JP2001131464A - Hardening resin composition for paint and article painted with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a paint composition with yields a coating with excellent weatherability, adhesion and overcoating properties and which gives a coating enough hydrophilicity to reduce the stain of the coating and does not form foams in the coating in painting. SOLUTION: A paint composition contains a vinyl copolymer component (A) which has a hydrolyzable silyl group, a weak solvent component (B) and an alkoxysilyl group-modified polybutadiene component (C) in a specific ratio and improves the decrease in stain preventing properties by the addition of an anti-foaming agent which is a problem in conventional paints.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a curable resin composition for paints. More specifically, for example, curable topcoat paints that can be suitably used for painting buildings, home appliances, industrial equipment, etc. made of metals, ceramics, glass, cement, ceramic base materials, plastics, wood, paper, fibers, and the like. The present invention relates to a resin composition and a painted product obtained by applying the curable resin composition for a paint.

[0002]

2. Description of the Related Art Conventionally, surfaces of industrial products such as ceramic compositions, buildings made of concrete and steel, and building materials are coated with paints such as fluororesin paints, acrylic urethane resin paints and acrylic silicone resin paints. By coating, the appearance of a building or the like is improved, and the anticorrosion property, weather resistance, and the like are improved. However, at the same time, due to the recent deterioration of the environment mainly in urban areas and an increase in awareness of protection of aesthetics and landscapes, it has been required that the above-mentioned paints have improved stain resistance. In response to this requirement, an acrylic silicone paint using a composition in which an organosilicate is blended with a hydrolyzable silyl group-containing acrylic resin has been developed as a paint that imparts stain resistance and has excellent weather resistance. () However, the paint has a problem that the hydrophilicity of the coating film and the effect of preventing contamination are slightly insufficient, and even if the hydrophilicity of the coating film and the effect of preventing contamination are obtained, bubbles are generated during coating. Had occurred. When an antifoaming agent is used to prevent foaming, there has been a problem that the hydrophilicity of the coating film is reduced and the effect of preventing contamination becomes insufficient. In addition, the acrylic silicone paint may have insufficient adhesiveness or may be blemishes due to re-application as compared with the fluorine-based paint and the acrylic urethane paint.

[0003]

SUMMARY OF THE INVENTION The present invention provides a coating film having excellent weather resistance and adhesion, and at the same time imparts sufficient hydrophilicity to the coating film to reduce the contamination of the coating film. An object of the present invention is to provide a coating composition that does not generate bubbles in a film.

[0004]

SUMMARY OF THE INVENTION The present invention provides a novel curable resin composition for coatings having the following constitution and a coated article obtained by applying the coating composition. Achieved. (1) A vinyl copolymer component having a hydrolyzable silyl group (A) component, a weak solvent (B) component, and the following general formula (1)

[0005]

Embedded image (Wherein, -R ¹ is -C _K H _2K at k = 1~12.-R ² is C _m
M = 1 to 3 with H _{2m + 1} . -Y is C _n H _{2n + 1} and n = 1 to 12
Or J = 1 to 3 with _{-O-C J H 2J + 1} . -X is -H,-
OH, -COOH or

[0006]

Embedded image Each of p, q, and r is a positive number, and 0.1 ≦ p / (p + q + r)
≦ 0.7. However, the order of each group of the repeating unit is not specified). Or the following general formula (2)

[0007]

Embedded image (Wherein, -R ¹ is -C _K H _2K at k = 1~12.-R ² is C _m
M = 1 to 3 with H _{2m + 1} . -R ³ - is -R ¹ - and k = 1 to 12 identical or different -C _K H _2K. Y is C _n H _{2n + 1} and n = 1
In 12 or _{-O-C J H 2J + 1} J = 1~3. -X is-
H, -OH, -COOH, or

[0008]

Embedded image -Z is -H, -OH, -COOH or -COOR ³ -
-R ³ is H is -R ¹ identical to or different C _K H _2K with k = 1
~ 12. Each of p, q, r, and s is a positive number, and 0.1 ≦ p /
(p + q + r + s) ≦ 0.7. However, the order of each group of the repeating unit is not specified), and a curable resin composition for coatings, which comprises an alkoxysilyl-modified polybutadiene (C) component having a number average molecular weight of 1500 to 100,000. 2) The curable resin composition for a coating according to 1), wherein the component (A) has a branched structure and / or a ring structure. 3) The component (A) is a vinyl monomer (a) having a silyl group represented by the following general formula (3), and a vinyl monomer (b) having a branched structure and / or a ring structure. ,
The curable resin composition for a coating according to 1) or 2), which is a vinyl copolymer obtained by copolymerizing another copolymerizable vinyl monomer (c) component.

[0009]

Embedded image (Wherein, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, when there are a plurality may .R ⁵ be different even if the same is a hydrogen atom, C 1 -C ~ 1
Represents an alkyl group having 0, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and when two or more are present, they may be the same or different. a
Represents an integer of 0 to 2. 4) The paint according to 3), which contains a vinyl monomer (d) having an alkyl group having 8 or more carbon atoms among other copolymerizable vinyl monomers of the component (c). Curable resin composition. 5) The curable resin composition for a paint according to any one of 1) to 4), wherein the weak solvent (B) component contains an aliphatic hydrocarbon. 6) In the general formula (1) or (2), at least a part of -X and -Z is -COOH, and -COOH is neutralized by a base selected from inorganic bases, ammonia, and amines. The curable resin composition for paint according to any one of 1) to 5), further comprising an alkoxysilyl group-modified polybutadiene (C) component. 7) The curable resin composition for a coating according to 1) to 6), wherein the component (C) is mixed in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the component (A). 8) The composition has the following general formula (4)

[0010]

Embedded image (Wherein, R ⁶ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group;
R ⁷ is a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, and b represents 0 or 1) and / or a partial hydrolytic condensation thereof. The curable resin composition for a paint according to any one of 1) to 7), further comprising a component (D). 9) The curable resin composition for paint according to any one of 1) to 8), wherein a curing catalyst (E) component is blended with the curable resin composition for paint. 10) The component (E) is selected from the group consisting of organic carboxylic acids, organic phosphoric esters, combined use of organic carboxylic acids and organic amines, combined use of organic phosphates and organic amines, and organometallic compounds. The curable resin composition for a paint according to any one of 1) to 9), wherein the curable resin composition is one kind or a mixture of two or more kinds. 11) The above-mentioned (A) 10 is added to the curable resin composition for paint.
1 to 2 parts by weight of a silicon compound and / or a partial hydrolysis condensate thereof (D) and 0.1 to 20 parts by weight of a curing catalyst (E) based on 0 parts by weight. ) The curable resin composition for a paint according to any one of the above items 10) to 10). 12) The curable resin composition for paints according to 1) to 11), wherein a defoamer for paints is blended with the resin composition for paints. 13) A coated article obtained by applying the coating composition according to any one of 1) to 12).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition for paints of the present invention has a main chain composed of a vinyl copolymer as a base resin having curability at room temperature in the presence of moisture. And / or a vinyl copolymer (A) having a hydrolyzable silyl group in the side chain.

