JP2892112B2 - One-part composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to various coatings such as architectural exteriors, automobiles, industrial machines, steel furniture, household appliances, plastics, and the like, particularly for applications requiring durability. The present invention relates to a one-part composition used for painting.

[Problems to be Solved by Conventional Techniques] Conventional thermosetting paints are those in which melamine is used as a cross-linking agent, such as alkyd melamine, acrylic melamine, and epoxy melamine. The problem was left unresolved.

In order to solve these problems, the present inventors have found a cross-linking method using a polyol resin and a hydrolyzable silyl group-containing resin that is completely different from a conventional cross-linking method using a polyol resin and a melamine resin. (See Japanese Patent Laid-Open No. 1-11952).

However, when a mixture of these polyol resin and the hydrolyzable silyl group-containing polymer is used without using a curing catalyst, the curing speed is low at room temperature or at a relatively low temperature, so that the curing speed is high. If the coating needs to be hardened, heating to a high temperature is necessary, which consumes a large amount of energy.

In general, such a defect can be improved by blending the curing catalyst immediately before use and increasing the curing speed of the coating film even at a relatively low temperature, but once the curing catalyst is blended. And these paints, coatings,
Adhesives, sealants or coupling agents harden in a short time and cannot be stored. For example, the remaining amount of a portion used for painting is completely wasted. A two-part composition).

Further, when the purpose is to form a coating film using siloxy crosslinking by the reaction between the hydroxyl group of the acrylic resin having a hydroxyl group and the alkoxysilyl group of the alkoxysilyl group-containing acrylic copolymer, an acrylic having a sufficient number of hydroxyl groups can be sufficiently crosslinked. A resin must be included in the composition. In this case, the hydroxyl group and the alkoxysilyl group react slowly even without a catalyst, resulting in gelation. What is more, to be able to store it stably for several months, including the curing catalyst,
Technically difficult.

[Means for Solving the Problems] As a result of intensive studies to solve these problems, the present inventors have found that a hydroxyl group-containing acrylic resin containing a curing catalyst and a specific alkoxysilyl group-containing acrylic copolymer are used. The present inventors have found that even a mixture with coalescing can be made into one liquid by adding methanol or methanol and a dehydrating agent, thereby completing the present invention.

That is, the present invention provides (A) an acrylic resin having a hydroxyl group, (B) a polymerizable unsaturated double bond in a molecule and a general formula: (Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group,
a represents 0, 1 or 2) an alkoxysilyl group-containing acrylic copolymer containing 5 to 90% by weight of a unit having an alkoxysilyl group represented by (C) a curing catalyst, (E) methanol and It relates to a one-part composition comprising (D) a dehydrating agent used as required.

[Examples] The acrylic resin having a hydroxyl group (hereinafter also referred to as an acrylic resin having a hydroxyl group (A)), which is the component (A) used in the present invention, exhibits coating properties such as hardness immediately after baking and solvent resistance. The main chain is substantially composed of an acrylic copolymer chain, so that the cured product has improved weather resistance, chemical resistance, water resistance and the like.

The acrylic resin (A) having a hydroxyl group can be obtained, for example, by copolymerization of a hydroxyl group-containing vinyl monomer with acrylic acid, methacrylic acid, a derivative thereof, or the like.

Examples of the hydroxyl group-containing vinyl monomer contained as the copolymer component include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether,
-Methylol (meth) acrylamide, Alonix 5700, 4-hydroxystyrene manufactured by Toa Gosei Chemical Industry Co., Ltd., HE-10, HE-20, HP manufactured by Nippon Shokubai Chemical Industry Co., Ltd.
10 and HP-20 (both terminally acrylate oligomers having hydroxyl groups), Blenmer PP series (polypropylene glycol methacrylate), Blenmer PE series (polyethylene glycol monomethacrylate), Blenmer PEP series (polyethylene Glycol polypropylene glycol methacrylate), Blemmer AP-400 (polypropylene glycol monoacrylate), Blemmer AE-350 (polyethylene glycol monoacrylate) Blemmer NKH
-5050 (polypropylene glycol polytrimethylene monoacrylate) and Blemmer GLM (glycerol monomethacrylate), hydroxyl-containing vinyl compound and ε
And ε-caprolactone-modified hydroxyalkylvinyl monomers obtained by reaction with -caprolactone.

