JPH1060216A - One-pack type composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a one-pack type composition having an excellent storage stability, coating workability and durability and useful for the coating of the exterior wall of buildings, etc., by using respectively specific acrylic resin, acrylic copolymer, curing catalyst, hydrolyzable silicon compound and solvent as essential components. SOLUTION: This composition is composed of (A) an OH-containing acrylic resin having a hydroxyl value of 10-300mgKOH/g and a number-average molecular weight of 1,500-40,000, (B) an acrylic copolymer having a group of the formula I (R<1> is a 1-10C alkyl; R<2> is H or a univalent hydrocarbon group; (a) is 0-2) and an alkoxysilyl group containing epoxy group and hydroxyl group, (C) preferably 0.1-10 pts.wt. (based on 100 pts.wt. of A+B) of a curing catalyst such as an organotin compound, (D) preferably 0.1-30 pts.wt. of a silicon compound of the formula II (R<3> and R<4> are each H or a univalent hydrocarbon group; (b) is 0-2) or its partially hydrolyzed and condensed product and (E) preferably 1-50 pts.wt. of a solvent such as an alkyl alcohol. The weight ratio of the component A to B (A/B) is preferably 8/2 to 2/8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a one-part coating used for various coatings, for example, for building exteriors, automobiles, industrial machines, steel furniture, household appliances, plastics, etc., and especially for applications requiring durability. Mold composition.

[0002]

2. Description of the Related Art Conventional thermosetting paints are those in which melamine is used as a crosslinking agent, such as alkyd melamine, acrylic melamine, epoxy melamine, etc. The problem was left unresolved.

[0003] In order to solve these problems, the present inventors have found a crosslinking method using a polyol resin and a hydrolyzable silyl group-containing resin which is completely different from the conventional crosslinking method using a polyol resin and a melamine resin. (See Japanese Patent Application Laid-Open No. 1-11952).

However, when a mixture of these polyol resins and a polymer containing a hydrolyzable silyl group is used without using a curing catalyst, the curing speed is low when heated at room temperature or a relatively low temperature. If a high rate of paint curing is required, heating to a high temperature is required, consuming a large amount of energy.

[0005] Such a defect can be improved generally by blending the curing catalyst immediately before use to increase the curing speed of the coating film even at a relatively low temperature.
Once a curing catalyst has been added, these paints, coatings, adhesives, sealants or coupling agents harden in a short time and cannot be stored. The amount is totally wasted (such compositions are commonly referred to as two-part compositions).

Further, when the purpose is to form a coating film utilizing siloxy crosslinking by the reaction between the hydroxyl group of an acrylic resin having a hydroxyl group and the alkoxysilyl group of an alkoxysilyl group-containing acrylic copolymer, the hydroxyl group which can be sufficiently crosslinked is used. It is necessary to include an acrylic resin having the following in the composition. In this case, the hydroxyl group and the alkoxysilyl group react slowly even without a catalyst, resulting in gelation. Much more
It is technically difficult to include a curing catalyst so that it can be stored stably for several months.

[0007]

The present inventors have made intensive studies to solve these problems, and as a result, have found that an acrylic resin containing a hydroxyl group containing a curing catalyst and an alkoxysilyl containing an epoxy group and a hydroxyl group. The inventors have found that even a mixture with a group-containing acrylic copolymer can be made into one liquid by adding a dehydrating agent and / or an alkyl alcohol, and have completed the present invention.

That is, the present invention provides (A) an acrylic resin having a hydroxyl group, (B) a general formula (I):

[0009]

