JP2002338899A - Curable resin composition for coating material and coated product coated with the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition for a coating material which can suitably be dissolved in a solvent substantially free of an aromatic component, and a coating film having good properties by using the curable resin composition for a coating composition. SOLUTION: The curable resin composition for a coating composition comprises (A) a copolymer whose main chain is substantially composed of a vinyl polymer and having at least one hydrolyzable silyl group at the terminal of the main chain and/or in the side chain in the molecule, simultaneously at least one alcoholic hydroxyl group at the terminal of the main chain and/or in the side chain, and furthermore >=50 wt.%, based on the total monomers, >=4C branched alkyl (meth)acrylate monomer and/or >=8C alkyl (meth)acrylate monomer and (B) a solvent substantially free of an aromatic component. The coating film is obtained by using the curable resin composition for a coating material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition for coatings that can be suitably dissolved even in a solvent containing substantially no aromatic component.

[0002]

2. Description of the Related Art As paints having high weather resistance, for example, fluorine resin paints, acrylic urethane resin paints, acrylic silicone resin paints and the like are known. In recent years, since environmental issues have become more important in recent years, the odor and safety of conventional strong solvent type solvents have been regarded as problems, and paints prepared by dissolving acrylic urethane resin or acrylic silicone resin in weak solvent type solvents Is being developed. For example, Japanese Patent Application Laid-Open
JP-A-228903 and JP-A-11-279480 disclose an acrylic silicone resin using a weak solvent as a solvent, and JP-A-2000-297242 discloses a combination of a silicone crosslink and a urethane crosslink using a weak solvent as a solvent. Resin is described.

[0003] However, even with a weak solvent type solvent,
Most of them contain an aromatic component, and there is a problem that the odor and safety of the solvent are not sufficient.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a curable resin composition for coatings which can be suitably dissolved in a solvent containing substantially no aromatic component.

[0005]

According to the present invention, the main chain is substantially composed of a vinyl polymer, and the terminal of the main chain and / or the side chain has the general formula (I)

[0006]

Embedded image (In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and 7 to 12 carbon atoms.
A is a monovalent hydrocarbon group selected from aralkyl groups
2 to 2. ) Contains at least one hydrolyzable silyl group bonded to the carbon atom in the molecule, and at least one alcoholic hydroxyl group at the terminal and / or side chain of the main chain, and further has an alkyl group Is a branched alkyl (meth) acrylate monomer having 4 or more carbon atoms and / or an alkyl (meth) acrylate monomer having an alkyl group having 8 or more carbon atoms in all monomers.
A curable resin composition for coatings comprising a vinyl copolymer (A) at 0% by weight or more and a solvent (B) containing substantially no aromatic component. (Claim 1) Formula (II) (R ³ O) _4-b —Si—R ⁴ _b (II) (wherein R ³ is carbon C 1 -C 10 alkyl group, a monovalent hydrocarbon group selected from aryl and aralkyl groups, when there are a plurality may be different even in the same .R ⁴ is C 1 -C A monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group, and b represents 0 or 1.) and / or a partially hydrolyzed condensate thereof (C) 0 .1
The curable resin composition for a paint according to claim 1, wherein the composition comprises from 100 to 100 parts by weight. (Claim 2) A polyisocyanate compound (D) having a isocyanate group content of 0.1 to 1.5 equivalents to the hydroxyl group of the curable resin composition for paints is further used as a crosslinking agent in the curable resin composition for paints. The curable resin composition for a paint according to claim 1 or 2, which is blended. (Claim 3) The curable resin composition for coatings is further added with a curing catalyst (E) 0.01.
The curable resin composition for a paint according to any one of claims 1 to 3, wherein the curable resin composition is blended with 10 to 10 parts by weight. (Claim 4) The curable resin composition for a paint according to any one of claims 1 to 4, wherein the solvent (B) having substantially no aromatic component has an aromatic content of 1.0% by weight or less. (Claim 5) A coated article obtained by applying the curable resin composition for a paint according to claim 3. (Claim 6) A coated article obtained by applying the curable resin composition for a paint according to claim 4. (Claim 7) A coated product obtained by applying the curable resin composition for a coating according to claim 5. (Claim 8).

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention contains a vinyl copolymer having a silyl group bonded to a hydrolyzable group as a base resin having curability at room temperature in the presence of moisture.