The component (A) has the general formula (3)

[0013]

Embedded image (Wherein, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, when there are a plurality may .R ⁵ be different even if the same is a hydrogen atom, C 1 -C ~ 1
Represents an alkyl group having 0, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and when two or more are present, they may be the same or different. a
Represents an integer of 0 to 2. It is preferable that the vinyl copolymer has at least one hydrolyzable silyl group represented by formula (1) and has a branched structure and / or a ring structure.
Here, “the main chain is composed of a vinyl copolymer chain” means that a copolymer block of a compound having a polymerizable CＣC bond and another compound, such as a vinyl group or a vinylidene group, is a vinyl copolymer chain. It means that it constitutes the main chain of the copolymer (A).

It is sufficient that at least one reactive silyl group is present in one molecule, but it is preferable that 2 to 10 reactive silyl groups be present from the viewpoint of providing sufficient curability and relaxing internal stress.

In the above formula (3), R ⁴ is a hydrogen atom or a group having 1 to 10 carbon atoms, preferably, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group or an n-propyl group.
It is a C1-C4 alkyl group, such as a butyl group and an i-butyl group. When the alkyl group has a prime carbon number of more than 10, the reactivity of the hydrolyzable silyl group decreases. Also, when R ⁴ is a group other than an alkyl group such as a phenyl group and a benzyl group, the reactivity of the hydrolyzable silyl group is reduced.

In the general formula (3), R ⁵ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably, for example, an alkyl group having 1 to 4 carbon atoms as exemplified for the aforementioned R ⁴ ;
For example, it is a monovalent hydrocarbon group selected from an aryl group preferably having 6 to 25 carbon atoms such as a phenyl group and an aralkyl group preferably having 7 to 12 carbon atoms such as a benzyl group. Among them, an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint that the composition of the present invention is excellent in curability.

In the above general formula (3), (R ⁴ O) _3-a
Is such that 3-a is 1 or more and 3 or less, that is, a is 0
~ 2, but vinyl copolymer (A)
A is 0 or 1 from the viewpoint that the curability of
It is preferred that Therefore, the number of bonds of R ² is 0 to
It is preferably 1.

R ⁴ O or R present in the general formula (3)
^When the number of ⁵ is 2 or more, R ⁴ or R contained in 2 or more
⁵ may be the same or different. Specific examples of the hydrolyzable silyl group represented by the general formula (3) include, for example, a group contained in a monomer containing a reactive silyl group described below.

The monomer unit other than the vinyl monomer unit containing a hydrolyzable silyl group contained in the vinyl copolymer (A) may be a vinyl unit having a branched structure and / or a ring structure. And units derived from monomers and other copolymerizable monomers.

The vinyl copolymer (A) has a number average molecular weight of 1000 to 300 from the viewpoint that physical properties such as durability of a coating film formed using the composition of the present invention are excellent.
00, more preferably 3000 to
25,000. In the present invention, the vinyl copolymer (A) may be used alone or in combination of two or more.

An example of a method for producing the vinyl copolymer (A) will be described. The vinyl copolymer (A) is, for example, a vinyl monomer (a) containing a reactive silyl group represented by the general formula (3), a vinyl monomer having a branched structure and / or a ring structure (B) It can be produced by copolymerizing another copolymerizable vinyl monomer (c). Although it can be produced by copolymerizing the components (a) and (c), it is preferable to copolymerize the component (b). By copolymerizing the component (b), solubility in a weak solvent and dilutability can be improved,
As a result, the gloss value of the coating film can be improved.

The hydrolyzable silyl group-containing vinyl monomer (a) has a compound represented by the general formula (5)

[0023]

Embedded image (Wherein, R ⁸ , R ⁹ and a are the same as those described above), which preferably contains a monomer unit containing a hydrolyzable silyl group bonded to a carbon atom represented by the formula:

The monomer (a) is not particularly limited as long as it is a vinyl monomer containing a hydrolyzable silyl group represented by the general formula (3).

[0025]

Embedded image General formula (6) such as

[0026]

Embedded image (Wherein, R ⁸ , R ⁹ , and a are the same as those described above, and represent R ¹⁰ hydrogen atom or methyl group);

[0027]

Embedded image General formula (7) such as

[0028]

Embedded image (Wherein, R ⁸ , R ⁹ , R ¹⁰ and a are the same as described above, and n is 1
Shows an integer of ~ 12. A) a compound represented by the formula:

[0029]

Embedded image General formula (8) such as:

[0030]

Embedded image (Wherein R ⁸ , R ⁹ , R ¹⁰ , a and n are the same as described above);

[0031]

Embedded image General formula (9) such as:

[0032]

Embedded image (Wherein, R ⁸ , R ⁹ , R ¹⁰ and a are the same as above, and m is 1
Which represents an integer of from 14 to 14)

[0033]

Embedded image General formula (10) such as

[0034]

Embedded image Wherein R ⁸ , R ⁹ , R ¹⁰ and a are the same as above, and P is 0
And an (meth) acrylate having a hydrolyzable silyl group bonded to a carbon atom at the terminal via a urethane bond or a siloxane bond. Among these, the compound represented by the general formula (6) is preferable in terms of excellent copolymerizability and polymerization stability, and excellent curability and storage stability of the obtained composition.

These monomers (a) may be used alone or in combination of two or more. The monomer (a) is
As described above, the monomer containing a hydrolyzable silyl group represented by the general formula (3) in the obtained vinyl copolymer (A) is 1 to 90%, more preferably 3 to 70%, Especially 3 ~
It is preferable to use it so as to contain 50%.

The monomer (b) is not particularly limited as long as it is a vinyl monomer having a branched structure and / or a ring structure. Specific examples thereof include isobutyl (meth) acrylate and t-butyl. (Meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and 3,3,5-trimethylcyclohexyl (meth) acrylate.
Particularly preferably, isobutyl (meth) acrylate, t
-Butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. The monomer (b) is 2
More than one species may be used in combination.

The above-mentioned monomer (c) comprises the above-mentioned component (a),
Any monomer copolymerizable with the component (b) may be used. Specific examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Tert-butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth) Acrylonitrile,
Glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) ) Acrylamide, N-methyl (meth) acrylamide (meth)
Acryloylmorpholine, a macromonomer AS-
6, AN-6, AA-6, AB-6, AK-6, etc. (all manufactured by Toa Gosei Chemical Industry Co., Ltd.), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-
Methylol (meth) acrylamide, 4-hydroxystyrene vinyltoluene, Alonix 5700, 4-hydroxystyrene manufactured by Toa Gosei Chemical Industry Co., Ltd., HE-10, HE-20, HP manufactured by Nippon Shokubai Chemical Industry Co., Ltd. -1
And HP-20 (all of which are acrylate oligomers having a hydroxyl group at the terminal), Blemmer-PP series (polypropylene glycol methacrylate) Blemmer-PE series (polyethylene) manufactured by NOF Corporation Glycol monomethacrylate) Blemmer-PEP series (polyethylene glycol polypropylene glycol methacrylate) Blemmer-AP-400 (polypropylene glycol monoacrylate), Blemmer-A
E-350 (polyethylene glycol monoacrylate)
G) (glycerol monomethacrylate), N-methylol (meth) acrylamide and other hydroxyalkyl esters of (meth) acrylic acid, and a reaction of a hydroxyl group-containing compound with ε-caprolactone. Ε-caprolactone-modified hydroxyalkyl vinyl-based copolymer compound Placel FA-1,
Placel FA-4, Placel FM-
1, Placel FM-4 (manufactured by Daicel Chemical Industries, Ltd.), TONE M-201 (manufactured by UCC), a polycarbonate-containing vinyl compound (as specific examples,
HEAC-1 (manufactured by Daicel Chemical Industries, Ltd.) and the like. Further, a phosphate ester group-containing (meth) acrylic compound such as a condensation product of a hydroxyalkyl ester of (meth) acrylic acid and phosphoric acid or a phosphoric acid ester, containing a urethane bond or a siloxane bond (meth)
Acrylate and the like.