Representative examples of the ε-caprolactone-modified hydroxyalkyl vinyl monomer include, for example, those represented by the formula: (Wherein, R represents H or CH ₃ , and n represents an integer of 1 or more)
Daicel Chemical Industries, Ltd. having a structure represented by
Placcel FA-1 (R = H, n = 1), Placcel FA-4
(R = H, n = 4), Placcel FM-1 (R = CH ₃ , n =
1) and Placcel FM-4 (R = CH ₃ , n = 4), UCC
TONE M-100 (R = H, n = 2) and TONE
M201 (R = CH ₃ , n = 1) and the like. By using a hydroxyl group-containing vinyl monomer, particularly an ε-caprolactone-modified hydroxyalkyl vinyl monomer, the impact resistance and flexibility of the coating film can be improved.

These hydroxyl group-containing vinyl monomers may be used alone or in combination of two or more.

Acrylic acid or methacrylic acid derivatives copolymerizable with a hydroxyl group-containing vinyl monomer are not particularly limited, and specific examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Ethylhexyl (meth) acrylate,
Stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) ) Acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, α-
Ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine, N-methylol (meth) acrylamide, a macromer manufactured by Toa Gosei Chemical Industry Co., Ltd. AS-6, AN-6,
Condensation of hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as AA-6, AB-6, AK-5, hydroxyalkyl esters of (meth) acrylic acid with phosphoric acid or phosphoric acid esters. Examples of the product include a phosphoric ester group-containing vinyl compound and a (meth) acrylate containing a urethane bond or a siloxane bond.

The copolymer may contain a segment formed by a urethane bond or a siloxane bond in the main chain within a range not exceeding 50% (wt%, the same applies hereinafter), and the copolymer other than the (meth) acrylic acid derivative May be included. The monomer is not limited,
Specific examples thereof include aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrene sulfonic acid, and vinyl toluene; unsaturated carboxylic acids such as maleic acid, fumaric acid, and itaconic acid; (Alkali metal salts, ammonium salts, amine salts, etc.), their acid anhydrides (maleic anhydride, etc.), or diesters or half esters thereof with linear or branched alcohols having 1 to 20 carbon atoms, etc. Esters of unsaturated carboxylic acids; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; vinyl compounds containing amino groups such as vinyl pyridine and aminoethyl vinyl ale; itaconic acid diamide crotonamide, maleic acid diamide; Fumaric diamide, N-vinylpi Amide group-containing vinyl compounds such as lolidone; other vinyl compounds such as methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinyl imidazole, vinyl sulfonic acid, etc. Is raised.

The acrylic resin (A) having a hydroxyl group is preferably produced by a solution polymerization method using an azo radical initiator such as azobisisobutyronitrile from the viewpoint of ease of synthesis.

In the solution polymerization, the molecular weight can be adjusted by using a chain transfer agent such as n-dodecyl mercaptan, t-dodecyl mercaptan, or n-butyl mercaptan as needed.

The polymerization solvent is not particularly limited as long as it is a non-reactive solvent. Also, an acrylic resin having a hydroxyl group (A)
May be a non-aqueous dispersion type in which polymer particles insoluble in a non-polar organic solvent such as heptane and pentane are dispersed.

The molecular weight and the like of the acrylic resin (A) having a hydroxyl group are not particularly limited, and may be any commonly used ones. However, coating properties such as durability (coating properties formed from the composition of the present invention) may be used. Number average molecular weight is 1,50 from the viewpoint of physical properties of the film)
It is preferably from 0 to 40,000, more preferably from 3,000 to 25,000, and preferably has a hydroxyl group capable of sufficiently crosslinking, and has a hydroxyl value from the viewpoint of physical properties of the coating film such as strength and durability. It is preferably from 10 to 300 mgKOH / g, more preferably from 30 to 150 mgKOH / g.

Such an acrylic resin (A) having a hydroxyl group may be used alone or in combination of two or more.

The alkoxysilyl group-containing acrylic copolymer (hereinafter, also referred to as an alkoxysilyl group-containing acrylic copolymer (B)), which is the component (B) used in the present invention, has a polymerizable unsaturated double bond in the molecule and a general formula : Is a polymer containing 5 to 90% of units derived from a monomer having an alkoxysilyl group represented by the formula: One molecule of the polymer contains at least one, and preferably two or more, alkoxysilyl groups represented by the above general formula. The alkoxysilyl group is present at the terminal of the polymer and / or at the side chain.

