JP2002338873A - Curable resin composition for coating material and coated item obtained by coating with the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alcoholic-hydroxyl-group-containing curable resin composition for a coating material which can be suitably dissolved in a solvent substantially containing no aromatic component; and a coating film formed by using the composition. SOLUTION: This curable resin composition for a coating material comprises (A) a vinyl copolymer which has a main chain substantially comprising a vinyl polymer, has one or more alcoholic hydroxyl groups at the end of the main chain and/or on a side chain, and contains, based on the total monomer units, at least 30 wt.% units derived from a branched alkyl (meth)acrylate having a 4C or higher alkyl group and/or an alkyl (meth)acrylate having an 8C or higher alkyl group and (B) a solvent substantially containing no aromatic component. Since a vinyl polymer is used, the resin composition has a sufficient solvent solubility. A coating film having good characteristics can be formed by using the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a branched alkyl (meth) acrylate monomer having an alkyl group of 4 or more and / or a (meth) acrylic acid having an alkyl group of 8 or more carbon atoms. The present invention relates to a resin composition and a coating film comprising a hydroxyl group-containing vinyl copolymer in which an alkyl monomer accounts for 30% by weight or more of all monomers and 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 disclose an acrylic silicone resin using a weak solvent as a solvent.
97242 describes a resin that uses both a silicone bridge and a urethane bridge using a weak solvent system as a solvent.

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

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a hydroxyl group-containing vinyl copolymer which can be suitably dissolved in a solvent containing substantially no aromatic component.

[0007]

According to the present invention, the main chain is substantially composed of a vinyl polymer, and at least one alcoholic hydroxyl group is contained in the molecule at the terminal and / or side chain of the main chain. The branched alkyl (meth) acrylate monomer having 4 or more carbon atoms and / or the alkyl (meth) acrylate monomer having 8 or more carbon atoms in the alkyl group is 30% by weight of all monomers. It has been found that by using a vinyl-based copolymer having a content of not less than 10%, the composition can be suitably dissolved even in a solvent containing no aromatic compound, and that when used as a coating material, a useful coated product can be obtained. That is,
In the present invention, the main chain is substantially composed of a vinyl polymer, the main chain terminal and / or the side chain contains at least one alcoholic hydroxyl group, and the alkyl group has 4 or more carbon atoms and is a branched type. Alkyl (meth) acrylate monomers and / or
Alternatively, the vinyl copolymer (A) in which the alkyl (meth) acrylate monomer having an alkyl group having 8 or more carbon atoms is 30% by weight or more of all monomers does not substantially contain an aromatic component. A curable resin composition for paints comprising a solvent (B). (Claim 1) The alcoholic hydroxyl group-containing vinyl copolymer (A) 1
Against 00 parts by weight, the general formula ^{(I) (R 1 O)} 4-a -Si-R 2 a (I) ( wherein, R ¹ represents an alkyl group having 1 to 10 carbon atoms, aryl and aralkyl groups R ² is selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group. The monovalent hydrocarbon group, a represents 0 or 1.) and / or a partial hydrolytic condensate thereof (C) 0.1
The curable resin composition for a paint according to claim 1, wherein the curable resin composition is blended in an amount of from 100 to 100 parts by weight. (Claim 2) A polyisocyanate compound (D) is used as a crosslinking agent in the curable resin composition for paints, wherein an isocyanate group is 0.1 to 1.
The curable resin composition for a paint according to claim 1 or 2, which is blended at a ratio of 5 equivalents. (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 aromatic content of the solvent containing substantially no aromatic component is 1.0% 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).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The number average molecular weight of the vinyl copolymer is preferably 2,000 to 30,000. More preferably, it is 3000-25000. Number average molecular weight is 2
If it is less than 000, curability and weather resistance tend to decrease, and if it exceeds 30,000, appearance and workability tend to decrease.

The vinyl copolymer contained in the resin composition of the present invention may be, for example, a monomer (a) containing an alcoholic hydroxyl group, a branched (meth) acryl having an alkyl group having 4 or more carbon atoms. It is produced by copolymerizing an acid alkyl monomer (b), an alkyl (meth) acrylate monomer having an alkyl group having 8 or more carbon atoms (c), and another vinyl monomer (d). be able to.

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 alcoholic hydroxyl group-containing vinyl monomer (a) is not particularly restricted but includes, for example, 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, Alonix 5700 manufactured by Toa Gosei Chemical Industry Co., Ltd.
(Trade name), HE-10, HE manufactured by Nippon Shokubai Chemical Industry Co., Ltd.
-20, HP-10 and HP-20 (all are trade names)
(Acrylic ester oligomers each having a hydroxyl group at the terminal), Blenmer PP series (polypropylene glycol methacrylate), Blenmer PE series (polyethylene glycol monomethacrylate), Blenmer PEP series (polyethylene glycol polypropylene glycol methacrylate) , Blenmer AP400 (polypropylene glycol monoacrylate), Blenmer AE350 (polyethylene glycol monoacrylate), and Blenmer GLM (glycerol monomethacrylate) (all trade names), ε-caprolactone by reaction of a hydroxyl group-containing vinyl compound with ε-caprolactone Modified hydroxyalkyl vinyl copolymerizable compound, HEAC-1 (trade name, manufactured by Daicel Chemical Industries, Ltd.) Polycarbonate-containing vinyl compounds such as (product name). These may be used alone or in combination of two or more.