Further, styrene, α-methylstyrene,
Aromatic hydrocarbon vinyl compounds such as chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, and vinyltoluene; unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, and (meth) acrylic acid, and alkali metal salts thereof Acid salts of unsaturated carboxylic acids such as maleic anhydride, diesters of these acid anhydrides with alcohols or amines having a linear or branched chain having 1 to 20 carbon atoms, Esters of unsaturated carboxylic acids such as half esters; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; vinyl compounds containing amino groups such as vinyl pyridine and aminoethyl vinyl ether; itaconic diamide and crotonic amide , Maleic diamide, fumar Diamide, amide group-containing vinyl compounds such as N- vinyl pyrrolidone; 2-hydroxy ethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride,
Chloroprene, propylene, butadiene, isoprene,
Other vinyl compounds such as fluoroolefin maleimide, N-vinylimidazole, vinylsulfonic acid and the like can be mentioned.

These monomers (c) may be used alone or in combination of two or more.

Among these components (c), it is preferable to include a vinyl monomer (d) having an alkyl group having 8 or more carbon atoms.

The component (d) may be a vinyl monomer having an alkyl group having 8 or more carbon atoms, and specific examples thereof include, for example, octyl (meth) acrylic acid.
, Decyl (meth) acrylate, lauryl (meth) acrylate, palmitoyl (meth) acrylate, stearyl (meth) acrylate, octadecanoyl (meth) acrylate, oleyl (meth) acrylate, etc. Is mentioned. Among them, decyl (meth) acrylate, lauryl (meth) acrylate, and palmitoyl (meth) acrylate are preferable because of their good weather resistance and good solubility in weak solvents.
And stearyl (meth) acrylate are preferred. Particularly preferred are lauryl (meth) acrylate, stearyl (meth) acrylate and isobornyl (meth) acrylate.

These monomers may be used alone.
More than one species may be used in combination.

The total amount of the monomers (b), (c) and (d) used may be appropriately adjusted according to the type and the amount of the monomer (a) used. 10-99%, more preferably 30-97%, especially 5
It is preferably from 0 to 97%. The amount of the monomer (b) used is 2 to 90% of the polymerization component, preferably 3 to 90%.
It is 80%, particularly preferably 5 to 70%. The monomers (c) and (d) may be appropriately adjusted depending on the Tg, molecular weight, and the like of the target polymer (A).

In the present invention, for the purpose of further improving the weather resistance of a coating film formed from the obtained composition of the present invention, for example, a segment formed by a urethane bond or a siloxane bond in the main chain may be used. It may be introduced at the time of producing the vinyl copolymer (A) within a range not exceeding 50%.

The vinyl copolymer (A) may contain a group such as a carboxyl group or an amino group. In such a case, the curability and adhesion are improved, but the vinyl copolymer (A) is bonded to the polymer chain. In the case of a carboxyl group or an amino group, the activity is weak, and it is difficult to obtain a cured product having good characteristics even if they are used instead of a curing catalyst to cure.

The vinyl copolymer (A) is disclosed in, for example, JP-A-54-36395 and JP-A-57-5595.
It can be produced by a hydrosilylation method or a solution polymerization method using a monomer containing a hydrolyzable silyl group described in JP-A No. It is particularly preferable to produce the polymer by a solution polymerization method using a contained monomer and an azo radical polymerization initiator such as azobisisobutyronitrile. The amount of the weak solvent (B) used is not particularly limited. Here, the weak solvent is a third type organic solvent of the Industrial Safety and Health Act and a solvent corresponding to the third type organic solvent. Those containing an aliphatic hydrocarbon as the component (B) are preferred. Examples of such examples include those containing hydrocarbons having a high boiling point (150 ° C. or higher), such as terpenes and mineral spirits. For example, naphtha No-6 (manufactured by Exxon Chemical Co., Ltd.), P-20 (Japan Energy) (stock)
Exxol D40 (Exxon Chemical Co., Ltd.).

The solvent (B) can be used as a polymerization solvent,
It may be used as a solvent, but in consideration of odor and repaintability
Most preferably, they are used for both. In addition, the solution weight
In such a case, if necessary, for example, n-dodecylmel
Captan, t-dodecylmercaptan, n-butylmer
Captan, γ-mercaptopropyltrimethoxysila
Γ-mercaptopropyltriethoxysilane, (C
H _ThreeO)_ThreeSi-SS-Si (OCH_Three)_Three, (CH
_ThreeO)_ThreeSi-S₈-Si (OCH_Three)_ThreeChain transfer agents such as
Can be obtained singly or in combination of two or more.
The molecular weight of the cryl copolymer (A) may be adjusted. When
In particular, for example, γ-mercaptopropyl trimethoxy
Chain transfer with alkoxysilyl groups such as orchids in the molecule
In the case of using an agent, the terminal of the vinyl copolymer (A)
Since a hydrolyzable silyl group can be introduced into
New The amount of the chain transfer agent used depends on the total amount of the polymerization components used.
0.05-10% of the quantity, especially 0.1-8%
Is preferred. The alkoxysilyl group-modified poly of the present invention
The butadiene (C) component has the general formula (1)

[0048]

Embedded imageRepresented by the number average molecular weight of 1500 to 100000
It is an alkoxysilyl group-modified polybutadiene. (formula
Where -R1 is -C_kH_2kAnd k = 1 to 12. -R2 is-
C_mH_{2m + 1}M = 1-3. -Y is -C_nH_{2n + 1}And n = 1 to
12, or -OC _JH_{2J + 1}And J = 1-3. -X is-
H, -OH, -COOH, or

[0049]

Embedded image Each of p, q, and r is an integer, and 0.1 ≦ p / (p + q +
r) ≦ 0.7. Provided that-of each group of the repeating unit
(A)-(B)-(C) -the order is not specified. Alternatively, the alkoxysilyl group-modified polybutadiene (D) component of the present invention is represented by the following general formula (2), and has a number average molecular weight of 1500 to 100,000.

[0050]

Embedded image (Wherein, -R ¹ is -C _k H _2k - in at k = 1~12.-R2 is -C _m H _{2m + 1} with m = 1~3.-Y is -C _n H _{2n + 1 n} = 1
12 or -O-C _J H _{2J + 1} in J = 1 to 3,. -X is -H, -OH, -COOH, or

[0051]

Embedded image (-Z is -H, -OH, -COOH, or -COOR
¹¹ same -R ¹¹ is a -R ¹ -H or different -C _K H _2K -
And K = 1 to 12. Each of p, q, r, and s is an integer.
1 ≦ p / (p + q + r + s) ≦ 0.7. However, the-(A)-(D)-(B)-(C) -order of each group of the repeating unit is not specified.

