JP2002338888A - Curable resin composition for coating material and coated product coated with the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition comprising a hydrolyzable silyl group- containing vinyl copolymer which can suitably be dissolved in a solvent substantially free of an aromatic component. SOLUTION: By using a composition comprising (A) a vinyl copolymer whose major 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, simultaneously at least one alcoholic hydroxyl group at the terminal of the main chain and/or in the side chain, and >=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, a curable resin composition for a coating material which has sufficient solvent solubility and, at the same time, controls an odor and harmfulness can be obtained, and further a coating film having good properties can be 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.

[0003] In recent years, since environmental problems have become more important, odor and safety of conventional strong solvent type solvents have been regarded as problems, and acryl urethane resins and acrylic silicone resins have been dissolved in weak solvent type solvents. Paints have been developed.

For example, JP-A-11-228903 and JP-A-11-279480 describe acrylic silicone resins using a weak solvent as a solvent.

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.

[0006]

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.

[0007]

According to the present invention, a solvent substantially free of an aromatic component is used as a main component, the main chain is substantially composed of a vinyl polymer, and the main chain terminal and / or side chain is used. Has the general formula (I)

[0008]

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. A) a branched alkyl (meth) acrylate monomer containing at least one hydrolyzable silyl group bonded to a carbon atom represented by the formula (1) in the molecule, wherein the alkyl group has 4 or more carbon atoms, and / or A vinyl copolymer (A) in which an alkyl (meth) acrylate monomer having an alkyl group having 8 or more carbon atoms is 50% by weight or more of all monomers, and a solvent containing substantially no aromatic component It is a curable resin composition for paints comprising (B). (Claim 1) also with respect to the vinyl copolymer (A) 100 parts by weight of the general formula (II) (R ³ O) in _{^{4-a -Si-R 4 a}} (II) ( wherein, R ³ is an alkyl group having 1 to 10 carbon atoms, 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 A silicon compound represented by a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, and a represents 0 or 1) and / or a partial hydrolyzed condensate thereof ( C).
The curable resin composition for a paint according to claim 1, wherein the curable resin composition comprises 1 to 100 parts by weight. (Claim 2) The curable resin composition for paints further comprises a curing catalyst (D) 0.1.
The curable resin composition for a paint according to claim 1, wherein the curable resin composition is contained in an amount of from 0.01 to 10 parts by weight. (Claim 3) The curable resin composition for a paint according to any one of claims 1 to 3, wherein the aromatic content of the solvent (B) substantially containing no aromatic component is 1.0% by weight or less. . (Claim 4) A coated article obtained by applying the curable resin composition for a paint according to claim 3. (Claim 5) A coated article obtained by applying the curable resin composition for a paint according to claim 4. (Claim 6).

[0009]

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.

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 is composed of a vinyl copolymer chain" is defined as 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. Copolymerizing an alkyl (meth) acrylate monomer (b), an alkyl (meth) acrylate monomer (c) having an alkyl group having 8 or more carbon atoms, and another vinyl monomer (d) Can be manufactured by

Specific examples of the vinyl monomer having a reactive silyl group include, for example,

[0018]

Embedded image General formula (III) such as

[0019]

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:

[0020]

Embedded image General formula (IV) such as

[0021]

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:

[0022]

Embedded image General formula (V) such as:

[0023]

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

[0024]

Embedded image General formula (VI) such as:

[0025]

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)

[0026]

Embedded image General formula (VII) such as

[0027]

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 general 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) in which the alkyl group has 4 or more carbon atoms include, for example, a vinyl monomer having a branched structure and / or a ring 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 above monomer (b) may be used in combination of two or more kinds.

Specific examples of the alkyl (meth) acrylate monomer (c) in which the alkyl group has 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.

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

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

Specific examples of the other monomer (d) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and trifluoroethyl (meth) acrylate. 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, 2- Dorokishiechiru (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4
-Hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, 4-hydroxystyrene, Alonix 5700 (trade name) manufactured by Toa Gosei Chemical Industry Co., Ltd., HE- manufactured by Nippon Shokubai Chemical Industry Co., Ltd. 10, 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 terminal), Blenmer PP series (polypropylene glycol methacrylate) manufactured by NOF Corporation, Blenmer PE series (polyethylene glycol monomethacrylate), Blemmer PEP series (polyethylene glycol polypropylene glycol methacrylate), Blemmer AP
400 (polypropylene glycol monoacrylate), Blemmer AE350 (polyethylene glycol monoacrylate), and Blemmer GLM (glycerol monomethacrylate) (all trade names), ε-caprolactone-modified hydroxy by the reaction of a hydroxyl group-containing vinyl compound with ε-caprolactone Alkyl vinyl copolymerizable compound, HEAC-1 manufactured by Daicel Chemical Industries, Ltd.
(Trade name) and other polycarbonate-containing vinyl compounds,
AS-6, AN-6, AA-6 which are macromonomers,
Compounds such as AB-6 and AK-5 (all manufactured by Toa Gosei Chemical Industry Co., Ltd.), Placel FA-1, Plac
cel FA-4, Placel FM-1, Pla
ccel FM-4, HEAC-1 (manufactured by Daicel Chemical Industries, Ltd.), containing phosphate ester groups such as condensation products of hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or phosphoric acid esters (Meth) acrylic compounds, (meth) acrylates containing urethane bonds and siloxane bonds, and aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene and vinyltoluene; maleic acid , Fumaric acid, itaconic acid, (meth)
Unsaturated carboxylic acids such as acrylic acid, salts thereof such as alkali metal salts, ammonium salts and amine salts; acid anhydrides of unsaturated carboxylic acids such as maleic anhydride; Esters of unsaturated carboxylic acids, such as diesters or halfesters with linear or branched alcohols or amines; vinyl acetate;
Vinyl esters and allyl compounds such as vinyl propionate and diallyl phthalate; vinyl compounds containing amino groups such as vinyl pyridine and aminoethyl vinyl ether;
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, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene , Butadiene, isoprene, fluoroolefin maleimide, N-vinylimidazole,
And other vinyl compounds such as vinyl sulfonic acid.