In the above formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Carbon number decreases the reactivity of the alkoxysilyl group is more than 10, R ¹ is also reactive decreases when, for example, a phenyl group or a benzyl group other than an alkyl group. Specific examples of R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an iso-butyl group.

In the above formula, R ² is a hydrogen atom or a monovalent hydrocarbon group selected from the group consisting of alkyl, aryl and aralkyl groups having 1 to 10, preferably 1 to 4 carbon atoms.

Specific examples of the alkyl group having 1 to 10 carbon atoms, which is one kind of R ² , include the same groups as those of R ^1, and specific examples of the aryl group include, for example, a phenyl group, and an aralkyl group. Specific examples include a benzyl group and the like.

 In the above formula, a represents 0, 1 or 2.

Specific examples of the alkoxysilyl group represented by the general formula include, for example, groups contained in an alkoxysilyl group-containing monomer described below.

The alkoxysilyl group-containing acrylic copolymer (B) is
Since the main chain is substantially composed of an acrylic copolymer chain, the cured product has improved weather resistance, chemical resistance, water resistance, and the like. Further, since the alkoxysilyl group is bonded to a carbon atom, the cured product has improved water resistance, alkali resistance, acid resistance, and the like.

When the number of alkoxysilyl groups in one molecule of the alkoxysilyl group-containing acrylic copolymer (B) is less than 1, the solvent resistance of a coating film obtained from the composition of the present invention is easily reduced.

The number average molecular weight of the alkoxysilyl group-containing acrylic copolymer (B) is 1,000 to 30,000, particularly preferably 3,000 to 25,000, from the viewpoint of physical properties such as durability of a coating film obtained from the composition of the present invention.

The alkoxysilyl group-containing acrylic copolymer (B) is
For example, it can be obtained by copolymerization of acrylic acid, methacrylic acid, a dielectric material thereof or the like with an alkoxysilyl group-containing monomer.

The acrylic or methacrylic acid dielectric is not limited, and specific examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and stearyl (meth) acrylate. ) Acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acyl Ruamido, N, N- dimethylacrylamide, N- methylacrylamide, acryloyl morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N
-Methylol (meth) acrylamide, Alonix M-5700 manufactured by Toa Gosei Chemical Industry Co., Ltd., AS-6, AN-6, AA-6, which are macromers manufactured by Toa Gosei Chemical Industry Co., Ltd.
AB-6, AK-5, Placcel manufactured by Daicel Chemical Industries, Ltd.
FA-1, Placcel FA-4, Placcel FM-1, Placcel FM
-4, a phosphate ester group-containing vinyl that is a condensation product of a hydroxyalkyl ester of an α, β-ethylenically unsaturated carboxylic acid such as a hydroxyalkyl ester of (meth) acrylic acid and a phosphoric acid or a phosphoric acid ester Examples include compounds or (meth) acrylates containing a urethane bond or a siloxane bond. When a hydroxyl group-containing monomer is used, its amount is preferably small (for example, 2% or less in the copolymer).

The alkoxysilyl group-containing monomer is not particularly limited except that it is a monomer having a polymerizable unsaturated double bond and having an alkoxysilyl group, and specific examples thereof include, for example, Also, (Meth) acrylates having an alkoxysilyl group at the terminal via a urethane bond or a siloxane bond.

The proportion of the unit derived from the alkoxysilyl group-containing monomer in the alkoxysilyl group-containing acrylic copolymer (B) is preferably 5 to 90% from the viewpoint of the curability of the composition and the durability of the coating film. ~ 70% is more preferred.

In the copolymer, a segment formed by a urethane bond or a siloxane bond may be contained in the main chain within a range not exceeding 50%, and a segment derived from a monomer other than the (meth) acrylic acid derivative may be contained. May be included.
The monomer is not limited, and specific examples thereof include aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, and vinyltoluene; maleic acid, fumaric acid, Unsaturated carboxylic acids such as itaconic acid, salts thereof (alkali metal salts, ammonium salts, amine salts, etc.),
Esters of unsaturated carboxylic acids such as anhydrides thereof (such as maleic anhydride) or diesters or half esters thereof with linear or branched alcohols having 1 to 20 carbon atoms; vinyl acetate, vinyl propionate, Vinyl esters and allyl compounds such as diallyl phthalate;
Amino group-containing vinyl compounds such as vinylpyridine and aminoethyl vinyl ether; itaconic acid diamide, crotonamide, maleic acid diamide, fumaric acid diamide, N
An amide group-containing vinyl compound such as vinyl pyrrolidone; 2
-Hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride,
Vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin, maleimide, N
-Other vinyl compounds such as vinylimidazole and vinylsulfonic acid.