In the general formula (1) or (2), -X
Preferably, at least a part of -Z and -Z is -COOH, and the -COOH is neutralized by a base selected from inorganic bases, ammonia and amines. Examples of the inorganic base include sodium hydroxide and calcium hydroxide, and examples of the amines include triethylamine, dimethylethanolamine, 2-amino, and 2-methyl-1.
-Pentanol and the like.

The alkoxysilyl group-modified polybutadiene (C) component of the present invention has a number average molecular weight of 1500 to 1000.
00, preferably 3,000 to 50,000, more preferably 5,000 to 30,000. If the average molecular weight is less than 1500, the effect of making the coating film hydrophilic tends to be insufficient, and if it exceeds 100,000, coating film defects such as cissing tend to occur. The repeating unit represented by formula (1)-(A)-(B)-(C)-or the repeating unit represented by formula (2)-(A)-(D)-
The molar ratio of (B)-(C) -dividing- (A)-is 100 ×
p / (p + q + r) or 100 × p / (p + q + r +
s) is 10 to 70 mol%. If the amount is less than 10 mol%, the effect of making the coating film hydrophilic becomes insufficient. It is not possible to introduce more than 70 mol% of alkoxysilyl groups.

The alkoxysilyl group-modified polybutadiene represented by the general formula (1) is produced, for example, by subjecting a butadiene polymer obtained by ion-polymerizing a butadiene monomer to a thiol having an alkoxysilyl group by an ene addition reaction. . The alkoxysilyl group-modified polybutadiene (C) component represented by the general formula (2) includes, for example, a butadiene polymer obtained by ion-polymerizing a butadiene monomer, a thiol having an alkoxysilyl group, and a thiol having no alkoxysilyl group. Can be produced by an ene addition reaction.

The polybutadiene used in the ene addition reaction contains two types of repeating units in the polymer, that is, one of which has a 1,2-vinyl structure (-in the formula).
(B)-), and the other has a repeating unit having a 2,3-vinyl structure (the structure of-(C)-in the formula) as an isomer and a repeating unit having a 1,2-vinyl structure. 10 mol% or more, preferably 30 mol% or more is required. When the amount is less than 10 mol%, even if an alkoxysilyl group is introduced into all of them by an ene addition reaction, the above-mentioned-
The molar ratio of (A)-(100 × p / (p + q + r) or 100 × p / (p + q + r + s)) is insufficient at 10%.
It is not possible to introduce an alkoxysilyl group in an amount exceeding 70 mol%, because the ene addition reaction does not proceed due to a steric hindrance effect.

Examples of the thiol having an alkoxysilyl group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane,
There are 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltributoxysilane, mercaptomethyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, and 10-mercaptodecyltrimethoxysilane. Examples of the thiol having no alkoxysilyl group include n-dodecyl mercaptan, 2-mercaptoethanol, thioglycolic acid, and 3-mercaptopropionic acid 2-ethylhexyl ester.

The ene addition reaction is preferably carried out in a solvent in which the reactants and products are dissolved, from the viewpoint of controlling the temperature and controlling the molecular weight during the reaction. As the solvent, a single solvent or a mixed solvent such as an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, an ester-based solvent, and a ketone-based solvent can be used. Alcohol solvents can also be used, but should be selected in consideration of the effect of the alkoxysilyl group on the reactivity.
In order to promote the ene addition reaction, radical polymerization of organic peroxides such as benzoyl peroxide and t-butyl peroxide, azo compounds such as hydrogen peroxide and azo-bis-isobityronitrile is initiated. Agents are available. In addition, substances that promote a redox reaction with thiols such as amines can also be used as reaction accelerators.

A modified product can be produced by reacting a functional group (hydroxyl group, carboxylic acid, epoxy group) contained in the molecule of polybutadiene with a suitable reactant. The reactants that can be used may be monofunctional or polyfunctional.
For example, there are isocyanates such as tolylene diisocyanate, carboxylic acids such as oleic acid, amines such as hexamethylene diamine, and alcohols such as octanol. These reactants may be low molecular or high molecular. Examples of the polymer reactant include a polyacrylate having a carboxyl group or an epoxy group at a terminal.

The amount of the alkoxysilyl group-modified polybutadiene (C) component to be used is 0.01 to 30 parts by weight, preferably 0.1 to 2 parts by weight, based on the vinyl copolymer (A) component.
0 parts, more preferably 0.5 to 10 parts by weight. 0.
If the amount is less than 01 parts by weight, the defoaming effect tends to decrease, and if it is 30 parts by weight or more, the weather resistance tends to decrease.

In the present invention, general formula (4)

[0061]

Embedded image (Wherein, R ⁶ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group;
R ⁷ is a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, and b represents 0 or 1) and / or a hydrolytic condensate thereof. It is preferred to use (D). By blending the component (D), the stain resistance of a coating film formed from the composition of the present invention can be further improved. Further, the adhesion between the coating film and the object to be coated can be improved.

In the general formula (4), R ⁶ has 1 to 10 carbon atoms, preferably, for example, a methyl group, an ethyl group, n
-Propyl group, i-propyl group, n-butyl group, alkyl group having 1 to 4 carbon atoms such as i-butyl group, aryl group,
It is preferably a monovalent hydrocarbon group selected from an aryl group having 6 to 9 carbon atoms such as a phenyl group and an aralkyl group, and preferably an aralkyl group having 7 to 9 carbon atoms such as a benzyl group.

When the alkyl group has more than 10 carbon atoms, the reactivity of the partially hydrolyzed condensate (D) of the silicon compound is reduced. Also, when R ⁶ is other than the above-mentioned alkyl group, aryl group and aralkyl group, the reactivity is lowered.

In the general formula (4), R ⁷ has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms similar to R ^6.
Aralkyl group, an aryl group, preferably an aryl group or an aralkyl group similar carbon number 6-9 and R ^6, preferably a monovalent hydrocarbon selected from the same aralkyl group having a carbon number of 7 to 9 and R ⁶ It is.

In the general formula (4), (R ⁶ O) _4-b
Is selected such that 4-b is 3 or more, that is, b is 0 to 1. However, from the viewpoint that the curability of a coating film formed from the composition of the present invention is improved, b is It is preferably 0.

When the number of (R ⁶ O) _4-b present in the general formula (4) is two or more, R ³ contained in two or more may be the same or different.

Specific examples of the silicon compound include tetraalkyl silicates such as tetramethyl silicate, tetraethyl silicate, ESI28, tetra n-propyl silicate, tetra i-propyl silicate, tetra n-butyl silicate and tetra i-butyl silicate. Methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrisec-octyloxysilane, methyltriphenoxysilane, methyltrimethoxysilane Examples include silane coupling agents such as isopropoxysilane and methyltributoxysilane.

Specific examples of the partially hydrolyzed condensate (D) of the silicon compound include those obtained by adding water to the above tetraalkylsilicate or trialkoxysilane and condensing it by a conventional method. For example, MSI51, MSI53, ESI40, E
SI48, HAS-1, HAS-10 (all manufactured by Colcoat Co., Ltd.), MS51, MS56, MS56S, MS
51B15, MS56SB5 (Mitsubishi Chemical Corporation)
M silicate 51, methyl silicate 56, silicate 40, silicate 45, silicate 48, ES4
8, a partially hydrolyzed condensate of tetraalkoxysilane such as FR-3 (all manufactured by Tama Chemical Co., Ltd.);
FP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The above silicon compound (D) may be used alone or in combination of two or more.

