JP2843408B2 - Thermosetting composition and painted product coated with the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention requires various coatings, for example, exteriors of buildings, automobiles, industrial machines, steel furniture, household appliances, plastics, and the like, and particularly requires durability. The present invention relates to a thermosetting composition used for coating and a coated product containing the same as a main component.

[Problems to be Solved by the Related Art] Conventional thermosetting paints are those in which melamine is used as a cross-linking agent, such as alkyd melamine, acrylic melamine, epoxy melamine, and the like. Is left unsolved.

In addition, acrylic melamine resin and alkyd melamine resin, which are generally used as automotive paints, have weather resistance,
Performances such as stain resistance, acid resistance, and water repellency are not always sufficiently satisfactory, and improvements are desired.

As a solution to these problems, a patent application has already been filed for a composition that is cured by a crosslinking method using a polyol resin and a hydrolyzable silyl group-containing resin that is completely different from a conventional crosslinking method using a polyol resin and a melamine resin ( See Japanese Patent Application Laid-Open No. 1-141952). However, it has been required to further improve water resistance and solvent resistance.

[Means for Solving the Problems] As a result of further studies, the present inventors have found that an acrylic polymer containing a specific functional group and further containing a hydroxyl group, an acrylic polymer containing a specific functional group and further containing an alkoxy group By using a silyl group-containing acrylic polymer so that the functional groups are in a specific combination, and heating and curing using a curing catalyst, a cured product that can improve the above problem is found. Thus, the present invention has been completed.

That is, the present invention provides (A) one or more groups selected from the group consisting of an acid anhydride group, an epoxy group, an amino group and a carboxyl group, and a hydroxyl group-containing number average molecular weight of 1,500 to 25,000.
20 to 50 parts of an acrylic polymer (parts by weight, hereinafter the same), (B) containing at least one group selected from the group consisting of an acid anhydride group, an epoxy group, an amino group and a carboxyl group, and 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, an aryl group and an aralkyl group, a is 0, 1 or 2) an acrylic polymer containing an alkoxysilyl group represented by the following formula and having a number average molecular weight of 1,000 to 25,000:
0 parts and (C) a curing catalyst, wherein the total of the components (A) and (B) is 100 parts, and the combination of the functional group contained in the component (A) and the functional group contained in the component (B) is Acid anhydride group / epoxy group,
A thermosetting composition containing at least one combination of an amino group / epoxy group and a carboxyl group / epoxy group, and a paint containing a metallic powder and / or a color pigment are applied. The present invention relates to a coated product having a surface coated with a top coat clear coating, wherein the top coating clear coating is a thermosetting coating mainly containing the thermosetting composition.

[Example] Acrylic containing at least one group selected from the group consisting of an acid anhydride group, an epoxy group, an amino group and a carboxyl group, which is the component (A) used in the present invention, and containing a hydroxyl group. A polymer (hereinafter also referred to as a hydroxyl group-containing polymer (A)) has a main chain substantially composed of an acrylic copolymer chain, and therefore has a weather resistance, a chemical resistance, and a water resistance of a cured product. Improve and so on.

There is no particular limitation on the molecular weight of the hydroxyl group-containing polymer (A), the hydroxyl value, and the like. Any commonly used one can be used, but the number average molecular weight is from 1,500 to 25,000, and more preferably from 3,000 to 25,000. Is preferred from the viewpoint of physical properties of a coating film (a coating film formed from the composition of the present invention) such as strength and durability, and has a hydroxyl value of 10 to 300 mg KOH / g, more preferably 20 to 250 mg KOH / g. Is preferred from the viewpoint of physical properties of the coating film such as strength and durability. Further, the number of groups selected from the group consisting of acid anhydride groups, epoxy groups, amino groups and carboxyl groups per molecule of the hydroxyl group-containing polymer (A) is 1
The number is preferably at least 2, more preferably from 2 to 30, from the viewpoint of water resistance and solvent resistance of the cured coating film. One type of such a component (A) may be used, or two or more types may be used in combination.

The hydroxyl group-containing polymer (A) can be obtained, for example, by copolymerizing a hydroxyl group-containing vinyl monomer, a monomer for introducing a functional group described later, an acrylic acid derivative, a methacrylic acid derivative, and the like.

Specific examples of the hydroxyl group-containing vinyl monomer contained as a copolymer component include, for example, 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, HP-20 (Acrylic ester ester oligomers each having a hydroxyl group at the end), such as Nippon Oil & Fats Co., Ltd. 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 NK
Hydroxyl-containing vinyl compounds such as H-5050 (polypropylene glycol polytrimethylene monoacrylate), Blemmer GLM (glycerol monomethacrylate) and ε
And ε-caprolactone-modified hydroxyalkyl vinyl monomers obtained by reaction with -caprolactone.

