JP3464552B2 - Thermosetting resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition using an acrylic resin component having a specific epoxy group and its application to a paint.

[0002]

2. Description of the Related Art Conventionally, various resin curing systems have been used in paints, adhesives, and photocurable resins. Of these, a curing system using an epoxy group is extremely useful because of its excellent reactivity and physical properties of the cured product, and is used in various fields. Glycidyl methacrylate is well known as an epoxy group-containing α, β-unsaturated monomer used in such a curing system. For example, Japanese Unexamined Patent Publication (Kokai) No. 2-45577 describes a coating composition utilizing a curing reaction of glycidyl methacrylate and a carboxyl group, and Japanese Unexamined Patent Publication (Kokai) No. 2-73825 discloses 3,4-epoxycyclohexyl. A coating composition for curing an alicyclic epoxy acrylate such as (meth) acrylate by a cationic curing reaction using a silanol group is described.

[0003]

However, glycidyl methacrylate has extremely high reactivity with a carboxyl group,
When it is used as a one-pack type coating composition, there arises a problem that the pot life is short. Further, (meth) acrylate having an alicyclic epoxy group such as 3,4-epoxycyclohexyl (meth) acrylate has high cation curing reactivity, and therefore, when used in a coating system containing a carboxyl group or with a hydroxyl group or the like. Even when the reaction of an epoxy group is used, when an acid having a relatively high acidity such as phosphoric acid, oxalic acid or p-toluenesulfonic acid is used as a catalyst, cationic polymerization can be easily carried out using the hydroxyl group in the system as an initiator. Pot life is shortened because it is awakened.
Therefore, there is a problem that it is difficult to select a curing catalyst having an appropriate pot life. Β-methylglycidyl methacrylate is known as another (meth) acrylate. This is mild in both the reactivity with the carboxyl group or the reactivity with the cation catalyst, but the pot life of the one-component paint can be extended, but it is necessary to increase the curing reaction time or increase the curing temperature. There is a problem that the allowable range of curing conditions is narrow. Moreover,
Glycidyl methacrylate and β-methylglycidyl methacrylate generally contain chlorine in their products because epichlorohydrin, β-methylepichlorohydrin and the like are used as raw materials. As a result, problems such as corrosion of the base material and yellowing of the coating film during the baking and curing reaction cannot be avoided. Further, the alicyclic epoxy has a rigid structure and the flexibility of the coating film is low. Similarly, also in glycidyl methacrylate and β-methylglycidyl methacrylate, the acrylic main chain and the epoxy which is the cross-linking point have a short carbon chain. When they are bonded to each other and formed into a coating film, it is a problem to impart a good balance between toughness and flexibility.

[0004]

Means for Solving the Problems As a result of intensive studies in view of the above points, the present inventors have found that the cationic polymerization reactivity using a cationic catalyst is milder than that of an alicyclic epoxy group, and the glycidyl group and β- Higher reactivity than methyl glycidyl group, on the other hand, reactivity with carboxyl group is slightly milder than glycidyl group, faster than β-methyl glycidyl group, and balance between pot life and curing reactivity in both curing systems. Is excellent and, in addition, the corrosion of the substrate,
The present invention has been completed by finding out a thermosetting resin composition having a specific epoxy group containing substantially no chlorine which causes yellowing of a coating film.

That is, the present invention is a thermosetting resin composition containing at least one acrylic resin component,
The following general formula (1) is added to any of the acrylic resin components.
And an epoxy group contained in the general formula (1) in any component of the thermosetting resin composition (hereinafter, abbreviated as "epoxy group of general formula (1)"). The present invention provides a thermosetting resin composition containing a functional group capable of reacting with. Further, the present invention provides the thermosetting resin composition, wherein any of the acrylic resin components contains a functional group capable of reacting with the epoxy group of the following general formula (1). Further, the functional group capable of reacting with the epoxy group represented by the following general formula (1) is a group selected from the group consisting of a carboxyl group, a hydroxyl group, a silanol group and a hydrolyzable alkoxysilanol group. A resin composition is provided. Further, since these thermosetting resin compositions use the epoxy group which separates the methylene chain from the main chain of the acrylic resin as a cross-linking point, when applied to a coating material, it is possible to impart flexibility to the coating film obtained. Such characteristics are extremely useful in that the coating film is less likely to be scratched. Therefore, the present invention further provides a coating composition containing the thermosetting resin composition. Hereinafter, the present invention will be described in detail.

