. The prepared paint was applied by air spray onto a Bonderite # 144-treated steel sheet (manufactured by Nippon Test Panel Co., Ltd.) so that the dry film thickness became 30 μm, and cured at room temperature for 1 week to prepare a test plate. (Evaluation) For the prepared test plate, according to the following method,
The matting properties, water resistance and chemical resistance were evaluated, and the evaluation results are shown in Table 4. (1) Matting property The 60-degree specular reflectance (%) of the prepared test plate was measured with a gloss meter (manufactured by Nippon Denshoku Co., Ltd.). (2) Water resistance The prepared test plate was immersed in tap water and allowed to stand for 240 hours, and the appearance of the coating film (bulging, cracking, gloss return) was visually observed and evaluated according to the following criteria.

：: No abnormality in the coating film △: An abnormality occurred in a part of the coating film ×: An abnormality occurred in the entire coating film (3) Chemical resistance (alkali resistance) The prepared test plate was treated with a saturated calcium hydroxide aqueous solution. The coating was immersed and allowed to stand for 240 hours, and the appearance of the coating film (bulging, cracking, gloss return) was visually observed and evaluated according to the following criteria.

：: No abnormality in the coating film Δ: An abnormality occurred in a part of the coating film ×: An abnormality occurred in the entire coating film

[0069]

[Table 4] According to Table 4, the paints obtained in Comparative Examples 1 and 2 showed high evaluation results in the matting property column of 45 and 50 in gloss value, and evaluation results in the water resistance and chemical resistance columns of Δ ( Abnormality occurs in a part of the coating film), indicating that this coating material is inferior in matting property and inferior in coating film performance.

The evaluation result in the matting property column of the coating material obtained in Comparative Example 3 was 19, indicating that the coating material was inferior in matting property.

In the paint obtained in Comparative Example 4, the evaluation result in the matting property column was as high as 60 in gloss value, and the evaluation result in the water resistance and chemical resistance columns was Δ (part of the coating film). This paint is inferior in matting properties and inferior in coating film performance.

On the other hand, according to Table 4, Examples 1 to 3 are shown.
In the paint obtained in the above, the evaluation result in the matting property column was low at less than 10 in gloss value, and the evaluation result in the water resistance and chemical resistance columns was ○ (no abnormality in the coating film). Was. Thus, it is shown that the paints obtained in Examples 1 to 3 are excellent in matting properties, water resistance and chemical resistance.

[0073]

The resin composition for a matte coating of the present invention has excellent matting properties and is suitable for coatings.

The resin composition for a matte coating of the present invention has excellent water resistance of the coating film and is suitable for the coating.

The paint of the present invention has excellent matting properties,
It has excellent chemical resistance and water resistance of the coating film, and is suitable as a matte paint.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshio Oshikubo F-term (reference) 4J038 CC021 CC022 CC071 CC072 CC101 CC102 CD041 CD042 CF021 CF022 CG011 CG012 CG071 CG072 CG141 CG142 CG161 CG162 CG171 CG172 CH031 CH032 CH041 CH042 CH051 CH052 CH061 CH062 CH171 CH172 CH191 CH192 CH201 CH202 DB221 DB222 DG271 DG291 GA02 GA03 GA06 GA07 GA09 GA10 GA12 KA03 NA02 NA14 NA01

Claims (4)

[Claims] 1. [I] (a) 30 to 6 styrene monomers
0% by weight, (b) 5 to 70% by weight of an alkyl methacrylate monomer in which the alkyl group bonded to the ester is an alkyl group having 2 or less carbon atoms, and (c) the (a)
Copolymer (A) soluble in organic solvent obtained by polymerizing 0 to 65% by weight of ethylenically unsaturated monomer other than (b)
And [II] a copolymer insoluble in an organic solvent in an organic solvent-soluble copolymer (B) obtained by copolymerizing an ethylenically unsaturated monomer substantially free of a styrene-based monomer. A non-aqueous dispersion type resin (D) containing a coalesced crosslinked particle (C) and a matte coating resin composition. 2. The copolymer (A) and the non-aqueous dispersion type resin (D) each having a hydroxyl value of 5 to 150 mgKOH / g.
The resin composition for a matte paint according to claim 1, which is: 3. A coating composition comprising the resin composition according to claim 1 and a curing agent. 4. The coating according to claim 3, wherein the curing agent is a polyisocyanate.