Representative examples of the ε-caprolactone-modified hydroxyalkylvinyl 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), UCC such as Placel FM-4 (R = CH ₃ , n = 4)
TONE M-100 (R = H, n = 2), TONE M201
(R = CH ₃ , n = 1). As a hydroxyl group-containing vinyl monomer, in particular, by using an ε-caprolactone-modified hydroxyalkyl vinyl monomer,
The impact resistance and flexibility of the coating film can be improved.

In order to introduce an acid anhydride group into the hydroxyl group-containing polymer (A), for example, maleic anhydride, itaconic anhydride or the like may be copolymerized. To introduce an epoxy group, for example, glycidyl (meth) acrylate or the like may be used. In order to introduce a carboxyl group, an unsaturated carboxylic acid such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid may be copolymerized to introduce an amino group. Include a primary amino group, a secondary amino group and 3
A vinyl monomer containing an amino group selected from the group consisting of secondary amino groups may be copolymerized.

Representative examples of the amino group-containing vinyl monomer include dimethylaminoethyl (meth) acrylate,
Various dialkylaminoalkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate; N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) N-) such as acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-diethylaminopropyl (meth) acrylamide, etc.
Dialkylaminoalkyl (meth) acrylamides; t
-Butylaminoethyl (meth) acrylate, t-butylaminopropyl (meth) acrylate, aziridinylethyl (meth) acrylate, pyrrolidinylethyl (meth) acrylate, piperidinylethyl (meth) acrylate, vinylpyridine, amino Ethyl vinyl ether and the like are mentioned, and dialkylaminoalkyl (meth) acrylates and N-dialkylaminoalkyl (meth) acrylamides are particularly preferred from the viewpoint of curability and the like.

The acrylic acid or methacrylic acid derivative copolymerizable with the 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, and 2-ethylhexyl. (Meth) acrylate,
Stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth) acrylonitrile, (meth) Acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, N-methylol (meth) acrylamide,
AS-6, a macromer manufactured by Toa Gosei Chemical Industry Co., Ltd.
A phosphate ester group-containing vinyl compound which is a condensation product of a hydroxyalkyl ester of (meth) acrylic acid and a phosphoric acid or a phosphoric acid ester, such as AN-6, AA-6, AB-6, and AK-5; (Meth) acrylates containing a urethane bond or a siloxane bond are exemplified.

The hydroxyl group-containing polymer (A) may contain a portion having a urethane bond or a siloxane bond in the main chain within a range not exceeding 50% (wt%, the same applies hereinafter). It may contain units from monomers. The monomer is not particularly limited, and specific examples thereof include, in addition to the above-described monomer for introducing a functional group, styrene, α-methylstyrene, chlorostyrene,
Aromatic hydrocarbon vinyl compounds such as styrenesulfonic acid and vinyltoluene; salts of unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid (alkali metal salts, ammonium salts, amine salts, etc.), and those having 1 carbon atom Esters of unsaturated carboxylic acids such as diesters or half-esters with up to 20 linear or branched alcohols; vinyl acetates and vinyl esters such as vinyl propionate and diallyl phthalate; allyl compounds; itaconic acid diamide;
Amide group-containing vinyl compounds such as crotonamide, maleic diamide, fumaric diamide, N-vinylpyrrolidone; methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinyl chloride, chloroprene,
Other vinyl compounds such as propylene, butadiene, isoprene, fluoroolefin, maleimide, and vinyl sulfonic acid.

A general polymerization method is used to obtain the hydroxyl group-containing polymer (A), but solution polymerization using an azo radical initiator such as azobisisobutyronitrile is particularly preferable from the viewpoint of ease of synthesis. preferable. The molecular weight can be adjusted by using a chain transfer agent such as n-dodecyl mercaptan, t-dodecyl mercaptan, or by changing the reaction temperature.

An acrylic copolymer containing at least one group selected from the group consisting of an acid anhydride group, an epoxy group, an amino group, and a carboxyl group, which is the component (B) used in the present invention, and containing an alkoxysilyl group. The compound (hereinafter also referred to as an alkoxysilyl group-containing polymer (B)) has a general formula at the terminal and / or side chain: Is a polymer having at least one, preferably 2 to 100 alkoxysilyl groups per molecule.

In the above formula, R ¹ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The carbon number is 10
And R ¹ is other than an alkyl group such as a phenyl group,
In the case of a benzyl group, the reactivity of the alkoxysilyl group decreases. Specific examples of R ¹ include, for example, a methyl group,
Examples include an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group and an iso-butyl group.

In the above formula, R ² is a hydrogen atom or an alkyl group, preferably 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.

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, a tolyl group, and a xylyl group. Specific examples of the aralkyl group include a benzyl group.

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

Examples of the alkoxysilyl group represented by the general formula include, for example, general formula: (Wherein R ¹ , R ² , and a are the same as described above, and R ³ is the same group as R ^2, and is a hydrogen atom or a monovalent group selected from the group consisting of an alkyl group, an aryl group, and an aralkyl group. A hydrocarbon group).