[0006]

[Chemical 7]

The acrylic resin having an epoxy-containing group represented by the general formula (1) is obtained by polymerizing an α, β-unsaturated monomer represented by the following general formula (2) alone or by using another polymer. It can be produced by copolymerizing with an α, β-unsaturated monomer.

[0008]

[Chemical 8]

The epoxy group-containing monomer represented by the general formula (2) is produced by epoxidizing an alkenyl group-containing (meth) acrylate represented by the following general formula (3) by an oxidation reaction. be able to.

[0010]

[Chemical 9]

First, a method for producing the alkenyl group-containing (meth) acrylate represented by the general formula (3) will be described. Alkenyl group-containing (meta) represented by general formula (3)
Acrylate is esterification of acrylic acid, methacrylic acid, or an ester thereof with an alcohol in which a hydroxyl group is bonded to a group having one or more double bonds in one molecule represented by the general formula (3 ′), or Manufactured by transesterification. Examples of alcohols represented by the general formula (3 ′) in which a hydroxyl group is bonded to a group having one or more double bonds in one molecule include 3-methyl-2-buten-1-ol and 3-methyl. -3-Butene-1-ol, 2,7-
Octadienol, 7-octen-1-ol, 1,7
-Compounds such as octadien-3-ol.

In the method for producing the alkenyl group-containing (meth) acrylate represented by the general formula (3), unsaturated carboxylic acids such as acrylic acid and methacrylic acid or esters of these with alcohols are used. Alkyl esters of the numbers 1 to 4 are used. The amount of (meth) acrylic acid or its ester to be used is theoretically 1.0 mol times, but preferably 0.1 to 10.0 mol times, relative to the alcohol.
Further, the molar ratio of 1.0 to 3.0 is most preferable in terms of reaction rate and economy. If it is less than 0.1, loss due to polymerization of unsaturated carboxylic acid is reduced, but recovery of alcohol requires a large amount of energy, which is not preferable. On the contrary, when it is 10 or more, it is preferable in terms of the selectivity and conversion of alcohol, but the loss due to the polymerization of unsaturated carboxylic acid is large, and it takes a lot of money to recover the unreacted unsaturated carboxylic acid. There is.

As the catalyst used in the method for producing the compound of the general formula (3), those known as esterification or transesterification catalysts can be used. Specifically, organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and fluorosulfuric acid, inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid,
Sodium alcoholate, lithium hydroxide, aluminum alcoholate, bases such as sodium hydroxide, tin octylate, dibutyltin dilaurate, monobutyltin oxide, tin compounds such as stannous chloride, tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, etc. Titanium compounds can be used. Of these, acids such as p-toluenesulfonic acid are preferable in terms of reaction rate. The amount of catalyst is 1 ppm to 10 relative to the starting material
%, Preferably 5 ppm to 1.0%. When the amount of the catalyst used is 1 ppm or less, there are disadvantages such as a slow reaction rate and a poor yield. On the contrary, when the amount is 10%, the product is colored and a gelled product is generated due to a side reaction, which is not desirable. .

The reaction can be carried out without solvent or with a solvent. Since water or alcohol is produced as the reaction progresses, it is effective to use a reaction solvent capable of azeotropically removing these, in order to increase the reaction rate. is there. As the reaction solvent, toluene, benzene, xylene, n-hexane, n
-Heptane, methyl isobutyl ketone and the like can be used. The amount of azeotropic solvent used is 0.1 to the reaction product.
It is 10 times, preferably 2 to 5 times. The azeotropic solvent distilled with water can be separated and reused. The reaction temperature is 6 in order to shorten the reaction time and prevent polymerization.
Advantageously, it is carried out at 5 to 150 ° C, preferably 75 to 120 ° C. If the temperature is lower than 65 ° C, the reaction rate is too slow,
If the temperature is 150 ° C. or higher, thermal polymerization of the unsaturated carboxylic acid occurs, which is not desirable.