[0008] The main chain of the vinyl copolymer is substantially composed of a vinyl monomer and, if necessary, a main chain obtained by copolymerizing other monomers.

Here, "the main chain consists of a vinyl copolymer chain" refers to a compound having a polymerizable carbon-carbon double bond or a compound having a polymerizable double bond, such as a vinyl group or a vinylidene group. It means that the copolymer block with another compound constitutes the main chain of the vinyl copolymer.

It is sufficient that at least one hydrolyzable silyl group is present in one molecule.
Further, from the viewpoint of relaxing the internal stress, it is preferable that 2 to 10 are present.

As the vinyl copolymer, a hydrosilylation method described in, for example, JP-A-54-36395 and JP-A-57-55954, or a monomer containing a reactive silyl group is used. Although it can be produced by a solution polymerization method, it is particularly preferable that it is produced by a solution polymerization method using a monomer having a reactive silyl group and a radical polymerization initiator from the viewpoint of ease of synthesis and the like.

The hydrolyzable group of the silicon group bonded to the hydrolyzable group includes a halogen group and an alkoxy group. Among them, an alkoxy group is useful because of easy control of the reaction.

The number average molecular weight of the vinyl copolymer is as follows:
2000-30000 is preferred. More preferably, 3
2,000 to 25,000. If the number average molecular weight is less than 2,000, the curability and weather resistance tend to decrease, and 3
If it exceeds 0000, the appearance and workability tend to decrease.

The vinyl copolymer is, for example, a monomer (a) containing a polymerizable double bond and a reactive silyl group bonded to a carbon atom, and a branched (C) alkyl group having 4 or more carbon atoms. Alkyl (meth) acrylate (b), alkyl (meth) acrylate having an alkyl group of 8 or more (c), monomer (d) containing an alcoholic hydroxyl group, and other It can be produced by copolymerizing a vinyl monomer (e). Specific examples of the vinyl monomer (a) containing a reactive silyl group include:
For example,

[0015]

Embedded image General formula (III) such as

[0016]

Embedded image (Wherein, R ⁵ represents a hydrogen atom or a methyl group;
⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. May be. R ⁷ represents an alkyl group having 1 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. A) a compound represented by the formula:

[0017]

Embedded image General formula (IV) such as

[0018]

Embedded image (Wherein, R ⁵ , R ⁶ , R ⁷ , and a are the same as above, and n is 1 to
Indicates an integer of 12. A) a compound represented by the formula:

[0019]

Embedded image General formula (V) such as:

[0020]

Embedded image (Wherein, R ⁵ , R ⁶ , R ⁷ , a, and n are the same as described above);

[0021]

Embedded image General formula (VI) such as:

[0022]

Embedded image Wherein R ⁵ , R ⁶ , R ⁷ and a are the same as above, and p is 1
Which represents an integer of from 14 to 14)

[0023]

Embedded image General formula (VII) such as

[0024]

Embedded image (Wherein, R ⁵ , R ⁶ , R ⁷ and a are the same as above, and q is 0 to 2)
And a (meth) acrylate having a reactive silyl group bonded to a carbon atom at the terminal via a urethane bond or a siloxane bond, and the like. .

Among these, the compounds represented by the above formula (V) are preferred from the viewpoints 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, 1 to 90% by weight of a monomer containing a reactive silyl group is contained in the obtained vinyl copolymer,
It is preferably used so that it is contained in an amount of up to 70% by weight, especially 3 to 50% by weight.

Specific examples of the branched alkyl (meth) acrylate monomer (b) having 4 or more carbon atoms in the alkyl group include, for example, a vinyl monomer having a branched structure and / or a cyclic structure. There is no particular limitation as long as it is a body,
Isobutyl (meth) acrylate, t-butyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
3,3,5, -Trimethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
Acrylate, tetrahydrofurfuryl (meth) acrylate, and 3,3,5-trimethylcyclohexyl (meth) acrylate are exemplified. Particularly preferably, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate.

The monomer (b) may be used alone,
Two or more kinds may be used in combination.

Specific examples of the alkyl (meth) acrylate monomer (c) having an alkyl group having 8 or more carbon atoms include, for example, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (Meth) acrylic
And palmitoyl (meth) acrylate, stearyl (meth) acrylate, octadecanoyl (meth) acrylate and oleyl (meth) acrylate. Of these, decyl (meth) acrylate, lauryl (meth) acrylate, palmitoyl (meth) acrylate, and stearyl (meth) acrylate are preferred from the viewpoint of good weather resistance and good solubility in solvents. Particularly preferably,
Lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate.