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

Since the main chain of the alkoxysilyl group-containing polymer (B) 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 carbon, water resistance, alkali resistance, acid resistance and the like are further improved. The alkoxysilyl group is a component that reacts with the hydroxyl group of the hydroxyl group-containing polymer (A) and contributes to crosslinking, and also causes the alkoxysilyl groups to react with each other and contribute to crosslinking. When the number of alkoxysilyl groups in one molecule of the component (B) is less than 1, the solvent resistance of the coating film properties decreases.

Groups selected from the group consisting of acid anhydride groups, epoxy groups, amino groups and carboxyl groups in the alkoxysilyl group-containing polymer (B) are the acid anhydride groups and epoxy groups in the hydroxyl group-containing polymer (A). And a group selected from the group consisting of an amino group and a carboxyl group, and reacting with a combination of an acid anhydride group / epoxy group, an amino group / epoxy group or a carboxyl group / epoxy group to form a cured coating from the composition of the present invention. Improves the solvent resistance and water resistance of the film.

The number of groups selected from the group consisting of an acid anhydride group, an epoxy group, an amino group and a carboxyl group per molecule of the alkoxysilyl group-containing polymer (B) is 1 or more, and more preferably 2 to 30. Are preferred from the viewpoint of solvent resistance and water resistance of the cured coating film.

The number average molecular weight of the component (B) is preferably from 1,000 to 25,000, more preferably from 3,000 to 25,000, from the viewpoint of coating film properties (strength and durability).

The alkoxysilyl group-containing polymer (B) includes, for example, an alkoxysilyl group-containing monomer, a monomer for introducing a functional group described later, acrylic acid, methacrylic acid,
It can be obtained by copolymerization with a derivative thereof or the like.

The alkoxysilyl group-containing monomer is not particularly limited except that it has a polymerizable unsaturated double bond and has an alkoxysilyl group represented by the general formula, and specific examples thereof include, for example, (Meth) acrylates having an alkoxysilyl group at the terminal via a urethane bond or a siloxane bond. These may be used alone or in combination of two or more.

The proportion of these alkoxysilyl group-containing monomer units in the alkoxysilyl group-containing polymer (B) is preferably from 5 to 90% from the viewpoint of the curability of the composition and the durability of the coating film.
11-70% is more preferred.

In order to introduce an acid anhydride group into the alkoxysilyl group-containing polymer (B), for example, maleic anhydride or itaconic anhydride may be copolymerized. To introduce an epoxy group, for example, glycidyl (meth) An acrylate may be copolymerized, and a carboxyl group may be introduced by, for example, copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid. For introduction, a vinyl monomer containing an amino group selected from the group consisting of primary amino group, secondary amino group, and tertiary amino group may be copolymerized.

Representative examples of the amino group-containing vinyl monomer include dimethylaminoethyl (meth) acrylate,
Various dialkylaminoalkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate; N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) N-) such as acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-diethylaminopropyl (meth) acrylamide, etc.
Dialkylaminoalkyl (meth) acrylamides; t
-Butylaminoethyl (meth) acrylate, t-butylaminopropyl (meth) acrylate, aziridinylmethyl (meth) acrylate, pyrrolidinylethyl (meth) acrylate, piperidinylethyl (meth) acrylate, vinylpyridine, amino Ethyl vinyl ether and the like are mentioned, and dialkylaminoalkyl (meth) acrylates and N-dialkylaminoalkyl (meth) acrylamides are particularly preferred from the viewpoint of curability and the like.

The derivative of acrylic acid or methacrylic acid is not particularly limited, and specific examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth).
Acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth) acrylonitrile, (Meth) acrylamide, α-
Ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-methylol (meth) ) Acrylamide, Alonix M-570 manufactured by Toa Gosei Chemical Industry Co., Ltd.
0, AS-, a macromer manufactured by Toa Gosei Chemical Industry Co., Ltd.
6, Praxel FA-1, Plaxel FA- manufactured by Daicel Chemical Industries, Ltd., such as 6, AN-6, AA-6, AB-6, and AK-5.
A, a phosphoric acid ester group-containing vinyl compound which is a condensation product of a hydroxyalkyl ester of (meth) acrylic acid or the like and a phosphoric acid or a phosphoric acid ester, such as Praxel FM-1 or Praxel FM-4, a urethane bond or a siloxane (Meth) acrylate containing a bond.