It is preferable to add a polymerization inhibitor in order to prevent thermal polymerization of the unsaturated carboxylic acid and to carry out the reaction in the presence of air during the reaction. The polymerization inhibitors used include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, α-nitroso β-naphthol, p-benzoquinone, 2,5-dihydroxy-p. Although quinone, copper salt, phenothiazine and the like can be used, hydroquinone and p-methoxyphenol are preferable in terms of stability and the like. The amount of the polymerization inhibitor added is 0.001 to the unsaturated carboxylate.
It is 5.0 wt%, preferably 0.01 to 1.0 wt%. If the addition amount is less than 0.001 wt%, the polymerization inhibition effect is small, and conversely if it is 5.0% or more, the effect is not improved and it is wasted. The reaction is preferably carried out under normal pressure or slightly reduced pressure. Since the esterification reaction crude liquid obtained by the reaction contains an excess of unsaturated carboxylic acid, it is preferable to wash or neutralize the reaction crude liquid to remove low boiling point components. Examples of the alkaline aqueous solution used for neutralization include NaOH, KOH, K ₂ CO ₃ , and Na.
Aqueous solutions such as ₂ CO ₃ , NaHCO ₃ , KHCO ₃ , NH ₃ etc. can be used, the concentration being freely usable within a wide range. After neutralization, if the low boiling point components are removed and the product is made into a product without washing with water, a neutralized salt will remain in the product, so it is preferable to wash with water after neutralization.

Next, a method for producing the epoxy group-containing monomer represented by the general formula (2) will be described. This is produced by epoxidation of the alkenyl group-containing (meth) acrylate represented by the general formula (3) obtained above. Any oxidizing agent may be used as long as it can epoxidize an unsaturated bond, and organic peracids such as peracetic acid, performic acid, perpropionic acid, m-chloroperbenzoic acid, trifluoroperacetic acid and perbenzoic acid, t Examples thereof include butyl hydroperoxide, cumyl hydroperoxide, tetralyl hydroperoxide, hydroperoxides of diisopropylbenzene hydroperoxides, and hydrogen peroxide. The molar ratio of the oxidizing agent and the alkenyl group-containing (meth) acrylate {oxidizing agent / alkenyl group-containing (meth) acrylate} is theoretically 1, but actually it is in the range of 0.1 to 10, preferably 0. .5-
The range is 2, more preferably 0.8 to 1.2. When the molar ratio is greater than 10, it is preferable in terms of conversion rate of alkenyl group-containing (meth) acrylate and reduction of reaction time, and reduction of loss due to polymerization of alkenyl group-containing (meth) acrylate, but side reaction due to excess oxidant and The selectivity of the oxidizing agent and the recovery of the unreacted oxidizing agent require a great deal of cost, which is not preferable. On the other hand, when the molar ratio is 0.1 or less, it is preferable in terms of conversion of the oxidant, selectivity, and prevention of side reaction of the product due to the oxidant, but loss due to polymerization of the alkenyl group-containing (meth) acrylate, There are drawbacks such as a large amount of cost for recovering the unreacted alkenyl group-containing (meth) acrylate.

The reaction temperature for epoxidation is lower than the upper limit so that the epoxidation reaction takes precedence over the decomposition reaction of the oxidant. For example, when peracetic acid is used, the temperature is 70 ° C. or lower, and t-butyl hydroperoxide is used. When it does, 150 degreeC or less is preferable. When the reaction temperature is low, it takes a long time to complete the reaction. Therefore, it is preferable to perform the reaction at 0 ° C. when using peracetic acid, or at a lower limit of 20 ° C. or more when using t-butyl hydroperoxide. A solvent may or may not be used in the epoxidation reaction, but for stabilization by dilution of the oxidant, benzene, toluene, aromatics such as xylene, chloroform, dimethyl chloride, carbon tetrachloride, Halides such as chlorobenzene, ester compounds such as ethyl acetate and butyl acetate, ketone compounds such as acetone and methyl isobutyl ketone, ether compounds such as 1,2-dimethoxyethane and the like can be used.