The above monomer (c) may be used alone,
Two or more kinds may be used in combination.

Alkyl (meth) acrylate monomer (b)
And / or the total amount of (c) used is 50% by weight, more preferably 70% by weight or more. 50% by weight
If it is less than 1, the solubility and dilutability of the vinyl polymer decrease.

Further, the alcoholic hydroxyl group-containing vinyl monomer (d) is not particularly limited.
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, -Hydroxystyrene, Alonix 5 manufactured by Toa Gosei Chemical Industry Co., Ltd.
700 (trade name), HE-1 manufactured by Nippon Shokubai Chemical Industry Co., Ltd.
0, HE-20, HP-10 and HP-20 (all are trade names) (all of which are acrylic acid ester oligomers having a hydroxyl group at the end), Blemmer PP series (polypropylene glycol methacrylate) manufactured by NOF Corporation, Blemmer PE series (polyethylene glycol monomethacrylate), Blemmer PEP series (polyethylene glycol polypropylene glycol methacrylate), Blemmer AP400 (polypropylene glycol monoacrylate), Blemmer AE35
0 (polyethylene glycol monoacrylate) and Blemmer GLM (glycerol monomethacrylate)
(Both trade names), hydroxyl-containing vinyl compound and ε-
Examples thereof include ε-caprolactone-modified hydroxyalkyl vinyl copolymerizable compound by reaction with caprolactone, and a polycarbonate-containing vinyl compound such as HEAC-1 (trade name) manufactured by Daicel Chemical Industries, Ltd. These may be used alone or in combination of two or more.

Of these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (2-hydroxyethyl (meth) acrylate) can impart excellent acid resistance and water resistance to the coating film. Meta)
Acrylates and 4-hydroxybutyl (meth) acrylate are preferred.

The amount of the alcoholic hydroxyl group-containing vinyl monomer (d) is preferably 3 to 30% by weight, more preferably 5 to 20% by weight. When the content is 3% by weight or less, the coating film hardness, adhesion, and weather resistance tend to decrease, and when the content is 30% by weight or more, the recoating property tends to decrease.

When the alcoholic hydroxyl group-containing vinyl monomer (d) is copolymerized, a urethane bond can be introduced into the cured coating film, and the adhesion to the organic coating film can be further improved. Become.

Specific examples of the other copolymerizable monomer (e) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3,3,5, -trimethylcyclohexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate,
Lauryl (meth) acrylate, palmitoyl (meth)
Acrylate, stearyl (meth) acrylate, octadecanoyl (meth) acrylate, oleyl (meth)
Acrylate, isobornyl (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, macromonomers AS-6, AN-6, AA-6, AB-6, AK-5
(Toa Gosei Chemical Industry Co., Ltd.), P
lacelFA-1, Placcel FA-4, P
lacel FM-1, Placel FM-4,
HEAC-1 (manufactured by Daicel Chemical Industries, Ltd.),
Phosphoric acid ester group-containing (meth) acrylic compounds such as condensation products of hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or phosphoric acid esters, (meth) acrylates containing urethane bonds or siloxane bonds, and styrene Aromatic vinyl compounds such as α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene and vinyltoluene; unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid and (meth) acrylic acid; Salts of alkali metal salts, ammonium salts, amine salts, etc. of unsaturated carboxylic acids such as maleic anhydride;
Esters of unsaturated carboxylic acids such as diesters or half esters with 20 linear or branched alcohols or amines; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; vinyl pyridine, aminoethyl Amino group-containing vinyl compounds such as vinyl ethers; amide group-containing vinyl compounds such as itaconic acid diamide, crotonic acid amide, maleic acid diamide, fumaric acid diamide, N-vinylpyrrolidone; 2-hydroxyethyl vinyl ether;
Other vinyl compounds such as methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinylimidazole, and vinyl sulfonic acid.

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 a main chain, a monomer Not more than 30% by weight of a segment derived from a monomer other than the monomer (a), the monomer (b), the monomer (c), the monomer (d), and the monomer (e). It may be introduced at the time of production of the vinyl copolymer within the range.

These may be used alone or in combination of two or more. The vinyl copolymer may contain a group such as a carboxyl group or an amino group, and in that case, curability and adhesion are improved.