Also, the alkoxysilyl group-containing polymer (B) is 50%
The main chain may contain a portion due to a urethane bond or a siloxane bond, or may contain a monomer other than the (meth) acrylic acid derivative within a range not exceeding the above. The monomer is not particularly limited, and specific examples thereof include, in addition to the above-described monomer for introducing a functional group, styrene, α-
Aromatic hydrocarbon vinyl compounds such as methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, and vinyltoluene; maleic acid, fumaric acid,
Salts of unsaturated carboxylic acids such as itaconic acid (alkali metal salts, ammonium salts, amine salts, etc.) and unsaturated carboxylic acids such as diesters or half esters thereof with linear or branched alcohols having 1 to 20 carbon atoms Esters; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; vinyl compounds containing an amide group such as itaconic diamide, crotonamide, maleic diamide, fumaric diamide, N-vinylpyrrolidone; 2-hydroxyethyl Vinyl ether,
Other vinyl compounds such as methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin, maleimide, N-vinylimidazole, and vinyl sulfonic acid.

The alkoxysilyl group-containing polymer (B) is described, for example, in JP-A-54-36395, JP-A-57-36109, and JP-A-58-1578.
Although it can be produced by a method disclosed in Japanese Patent Publication No. 10-210, it is most 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, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ
- mercaptopropyl methyldimethoxysilane, .gamma.-mercaptopropyl methyl diethoxy _{silane, (CH 3 O) 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, a chain transfer agent having the alkoxysilyl group in the molecule, for example, γ
-With mercaptopropyltrimethoxysilane,
An alkoxysilyl group can be introduced at the terminal of the polymer.

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 limitation.

Such an alkoxysilyl group-containing polymer (B) contains 1
Seeds may be used, or two or more kinds may be used in combination.

The use ratio of the alkoxysilyl group-containing polymer (B) is as follows:
Component (A) / component (B) preferably has a weight ratio of 5/5 to 2/8. If the ratio of component (A) / component (B) exceeds 5/5, the water resistance of the coating film properties decreases, and if it is less than 2/8, the appearance and hardness of the coating film are improved by blending component (A). The effect cannot be obtained sufficiently.

The component (A) and the component (B) include, in combination of the acid anhydride group / epoxy group, amino group / epoxy group, and carboxyl group / epoxy group, these reactive functional groups as component (A) and component (B). Although included separately in the components, these combinations may be only one, or may include two or more combinations.

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, dioctyltin dilaurate, dioctyltin dimaleate, and tin octylate. Organic tin compounds such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate,
Phosphoric acid or phosphoric acid ester such as diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, acrylic glycidyl ether, γ-glycidoxypropyl trimethoxysilane, γ Glycidoxypropyltriethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, Yuka Ciel Epoxy Co., Ltd. Cardura E, Yuka Ciel Epoxy Co., Ltd. Epicoat 828, Epicoat 1001
Addition reaction product of an epoxy compound such as epoxy acid and phosphoric acid and / or monoacid phosphate; organic titanate compound; organoaluminum compound; acidic compound such as maleic acid and paratoluenesulfonic acid; hexylamine;
Amines such as 2-ethylhexylamine, N, N-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 anhydrides thereof, and reactive silicon compounds , An organic titanate compound, an organic aluminum compound or a mixture thereof is preferred because of its high activity.

One of such curing catalysts (C) may be used.
More than one species may be used in combination.

Although there is no particular limitation on the amount of the curing catalyst (C),
With respect to 100 parts of the solid content of the component (A) and the component (B),
Usually 0.1 to 20 parts, preferably 0.1 to 10 parts. 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 coating film properties (appearance) tend to decrease.

A dehydrating agent may or may not be used in the composition of the present invention, but by using the dehydrating agent, long-term stability and stability without any problem even when used repeatedly can be ensured.

Specific examples of the dehydrating agent include, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, methyl silicate, ethyl silicate and the like. And a hydrolyzable ester compound. These hydrolyzable ester compounds may be added before the polymerization of the alkoxysilyl group-containing polymer (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, but is usually 100 parts or less based on 100 parts of the solid content of the components (A) and (B).
Preferably it is 50 parts or less.

Further, by using a dehydration accelerator in combination, the effect of the dehydration agent can be enhanced.

As the dehydration accelerator, for example, hydrochloric acid, sulfuric acid, phosphoric acid,
Inorganic acids such as sulfuric acid; formic acid, acetic acid, oxalic acid, benzoic acid,
Organic acids such as phthalic acid, p-toluenesulfonic acid, acrylic acid and methacrylic acid; metal salts of carboxylic acids such as alkyl titanates and lead octylate; carboxylic acids such as tin octylate, dibutyltin dilaurate and dioctyltin malate Organotin compounds such as sulfides such as monobutyltin sulfide and dioctyltin mercaptide; organotin compounds such as mercaptides; organic tin oxides such as dioctyltin oxide; organic tin oxide and ethyl silicate, ethyl silicate 40, dimethyl maleate, phthalate Organotin compounds by reaction with ester compounds such as dioctyl acid; tetraethylenepentamine, triethylenediamine, N-β-aminoethyl-
amines such as γ-aminopropyltrimethoxysilane;
Alkaline catalysts such as potassium hydroxide and sodium hydroxide are effective, but organic acids, inorganic acids and organic tin compounds are particularly effective.