The alkoxysilyl group-containing acrylic copolymer (B) is
For example, JP-A-54-36395, JP-A-57-36109,
Although it can be produced by the method disclosed in JP-A-58-157810, it is produced by a solution polymerization method using an azo radical initiator such as azobisisobutyronitrile from the viewpoint of ease of synthesis. Is most preferred.

In the solution polymerization, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ
- mercaptopropyl methyldimethoxysilane, .gamma.-mercaptopropyl methyl diethoxy _{silane, (H 3 CO) 3 Si} -S-S-Si- (OCH 3) 3, (CH 3 O) 3 Si-S 8 -Si (OCH ₃ ) The molecular weight can be adjusted by using a chain transfer agent such as ₃ . In particular, when a chain transfer agent having an alkoxysilyl group in the molecule, for example, γ-mercaptopropyltrimethoxysilane, an alkoxysilyl group can be introduced to the terminal of the silyl group-containing acrylic copolymer.

Polymerization solvents used in the solution polymerization include hydrocarbons (toluene, xylene, n-hexane, cyclohexane, etc.), acetates (ethyl acetate, butyl acetate, etc.), alcohols (methanol, ethanol, isopropanol, n-butanol). Non-reactive solvents such as ethers (ethyl cellosolve, butyl cellosolve, cellosolve acetate, etc.), ketones (methyl ethyl ketone, ethyl acetoacetate, acetylacetone, diacetone alcohol, methyl isobutyl ketone, acetone, etc.). There is no.

Such an alkoxysilyl group-containing polymer (B) is
One type may be used or two or more types may be used in combination.

There is no particular limitation on the proportion of the alkoxysilyl group-containing polymer (B) used, but the weight ratio of component (A) / component (B) is as follows.
9/1 to 1/9 is preferred, and 8/2 to 2/8 is more preferred. When the ratio of the component (A) / component (B) exceeds 9/1, the water resistance of the coating film obtained from the composition of the present invention tends to decrease. There is a tendency for the characteristics to be blended to be insufficient.

Specific examples of the curing catalyst (hereinafter also referred to as curing catalyst (C)) as the component (C) used in the present invention include, for example, dibutyltin dilaurate, dibutyltin dimaleate,
Organotin compounds such as dioctyltin dilaurate, dioctyltin dimaleate, tin octylate; phosphoric acid,
Monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecylphosphocyclohexene oxide,
Glycidyl methacrylate, glycidol, acrylic glycidyl ether, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, , Cardura E manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, Epicoat 100 manufactured by Yuka Shell Epoxy Co., Ltd.
Addition products of epoxy compounds such as 1 with phosphoric acid and / or monoacid phosphate; organic titanate compounds; organoaluminum compounds; maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid Acid, phthalic acid, trimellitic acid, pyromellitic acid, acid anhydrides thereof, acidic compounds such as paratoluenesulfonic acid; hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine, dodecylamine, etc. Amines; these amines and acidic amines, N, N
Amines such as dimethyldodecylamine and dodecylamine; mixtures or reactants of these amines with acidic phosphate esters; and alkaline compounds such as sodium hydroxide and potassium hydroxide.

Among these curing catalysts (C), organotin compounds, acid phosphates, mixtures or reactants of acid phosphates and amines, saturated or unsaturated polycarboxylic acids or acid anhydrides thereof, reactive silicon compounds, An organic titanate compound, an organic aluminum compound or a mixture thereof is preferred because of its high activity.

Such a curing catalyst (C) may be used alone,
More than one species may be used in combination.

There is no particular limitation on the amount of the component (C), but (A)
The amount is usually 0.1 to 20 parts, preferably 0.1 to 10 parts, based on 100 parts (parts by weight, hereinafter the same) of the solid content of the component and the component (B). If the amount of the component (C) is less than 0.1 part, the curability tends to decrease, and if it exceeds 20 parts, the appearance of the coating film tends to decrease.

The composition of the present invention contains methanol (component (E)) and, if necessary, a dehydrating agent (component (D)).

Specific examples of the dehydrating agent as the component (D) include, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
Examples include hydrolyzable ester compounds such as vinyltrimethoxysilane, methyl silicate, and ethyl silicate. These hydrolyzable ester compounds may be added before the polymerization of the alkoxysilyl group-containing acrylic copolymer (B), may be added after the polymerization, or may be added during the polymerization.