Among the partial hydrolytic decomposition condensates (D) of the silicon compound, the compatibility with the vinyl copolymer (A) and the curability of the obtained composition of the present invention are good, and In terms of controlling the adhesion of contaminants, since the hardness of a coating film formed by using MSI5 is superior, MSI5
1, MS51, MS56, MS56S (partially hydrolyzed condensate of tetramethoxysilane), ESI40, silicate 45, silicate 48, ESI48, ES-48
(Partial hydrolysis condensate of tetraethoxysilane), FR
It is preferable to use a partially hydrolyzed condensate of tetraalkoxysilane such as -3 (partially methoxy-substituted condensate of partially hydrolyzed condensate of tetraethoxysilane). Compounds such as G.48, ES-48, ESI48, and FR-3 are more preferable in that the compounding amount can be reduced.

The amount of the partially hydrolyzed condensate (D) of the silicon compound is 2 to 100 parts by weight of the component (A).
200 parts by weight, preferably 2 to 50 parts by weight, more preferably 2 to 30 parts by weight. When the use amount of (D) exceeds 200 parts, the appearance such as the surface gloss of the coating film is reduced,
Cracks and the like tend to occur.

As the curing catalyst (E), organic carboxyl,
There are organic amines, and combinations thereof. Specific examples of organic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, octylic acid, 2-ethylhexanoic acid, decanoic acid, dodecanoic acid, benzoic acid, phthalic acid, fumaric acid, and maleic acid , Succinic acid, itaconic acid and their anhydrides. Specific examples of the organic amine include a primary amine such as laurylamine, a tertiary amine such as triethylamine and dimethyllaurylamine, and a cyclic amine such as morpholine. As the combination of the organic carboxylic acid and the organic amine, acetic acid / dimethyllaurylamine, hexanoic acid / laurylamine, 2-ethylhexanoic acid / dimethyllaurylamine, and 2-ethylhexanoic acid / laurylamine are used in consideration of the balance between the curing activity and the pot life. Combinations are preferred. More preferably, 2
-A combination of ethylhexanoic acid / dimethyllaurylamine and 2-ethylhexanoic acid / laurylamine.
Specific examples of the organic phosphate include di (2-ethylhexyl) monophosphate and di (2-ethylhexyl) diphosphate. Di (2-ethylhexyl) monophosphate is preferred from the viewpoint of the balance between curing activity and pot life. This organic phosphate may be used alone or in combination with the above-mentioned organic amine. A preferred combination is di (2-ethylhexyl). Monophosphate / dimethyllaurylamine and di (2-ethylhexyl) monophosphate / laurylamine, more preferably di (2-ethylhexyl) monophosphate / dimethyllaurylamine. The combination substance may be used alone or in combination of two or more.

As the curing catalyst (E), an organometallic compound can also be used. Typical examples thereof include an organotin compound and an aluminum chelate. Dioctyltin bis (2-ethylhexyl maleate), dioctyltin oxide or condensate of dibutyltin oxide and silicate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin distearate, dibutyltin diacetylacetate Nart, dibutyltin bis (ethyl maleate)
G), dibutyltin bis (butyl maleate), dibutyltin bis (2-ethylhexyl maleate), dibutyltin bis (oleyl maleate), stanna octoate, tin stearate, di-n-butyltin rallate There is an oxide. Examples of the tin compound having an S atom in the molecule include dibutyltin bisisononyl-3-mercaptopropione-
Dioctyltin bisisononyl-3-mercaptopropionate, octylbutyltinbisisononyl-3-mercaptopropionate, dibutyltinbisisooctylthioglucolate, dioctyltin bisisooctylthioglucolate, octyl Butyltin bisisooctylthioglucolate is an example of the organotin compound.

Examples of the aluminum chelate compound include ethyl acetoacetate aluminum diisopropylate,
Aluminum tris (acetyl acetate), aluminum tris (ethyl acetoacetate), aluminum monoacetyl acetonate bis (ethyl aceto acetate), alkyl acetyl acetate aluminum diisopropylate and the like can be mentioned.

As the aluminum chelate compound, when aluminum tris (ethyl acetoacetate) and aluminum tris (acetyl acetonate) are blended with isocyanate, a good balance between storage stability and pot life is obtained. This is preferable in that the contact angle of the coating film becomes small.

The curing catalyst (E) may be used alone, or two or more different types or the same type may be used in combination.

The curing catalyst (E) is used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 13 parts by weight, more preferably 0.5 to 13 parts by weight, per 100 parts by weight of the component (A).
To 10 parts by weight. When the use amount of (E) exceeds 20 parts, appearance properties such as surface gloss of a coating film formed using the composition tend to decrease.

The curable resin composition for paints of the present invention is significantly improved in defoaming properties by incorporating a generally used antifoaming agent for paints. In addition, since the curable resin composition for a coating composition of the present invention contains an alkoxysilyl group-modified polybutadiene (C) component, the resulting coating film shows good stain resistance with almost no decrease in stainability.

In the present invention, a pigment can be blended if necessary. As the pigment, various pigments can be used depending on a desired color. Representative pigment types include, for example, titanium oxide, ultramarine, navy blue,
Inorganic pigments such as zinc white, red iron, lead white, carbon black, transparent iron oxide, and aluminum powder; organic pigments such as azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, and phthalocyanine pigments And the like.

The mixing ratio of the pigment is preferably 0 to 150 parts with respect to 100 parts of the component (A).

Further, the above composition contains additives such as diluents, ultraviolet absorbers, light stabilizers, anti-sagging agents and leveling agents; fibrous materials such as nitrocellulose and cellulose acetate butyrate; epoxy resins, melamine resins, Resins such as vinyl chloride resin, fluororesin, chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, and polysiloxane may be appropriately added.

The curable resin composition for a coating material of the present invention is applied to an object to be coated by a usual method such as dipping, spraying, application using a brush or the like, and is usually at room temperature or at about 30 ° C. or higher. Bake and cure.

The curable composition for paints of the present invention is generally used as a multilayer film. In this case, a permeable epoxy sealer, an acrylic rubber-based waterproof coating, an acrylic emulsion, an inorganic filler-containing reactive epoxy emulsion, or the like is used as the undercoat. Further, for the purpose of ensuring the durability (prevention of cracks, etc.) by improving the adhesion to the base coat, the adhesion to the substrate, the impact resistance, and the followability to the undercoat, acrylics usually used as a top coat. Paints, urethane paints, and fluororesin paints can be used as the intermediate coat and / or undercoat. Further, as these paints, low-contamination type paints containing the above-mentioned silicate components can also be used. The curable resin composition for paints of the present invention is, for example, metal, ceramics, glass, cement, ceramic moldings,
It is suitably used as a top coating for buildings, home appliances, industrial equipment and the like made of plastic, wood, paper, fiber and the like. Next, the curable resin composition for a top coating composition of the present invention will be described in more detail based on Examples, but the present invention is not limited to only these Examples.