The solvent (B) containing substantially no aromatic component means that the aromatic component is 1.
0% by weight or less, further 0.7% by weight or less, especially 0.1% by weight.
5% by weight of solvent is preferred. In addition, regarding the amount of its use, considering harmfulness and regulations such as the PRTR law,
% Is preferably used. Particularly preferably, 90
% Or more.

Other solvents that can be used include alcohols, esters, ketones and the like. In the case of alcohols, reaction with isocyanates is considered, and ester and ketone solvents are considered to attack the substrate. Therefore, it is preferable that the amount used is as small as possible.

Specific examples of the solvent (B) containing substantially no aromatic component include Exol D40, Exol D80, Isobar G (manufactured by ExxonMobil Corp.), IP Solvent (Idemitsu Petrochemical Co., Ltd.) )
Such as naphthene or paraffinic solvents, hydrogenated products of xylene such as MCH (manufactured by Nippon Steel Chemical Co., Ltd.) or other solvents containing aromatics, and so-called hydrocarbons such as hexane and heptane. Solvent.

The solvent (B) containing substantially no aromatic component may be used as a polymerization solvent or a diluting solvent, but may be used for both in consideration of odor and harmfulness. Most preferred. Further, after polymerization with a solvent other than the above-mentioned solvent (B), the solvent may be removed once, and then diluted and dissolved again with the solvent (B) containing no aromatic component.

The silicon compound and / or its partially hydrolyzed condensate (C) (hereinafter referred to as silicon compounds (C)) has the general formula (II) (R ³ O) _4-b -Si
—R ⁴ _b (II) (wherein, R ³ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 7 carbon atoms)
A monovalent hydrocarbon group selected from 12 aralkyl groups, R
⁴ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and b represents 0 or 1). A component mainly for improving the stain resistance of the coating film, wherein the vinyl copolymer (A) 10
The amount is preferably 0.1 to 100 parts by weight, more preferably 5 to 80 parts by weight, and still more preferably 10 to 50 parts by weight with respect to 0 parts by weight.

When the amount of the silicon compound (C) is less than 0.1 part by weight, the stain resistance of the coating film decreases,
If it exceeds 100 parts by weight, cracks tend to occur, the coating film becomes brittle, and the curability tends to decrease.

In the general formula (II), R ³ has 1 to 10 carbon atoms, preferably, for example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
An alkyl group having 1 to 4 carbon atoms such as a butyl group, preferably an aryl group having 6 to 9 carbon atoms such as a phenyl group,
Preferably, it is a monovalent hydrocarbon group selected from aralkyl groups 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 silicon compound (C) decreases. R ³ is the alkyl group, the aryl group,
Even in the case other than the aralkyl group, the reactivity decreases.

In the general formula (II), R ⁴
Carbon atoms 1 to 10, preferably similar to several atoms and R ³
4 alkyl group, preferably 6 to 9 carbon atoms as defined for R ^3.
, Preferably a monovalent hydrocarbon selected from the same aralkyl groups having 7 to 9 carbon atoms as R ³ .

In the general formula (II), (R ³ O)
_4-b is selected so that 4-b is 3 or more, that is, a is 0 or 1, but from the viewpoint that the curability of the coating film formed from the composition of the present invention is improved. , B is preferably 0.

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

Specific examples of the silicon compound (II) include, for example, tetramethyl silicate, tetraethyl silicate, tetra n-propyl silicate, tetra i
-Propyl silicate, tetra n-butyl silicate,
Tetraalkyl silicates such as tetra-i-butyl silicate; methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3
Silane coupling agents such as -glycidoxypropyltrimethoxysilane, methyltrisec-octyloxysilane, methyltriphenoxysilane, methyltriisopropoxysilane, and methyltributoxysilane.

Specific examples of the silicon compounds (C) include those obtained by adding water to the above-mentioned tetraalkylsilicate or trialkoxysilane and condensing it by a usual method.
MSi53, ESi28, ESi40, HAS-1, H
EMS series such as AS-10, EMS70 / 30 and EMS60 / 40, EPSi series (all manufactured by Colcoat Co., Ltd.), MS51, MS56, MS51B15, M
S56S, MS56SB5 (Mitsubishi Chemical Corporation)
Manufactured), silicate 40, silicate 45, silicate 4
8, partially hydrolyzed decomposed condensates of tetraalkyl silicates such as FR-3 (manufactured by Tama Chemical Co., Ltd.) and partially hydrolyzed condensates of trialkoxysilanes such as AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.) Decomposition decomposition condensate;