The amount used when the dehydrating agent is used is not particularly limited, but is usually 100 parts or less, preferably 50 parts or less, based on 100 parts of the solid content of the components (A) and (B).
Usually, it is 0.5 to 100 parts, preferably 1 to 50 parts.

The effect can be further enhanced by using a dehydration accelerator together with a dehydration agent.

Preferred specific examples of the dehydration accelerator include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid; formic acid, acetic acid,
Organic acids such as oxalic acid, benzoic acid, phthalic acid, p-toluenesulfonic acid, allylic acid and methacrylic acid; metal salts of carboxylic acids such as alkyl titanates and lead octylate;
Carboxylic acid type organic tin compounds such as tin octylate, dibutyltin dilaurate, dioctyltin maleate; sulfide type and mercaptide type organic tin compounds such as monobutyltin sulfide and dioctyltin mercaptide; organic tin oxides such as dioctyltin oxide; organic tin oxide Organic tin compounds by the reaction of the compound with an ester compound such as ethyl silicate, ethyl silicate 40, dimethyl maleate or dioctyl phthalate; tetraethylenepentamine, triethylenediamine, N-β-aminoethyl-
amines such as γ-aminopropyltrimethoxysilane;
Examples include, but are not limited to, alkali catalysts such as potassium hydroxide and sodium hydroxide. Of these, organic acids, inorganic acids and organic tin compounds are particularly effective.

These dehydration accelerators are usually 0.0001 per 100 parts of the dehydration agent.
To 20 parts, preferably 0.001 to 10 parts. When a compound which is also the component (C) is used as a dehydration accelerator, in addition to the amount of the component (C) used, 0.1 to 20 parts,
Preferably 0.1 to 10 parts are used.

Methanol is used as a solvent in the composition of the present invention.

The amount of the methanol used as the component (E) is not particularly limited, but the solid content of the components (A) and (B) is not particularly limited.
100 parts, usually 100 parts or less, preferably 50 parts or less, when using a solvent alone without using a dehydrating agent, usually
0.5 to 100 parts, preferably 2 to 50 parts.

When methanol as component (E) is used in combination with the above-mentioned dehydrating agent, it is compared with the case where the composition comprising component (A), component (B), component (C) and component (D) is stored. Storage stability is significantly improved. The amount of the solvent exhibiting such an effect varies depending on the molecular weight and composition of the component (A) and the component (B) in the composition of the present invention, and cannot be specified unconditionally. What is necessary is just to adjust so that it may become solid content concentration, viscosity, etc.

A hydrolyzable silicon compound can be added to the composition of the present invention in order to improve coating properties such as adhesion, hardness, and solvent resistance. The hydrolyzable silicon compound is a compound having a hydrolyzable silyl group at a terminal or a side chain. Preferred specific examples thereof include, for example, a hydrolyzable silane compound, a partially hydrolyzed condensate, a reaction product thereof, And the like.

Specific examples of the hydrolyzable silane compound include, for example, methyl silicate, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane,
Octyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-
Aminopropyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dibutyldimethoxysilane, diphenyldimethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, triphenylmethoxysilane,
Ethyl silicate, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, octyltriethoxysilane, dodecyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryl Roxypropyltriethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, Examples thereof include dibutyldiethoxysilane, diphenyldiethoxysilane, vinylmethyldiethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, trimethylethoxysilane, triethylethoxysilane, and triphenylmethoxysilane.

The partially hydrolyzed condensate of the hydrolyzable silane compound is, for example, a single or a plurality of the silane compounds, a required amount of H ₂ O is added, and if necessary, a small amount of a condensation catalyst such as hydrochloric acid or sulfuric acid is added. In addition, it can be easily obtained by raising the temperature to room temperature to 100 ° C. and proceeding with condensation while removing generated alcohol. For example, examples of the compound containing a methoxysilyl group as a partially hydrolyzed condensate of methyl silicate include methyl silicate 47, methyl silicate 51 and methyl silicate 51 manufactured by Nippon Colcoat Chemical Co., Ltd.
55, methyl silicate 58, methyl silicate 60, and the like. Examples of compounds having a methoxysilyl group as a partially hydrolyzed condensate such as methyltrimethoxysilane and cimethyldimethoxysilane include Shin-Etsu Chemical Co., Ltd.
AFP-1, AFR-2, AFP-6, KR213, KR217, KR921
8; TSR165 and TR3357 manufactured by Toshiba Silicone Co., Ltd .; Y-1587, FZ-3701 and FZ-3704 manufactured by Nippon Unicar Co., Ltd. Examples of the compound containing an ethoxysilyl group in a partial hydrolysis condensate of ethyl silicate include:
Ethyl silicate 40, HA manufactured by Nippon Colcoat Chemical Co., Ltd.
S-1, HAS-6, HAS-10 and the like.