Production Example 1 (Production of Vinyl Copolymer (A)) A weak solvent (Naphtha No. 6) was placed in a reactor equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel. Exxon Chemical Co., Ltd.) (30 parts) was charged and heated to 110 ° C. while introducing nitrogen gas. Thereafter, 8 parts of γ-methacryloxypropyltrimethoxysilane, methyl methacrylate
35 parts, i-butyl methacrylate 17 parts, lauryl methacrylate 40 parts, terpene 30 parts and AI
A mixture consisting of 1.5 parts of BN (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped at a constant rate over 4 hours by a dropping funnel.

After completion of the dropwise addition, 0.2 part of V-59 (2,2'-azobis (2-methylbutyronitrile) and 20 parts of a weak solvent were added dropwise at a constant speed over 0.5 hour. After aging for 1.5 hours, the mixture was cooled, and a weak solvent was added to the resin solution to obtain a vinyl copolymer (A) having a resin solid content of 50%.
-1 was obtained. The average molecular weight of the obtained vinyl copolymer (A) -1 was 10,000.

Production Example 2 (Production of Vinyl Copolymer (A)) A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel was used as a weak solvent (LAWS, shell). (Chemical Co., Ltd.) was charged, and the temperature was raised to 110 ° C. while introducing nitrogen gas. Thereafter, it is composed of 10 parts of γ-methacryloxypropyltrimethoxysilane, 33 parts of stearyl methacrylate, 37 parts of methyl methacrylate, 20 parts of t-butyl methacrylate, 0.3 parts of AIBN, and 30 parts of a weak solvent. The mixture was dropped at a constant speed over 4 hours by a dropping funnel.

After completion of the dropping, 0.03 part of V-59 and 20 parts of a weak solvent were dropped at a constant speed over 0.5 hour, and
After aging for 1.5 hours at 0 ° C., the mixture was cooled, and a weak solvent was added to the resin solution to obtain a vinyl copolymer (A) -2 having a resin solid concentration of 50%. Obtained vinyl copolymer (A)-
The average molecular weight of 2 was 25,000.

Production Example 3 (Production of vinyl copolymer (A)) In Production Example 1, 10 parts of γ-methacryloxypropyltrimethoxysilane and 3 parts of lauryl methacrylate were used.
The resin solids concentration was changed in the same manner as in Production Example 1 except that 1 part, methyl methacrylate was changed to 53 parts, i-butyl methacrylate was changed to 6 parts, and AIBN was changed to 0.9 part. 50
% Of a vinyl copolymer (A) -3 was obtained. The number average molecular weight of the obtained vinyl copolymer (A) -3 was 15,000.

Production Example 4 (Production of vinyl copolymer (A)) In Production Example 1, 13 parts of γ-methacryloxypropyltrimethoxysilane and 0 parts of lauryl methacrylate were used.
Production Example 1 except that 7 parts of methyl methacrylate, 70 parts of i-butyl methacrylate and 10 parts of 2-ethylhexyl acrylate were used, and AIBN was changed to 1.5 parts. In the same manner as in the above, a vinyl copolymer (A) -4 having a resin solid content of 50% was obtained. The number average molecular weight of the obtained vinyl copolymer (A) -4 was 10,000.

Production Example 5 (Production of Vinyl Copolymer (A)) In Production Example 1, in addition to the solvent initially charged, ESi48 (manufactured by Tama Chemical) (E) -1 which is a silicate compound
Was charged in the same manner, and the others were polymerized in the same manner to obtain a vinyl copolymer (A) -5 having a solid content of 50%. The number average molecular weight of the obtained vinyl copolymer (A) -5 is 1000
It was 0.

Production Example 6 (Production of vinyl copolymer (A): when component (b) is not contained) In Production Example 1, 34 parts of lauryl methacrylate was added.
Except that the monomer composition was changed to 58 parts of methyl methacrylate, 0 parts of i-butyl methacrylate, and 1.5 parts of AIBN, the resin solids concentration was 5 in the same manner as in Production Example 1.
0% of a vinyl copolymer (A) -6 was obtained. The number average molecular weight of the obtained vinyl copolymer (A) -6 was 10,000.

Production Example 7 (Synthesis of alkoxysilyl group-modified polybutadiene (C) -1) 3-mercaptopropylmethyldimethoxysilane 72 was placed in a 1-liter reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, a cooling tube, and a dropping funnel. Then, the mixture was heated and stirred while blowing nitrogen gas into it. When the temperature inside the reactor is 11
While maintaining the temperature at 5 ± 5 ° C., a solution prepared by mixing and dissolving 100 g of polybutadiene (1,2 vinyl content 95% or more, number average molecular weight 100) in 100 g of xylene is added dropwise over 2 hours. Next, a solution in which 4 g of benzoyl peroxide is dissolved in 37.9 g of xylene is added dropwise over 2 hours while maintaining the temperature in the reactor at 115 ± 5 ° C. In addition, 120 ° C
After stirring for 2 hours while maintaining the temperature, the mixture was cooled to 30 ° C. or lower to obtain a reaction product. As a result of analyzing the obtained reaction product by an infrared spectrometer, it was found that the reaction product was a mixture of polybutadiene and 3-mercaptopropylmethyldimethoxysilane.
The absorption around 10, 990 and 1640 cm ^-1 was remarkably reduced, and it was confirmed that a reaction product due to ene unreactable reaction was obtained. The molecular weight of the obtained reaction product was measured by GPC (gel permeation chromatography).
1700.

Production Example 8 (Synthesis of alkoxysilyl group-modified polybutadiene (C) -2) 3-mercaptopropyltrimethoxysilane 145 was placed in a 1-liter reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, a cooling tube, and a dropping funnel. 0.5 g and n-dodecyl mercaptan (10.5 g) were added, and the mixture was heated and stirred while blowing nitrogen gas therein. While maintaining the temperature in the reactor at 115 ± 5 ° C., 100 g of polybutadiene (1,2 vinyl content 95% or more, number average molecular weight 300) was added to 100 g of xylene.
Is added dropwise over 2 hours. next,
38.0 g of t-butyl peroxide in 78.0 g of xylene
Is dissolved over 2 hours while maintaining the temperature in the reactor at 115 ± 5 ° C. Further, stirring was continued for 2 hours while maintaining the temperature at 120 ° C., and then cooled to 30 ° C. or lower to obtain a reaction product. The obtained reaction product was analyzed in the same manner as in Production Example 7, and as a result, it was confirmed that a reaction product due to an ene unreactable reaction was obtained. The molecular weight was 7,800.

Example 1 According to the formulation shown in Table 1, 50 parts of pigment (F) -1 and a solution of vinyl copolymer (A) -1 obtained in Production Example 1 (30 parts in terms of resin solid content) Was dispersed in a paint conditioner for 2 hours using a glass bead to obtain a paste-like composition. Next, a solution of the vinyl copolymer (A) -2 obtained in Production Example 2 (70% in terms of resin solid content) was added to this composition.
Part) and an alkoxysilyl group-modified polybutadiene (C)
-1 is the total resin solid content of (A) -1 and (A) -2 is 100
3 parts per part was added, diluted with the solvent (B) -1 and stirred with a stirrer for 5 minutes to obtain a white enamel having a solid concentration of 45%.