Among the silicon compounds (C),
MSi 51 and MS5 are used in terms of controlling the adhesion of contaminants to the coating film formed using the vinyl resin (A).
1, MS56, MS51B15, MS56S, MS56
SB5 (partially hydrolyzed decomposition condensate of tetramethoxysilane), ESi 40, silicate 40, silicate 45,
Partially hydrolyzed and condensed condensate of tetraalkyl silicate such as silicate 48, ESi48 (partially hydrolyzed condensate of tetraethoxysilane), FR-3, EMS series (co-partially hydrolyzed condensate of tetramethoxysilane and tetraethoxysilane) It is preferable to use

Further, among the silicon compounds (C), MS56 and MS56S having a high degree of condensation, silicate 45, silicate 48ESi48, FR-3, EMS
Series and the like are preferable from the viewpoint of controlling the adhesion of contaminants to the coating film from the beginning.

The solvent (B) containing substantially no aromatic component means that the aromatic component is 1.
0% by weight or less, further 0.7% by weight or less, especially 0.1% by weight.
5% by weight of solvent is preferred. In addition, the amount of its use is 50% in consideration of hazards and regulations such as the PRTR law.
% Is preferably used. Particularly preferably, 80
% Or more.

The curable resin composition for paints of the present invention contains a polyisocyanate compound (D) as a crosslinking agent.

Examples of the polyisocyanate compound (D) include compounds having two or more isocyanate groups in one molecule. Examples thereof include aliphatic compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; Alicyclic compounds such as xylene diisocyanate, isophorone diisocyanate and cyclohexane diisocyanate; and aromatic compounds such as tolylene diisocyanate and diphenylmethane diisocyanate. These may be used alone,
Two or more kinds may be used in combination.

Blocked polyisocyanate compounds can also be used. Specifically, the above polyisocyanate compounds can be used as lactam-based blocking agents such as ε-caprolactam; alcohol-based blocking agents such as ethanol, propanol and butanol. Agents: those blocked with an oxime blocking agent such as acetoxime. These may be used alone or in combination of two or more.

The mixing ratio of the above-mentioned alcoholic hydroxyl group-containing vinyl copolymer and the above-mentioned polyisocyanate compound or block polyisocyanate compound is such that the above-mentioned polyisocyanate compound or block polyisocyanate is added to the above-mentioned alcoholic hydroxyl group-containing vinyl copolymer. It is preferable that the isocyanate group of the polyisocyanate compound be 0.5 to 1.5 equivalents. More preferably, 0.8 to
1.2 equivalents. If it is less than 0.5 equivalent, the weather resistance and water resistance of the coating film tend to decrease, and if it exceeds 1.5 equivalent, the appearance and weather resistance tend to decrease.

The curable resin composition for paints of the present invention may further contain a curing catalyst (E).

Specific examples of the curing catalyst (E) include organic tin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate, dibutyltin bis (mercapto acid ester), and the like. Ethyl acetoacetate aluminum diisopropylate, aluminum tris (acetyl acetate), aluminum tris (ethyl acetoacetate), aluminum monoacetylacetonate bis (ethyl acetoacetate), alkyl acetyl acetate aluminum diisopropylate Organic titanate compounds;
Organometallic compounds such as organozinc compounds can be mentioned. These may be used alone or in combination of two or more.
Further, specific examples of the curing catalyst (E) include an acid catalyst. Examples of the acid catalyst include a phosphate ester catalyst, a sulfonic acid catalyst, a system in which phosphoric acid is mixed with an organic amine, a system in which sulfonic acid and an organic amine are mixed, and a system in which an organic amine is mixed with an organic carboxylic acid.

These can be added in an amount of 0.1 to 10 parts by weight based on the hydrolyzable silyl group-containing vinyl copolymer (A) component. The amount is preferably from 0.2 to 8 parts by weight, particularly preferably from 0.5 to 5 parts by weight.

The above curing catalysts can be used alone or in combination of two or more.

Specific examples of the organic phosphoric ester type include:
Phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate
Phosphoric acid or a phosphoric acid ester such as diethyl phosphate, didodecyl phosphate and the like. In the sulfonic acid system, dodecylbenzenesulfonic acid is typical.

Among these, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate and the like are preferred from the viewpoint of solubility in a solvent containing substantially no aromatic component.