The dehydration accelerator is used in an amount of 0.0001 to 20 times, preferably 0.001 to 10 parts, per 100 parts of the dehydrating agent. When the compound which is also the component (C) is used as the dehydration accelerator, the amount used is the same as the amount of the component (C).

A solvent may be used in the composition of the present invention, and the solvent used may be a non-reactive solvent.

Specific examples of such a solvent include, for example, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, and the like used in general paints and coating agents. Examples include ethers, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, ketone esters, ester ethers, and the like. Among these, the use of a solvent containing an alkyl alcohol is preferred from the viewpoint of improving the stability of the composition of the present invention.

As the alkyl alcohol, an alcohol having an alkyl group having 1 to 10 carbon atoms is preferable. For example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Isobutyl alcohol, sec-butyl alcohol, tert
-Butyl alcohol, n-amino alcohol, isoamyl alcohol, hexyl alcohol, octyl alcohol, cellosolve and the like are used. The amount of the alcohol 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).

The combined use of an alcohol, especially an alkyl alcohol and a dehydrating agent has a remarkable effect on the storage stability when the components (A), (B) and (C) of the composition of the present invention are mixed and stored. The amount of the solvent used depends on the molecular weight or composition of the component (A) and the component (B), and is adjusted according to the solid content concentration or viscosity required for practical use.

A hydrolyzable silane compound, a condensate thereof, a reaction product thereof, or a mixture thereof may be added to the composition of the present invention in order to improve properties such as adhesion, hardness, and solvent resistance.

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-mercaptoproltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-propyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dibutyldimethoxy Silane, 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-propyltriethoxysilane, dimethyldiethoxy Examples thereof include silane, diethyldiethoxysilane, dibutyldiethoxysilane, diphenyldiethoxysilane, vinylmethyldiethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, trimethylethoxysilane, triethylethoxysilane, and triphenylmethoxysilane.

Condensates such as partially hydrolyzed condensates of these hydrolyzable silane compounds may be used alone or as a mixture of a plurality of the silane compounds, a necessary amount of water may be added, and if necessary, a condensation catalyst such as hydrochloric acid or sulfuric acid may be used. It is easily obtained by adding a small amount, 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, Methyl Silicate 55, Methyl Silicate 58, Methyl Silicate 60 manufactured by Nippon Colcoat Chemical Co., Ltd. Can be Examples of the compound containing a methoxysilyl group as a partially hydrolyzed condensate such as methyltrimethoxysilane and dimethyldimethoxysilane include AFP-1, AFR-2, and AFP- manufactured by Shin-Etsu Chemical Co., Ltd.
6, KP213, KR217, KR9218; T manufactured by Toshiba Silicone Co., Ltd.
SR165, TR3357; Y-1587, FZ- manufactured by Nippon Unicar Co., Ltd.
3701, 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, HAS-6, HAS-10 manufactured by Nippon Colcoat Co., Ltd.

Examples of the reactant of the hydrolyzable silane compound include a reactant of a silane coupling agent having an amino group and a silane coupling agent having an epoxy group, a silane coupling agent having 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.

The amount of the hydrolyzable silane compound, its condensate, its reactant or a mixture thereof is not particularly limited, but is usually 100 parts or less, preferably 100 parts or less, per 100 parts of the solid content of the components (A) and (B). Is less than 50 parts.

A polyorganosiloxane may be added to the composition of the present invention to impart water repellency to the cured coating film.

The polyorganosiloxane can be freely selected as long as it has a reactive functional group and is compatible with the hydroxyl group-containing polymer (A) and the alkoxysilyl group-containing polymer (B), and is not particularly limited. . The structure of the polyorganosiloxane may be any structure such as linear, branched, network, or cyclic.As the organo group, a hydrogen atom or an alkyl group, an alkenyl group, an aryl group, a methyl group,
Examples include an ethyl group, a propyl group, a butyl group, a hexyl group, an allyl group, and a phenyl group. Among these organo groups, industrially produced, inexpensive methyl groups,
Phenyl groups are practically advantageous. Examples of the reactive functional group include a silanol group, an alkoxysilyl group, an alcoholic hydroxyl group, a glycidyl group, an amino group, a mercapto group, a carboxyl group, an amide group, a vinyl group, and a (meth) acryloxy group. Silyl group and alcoholic hydroxyl group Is preferred. The number of reactive functional groups in the polyorganosiloxane is preferably one or more per molecule.

The molecular weight of the polyorganosiloxane can be freely selected as long as it is within a compatible range. However, as the molecular weight increases, the compatibility decreases.
The number is preferably 300 to 300, more preferably 2 to 100, and particularly preferably 3 to 50.