Example 2 Similarly, according to the composition shown in Table 1, 50 parts of a pigment and a solution of the vinyl copolymer (A) -1 obtained in Production Example 1 (30 parts in terms of resin solid content) were glass beads. Was dispersed in a paint conditioner for 2 hours to obtain a paste-like composition. Next, a solution of the vinyl copolymer (A) -2 obtained in Production Example 2 in this composition (70 parts in terms of resin solid content)
And an alkoxysilyl group-modified polybutadiene (C) -1
Was added to 100 parts of the total resin solid content of (A) -1 and (A) -2, diluted with the solvent (B) -1 and stirred with a stirrer for 5 minutes to obtain a solid content concentration of A white enamel of 60% was obtained. 20 parts of silicate compound (D) -1 was added to the obtained white enamel. Next, the curing catalyst (E)
-1 with respect to a total of 100 parts of the vinyl copolymer (A).
Was added. Further, the solvent (B) was added and the mixture was stirred for 5 minutes using a stirrer to obtain a composition having a solid concentration of 45%.

Example 3 A solution (in terms of resin solid content) of 50 parts of (F) -1 as a pigment and the vinyl copolymer (A) -1 obtained in Production Example 1
30 parts were dispersed with a paint conditioner using a glass bead for 2 hours to obtain a paste-like composition. next,
A solution of the vinyl copolymer (A) -2 obtained in Production Example 2 (70 parts in terms of resin solid content), 10 parts of a silicon compound or the like (D) -1 and 10 parts of an alkoxysilyl group modified with this composition Polybutadiene (C) -1 is converted to (A) -1 and (A)
-3 was added to 100 parts of the total resin solid content, diluted with the solvent (B) -1, stirred with a stirrer for 5 minutes,
A white enamel having a solid content of 60% was obtained. One part of the curing catalyst (E) -1 was added to the obtained white enamel. Further, the solvent (B) was added and the mixture was stirred for 5 minutes using a stirrer to obtain a composition having a solid concentration of 45%.

Examples 4 to 9 According to the formulations shown in Table 1, the solid content was adjusted to 4
5% of the composition was obtained. Comparative Example 1 (white enamel) Kanekazemurak (YC3623 / Kaneka Chemical Industry Co., Ltd.)
AM1532, curing catalyst ZT118Z) to prepare a white enamel. Titanium oxide CR-956 as pigment
6 parts, AM1532 (30 parts in terms of resin solid content), xylene paint conditioner using glass beads
For 2 hours to obtain a paste-like composition. Next, Y
C3623 (70 parts in terms of resin solids) and xylene were added, and the mixture was stirred for 5 minutes using a stirrer to give a solids concentration of 60.
% Of white enamel was obtained. One part of a curing catalyst ZT118Z was added to the obtained white enamel. Further, the solvent (B) was added and the mixture was stirred for 5 minutes using a stirrer to obtain a composition having a solid concentration of 45%.

Comparative Example 2 (White Enamel) Kaneka Zemulak (# 3653 / A) manufactured by Kanegafuchi Chemical Industry Co., Ltd.
M1532, curing catalyst BT159Z) to prepare a white enamel. Titanium oxide CR-9566 parts, AM1532 (30 parts in terms of resin solid content) as pigments, and xylene in a paint conditioner using a glass bead.
The mixture was dispersed for a time to obtain a paste-like composition. Next, # 36
53 (70 parts in terms of resin solid content) and xylene were added, and the mixture was stirred for 5 minutes using a stirrer to obtain a white enamel having a solid content concentration of 60%. A curing catalyst BT1 is added to the obtained white enamel.
One part of 59Z was added. Further, the solvent (B) was added, and the mixture was stirred for 5 minutes using a stirrer.
Was obtained.

[0099]

[Table 1] The surface state, gloss, stain resistance, weather resistance, contact angle, adhesiveness, and shrinkage during recoating of the obtained coating film were evaluated according to the following methods. Regarding (a) to (e), the obtained composition was coated on an aluminum plate (A5052P) so as to have a dry film thickness of 20 to 30 μm to obtain a sample. (A) Surface condition The coating film surface was visually observed and evaluated based on the following evaluation criteria. (Evaluation Criteria) A: No cracks were observed and the surface condition was good. B: Fine cracks are partially observed. C: Cracks are observed throughout. (B) Gloss The gloss of the coating film surface is determined by GM according to JIS K5400.
It measured using the 268 gloss meter (made by Minolta). (60
(Gloss) (c) Stain resistance (ΔL value) The color of the paint film surface after two weeks of painting and the paint film surface after being left outdoors for 3 months (exposed outdoors) in Settsu City, Osaka is CR-30.
Each was measured using a 0 color difference meter (manufactured by Minolta), and the difference (ΔL value) was obtained from the obtained L value (brightness). (D) Weather resistance (gloss retention) Using a sunshine weatherometer, the gloss of the coating surface immediately after formation and the gloss of the coating surface after 2,000 hours were measured, and the gloss retention after 2,000 hours ( %). (E) Contact angle The initial contact angle of the coating film surface on the 7th day after painting and the contact angle after leaving it outdoors in Settsu City, Osaka for 3 months (outdoor exposure) were measured with a contact angle measuring instrument (CA- manufactured by Kyowa Interface Science Co., Ltd.). S150). (F) A sample was prepared by the following method for the evaluation of shrinkage.

A phthalic acid-based enamel (SD
Marine; manufactured by Kansai Paint Co., Ltd.), 1.4 to 1.6 kg
/ M ² was exposed to a sunshine weatherometer test for 600 hours, and then the compositions shown in Table 2 were applied to a dry film thickness of 20 to 30 μm to obtain samples. One day after coating the composition obtained with the composition shown in Table 2, a scratch was made on the sample to reach the substrate with a cutter, and the composition obtained with the composition shown in Table 2 was again placed on the wound. The next day, the second day, the third day,
On the sixth day, the tenth day, and the 14th day, a top coat was applied with a brush, and the state of the coating film in each period was observed, and it was confirmed whether there was any smudge or the like. In the above evaluation, phthalic acid-based enamel (SD
The same evaluation was performed when a chlorinated rubber-based enamel (Kurinrabatect; manufactured by Kansai Paint Co., Ltd.) was applied instead of Marin (Kansai Paint Co., Ltd.).

The following criteria were used to evaluate the degree of shrinkage during recoating.

(Evaluation Criteria) ；: No abnormality is observed in the coating film. Δ: Bleeding occurs only in the cut portion. ×: Spots occurred on the entire surface of the recoat portion. (G) Adhesion A commercially available E-spec undercoat on the slates (Isamu Paint Co., Ltd.)
Was applied, and a top coat was applied the next day. Room temperature (2
(3 °, humidity 55%)
Evaluation was performed by measuring the grid adhesion in accordance with 5400. The same evaluation was performed on phthalic acid-based enamels and chlorinated rubber-based enamels for which the evaluation was made. (Evaluation results) 10: 100/100 8: 80/100 6: 60/100 4: 40/100 2: 20/100 0: 0/100 (h) Odor The composition is spread or roll coated. The odor was evaluated according to the following criteria.