In the solution polymerization, if necessary, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, (CH ₃ O) ₃ Si-S-S-S-S
i (OCH ₃ ) ₃ , (CH ₃ O) ₃ Si—S ₈ —Si (OC
The molecular weight of the obtained vinyl copolymer may be adjusted by using a chain transfer agent such as H ₃ ) ₃ alone or in combination of two or more kinds. In particular, when a chain transfer agent having an alkoxysilyl group in a molecule such as γ-mercaptopropyltrimethoxysilane is used, a reactive silyl group can be introduced into a terminal of the vinyl copolymer, which is preferable. . The amount of the chain transfer agent to be used is preferably 0.05 to 10% by weight, particularly preferably 0.1 to 8% by weight, based on the total amount of the polymerization components used.

Since the vinyl polymer is moisture-curable, it is preferable to use a dehydrating agent for the purpose of maintaining stability. Examples of the dehydrating agent include a hydrolyzable ester compound. Specific examples thereof include hydrolyzable ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthobutyrate, triethyl orthobutyrate, and dimethoxymethane. , 1,1-dimethoxyethane, 1,1-dimethoxyethane, 1,1-dimethoxypropane, 1,1-dimethoxybutane; methyl silicate, ethyl silicate, methyl trimethoxy silane and the like. Of these, methyl orthoacetate is preferred from the viewpoint of dehydration effect. These may be used alone or in combination of two or more.

The curable resin composition for paints of the present invention may contain, for example, additives usually used in paints, such as diluents, ultraviolet absorbers, light stabilizers, anti-sagging agents, leveling agents; silanes such as aminosilanes. Coupling agents; cellulose such as nitrocellulose, cellulose acetate butyrate; epoxy resin, melamine resin, vinyl chloride resin,
Resins and pigments such as fluororesin, chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, and polysiloxane may be appropriately added.

The pigment is not particularly limited, and its amount is not particularly limited. For example, inorganic pigments such as titanium oxide, ultramarine, navy blue, zinc white, red iron oxide, graphite, lead white, carbon black, transparent iron oxide, aluminum powder, etc., which are commonly used in paints, azo pigments, triphenylmethane pigments, quinoline pigments Pigments such as organic pigments such as pigments, anthraquinone pigments and phthalocyanine pigments are selected.

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, brushing, spraying, or the like. Bake at ℃ or more to cure.

Next, the curable resin composition for paints of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples. Production Example Production of Vinyl Polymer The component (A) in Table 1 was charged into a reactor equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube, and dropping funnel.
After the temperature was raised to 110 ° C. while introducing nitrogen gas, a mixture of the components (A) in Table 1 was dropped at a constant speed from the dropping funnel over 5 hours. Next, the mixed solution of the component (c) was dropped at a constant speed over 1 hour. Thereafter, the mixture was continuously stirred at 110 ° C. for 2 hours and cooled to room temperature. Finally, the component (D) in Table 1 was added and stirred.

Each vinyl copolymer of the obtained hydrolyzable silyl group- and hydroxyl group-containing vinyl polymers (A-1 to A-8) and hydrolyzable silyl group-containing vinyl copolymer (A-9) Table 1 shows the solid content concentration of the union and the number average molecular weight measured by GPC.

[0072]

[Table 1] In addition, the component in a table | surface shows the following. Solvent Exol D40; IP1620 manufactured by Exxon-Mobil Chemical Co., Ltd .; MCH (methylcyclohexane) manufactured by Idemitsu Petrochemical Co., Ltd .; Pegasol AN45 manufactured by Nippon Steel Chemical Co., Ltd. (containing about 30% of an aromatic component); Example manufactured by the company Solvent dilutability ESi48 as a silicon compound (C) with respect to 100 parts by weight of the resin solid content of the vinyl polymer (A) obtained.
After adding 20 parts by weight of (a partially hydrolyzed condensate of tetraethyl silicate manufactured by Colcoat Co., Ltd.), the mixture was diluted with a polymerization solvent so that the solid content concentration became 50% by weight. Then, 2 parts by weight based on 100 parts by weight of the vinyl polymer (A)
Under an atmosphere of 0 ° C. and 5 ° C., Exol D40 was added as a solvent (B) containing substantially no aromatic component at a certain ratio, and the dilutability until white turbidity was observed was confirmed.