Specific examples of such a polyorganosiloxane include, for example, silicone rubber, silicone varnish, a silicone intermediate for modifying an organic polymer, reactive polydimethylsiloxane used as a reactive silicone oil, reactive polydiphenylsiloxane, and dimethyl. A reactive polymethylphenylsiloxane of the copolymerization type of diphenyl, (R is a group selected from the group consisting of a phenyl group, an alkyl group having 1 to 4 carbon atoms and a hydroxyl group), (R is a group selected from the group consisting of a phenyl group, an alkyl group having 1 to 4 carbon atoms and a hydroxyl group, and l, m, and n are each 1 to 5), The amount of the polyorganosiloxane 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).

The composition of the present invention may contain additives such as diluents, pigments (including extenders), ultraviolet absorbers, anti-settling agents, and leveling agents, depending on the use; fibrous materials such as nitrocellulose and cellulose acetate butyrate; Epoxy resin, melamine resin, vinyl chloride resin, chlorinated polyolefin, chloride rubber, polyvinyl butyral, alkyd resin, oil-free alkyd resin, acrylic-modified alkyd resin,
A resin such as an acrylic resin, a hydroxyl group-containing fluororesin, a polyester polyol, a polyether polyol, or a polyurethane polyol may be added.

The method for preparing the composition of the present invention comprising the above components is not particularly limited. For example, components (A) and (B) are cold-blended or components (A) and (B) are mixed. Are mixed and then partially reacted by heating (hot blending) or the like, and then mixed with the component (C).

The composition of the present invention, for example, dipping, spraying, brush coating, after applying to the substrate by a conventional method such as a method using a roll coater or a flow coater, 30 ℃ or more,
Preferably, it can be cured at 55 to 350 ° C.

The thermosetting composition of the present invention is useful as a paint, an adhesive, a sealant, a modifier for plastics, etc., and particularly when used as a paint, has excellent weather resistance, adhesion, hardness, and durability. Excellent coating film.

 Next, the coated article of the present invention will be described.

The coating of the present invention may be a metallic powder and / or
A paint containing a color pigment (a pigment containing a metallic powder is also referred to as a metallic base coat, a paint containing a color pigment is also referred to as a solid color coat) is applied, and the thermosetting composition as a main component is applied to the painted surface. Since the top coat clear paint (thermosetting paint) is a coated product, the coated product is excellent in weather resistance, acid resistance, stain resistance and the like.

The paint containing the metallic powder and / or the color pigment is not particularly limited. For example, amino alkyd resin, oil-free alkyd resin, thermosetting acrylic resin, thermosetting urethane resin, nitrified cotton lacquer, modified acrylic lacquer, straight acrylic Lacquer, room temperature curing urethane resin, acrylic enamel resin, oxidation curing alkyd resin, oxidation curing denaturation (CAB etc.) alkyd resin, room temperature or heat curing type fluorine resin, hydrolyzable silyl group-containing resin, hydroxyl group-containing vinyl polymer and water Those containing a mixture with a degradable silyl group-containing polymer as a main component are exemplified. Further, the type of the paint may be any type such as a solution paint using an organic solvent as a medium, a non-aqueous dispersion paint, a multi-liquid paint, a powder paint, a slurry paint, and a water paint.

The metallic powder and the coloring pigment may be known and commonly used, and any metallic powder and coloring pigment may be used. Examples of the metallic powder include aluminum powder, copper powder, and mica powder. Examples of the coloring pigment include organic pigments such as phthalocyanine blue, toluidine red, and benzidine yellow, and inorganic pigments such as titanium oxide, carbon black, and bengalara. Pigments. These metallic powders and coloring pigments may be used alone or in combination of two or more.

Further, by using an ultraviolet absorber or a light stabilizer in the paint containing the metallic powder and / or the color pigment, the weather resistance can be further improved.

As the ultraviolet absorber, conventionally known ones can be widely used, and for example, benzophenone-based, triazole-based, phenyl salicylate-based, diphenylacrylate-based, and acetophenone-based ultraviolet absorbers are preferable.

As the light stabilizer, conventionally known light stabilizers can be widely used, such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4). -Piperidyl) sebacate, 2- (3,5-di-tert)
-Butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6-tetramethyl-4- Piperidyl) -1,2,3,4-butanetetracarboxylate and tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate. Can be These may be used alone or in combination of two or more.

Further, in a paint containing a metallic powder and / or a color pigment, the silane compound, a condensate thereof, a reaction product thereof, or a mixture thereof is used in order to improve the adhesion between the coating film and the top coat clear coating film. It may be added. The amount of addition depends on the metallic powder and / or
It is usually 50 parts or less, preferably 20 parts or less, in 100 parts of the paint containing the color pigment.

When the above-mentioned ultraviolet absorber and light stabilizer are mixed with the above-mentioned top coat clear paint, the weather resistance is remarkably improved. Also,
By using the ultraviolet absorber and the light stabilizer together, the weather resistance can be further improved.