Among 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 (a) to be used is preferably 6 to 30 parts by weight, more preferably 7 to 20 parts by weight. When the amount is 3 parts by weight or less, the coating film hardness, adhesion, and weather resistance tend to decrease, and when the amount is 30 parts by weight or more, the recoating property tends to decrease.

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 if 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 octyl (meth) acrylate, decyl (meth) acrylate, and 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 used amount of (c) is 30 parts by weight, more preferably 50 parts by weight or more. If the amount is less than 30 parts by weight, the solubility and dilutability of the vinyl polymer will be reduced.

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, mac AS-6 is a monomer,
Compounds such as AN-6, AA-6, AB-6, and AK-5 (all manufactured by Toagosei Chemical Industry Co., Ltd.), Placel
FA-1, Placel FA-4, Place
l FM-1, Placel FM-4, HEAC-
1 (manufactured by Daicel Chemical Industries, Ltd.), a phosphate group-containing (meth) acrylic compound such as a condensation product of a hydroxyalkyl ester of (meth) acrylic acid and phosphoric acid or a phosphoric ester, (Meth) acrylate and styrene containing urethane bond or siloxane bond, α
-Aromatic hydrocarbon vinyl compounds such as -methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, and vinyltoluene; maleic acid, fumaric acid,
Unsaturated carboxylic acids such as itaconic acid and (meth) acrylic acid, salts thereof such as alkali metal salts, ammonium salts and amine salts; acid anhydrides of unsaturated carboxylic acids such as maleic anhydride; these acid anhydrides and carbon Esters of unsaturated carboxylic acids such as diesters or half-esters with alcohols or amines having a linear or branched chain of formulas 1 to 20; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; vinyl pyridine , Aminoethyl vinyl ether and other amino group-containing vinyl compounds; itaconic acid diamide, crotonic acid amide, maleic acid diamide, fumaric acid diamide, N-
Amide group-containing vinyl compounds such as vinylpyrrolidone;
2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride,
Vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-
And other vinyl compounds such as vinylimidazole and vinylsulfonic 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 on the 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 50% 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, 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 may attack the base. 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 (all 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.

In the solution polymerization, if necessary, for example, n-dodecylmercaptan, t-dodecylmercaptan, n-butylmercaptan, 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. 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.

[0027] The silicon compound and / or a partial hydrolytic condensate thereof (C) (hereinafter, silicon compounds that (C)) of the general formula ^{(I) (R 1 O)} 4-a -Si-R 2 a (I) (wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, 6 carbon atoms)
Monovalent hydrocarbon group selected from aryl groups and aralkyl groups having 7 to 12 carbon atoms of to 10, R ² is a carbon number 1 to 1
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 a 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 (I), R ¹ has 1 to 10 carbon atoms, preferably, for example, a methyl group, an ethyl group, n
Alkyl groups having 1 to 4 carbon atoms such as -propyl group, i-propyl group, n-butyl group and i-butyl group, preferably aryl groups having 6 to 9 carbon atoms such as phenyl group, preferably benzyl group, for example. And a monovalent hydrocarbon group selected from aralkyl groups having 7 to 9 carbon atoms.

When the alkyl group has more than 10 carbon atoms, the reactivity of the silicon compound (C) decreases. R ¹ is the alkyl group, the aryl group,
Even in the case other than the aralkyl group, the reactivity decreases.

In the general formula (I), R ² has 1 to 10 carbon atoms, preferably ¹ to 4 carbon atoms similar to R ^1.
, Preferably a monovalent hydrocarbon selected from the same aryl groups having 6 to 9 carbon atoms as R ^1, and preferably the same aralkyl groups having 7 to 9 carbon atoms as R ¹ .

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

When the number of (R ¹ O) _4-a present in the general formula (I) is two or more, R ¹ contained in two or more may be the same or different.

Specific examples of the silicon compounds (C) 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, for example, those obtained by adding water to the above-mentioned tetraalkylsilicate or trialkoxysilane and condensing it by an ordinary 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)
Co., Ltd.), silicate 40, silicate 45, silicate 48, FR-3 (above, manufactured by Tama Chemical Co., Ltd.), and partially hydrolyzed decomposed condensates of tetraalkyl silicates, for example, AFP-1 (Shin-Etsu Chemical Co., Ltd.) (Manufactured by Co., Ltd.).

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 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, for example, by converting a lactam blocking agent such as ε-caprolactam or an alcohol blocking agent such as ethanol, propanol or 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 hydroxyl group of 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, for example, organotin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate, and dibutyltin bis (mercapto acid ester). 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 (E), 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. These are a hydrolyzable silyl group-containing vinyl copolymer (A) component 100
0.1 to 10 parts by weight can be blended with respect to parts by weight. The amount is preferably 0.2 to 8 parts by weight,
5 to 5 parts by weight are particularly preferred.