These may be used alone or in combination of two or more.

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 A segment derived from a monomer other than the monomer (a), the monomer (b), the monomer (c), and the monomer (d), and the like, in a range not exceeding 30% by weight. May be introduced at the time of manufacturing.

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, in which case the curability and adhesion are improved, but the carboxyl group or amino group bonded to the polymer chain is improved. Group, the activity is weak,
It is difficult to obtain a cured product having good characteristics even if these are used in place of the curing catalyst and cured.

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,
Preferably, it is used in an amount of at least% by weight. Particularly preferably,
90% by weight or more.

Other solvents that can be used include alcohol solvents, ester solvents, ketone solvents, and the like. However, since these solvents may attack the substrate, 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 and paraffin solvents, hydrogenated products of xylene or other solvents containing aromatics such as MCH (manufactured by Nippon Steel Chemical Co., Ltd.), and so-called hydrocarbon solvents such as hexane and heptane. .

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, 6 carbon atoms)
R ⁴ is a monovalent hydrocarbon group selected from an aryl group having 10 to 10 and an aralkyl group having 7 to 12 carbon atoms;
A monovalent hydrocarbon group selected from an alkyl group having 0, 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). It is a component that is blended mainly for the purpose of improving the property, and is preferably blended in an amount of 0.1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the vinyl copolymer (A). ~ 80 parts by weight, more preferably 10 ~
50 parts by weight.

When the amount of the silicon compound (C) is less than 0.1% 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 such that 4-b is 3 or more, that is, b 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 compounds (II) include tetramethyl silicate, tetraethyl silicate, tetra n-propyl silicate, tetra i-propyl silicate, tetra n-butyl silicate, tetra i-butyl silicate and the like. Alkyl silicate; methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrisec-octyloxysilane, methyltriphenoxysilane, Examples thereof include silane coupling agents such as 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. Partial hydrolytic decomposition condensates of tetraalkyl silicates such as FR-3 (manufactured by Tama Chemical Co., Ltd.), and partial hydrolysis 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 curable resin composition for paints of the present invention may optionally contain a curing catalyst (D).

Specific examples of the curing catalyst (D) include, for example, organotin 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.

As a specific example of the curing catalyst (D), an acid catalyst is further exemplified. 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. A system in which an organic amine is blended with an organic carboxylic acid is preferable from the viewpoint of achieving a balance between curability and pot life.

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 phosphates 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.

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%, particularly preferably 0.1 to 8% of the total amount of the used polymerization components.

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 and leveling agents; 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 immersion, 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.

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

[0067]

[Table 1] In addition, the component in a table | surface shows the following. Solvent Exol D40; Isobar G manufactured by Exxon-Mobil Chemical Co., Ltd. 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. Exxon-Mobil Chemical Co., Ltd. Example Solvent Dilution ESi48 (manufactured by Colcoat Co., Ltd.) as a silicon compound (C) with respect to 100 parts of the resin solid content of the vinyl polymer (A) obtained. Was added, and then diluted with a polymerization solvent so that the solid content concentration became 50%. A solvent (B) containing substantially no aromatic component under an atmosphere of 20 ° C. and 5 ° C. with respect to 100 parts by weight of the vinyl polymer (A),
Exol D40 was added at a certain ratio to confirm dilutability until cloudiness was produced.

[0068]

[Table 2] Preparation of White Enamel MS56S (tetramethyl silicate manufactured by Mitsubishi Chemical Corporation) was used as a silicon compound (C) for 100 parts of the resin solid content of the vinyl copolymer (A) -1 obtained in Production Example 1. Titanium oxide (CR-95, manufactured by Ishihara Sangyo Co., Ltd.) as a pigment in a mixture obtained by adding 15 parts of a partially hydrolyzed condensate)
Forty parts were added and dispersed with a paint conditioner using glass beads for 2 hours to obtain a white enamel having a solid content of 60%.