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Wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or a monovalent carbon atom selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group. A hydrogen group, a represents 0, 1 or 2), an alkoxysilyl group-containing acrylic copolymer containing an epoxy group and a hydroxyl group, (C)
One-pack composition comprising a curing catalyst, (D) a hydrolyzable silicon compound and (E) a solvent (Claim 1), (A)
The one-pack composition (Claim 2), wherein the acrylic resin having a hydroxyl group as a component has a hydroxyl value of 10 to 300 mgKOH / g and a number average molecular weight of 1,500 to 40,000. Component (B), an alkoxysilyl group-containing acrylic copolymer, has a polymerizable unsaturated 2
The one-pack composition (Claim 3), which is a polymer containing 5-90% by weight of units derived from an alkoxysilyl group-containing monomer having a heavy bond and an alkoxysilyl group.
(C) a curing catalyst as a component, which comprises an organotin compound, an acid phosphate, a mixture or a reaction product of an acid phosphate and an amine, a saturated or unsaturated polycarboxylic acid,
The one-part composition according to claim 1, which is an acid anhydride of a saturated or unsaturated polycarboxylic acid, a reactive silicon compound, an organic titanate compound, an organic aluminum compound or a mixture thereof. The hydrolyzable silicon compound as a component is (D-1) a general formula (II): (R ³ O) _4-b Si (R ⁴ ) _b (II) (wherein R ³ and R ⁴ are each independently A hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group; b represents 0, 1 or 2); D-2) The one-part composition according to claim 1, which is a partial hydrolysis condensate of the silicon compound (Claim 5), and the solvent as the component (E) is an alkyl alcohol. Liquid composition (Claim 6) About.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Acrylic resin having a hydroxyl group, which is a component (A) used in the present invention (hereinafter also referred to as "hydroxyl group-containing acrylic resin (A)"), has a coating film having hardness immediately after baking and solvent resistance. It is a component used to exhibit physical properties. The main chain of the component 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 copolymerizing a vinyl monomer having a hydroxyl group 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, and N-methylol (meth) acrylamide. Alonix 5700, 4-hydroxystyrene manufactured by Toa Gosei Chemical Industry Co., Ltd., HE-1 manufactured by Nippon Shokubai Chemical Industry Co., Ltd.
0, HE-20, HP-10 and HP-20 (all acrylate oligomers having a hydroxyl group at the end), Blenmer PP series (polypropylene glycol methacrylate), Blenmer PE series (polyethylene glycol mono) manufactured by NOF Corporation (Methacrylate), Blemmer 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 Blenmer GLM (glycerol monomethacrylate), and ε-caprolactone-modified hydroxyalkyl vinyl monomers obtained by reacting a hydroxyl group-containing vinyl compound with ε-caprolactone.

Representative examples of the ε-caprolactone-modified hydroxyalkyl vinyl monomer include, for example, those represented by the formula:

[0015]

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(Wherein R is H or CH ₃ , and n is an integer of 1 or more). Placel FA-1 (R = H, n) manufactured by Daicel Chemical Industries, Ltd.
= 1), Placel FA-4 (R = H, n =
4), Placel FM-1 (R = CH ₃ , n =
1) and Placel FM-4 (R = CH ₃ , n
= 4), TONE M-100 manufactured by UCC (R =
H, n = 2) and TONE M201 (R = CH ₃ ,
n = 1). By using an ε-caprolactone-modified hydroxyalkyl vinyl monomer as the hydroxyl group-containing vinyl monomer, the impact resistance and flexibility of the coating film can be improved.

These hydroxyl group-containing vinyl monomers have the following structure:
Seeds may be used, or two or more kinds may be used in combination.

The derivative of acrylic acid or methacrylic acid copolymerizable with a hydroxyl group-containing vinyl monomer is not particularly limited, and specific examples thereof include, for example, methyl (meth)
Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-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, acryloyl Morpholine, N-methylol (meth) acrylamide, AS, a macromer manufactured by Toa Gosei Chemical Industry Co., Ltd.
-6, AN-6, AA-6, AB-6, AK-5, hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or A phosphate ester group-containing vinyl compound which is a condensation product with phosphate esters,
(Meth) acrylates containing a urethane bond or a siloxane bond are exemplified.

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% (% by weight, hereinafter the same). A segment derived from a monomer other than the acid derivative may be included. The monomer is not limited, and specific examples thereof include, for example, styrene, α-
Aromatic hydrocarbon-based vinyl compounds such as methylstyrene, chlorostyrene, styrenesulfonic acid, and vinyltoluene; unsaturated carboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and salts thereof (alkali metal salts, ammonium salts, amines) Salts thereof), their anhydrides (such as maleic anhydride), or esters of unsaturated carboxylic acids such as diesters or half-esters thereof with linear or branched alcohols having 1 to 20 carbon atoms; vinyl acetate,
Vinyl esters and allyl compounds such as vinyl propionate and diallyl phthalate; amino group-containing vinyl compounds such as vinyl pyridine and aminoethyl vinyl ether; amide groups such as itaconic diamide crotonamide, maleic diamide, fumaric diamide, and N-vinyl pyrrolidone Other vinyl compounds such as methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinyl imidazole, and vinyl sulfonic acid.