Examples of the reactant of the hydrolyzable silane compound include a reactant of a silane coupling agent containing an amino group and a silane coupling agent containing an epoxy group; a silane coupling agent containing an amino group and ethylene oxide, butylene oxide, epichlorohydrin. Epoxidized soybean oil, a reaction product of a compound containing an epoxy group such as Epicoat 828 or Epicoat 1001 manufactured by Yuka Shell Epoxy Co .; a silane coupling agent containing an epoxy group with ethylamine, diethylamine, triethylamine, ethylenediamine, Aliphatic amines such as hexanediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; aromatic amines such as aniline and diphenylamine; alicyclic amines such as cyclopentylamine and cyclohexylamine Reaction products with amines such as amines and ethanolamines.

Such a hydrolyzable silicon compound may be used alone or in combination of two or more.

The amount of the hydrolyzable silicon compound used is not particularly limited, but is usually 0.01 to 100 parts, preferably 0.1 to 100 parts by weight per 100 parts (parts by weight, hereinafter the same) of the solid content of the components (A) and (B). 30 copies. If the amount of the hydrolyzable silicon compound used is less than 0.01 part, the effect of addition cannot be sufficiently obtained, and if it exceeds 100 parts, the appearance of the coating film obtained from the composition of the present invention tends to decrease.

The composition of the present invention may contain additives such as diluents, pigments (including extender pigments), ultraviolet absorbers, light stabilizers, anti-settling agents, and leveling agents, depending on the application; nitrocellulose, cellulose acetate butyrate, and the like. Resins such as epoxy resin, melamine resin, vinyl chloride resin, chlorinated polypropylene, chlorinated rubber and polyvinyl butyral;
A filler or the like may be added.

 Next, a method for preparing the composition of the present invention will be described.

The preparation method is not particularly limited. For example, the component (A) and the component (B) are cold-blended or mixed and then partially reacted by heating (hot blending), and then the component (C) is mixed with the component (C). , (D) component and / or (E)
The composition of the present invention is prepared, for example, by mixing with the components.

The composition of the present invention thus prepared utilizes a crosslinking reaction in which a hydroxyl group of an acrylic resin (A) having a hydroxyl group reacts with a silyl group of an alkoxysilyl group-containing polymer (B). Is clearly distinguished from the technology using melamine as a crosslinking agent.

Further, the composition of the present invention has excellent storage stability due to the effects of a dehydrating agent and a solvent.

Such a composition of the present invention is useful as a coating agent used for various coatings such as architectural exteriors, automobiles, industrial machines, steel furniture, household appliances, plastics, and the like, particularly for applications requiring durability. And
For example, dipping, spraying, after applying to the substrate by a conventional method such as brushing, usually 30 ° C. or more, preferably 55 to 350
By curing at a temperature of ° C, a coating film having excellent durability can be formed.

Next, the composition of the present invention will be described more specifically based on examples.

Production Example 1 [Synthesis of alkoxysilyl group-containing polymer (B)] 45.9 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, and nitrogen gas was charged. After the temperature was raised to 110 ° C. while introducing the mixture, a mixture (b) having the following composition was dropped at a constant speed over a period of 5 hours using a dropping funnel.

(Mixture (b)) Styrene 12.8 parts Methyl methacrylate 50.1 parts Stearyl methacrylate 6.9 parts γ-methacryloxypropyl trimethoxysilane 30.2 parts Xylene 13.5 parts 2,2'-azobisisobutyronitrile 4.5 parts of mixture (b) After completion of the dropwise addition, 0.5 part of 2,2'-azobisisobutyronitrile and 5 parts of toluene were added dropwise at a constant speed over 1 hour. After dropping, the mixture was aged at 110 ° C for 2 hours, cooled, and xylene was added to the resin solution to obtain a solid content of 60%.
It was adjusted to become. Table 1 shows the properties of the obtained resin solution (1).