The amount of the ultraviolet absorber is usually 0.1 to 10 parts, preferably 1 to 100 parts of the solid content of the top coat clear paint.
~ 5 parts. The amount of the light stabilizer is usually 0.1 to 10 parts, based on 100 parts of the solid content of the top coat clear paint,
Preferably, it is 1 to 5 parts.

Although there is no particular limitation on the method for producing the coated material of the present invention, for example, the object is coated with the paint containing the metallic powder and / or the coloring pigment, set for a few minutes, and then top-coated with wet-on-wet. Apply clear paint and heat cure (2 coats, 1 bake method), or apply paint containing metallic powder and / or color pigment and heat cure, then apply top coat clear paint and heat cure (Two-coat, two-bake method).
The thickness of the coating film is not particularly limited, but the thickness of the coating film containing the metallic powder (or) coloring pigment is preferably 10 to 30 μm from the viewpoint of concealment, and the thickness of the top coat clear coating film is durable. From the viewpoint of properties and the like, 20 to 50 μm is preferable.

The coating film thus formed exhibits excellent performance in properties such as appearance and weather resistance.

The object on which the coating film is formed is, for example, a building, an automobile, an industrial machine, steel furniture, a household appliance, a plastic product, and the like, and the above-mentioned paint is used for an overcoat finish.

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

Production Examples 1 to 3 [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. After the temperature was raised to 110 ° C. while introducing gas, the mixture (b-1), (b-2) or (b-
3) was dropped at a constant speed over 5 hours using a dropping funnel.

After the completion of the dropwise addition of the mixtures (b-1) to (b-3), 2,2 '
-0.5 parts of azobisisobutyronitrile and 5 parts of toluene
Was dripped at a constant speed over 1 hour. After completion of dropping, the mixture was aged at 110 ° C. for 2 hours, cooled, and xylene was added to the resin solution to adjust the solid content to 60%.

Production Examples 4 to 7 [Synthesis of Hydroxy Group-Containing Polymer (A)] Instead of 45.9 parts of xylene, 31.3 parts of butyl acetate and 9.5 parts of xylene were charged, and the mixture shown in Table 2 was prepared in the same manner as in Production Examples 1 to 3 ( a-1), (a-2), (a-3)
Or (a-4) was added.

After the completion of the dropwise addition of the mixtures (a-1) to (a-4), 2,2 '
-0.2 parts of azobisisobutyronitrile and 3.8 parts of toluene
Was dripped at a constant speed over 1 hour. After completion of the dropwise addition, the mixture was aged at 110 ° C. for 2 hours, then cooled, and the solid content of the resin solution was adjusted to 60% with xylene.

Examples 1 to 4 and Comparative Example 1 Paints having compositions (units by weight) shown in Table 3 were prepared. In Table 3, the components (A) and (B) are indicated by the number of the mixture used for the synthesis of the resin solution used.

Examples 5 to 8 and Comparative Examples 2 to 3 A coated plate in which an epoxyamide-based cationic electrodeposition primer and an intermediate coating surfacer were applied to a mild steel plate which had been subjected to degreasing and phosphate conversion treatment was used as a test piece, and a base coat ( After coating acrylic melamine resin paint), a top coat clear paint shown in Table 4 was applied on a wet-on-wet basis, and the coating was baked at 140 ° C. for 30 minutes after setting for 20 minutes. The film thickness was about 15 μm in base coat and about 30 μm in top coat clear in dry film thickness. Table 4 shows the results of the evaluation of the obtained coated articles as described below.

Appearance: Comprehensive visual evaluation of gloss and lingering sensation.は indicates good, Δ indicates normal, and × indicates poor.

Adhesion: A crosscut (2 mm x 2 mm) cellophane tape peeling test is performed, and 25/25 is evaluated as 10 points and 0/25 is evaluated as 0 points.

Hardness: Measured according to JIS K 5400.

Acid resistance: 38% H ₂ SO ₄ was 5-6 drops spot, allowed to stand at room temperature for 24 hours. After wiping, examine the traces.

○: No abnormality △: Trace remains slightly glossy ×: Completely glossy Stain resistance: Applying engine oil after traveling about 5,000km, 50 ℃, 98
Charge for 24 hours under% RH condition. Then take out and wipe off, and compare with the untested part.

：: No change △: Slight discoloration ×: There is a clear difference Weather resistance: Using Atlas Co., Ltd., UV irradiation at 70 ° C for 8 hours, water coagulation (dark) at 50 ° C for 4 hours, 70 cycles
An accelerated test is performed at 0 hours and 2800 hours to evaluate the gloss retention.

Contact angle: Using a contact angle meter CA-P type manufactured by Kyowa Interface Science Co., Ltd., a contact angle (degree) to water is determined.

Rubbing property: MEK (methyl ethyl ketone) is contained in absorbent cotton, and the state after rubbing each test plate 200 times under the same conditions is observed. The state of no change is evaluated as 、, and the state of a slight scratch on the surface is evaluated as ○.