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

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

The polymerization solvent is not particularly limited as long as it is a non-reactive solvent. Further, the acrylic resin (A) having a hydroxyl group 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 any commonly used ones can be used. However, coating properties such as durability (formed from the composition of the present invention) can be used. The number average molecular weight is preferably from 1,500 to 40,000 from the viewpoint of
More preferably, 3,000 to 25,000,
Further, it preferably has a hydroxyl group capable of sufficiently cross-linking, and preferably has a hydroxyl value of 10 to 300 mgKOH / g from the viewpoint of coating properties such as strength and durability.
More preferably, it is １５０150 mgKOH / g.

The acrylic resin (A) having such 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 general formula at the terminal and / or the side chain. (I):

[0026]

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A polymer having at least one, preferably at least two, alkoxysilyl groups in one molecule and having an epoxy group and a hydroxyl group.

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

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 carbon atoms, 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 for R ^1, and specific examples of the aryl group include, for example, a phenyl group. Specific examples of the aralkyl group include a benzyl group.

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

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

Since the alkoxysilyl group-containing acrylic copolymer (B) has a main chain substantially consisting 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 the coating film obtained from the composition of the present invention tends to decrease.

The number average molecular weight of the alkoxysilyl group-containing acrylic copolymer (B) is from 1,000 to 30,0 in view of physical properties such as durability of a coating film obtained from the composition of the present invention.
00, particularly preferably 3,000 to 25,000.

The alkoxysilyl group-containing acrylic copolymer (B) can be obtained, for example, by copolymerizing acrylic acid, methacrylic acid, a derivative thereof and the like with an alkoxysilyl group-containing monomer.

The acrylic acid or methacrylic acid derivative is not limited, and specific examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Butyl (meth) acrylate, 2-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, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, Alonix M manufactured by Toa Gosei Chemical Industry Co., Ltd. −57
00, A, a macromer manufactured by Toa Gosei Chemical Industry Co., Ltd.
S-6, AN-6, AA-6, AB-6, AK-5, Placel FA-1 manufactured by Daicel Chemical Industries, Ltd.
Placel FA-4, Placel FM-
1, Plascel FM-4, phosphoric acid which 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 phosphoric acid or a phosphoric acid ester Examples include an ester group-containing vinyl compound or a (meth) acrylate containing a urethane bond or a siloxane bond. When a hydroxyl group-containing monomer is used,
It is preferable to use a small amount (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.

[0039]

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Also,

[0041]

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(Meth) having an alkoxysilyl group at the terminal via a urethane bond or a siloxane bond.
Acrylate and the like.

The proportion of the unit derived from the alkoxysilyl group-containing monomer in the alkoxysilyl group-containing acrylic copolymer (B) is from 5 to 90% in view of the curability of the composition and the durability of the coating film. Preferably, 11 to 70% is more preferable.

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%, and may be derived from a monomer other than the (meth) acrylic acid derivative. 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.), their acid anhydrides (maleic anhydride, etc.), or linear carboxylic acids having 1 to 20 carbon atoms Is an ester of an unsaturated carboxylic acid such as a diester or a half ester with a branched alcohol; a vinyl ester or an allyl compound such as vinyl acetate, vinyl propionate or diallyl phthalate; a vinyl compound containing an amino group such as vinyl pyridine or aminoethyl vinyl ether; Itaconic acid diamide, crotonamide, male Amide group-containing vinyl compounds such as acid diamide, fumaric acid diamide, and N-vinyl pyrrolidone; 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin, maleimide, And other vinyl compounds such as N-vinylimidazole and vinylsulfonic acid.

The alkoxysilyl group-containing acrylic copolymer (B) can be produced by a method described in, for example, JP-A-54-36395, JP-A-57-36109, and JP-A-58-157810. However, from the viewpoint of easiness of synthesis and the like, it is most preferable to produce it by a solution polymerization method using an azo radical initiator such as azobisisobutyronitrile.

In the above solution polymerization, n
-Dodecyl mercaptan, t-dodecyl mercaptan,
n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane,
_{(H 3 CO) 3 Si-} S-S-Si- (OCH 3) 3, (C
_{H 3 O) 3 Si-S} 8 -Si (OCH 3) using a chain transfer agent such as _3, it is possible to adjust the molecular weight. 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.

The polymerization solvent used in the solution polymerization includes hydrocarbons (toluene, xylene, n-hexane, cyclohexane, etc.), acetates (ethyl acetate, butyl acetate, etc.), alcohols (methanol, ethanol, isopropanol, etc.). Non-reactive solvents such as n-butanol), 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 particular limitation.