Production Example 2 [Synthesis of Acrylic Resin (A) Having Hydroxyl Group] Instead of 45.9 parts of xylene, 31.3 parts of butyl acetate and 9.5 parts of xylene were charged, and a mixture (a) having the following composition was added in the same manner as in Production Example 1.

(Mixture (a)) Xylene 18 parts Styrene 28.3 parts Methyl methacrylate 7.1 parts N-butyl acrylate 32.5 parts Methacrylic acid 0.3 parts Placcel FM-1 ^{* 1} 31.8 parts 2,2'-azobisisobutyronitrile 4.5 parts [Note] * 1: Methacrylic acid 2 manufactured by Daicel Chemical Industries, Ltd.
-Hydroxyethyl / ε-caprolactone = 1/1 adduct After the completion of the dropwise addition of the mixture (a), 0.2 parts of 2,2′-azobisisobutyronitrile and 3.8 parts of toluene were added dropwise at a constant rate over 1 hour. After dropping, the mixture was aged at 110 ° C for 2 hours, cooled, and xylene was added to the resin solution to obtain a solid content of 60%.
It was adjusted to become. Table 1 shows the properties of the obtained resin solution (2).

Production Example 3 The mixture (a) used in Production Example 2 was mixed with the following mixture (a-
Resin solution (3) in the same manner as in Production Example 2 except for (2)
Was manufactured. Table 1 shows the properties of the obtained resin solution (3).

(Mixture (a-2)) Xylene 18 parts Styrene 28.3 parts Methyl methacrylate 38.9 parts N-butyl acrylate 32.5 parts Methacrylic acid 0.3 parts 2,2'-azobisisobutyronitrile 4.5 parts Examples 1 to 3 and Comparative Examples 1 to 5 The compositions shown in Table 2 were prepared using the resin solutions obtained in Production Examples 1 to 3.

The obtained composition was subjected to a storage test at 50 ° C. for 7 days and 20 days in a sealed state, and the viscosity before and after storage was measured using a B-type viscometer.
Measured at 23 ° C. The results are shown in Table 2.

The evaluation results in Table 2 show that the composition of the present invention is a one-pack composition having improved storage stability.

[Effects of the Invention] The composition of the present invention is excellent in storage stability and excellent in workability in a coating process despite being a one-pack composition.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08K 5/00 5:05 5:57 5:52 5:09 5:54 5:56 5:10) (58) Fields surveyed (Int.Cl. ⁶ , DB name) C08L 33 / 14,43 / 04 C08K 5/00-5/56 C09D 133 / 14,143 / 04

Claims (7)

(57) [Claims] (A) an acrylic resin having a hydroxyl group, (B) a polymerizable unsaturated double bond in a molecule and a general formula: (Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group,
a represents 0, 1 or 2) an alkoxysilyl group-containing acrylic copolymer containing 5 to 90% by weight of units derived from a monomer having an alkoxysilyl group represented by (C) a curing catalyst and (E) methanol One-part composition. (A) an acrylic resin having a hydroxyl group, (B) a polymerizable unsaturated double bond in the molecule and a general formula: (Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group,
a represents 0, 1 or 2) an alkoxysilyl group-containing acrylic copolymer containing 5 to 90% by weight of a unit having a alkoxysilyl group represented by the formula (C): a curing catalyst; (D) a dehydrating agent; (E) A one-pack composition comprising methanol. 3. The one-pack composition according to claim 1, wherein the acrylic resin having a hydroxyl group as the component (A) has a hydroxyl value of 10 to 300 mg KOH / g and a number average molecular weight of 1,500 to 40,000. . 4. The curing catalyst as the component (C) may be an organotin compound, an acidic phosphoric acid ester, a mixture or a reaction product of an acidic phosphoric acid ester and an amine, a saturated or unsaturated polyvalent carboxylic acid, or a saturated or unsaturated compound. Acid anhydrides of polycarboxylic acids, reactive silicon compounds, organic titanate compounds,
3. The one-part composition according to claim 1, which is an organoaluminum compound or a mixture thereof. 5. The one-part composition according to claim 2, wherein the dehydrating agent as the component (D) is a hydrolyzable ester compound. 6. The one-part composition according to claim 2, which comprises a hydrolyzable ester compound as a dehydrating agent as the component (D). 7. The one-part composition according to claim 2, which comprises a hydrolyzable ester compound as a dehydrating agent (D), and further comprises a dehydration accelerator.