(Evaluation Criteria) ：: No nose-like odor is felt, and the paint can withstand coating for a long time. ×: Strong odor, cannot withstand long-time coating. (I) Defoaming property ：: No abnormality is observed in the coating film. Δ: Some unevenness is observed in the coating film. X: The coating film defect is seen in the whole coating film.

The compositions formulated in Examples 1 to 9 are as follows. Solvent (B) (B) -1; Naphtha No. 6 (manufactured by Exxon Chemical Co., Ltd.) (B) -2; P-20 (manufactured by Japan Energy Co., Ltd.) (B) -3; Exol D40 (Exxon Chemical Co., Ltd.)
Silicate compound (D) (D) -1; ethyl silicate 48 (manufactured by Corcoat) (D) -2; silicate 48 (manufactured by Tama Chemical) (D) -3; ES-48 ( (D) -4; FR-3 (manufactured by Tama Chemical) Curing catalyst (E) (E) -1; dibutyltin bisbutylmaleate (E) -2; dioctyltinbis (2-ethylhexylmaleate) (E) -3; Dibutyltin bisoleyl maleate (E) -4; Mixture of 2-ethylhexanoic acid / dimethyldodecylamine blended so that the acid / base equivalent becomes 1 / 1.03, and pigment The following three types were used. (F) -1: CR-95 (white: titanium oxide) manufactured by Ishihara Sangyo Co., Ltd. (F) -2: Iron oxide (red) (F) -3: Phthalocyanine blue

[0105]

[Table 2] As shown in Table 2, the cured coating films obtained in Examples 1 to 9 had excellent recoatability and a small contact angle on the surface when the alkoxysilyl group-modified polybutadiene (C) was blended, and had excellent resistance. It can be seen that the compound shows a stain resistance and further shows a stain resistance when a silicon compound (D) is further added.

[0106]

The curable resin composition for coatings of the present invention dissolves very well in a weak solvent, and the coated product obtained by applying the same has excellent recoatability on various substrates and undercoats. As shown, paint with low odor is provided. Furthermore, when an alkoxysilyl group-modified polybutadiene (C) is blended, the contact angle of the surface is small, and excellent contamination resistance is exhibited.
When the silicone compound (D) is blended, the contact angle of the coating film is smaller and the coating film is excellent in stain resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C09D 157/10 C09D 157/10 183/06 183/06 (72) Inventor Jin Tamai 2 Ibo, Takasago City, Hyogo Prefecture 5-18-18-405 (72) Inventor Toshiro Nambu 7172-2-20 Tsutsujigaoka, Tarumizu-ku, Kobe City, Hyogo Prefecture Reference) 4J038 CA022 CA102 CL001 DL051 DL052 EA011 GA01 GA03 GA06 GA07 GA13 GA15 JA02 JA35 JB01 JC24 JC32 JC38 KA04 KA06 KA07 KA09 MA14 NA03 NA05 NA06 NA12 NA24 PA20 4J100 AP01P AP01Q AS02P AS02Q BA02H BA02H BAH BAH BAH BAH BC54H CA01 CA04 CA05 CA16 CA27 CA31 DA01 HA31 HA61 HB34 HB43 HC36 HC43 HC54 HC70 HC78 HE14 JA01

Claims (13)

[Claims] 1. A vinyl copolymer component having a hydrolyzable silyl group (A), a weak solvent (B), and the following general formula (1): (Wherein, -R ¹ is -C _K H _2K at k = 1~12.-R ² is C _m
M = 1 to 3 with H _{2m + 1} . -Y is C _n H _{2n + 1} and n = 1 to 12
Or J = 1 to 3 with _{-O-C J H 2J + 1} . -X is -H,-
OH, -COOH or Each of p, q, and r is a positive number, and 0.1 ≦ p / (p + q + r)
≦ 0.7. However, the order of each group of the repeating unit is not specified). Alternatively, the following general formula (2): (Wherein, -R ¹ is -C _K H _2K at k = 1~12.-R ² is C _m
M = 1 to 3 with H _{2m + 1} . -R ³ - is -R ¹ - and k = 1 to 12 identical or different -C _K H _2K. Y is C _n H _{2n + 1} and n = 1
In 12 or _{-O-C J H 2J + 1} J = 1~3. -X is-
H, -OH, -COOH or -Z is -H, -OH, -COOH or -COOR ³ -
-R ³ is H is -R ¹ identical to or different C _K H _2K with k = 1
~ 12. Each of p, q, r, and s is a positive number, and 0.1 ≦ p /
(p + q + r + s) ≦ 0.7. However, the order of each group of the repeating unit is not specified), and a curable resin composition for coatings, which comprises an alkoxysilyl-modified polybutadiene (C) component having a number average molecular weight of 1500 to 100,000. 2. The curable resin composition according to claim 1, wherein the component (A) has a branched structure and / or a ring structure. (3) The component (A) is a vinyl monomer having a silyl group represented by the following general formula (3): The component (a), a vinyl monomer having a branched structure and / or a ring structure ( 3. The curable resin for paint according to claim 1, wherein the curable resin is a vinyl copolymer obtained by copolymerizing the component (b) and other copolymerizable vinyl monomers (c). Composition. Embedded image (Wherein, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, when there are a plurality may .R ⁵ be different even if the same is a hydrogen atom, C 1 -C ~ 1
Represents an alkyl group having 0, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and when two or more are present, they may be the same or different. a
Represents an integer of 0 to 2. ) 4. A vinyl monomer (d) having an alkyl group having 8 or more carbon atoms among other copolymerizable vinyl monomers of the component (c). The curable resin composition for a paint according to the above. 5. The curable resin composition for a paint according to claim 1, wherein the weak solvent (B) component contains an aliphatic hydrocarbon. 6. In the above general formula (1) or (2),
An alkoxysilyl group-modified polybutadiene (C), wherein at least a part of X and -Z is -COOH, and the -COOH is neutralized by a base selected from inorganic bases, ammonia and amines. The curable resin composition for a paint according to any one of claims 1 to 5, which comprises a component. 7. The composition according to claim 1, wherein the component (C) is added in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the component (A).
7. The curable resin composition for a coating according to items 6 to 6. 8. The composition according to claim 1, wherein the composition has the following general formula (4): (Wherein, R ⁶ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group;
R ⁷ is a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, and b represents 0 or 1) and / or a partial hydrolytic condensation thereof. The curable resin composition for a paint according to any one of claims 1 to 7, further comprising a component (D). 9. The curable resin composition for paints according to claim 1, wherein a curing catalyst (E) is added to the curable resin composition for paints. 10. The composition according to claim 1, wherein the component (E) is an organic carboxylic acid,
An organic phosphate, a combination of an organic carboxylic acid and an organic amine, a combination of an organic phosphate and an organic amine, or a mixture of one or more selected from the group consisting of organometallic compounds. 10. The curable resin composition for a paint according to any one of 1 to 9. 11. The curable resin composition for a coating composition contains the silicon compound and / or 100 parts by weight of (A).
Or containing the partial hydrolysis condensate (D) in an amount of 2 to 200 parts by weight and the curing catalyst (E) in an amount of 0.1 to 20 parts by weight. Curable resin composition for paints. 12. The curable resin composition for paints according to claim 1, wherein a defoamer for paints is blended with the resin composition for paints. 13. A coated product obtained by applying the coating composition according to any one of claims 1 to 12.