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

Further, specific examples of the organic phosphates include phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate. Phosphoric acid or a phosphoric acid ester such as dimethyl phosphate, 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.

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; 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 vinyl polymer of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to 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.

The obtained hydroxyl-containing vinyl polymer (A-
1 to A-7) solid content concentration of each vinyl copolymer, GP
Table 1 shows the number average molecular weight measured at C.

[0053]

[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 .; Example ( manufactured by Exxon-Mobil Chemical Co., Ltd. ) (solvent dilutability) ESi48 (Colcoat Co., Ltd.) was used as a silicon compound (C) for 100 parts of the resin solid content of the vinyl polymer (A) obtained. Was added, and the mixture was diluted with a polymerization solvent so that the solid content concentration became 50%. Thereafter, Exol D40 is added as a solvent (B) containing substantially no aromatic component in an atmosphere of 20 ° C. and 5 ° C. to 100 parts by weight of the vinyl polymer (A). The dilutability up to the occurrence of cloudiness was confirmed.

[0054]

[Table 2] Production of White Enamel To 100 parts of the resin solid content of the vinyl copolymer (A) -1 obtained in Production Example 1, titanium oxide (CR-
90, manufactured by Ishihara Sangyo Co., Ltd.), and dispersed for 2 hours with a paint conditioner using glass beads to obtain a white enamel having a solid content of 60%.

With respect to 100 parts of the solid resin content of the obtained white enamel, MS56S was used as a silicon compound (C).
TSS100 (Asahi Kasei Kogyo Co., Ltd.) as a polyisocyanate (D) was added to a mixture obtained by adding 15 parts of (a partially hydrolyzed condensate of tetramethyl silicate manufactured by Mitsubishi Chemical Corporation).
Exol D) is 1.0 equivalent part of isocyanate group with respect to the hydroxyl group of the vinyl polymer.
40 was added and stirred to obtain a composition having a solid content of 45%.

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

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

[0058]

[Table 3] The surface state, gloss, contact angle, and stain 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.). (2) Adhesion The multi-layer coating material RE and the base adjustment coating material E, each of which was evaluated for fineness, were 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 (e) Stain resistance (ΔL value) Coating film 7 days after curing The color of the surface and the surface of the coating film after leaving for 3 months outdoors (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). Table 3 summarizes the results.

The components shown 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; Catalyst (E) U-20; Organotin compound manufactured by Nitto Kasei Corporation

[0060]

According to the present invention, the main chain is substantially composed of a vinyl polymer, the main chain terminal and / or the side chain contains at least one alcoholic hydroxyl group, and the alkyl group has 4 or more carbon atoms. And the branched alkyl (meth) acrylate monomer and / or the alkyl (meth) acrylate monomer having an alkyl group having 8 or more carbon atoms is 30% of all monomers.
Curable resin for coatings having sufficient solvent solubility by using a vinyl-based polymer comprising a vinyl-based copolymer (A) in an amount of at least 10% by weight and a solvent (B) containing substantially no aromatic component. A composition can be obtained, and a coating film having good properties can be obtained by using the curable resin composition for a paint.

Continued on front page F-term (reference) 4D075 CA13 CA32 CA34 CA36 CA38 CA44 CB04 EA07 EB07 EB12 EB14 EB15 EB16 EB38 EB43 EB45 EB47 EB56 EC07 EC08 EC30 EC37 EC54 4J038 CG141 CH031 CH041 CH121 DG191 DG261 DL03 DL03 DL03

Claims (8)

[Claims] (1) a main chain substantially consisting of a vinyl polymer,
At least one alcoholic hydroxyl group at the terminal and / or side chain of the main chain, wherein the alkyl group has 4 or more carbon atoms and the branched alkyl (meth) acrylate monomer and / or the alkyl group has A paint comprising a vinyl copolymer (A) in which the alkyl (meth) acrylate monomer of 8 or more accounts for 30% by weight or more of all monomers and a solvent (B) containing substantially no aromatic component. Curable resin composition. Wherein said alcoholic hydroxyl group-containing vinyl copolymer (A) with respect to 100 parts by weight, the general formula ^{(I) (R 1 O)} 4-a -Si-R 2 a (I) ( wherein , R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, and when a plurality of R ¹ are present, they may be the same or different. ² is 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 hydrolytic condensation thereof Product (C) 0.1
The curable resin composition for a paint according to claim 1, wherein the curable resin composition is blended in an amount of from 100 to 100 parts by weight. 3. A polyisocyanate compound (D) having a isocyanate group content of 0.1 to 1.5 with respect to a hydroxyl group of the curable resin composition for paint, as a crosslinking agent in the curable resin composition for paint. The curable resin composition for a paint according to claim 1 or 2, which is blended in an equivalent ratio. 4. The curable resin composition for paints according to claim 1, wherein the curable resin composition for paints further comprises 0.01 to 10 parts by weight of a curing catalyst (E). 5. The curable resin composition for a paint according to claim 1, wherein the solvent having substantially no aromatic component has an aromatic content of 1.0% by weight or less. 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.