[0073]

[Table 2] Preparation of white enamel MS56S (tetramethylsilicate manufactured by Mitsubishi Chemical Corporation) as silicon compounds (C) based on 100 parts by weight of the resin solid content of the vinyl copolymer (A) -1 obtained in Production Example 1. Of a partially hydrolyzed condensate) was added to the mixture, to which 40 parts by weight of titanium oxide (CR-95, manufactured by Ishihara Sangyo Co., Ltd.) was added as a pigment, and glass paint was used for 2 hours with a paint conditioner. It was dispersed to obtain a white enamel having a solid content of 60% by weight.

With respect to 100 parts by weight of the solid content of the obtained white enamel, TSE as polyisocyanate (D) was used.
100 (manufactured by Asahi Kasei Kogyo Co., Ltd.) is equivalent to 1.0 equivalent part of isocyanate groups based on hydroxyl groups of the vinyl polymer, and 0.4 parts by weight of U-20 (manufactured by Nitto Kasei Corporation) as a curing catalyst (E). Curing adjusting component (F) Further, Exol D40 was added as a thinner and stirred to obtain a composition having a solid content of 45% by weight.

According to the composition shown in Table 3,
A composition having a solid content of 45% by weight was obtained.

The obtained composition was immediately applied on an aluminum plate (A5052P) by air spray so that the dry film thickness became about 30 μm, and cured (cured) at 23 ° C. for 7 days to obtain a coating film. Table 3 shows the results.

[0077]

[Table 3] The surface state, gloss, contact angle, adhesion, bleeding upon recoating, stain resistance, and weather resistance of the obtained coating film were evaluated according to the following methods. (A) Surface condition The coating film surface was visually observed and evaluated based on the following evaluation criteria. (Evaluation criteria) A: The surface condition is good. B: Clouding and spots are partially observed. C: Clouding and spots 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
(C) Gloss) (c) Contact angle The static contact angle of the coating film surface with water on the 7th day after formation was measured with a contact angle measuring device (CA-S150, manufactured by Kyowa Interface Science Co., Ltd.). (D) Adhesion The obtained composition was coated on a slate plate using a multi-layer coating material RE (Isamu Tile W; manufactured by Isamu Paint Co., Ltd.) and a base adjustment coating material E (aqueous soft surf SG; 1.4)
The coating was applied to 1.6 kg / m ² , cured at 23 ° C. for 1 day, and coated with the white enamel composition shown in Examples at a dry film thickness of 20 to 30 μm to obtain a sample. 23 ° C,
After curing for 7 days under the condition of 55% RH, a 1 mm grid adhesion test was carried out in accordance with JIS K5400.

Further, an aluminum plate (A5052P)
A weak solvent type epoxy (mild bosei; SK Kaken Co., Ltd.) was applied on the upper surface so as to have a dry film thickness of 30 μm, and exposed outdoors for 2 weeks. Thereafter, dirt on the surface of the coating film was gently wiped, and the white enamel composition shown in the Examples was dried to a film thickness of 20 to
The sample was painted at 30 μm. 23 ° C, 55% R
After curing under H condition for 7 days, immersed in 50 ° C warm water for 7 days,
A 1 mm grid adhesion test was performed in accordance with JIS K5400.

Further, a clear resin composition is applied to a glass plate so as to have a dry film thickness of 20 to 30 μm (provided that TSE100 (manufactured by Asahi Kasei Kogyo Co., Ltd.) is used as a polyisocyanate (D)). The isocyanate group is 1.0 equivalent part to the hydroxyl group, and the curing catalyst (E) is U-2.
0 (manufactured by Nitto Kasei Co., Ltd.) is 0.4
Part), similarly, after curing for 7 days under the conditions of 23 ° C. and 55% RH, a 1-mm grid adhesion test was performed in accordance with JIS K5400. (Evaluation results) 10: 100/100 8: 80/100 6: 60/100 4: 40/100 2: 20/100 0: 0/100 (e) Odor Spray or roller coating of the composition The odor was evaluated according to the following criteria.

(Evaluation Criteria) 鼻: No nose-like odor is felt, and the paint can withstand coating for a long time. Δ: Some odor is felt. ×: Strong odor, cannot withstand long-time coating. (F) Stain resistance (ΔL value) The color of the surface of the coating film after 7 days of curing and the color of the coating surface after being left outdoors for 3 months (exposed outdoors) in Settsu City, Osaka is CR-300.
Each was measured using a color difference meter (manufactured by Minolta), and the obtained L was measured.
The difference (ΔL value) was determined from the value (brightness). (G) Weather resistance (gloss retention) Using a Sunshine Weatherometer, the gloss of the coating surface after 7 days of curing and the gloss of the coating surface after 2000 hours were measured, and the gloss retention after 2000 hours. (%)
I asked. Table 3 summarizes the results. Comparative Example 2
As for, the gloss retention after 7 days of curing is extremely low, so the gloss retention is not described.