As the alkoxysilyl group-containing polymer (B), one kind may be used alone, or two or more kinds may be used in combination.

There are no particular restrictions on the proportion of the alkoxysilyl group-containing polymer (B) used, but the weight ratio of component (A) / component (B) is preferably 9/1 to 1/9, and 8/2 to 2/9. / 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, and when the ratio is less than 1/9, the component (A) decreases. There is a tendency for the characteristics to be blended to be insufficient.

Specific examples of the curing catalyst used as the component (C) in the present invention (hereinafter, also referred to as curing catalyst (C)) include:
For example, organic tin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, and 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,

[0051]

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Cardura E manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.
An addition reaction product of an epoxy compound such as Epicoat 1001 with phosphoric acid and / or a monoacid phosphate;
Organic titanate compounds; Organoaluminum compounds; Maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic acid, their acid anhydrides, paratoluenesulfonic acid Acidic compounds such as hexylamine and di-2
Amines such as -ethylhexylamine, N, N-dimethyldodecylamine and dodecylamine; amines such as these and acidic amines, N, N-dimethyldodecylamine and dodecylamine; mixtures of these amines and acidic phosphate esters Or reactants; 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, A silicon compound, an organic titanate compound, an organic aluminum compound or a mixture thereof is preferred because of its high activity.

These curing catalysts (C) may be used alone or in combination of two or more.

The amount of the component (C) is not particularly limited, but is usually 0.1 to 20 parts per 100 parts (parts by weight, hereinafter the same) of the solid content of the components (A) and (B). Preferably it is 0.1 to 10 parts. When the use amount of the component (C) is less than 0.1 part, the curability tends to decrease, and 2
If the amount exceeds 0 parts, the appearance of the coating film tends to decrease.

The composition of the present invention contains a hydrolyzable silicon compound (component (D)) and a solvent (component (E)).

The hydrolyzable silicone compound (D) is added to the composition of the present invention in order to improve the 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, vinyl Trimethoxysilane, 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, ethylsilicate, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, octyltriethoxysilane, Dodecyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dibutyldiethoxysilane, diphenyldiethoxysilane , Vinylmethyldiethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane and the like.

The partially hydrolyzed condensate of the hydrolyzable silane compound may be obtained, for example, by mixing the above silane compound alone or in combination, adding a required amount of H ₂ O, and, if necessary, condensing with hydrochloric acid, sulfuric acid or the like. Add a small amount of catalyst, room temperature to 10
It can be easily obtained by setting the temperature to 0 ° C. and proceeding with condensation while removing the produced alcohol. For example, examples of the compound containing a methoxysilyl group as a partial hydrolysis condensate of methyl silicate include methyl silicate 47 and methyl silicate 5 manufactured by Nippon Colcoat Chemical Co., Ltd.
1, methyl silicate 55, methyl silicate 58, methyl silicate 60, and the like. Examples of compounds having a methoxysilyl group as a partial hydrolysis condensate such as methyltrimethoxysilane and dimethyldimethoxysilane include Shin-Etsu Chemical Co., Ltd. AFP-1, AFR-
2, AFP-6, KR213, KR217, KR921
8; TSR165, TR33 manufactured by Toshiba Silicone Co., Ltd.
57; Y-1587, FZ-3 manufactured by Nippon Unicar Co., Ltd.
701, FZ-3704 and the like. Examples of the compound containing an ethoxysilyl group as a partially hydrolyzed condensate of ethyl silicate include ethyl silicate 40, HAS-1 and HAS manufactured by Nippon Colcoat Chemical Co., Ltd.
-6 and HAS-10.

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. Reaction products of epoxide, epichlorohydrin, epoxidized soybean oil, and other compounds having an epoxy group, such as Epicoat 828 and Epicoat 1001 manufactured by Yuka Shell Epoxy Co .; a silane coupling agent containing an epoxy group and ethylamine, diethylamine, triethylamine Aliphatic amines such as ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, aromatic amines such as aniline and diphenylamine, cyclopentylamine, cyclohexyl Alicyclic amines such as tromethamine, reaction products of amines such as ethanol amine and the like.

Such a hydrolyzable silicon compound is 1
Seeds may be used, or two or more kinds may be used in combination.

The amount of the hydrolyzable silicon compound to be used is generally 0.01 to 100 parts, preferably 0.1 to 30 parts, per 100 parts of solids of the components (A) and (B).
Department. The amount of the hydrolyzable silicon compound used is 0.0
If the amount is less than 1 part, the effect of addition cannot be sufficiently obtained, and 10
When the amount exceeds 0 parts, the appearance of the coating film obtained from the composition of the present invention is deteriorated.