Gel fraction change: Each paint is applied on a fluorine film,
Baking for 0 minutes to produce a film having a thickness of 30 μm. The gel fraction of the obtained film (acetone extraction method) and the gel fraction after immersing the film in warm water of 60 ° C. for one month are examined.

From the results shown in Table 4, it can be seen that the paint comprising the composition of the present invention is excellent in acid resistance and stain resistance, which are problems of conventional acrylic melamine. In addition, improvement of water resistance and solvent resistance by combining functional groups, and improvement of water repellency by containing a polyorganosiloxane are also observed.

Production Example 8 [Synthesis of Hydroxyl-Free Polymer] Instead of mixture (a-1) used in Production Example 4, the following mixture (a-5) was used, and the number average molecular weight was 10,000 and the solid content was 60.
% Resin solution (a-5) was prepared.

Mixture (a-5) Styrene 28.3 parts Methyl methacrylate 37.2 parts n-butyl acrylate 32.5 parts Methacrylic acid 2.0 parts Xylene 18 parts 2,2'-azobisisobutyronitrile 1.8 parts Comparative Examples 4 to 5 A paint having the composition shown (units by weight) was prepared. The components (A) and (B) in Table 5 indicate the resin solution used by the number of the mixture used in the synthesis.

Comparative Examples 6 and 7 After a base coat (acryl melamine resin paint) was applied on the test piece in the same manner as in Example 5, a top coat clear paint shown in Table 5 was applied on a wet-on-wet basis. The obtained coated product was evaluated in the same manner as in Example 5. The results are shown in Table 6.

[Effect of the Invention] When the thermosetting composition of the present invention is used, weather resistance, adhesion,
A coated article having a coating film excellent in hardness and the like and excellent in water resistance and solvent resistance can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-75649 (JP, A) JP-A-2-73661 (JP, A) JP-A-1-141952 (JP, A) JP-A-2- 251274 (JP, A) JP-A-60-48172 (JP, A) JP-A-62-187749 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 23 / 00-101 / 14 C09D 123/00-201/10

Claims (10)

(57) [Claims] (A) a number average molecular weight of 1,50 containing at least one group selected from the group consisting of an acid anhydride group, an epoxy group, an amino group and a carboxyl group, and containing a hydroxyl group;
20 to 50 parts by weight of an acrylic polymer of 0 to 25,000, (B) containing one or more groups selected from the group consisting of an acid anhydride group, an epoxy group, an amino group and a carboxyl group, 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, an aryl group and an aralkyl group, a is 0, 1 or 2) an acrylic polymer containing an alkoxysilyl group represented by the following formula and having a number average molecular weight of 1,000 to 25,000:
0 parts by weight and (C) a curing catalyst, wherein the total of the components (A) and (B) is 100 parts by weight, and the functional group contained in the component (A) and the functional group contained in the component (B) A thermosetting composition comprising a combination of at least one of an acid anhydride group / epoxy group, an amino group / epoxy group and a carboxyl group / epoxy group. 2. The composition according to claim 1, wherein the hydroxyl group-containing acrylic polymer as the component (A) has a hydroxyl value of 10 to 300 mgKOH / g. 3. An acrylic polymer containing an alkoxysilyl group, which is a component (B), comprises an acid anhydride group, an epoxy group,
It contains at least one group selected from the group consisting of an amino group and a carboxyl group, and has a general formula: (Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² and R ³ are each a hydrogen atom or a monovalent hydrocarbon group selected from the group consisting of an alkyl group, an aryl group and an aralkyl group, a
The composition according to claim 1, which is a polymer having a group represented by the following formula: 4. An acrylic polymer containing an alkoxysilyl group, which is the component (B), contains 5 to 5 units of an alkoxysilyl group-containing monomer having a polymerizable unsaturated double bond.
The composition according to claim 1, which is a polymer containing 90% by weight. 5. 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. Acid anhydrides of polycarboxylic acids, reactive silicon compounds, organic titanate compounds,
The composition according to claim 1, which is an organoaluminum compound or a mixture thereof. 6. A method according to claim 1, which comprises a hydrolyzable ester compound as a dehydrating agent and an alkyl alcohol as a solvent.
A composition as described. 7. The composition according to claim 1, comprising a hydrolyzable silane compound as a physical property modifier, a condensate thereof, a reactant thereof, a polyorganosiloxane or a mixture thereof. 8. A coated product in which a coating containing a metallic powder and / or a coloring pigment is applied, and the coated surface is coated with a topcoat clear coating, wherein the topcoat clear coating is applied. A coated article characterized in that it is a thermosetting coating mainly comprising the composition described in (1). 9. The coated article according to claim 7, wherein the top coat clear coating contains an ultraviolet absorber and / or a light stabilizer. 10. The coated article according to claim 7, wherein the paint containing the metallic powder and / or the color pigment contains a silane compound, a condensate thereof, a reactant thereof, or a mixture thereof.