The components in the table are as follows. Silicon compounds (C) MS56S; ESi48 manufactured by Mitsubishi Chemical Corporation; EMS (70/30) manufactured by Colcoat Corporation; polyisocyanate (D) TSE100 manufactured by Colcoat Corporation; TSS100 manufactured by Asahi Kasei Corporation; TSA100 manufactured by Asahi Kasei Corporation Asahi Kasei Kogyo Co., Ltd. curing catalyst (E) U-15; Nitto Kasei Co., Ltd. organic tin compound U-20; Nitto Kasei Co., Ltd. organic tin compound U-350; Nitto Kasei Co., Ltd. (F) F-1; γ-mercaptopropyltrimethoxysilane F-2; n-dodecylmercaptan

[0082]

According to the present invention, the main chain consists essentially of a vinyl polymer, and the terminal of the main chain and / or the side chain has the general formula (I)

[0083]

Embedded image (In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and 7 to 12 carbon atoms.
A is a monovalent hydrocarbon group selected from aralkyl groups
2 to 2. ) Contains at least one hydrolyzable silyl group bonded to the carbon atom in the molecule, and at least one alcoholic hydroxyl group at the terminal and / or side chain of the main chain, and further has an alkyl group Is a branched alkyl (meth) acrylate monomer having 4 or more carbon atoms and / or an alkyl (meth) acrylate monomer having an alkyl group having 8 or more carbon atoms in all monomers.
By containing 0% by weight or more of the vinyl copolymer (A) and the solvent (B) containing substantially no aromatic component, it has sufficient solvent solubility, and has odor and harmfulness. Thus, a curable resin composition for coatings with reduced paint loss can be obtained, and a coating film having good properties can be obtained using the curable resin composition for coatings.

Claims (8)

[Claims] (1) a main chain substantially consisting of a vinyl polymer,
General formula (I) is added to the terminal and / or side chain of the main chain. (In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and 7 to 12 carbon atoms.
A is a monovalent hydrocarbon group selected from aralkyl groups
2 to 2. ) Contains at least one hydrolyzable silyl group bonded to the carbon atom in the molecule, and at least one alcoholic hydroxyl group at the terminal and / or side chain of the main chain, and further has an alkyl group Is a branched alkyl (meth) acrylate monomer having 4 or more carbon atoms and / or an alkyl (meth) acrylate monomer having an alkyl group having 8 or more carbon atoms in all monomers.
A curable resin composition for paints comprising a vinyl copolymer (A) at 0% by weight or more and a solvent (B) containing substantially no aromatic component. 2. The compound of the general formula (II) (R ³ O) _4-b —Si—R ⁴ _b (II) (where R ³ is a carbon atom) based on 100 parts by weight of the vinyl copolymer (A). C 1 -C 10 alkyl group, a monovalent hydrocarbon group selected from aryl and aralkyl groups, when there are a plurality may be different even in the same .R ⁴ is C 1 -C A monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group, and b represents 0 or 1.) and / or a partially hydrolyzed condensate thereof (C) 0 .1
The curable resin composition for a paint according to claim 1, wherein the composition comprises from 100 to 100 parts by weight. 3. The curable resin composition for paints further comprises a polyisocyanate compound (D) as a crosslinking agent, wherein the isocyanate group is 0.1 to 0.1 to the hydroxyl group of the curable resin composition for paints.
The curable resin composition for a paint according to claim 1 or 2, which is blended in an amount of 1.5 equivalents. 4. A curable resin composition for a coating material, further comprising 0.01 to 10 parts by weight of a curing catalyst (E).
4. The curable resin composition for a coating according to any one of items 1 to 3. 5. A solvent (B) containing substantially no aromatic component.
5. The aromatic content of the compound is 1.0% by weight or less.
The curable resin composition for a coating according to any one of the above. 6. A coated product obtained by applying the curable resin composition for coating according to claim 3. 7. A coated product obtained by applying the curable resin composition for a coating according to claim 4. 8. A coated product obtained by applying the curable resin composition for a coating according to claim 5.