As the solvent used in the composition of the present invention, any non-reactive solvent can be used.

Specific examples of such solvents include, for example, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, and the like used in general paints and coating agents. Esters, ethers, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, ketone esters, ester ethers and the like can be mentioned.

Preferred examples of the solvent as the component (E) include alcohols having 1 to 10 carbon atoms in the alkyl group. Examples of such alcohols include methyl alcohol, ethyl alcohol and n-propyl. Alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, octyl alcohol, cellosolve and the like are used.

The amount of the solvent such as the alcohol used 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). When the solvent is used alone, the amount is usually 0.5 to 100 parts, preferably 2 to 50 parts.

When the above alcohol, particularly an alkyl alcohol, is used as the component (E), and when used in combination with a dehydrating agent described below, a composition comprising the components (A), (B), (C) and the dehydrating agent Storage stability is remarkably improved as compared with the case where is stored. 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 dehydrating agent can be added to the composition of the present invention to improve storage stability.

Specific examples of the dehydrating agent include, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyltrimethoxysilane, γ
-Hydrolysable ester compounds such as methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, methylsilicate and ethylsilicate. 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 of the dehydrating agent used is not particularly limited.
The amount 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).
When the dehydrating agent is used alone without using a solvent, the dehydrating agent is usually used in an amount of 0.1.
5 to 100 parts, preferably 1 to 50 parts.

When a dehydrating agent is used in combination with a dehydration accelerator, the effect can be further enhanced.

Preferred specific examples of the dehydration accelerator include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid;
Organic acids such as formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, p-toluenesulfonic acid, acrylic acid and methacrylic acid; metal salts of carboxylic acids such as alkyl titanates and lead octylate; tin octylate and dibutyl Tin dilaurate,
Carboxylic acid-type organotin compounds such as dioctyltin maleate; sulfide-type and mercaptide-type organotin compounds such as monobutyltin sulfide and dioctyltin mercaptide; organic tin oxides such as dioctyltin oxide;
Organotin compound by reaction of organotin oxide with an ester compound such as ethyl silicate, ethyl silicate 40, dimethyl maleate, dioctyl phthalate; tetraethylenepentamine, triethylenediamine, N-β-
Examples thereof include, but are not limited to, amines such as aminoethyl-γ-aminopropyltrimethoxysilane; and 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 used in an amount of 0.0001 to 20 parts, preferably 0.001 part, per 100 parts of the dehydrating agent.
10 to 10 parts are used. When the compound which is also the component (C) is used as the dehydration accelerator, the compound is used in an amount of 0.1 to 20 parts, preferably 0.1 to 20 parts, in addition to the amount of the component (C).
10 parts are used.

The composition of the present invention may contain additives such as diluents, pigments (including extenders), ultraviolet absorbers, light stabilizers, anti-settling agents, and leveling agents, depending on the intended use; nitrocellulose, cellulose acetate Cellulose such as butyrate; resins such as epoxy resin, melamine resin, vinyl chloride resin, chlorinated polypropylene, chlorinated rubber, and polyvinyl butyral; and fillers 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 components (A) and (B) may be cold-blended or
After being mixed and then partially reacted by heating (hot blending) or the like, component (C), component (D) and component (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 the hydroxyl group of the acrylic resin (A) having a hydroxyl group reacts with the silyl group of the alkoxysilyl group-containing polymer (B). It is clearly distinguished from the conventional technology using melamine as a crosslinking agent.

The composition of the present invention has excellent storage stability due to the effect of the solvent and, if necessary, the dehydrating agent used.

The composition of the present invention can be used as a coating for various coatings such as architectural exteriors, automobiles, industrial machines, steel furniture, household appliances, plastics, etc., especially for applications requiring durability. It is useful as an agent, and is applied to an object to be coated by a conventional method such as dipping, spraying, or brushing, and then cured at 30 ° C. or more, preferably 55 to 350 ° C., and has excellent durability. Can be formed.

Next, the composition of the present invention was prepared based on Examples.
This will be described more specifically.