One part of U-15 (manufactured by Nitto Kasei Co., Ltd.) as a curing catalyst (D), a silane coupling agent (E), and a curing adjusting component were used for 100 parts of the resin solid content of the obtained white enamel. (F) In addition, Exol D4 as a thinner
0 and the mixture was stirred to obtain a composition having a solid content of 45%.

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

The obtained composition was coated on an aluminum plate (A50).
52P) was applied by air spray to a dry film thickness of about 30 μm, and cured (cured) at 23 ° C. for 7 days to obtain a coating film. Table 3 shows the results.

[0072]

[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) The obtained composition is coated on a slate plate with 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;
SK Chemicals Co., Ltd.) was applied at 1.4 to 1.6 Kg / m 2 and cured at 23 ° C. for one day, and the white enamel composition shown in Example was dried to a film thickness of 20 to 30 μm. And painted as a sample. The sample was scratched to reach the substrate with a cutter.
On the 1st, 2nd, 3rd, 5th, 7th, and 14th days under RH conditions, the top coat was applied with a brush, and the state of the coating film in each period was observed, and it was confirmed whether or not there was any smudge. . Topcoat Rico-
At the time of inspection, the following criteria were evaluated.

(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. (E) Adhesiveness The multi-layer coating material RE and the base adjustment coating material E, each of which has been evaluated for fineness, are 23
After curing at a temperature of 1 ° C. for one day, a white enamel as shown in Examples was applied.
After curing for 7 days at 23 ° C and 55% RH, JISK5
A 1 mm grid adhesion test was performed according to the standard 400. (Evaluation results) 10: 100/100 8: 80/100 6: 60/100 4: 40/100 2: 20/100 0: 0/100 (f) Odor The composition was spray-coated or roller-coated. The odor in each case 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. (G) Stain resistance (ΔL value) The color of the paint film surface after 7 days of curing and that of the paint film surface after being left outdoors for 3 months (outdoor exposure) in Settsu City, Osaka are 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). (H) 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 shown in the table are as follows. Silicon compounds (C) ESi48; Colcoat Co., Ltd. Si48; Tama Chemical Co., Ltd. curing catalyst (D) U-15; Nitto Kasei Co., Ltd. organic tin compound U-20; Nitto Kasei Co., Ltd. organic tin compound Silane cup Ring agent (E) E-1; a reactant of aminoethylaminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane in a ratio of 1: 2.2 (molar ratio) E-2; aminoethylaminopropyltrimethoxysilane cured Adjusting component (F) F-1; γ-mercaptopropyltrimethoxysilane F-2; n-dodecyl mercaptan

[0076]

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)

[0077]

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. A) a branched alkyl (meth) acrylate monomer containing at least one hydrolyzable silyl group bonded to a carbon atom represented by the formula (1) in the molecule, wherein the alkyl group has 4 or more carbon atoms, and / or A vinyl copolymer (A) in which an alkyl (meth) acrylate monomer having an alkyl group having 8 or more carbon atoms is 50% by weight or more of all monomers, and a solvent containing substantially no aromatic component By using the vinyl copolymer composition comprising (B), it is possible to obtain a curable resin composition for coatings that has sufficient solvent solubility and that suppresses odor and harmfulness. A coating film having good characteristics can be obtained using the curable resin composition.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D075 CA13 CA32 CA34 CA36 CA38 CA44 CB04 EA07 EB07 EB12 EB14 EB15 EB16 EB19 EB20 EB22 EB32 EB33 EB43 EB47 EB56 EC07 EC08 EC30 EC37 EC54 4J038 CG141 CH031 CH041 NA27

Claims (6)

[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. A) a branched alkyl (meth) acrylate monomer containing at least one hydrolyzable silyl group bonded to a carbon atom represented by the formula (1) in the molecule, wherein the alkyl group has 4 or more carbon atoms, and / or A vinyl copolymer (A) in which an alkyl (meth) acrylate monomer having an alkyl group having 8 or more carbon atoms is 50% by weight or more of all monomers, and a solvent containing substantially no aromatic component A curable resin composition for coatings comprising (B). Relative wherein said vinyl copolymer (A) 100 parts by weight of the general formula ^{(II) (R 3 O)} 4-a -Si-R 4 a (II) ( wherein, R ³ is R ⁴ is a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group having 1 to 10 carbon atoms, and when there are a plurality of carbon atoms, they may be the same or different. A monovalent hydrocarbon group selected from 1 to 10 alkyl groups, aryl groups and aralkyl groups, a represents 0 or 1.) and / or a partially hydrolyzed condensate thereof (C) To 0.
The curable resin composition for a paint according to claim 1, wherein the curable resin composition comprises 1 to 100 parts by weight. 3. The curable resin composition for a paint further comprises 0.01 to 10 parts by weight of a curing catalyst (D).
Or the curable resin composition for coating according to 2. 4. A solvent (B) containing substantially no aromatic component.
The curable resin composition for paint according to any one of claims 1 to 3, wherein the aromatic content of the resin is 1.0% by weight or less. 5. A coated product obtained by applying the curable resin composition for a coating according to claim 3. 6. A coated product obtained by applying the curable resin composition for a coating according to claim 4.