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, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel. After heating to 110 ° C. while introducing nitrogen gas,
The 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-methacryloxypropyltrimethoxysilane 30.2 parts Xylene 13.5 parts 2,2′- Azobisisobutyronitrile 4.5 parts

After the addition of the mixture (b) was completed, 0.5 parts of 2,2'-azobisisobutyronitrile and 5 parts of toluene were added dropwise at a constant rate over 1 hour. After completion of the dropwise addition, the mixture was aged at 110 ° C. for 2 hours and cooled, and xylene was added to the resin solution to adjust the solid content to 60%. Table 1 shows the properties of the obtained resin solution (1).

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

(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: 2-hydroxyethyl methacrylate / ε-caprolactone = 1/1 adduct manufactured by Daicel Chemical Industries, Ltd.

After the completion of the dropwise addition of the mixture (A), 0.2 parts of 2,2'-azobisisobutyronitrile and 3.
Eight parts were dropped at a constant speed over 1 hour. After the completion of dropping, 110
After aging at 2 ° C. for 2 hours, the mixture was cooled, and xylene was added to the resin solution to adjust the solid content to 60%. Table 1 shows the properties of the obtained resin solution (2).

Production Example 3 [Synthesis of alkoxysilyl group-containing acrylic resin (B)]
After charging 15.6 g of xylene and 10.4 g of n-butyl alcohol in a reactor equipped with a stirrer, thermometer, nitrogen introduction tube, dropping funnel and cooling tube and heating them to 110 ° C., a mixture having the following composition (B) Was added continuously over 4 hours.

(Mixture (B)) Styrene 13 g γ-methacryloxypropyltrimethoxysilane 10 g n-butyl methacrylate 17 g cyclohexyl methacrylate 20 g 2-ethylhexyl acrylate 15 g glycidyl methacrylate 20 g 2-hydroxyethyl methacrylate 5 g azobisisobutyronitrile 5 0.7 g xylene 10 g n-butyl alcohol 5 g methanol 2 g

After the addition of the mixture (B) was completed, a solution prepared by dissolving 0.3 g of azobisisobutyronitrile separately prepared in 5 g of toluene was added over 30 minutes. After 1 hour and 30 minutes, polymerization was carried out. Xylene was added to the obtained resin solution to adjust the nonvolatile concentration to 60%. Table 1 shows the properties of the obtained resin solution (3). The number average molecular weight of the obtained resin was determined by the GPC method.

[0090]

[Table 1]

Reference Examples 1-4 and Comparative Comparative Examples 1-2 Using the resin solutions obtained in Production Examples 1 and 2, the compositions shown in Table 2 were prepared.

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 at 23 ° C. using a B-type viscometer. Table 2 shows the results.

[0093]

[Table 2]

The evaluation results in Table 2 show that the composition of Reference Example was a one-pack composition having improved storage stability.

Examples 1-4 and Comparative Examples 1-2 The compositions shown in Table 3 were prepared using the resin solutions obtained in Production Examples 2 and 3, and evaluated in the same manner as in Reference Example 1. Table 3 shows the results.

[0096]

[Table 3]

[0097]

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

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08K 5/54 C08K 5/54 5/57 5/57 C08L 43/04 C08L 43/04 83/07 83/07 // C08F 290/06 C08F 290/06 C09D 133/14 C09D 133/14 143/04 143/04

Claims (6)

[Claims] (A) an acrylic resin having a hydroxyl group,
(B) General formula (I): (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 an epoxy group and a hydroxyl group, (C) a curing catalyst, (D)
A one-pack composition comprising a hydrolyzable silicon compound and a solvent (E). 2. The one-pack type acrylic resin 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. Composition. 3. An alkoxysilyl group-containing acrylic copolymer as the component (B) may contain 5-90 units of an alkoxysilyl group-containing monomer having a polymerizable unsaturated double bond and an alkoxysilyl group in a molecule. The one-part composition according to claim 1, which is a polymer containing 1% by weight. 4. The curing catalyst as the component (C) is 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 polycarboxylic acid, a saturated or unsaturated compound. The one-part composition according to claim 1, which is an acid anhydride of a polycarboxylic acid, a reactive silicon compound, an organic titanate compound, an organic aluminum compound or a mixture thereof. 5. The hydrolyzable silicon compound as the component (D) is represented by (D-1) a general formula (II): (R ³ O) _4-b Si (R ⁴ ) _b (II) R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, and b represents 0, 1 or 2) The one-part composition according to claim 1, which is a silicon compound to be obtained and / or (D-2) a partially hydrolyzed condensate of the silicon compound. 6. The one-part composition according to claim 1, wherein the solvent as the component (E) is an alkyl alcohol.