Further, a polymerization inhibitor is added to prevent thermal polymerization of the alkenyl group-containing (meth) acrylate. The polymerization inhibitor used is hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol,
3-Hydroxythiophenol, α-nitroso β-naphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, copper salt and the like can be used, but hydroquinone and p-methoxyphenyl are preferable in terms of stability and the like. Addition amount of polymerization inhibitor is alkenyl group-containing (meth)
The amount is 0.001 to 5.0% by weight, preferably 0.01 to 1.0% by weight, based on the acrylate. Addition amount is 0.0
If it is less than 01 wt%, the effect of inhibiting polymerization is small, and conversely if it is 5.0 wt% or more, the effect is not improved and it is wasted. The polymerization inhibitor is added by dissolving it in the alkenyl group-containing (meth) acrylate immediately before the epoxidation reaction. Further, in order to prevent thermal polymerization of the alkenyl group-containing (meth) acrylate, it is preferable to carry out in the presence of air during the reaction.

When an organic peracid is used as an oxidant, the crude liquid of the epoxidation product obtained by the above reaction is reacted in order to prevent the polymerization of the alkenyl group-containing (meth) acrylate and the ring opening of the epoxy group of the product. It is preferable to wash or neutralize the crude liquid to remove low boiling point components. Examples of the alkaline aqueous solution used for neutralization include NaOH, KOH, K _{2
CO 3, Na 2 CO 3,} NaHCO 3, can be used an aqueous solution such as KHCO _3, NH _3, that upon its concentration may be used freely within wide limits. After neutralization, if the low boiling point components are removed and the product is commercialized without washing with water, a neutralized salt will remain in the product, so it is preferable to wash with water after neutralization. A thin film evaporator or the like is preferably used to remove the deboiling components from the reaction crude liquid which has been neutralized or washed with water.
In this way, the epoxy group-containing monomer represented by the general formula (2) is obtained.

An acrylic resin having an epoxy group represented by the general formula (1), which constitutes the thermosetting resin composition of the present invention, is prepared by using the monomer represented by the general formula (2) obtained above. A method for producing a resin system will be described. The acrylic resin having an epoxy-containing group represented by the general formula (1) is obtained by polymerizing a monomer having an epoxy group represented by the general formula (2) alone or by copolymerizing with another α. , .Beta.-unsaturated monomers are copolymerized, and as such other monomers, various .alpha.,. Beta.-unsaturated monomers used in ordinary acrylic resin production are used. can do.

Examples of such α, β-unsaturated monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic acid and fumaric acid. 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate,
Caprolactone adduct of hydroxyethyl (meth) acrylate (PCL FA-1, FM manufactured by Daicel Chemical Industries, Ltd.
-1, etc.), hydroxyl group-containing monomers such as allyl alcohol and 2-methylallyl alcohol; amino group-containing monomers such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate; amides such as acrylic acid amide and methacrylic acid amide Group-containing monomer; nitrile group-containing monomer such as acrylonitrile and methacrylonitrile;
A silyl group-containing monomer such as γ-trimethoxysilylpropyl methacrylate; an alkyl group-containing monomer such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, and 2-ethylhexyl acrylate Polymers; Polymerizable aromatic compounds such as styrene and α-methylstyrene; Other polymerizable monomers such as ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, butadiene, isoprene, etc. be able to. These other monomers may be copolymerized alone or in combination of two or more. In addition,
Polymerization of a monomer having an epoxy group represented by the general formula (2), copolymerization with another α, β-unsaturated monomer, and post-treatment thereof are carried out by the acrylic resin exemplified below. Can be carried out using any known means used for the production of

As the polymerization initiator, benzoyl peroxide, t
-Butyl oxide, cumene hydroperoxide and other organic peroxides; azoisobisisobutyronitrile, azobis (2,4-dimethyl) valeronitrile and other organic azo compounds; potassium persulfate, ammonium persulfate, sodium persulfate Inorganic water-soluble radical initiators such as hydrogen peroxide and redox type initiators are preferably used. Further, as a chain transfer agent, ethyl mercaptan,
It is possible to use mercaptans such as methyl mercaptan and the like, α-methylstyrene dimer, or halogenated carbons such as carbon tetrachloride and carbon tetrabromide.

The acrylic resin having an epoxy-containing group represented by the general formula (1) used in the present invention is a homopolymer of an α, β-unsaturated monomer represented by the general formula (2). In addition to the case, in the case of copolymerizing with other α, β-unsaturated monomer, depending on the charging ratio of the reaction conditions, usually, they are a mixed composition of various randomly polymerized resin components, In any of these cases, the average molecular weight according to the GPC method is usually 500 to 30 × 10 ⁴ , more preferably 1,
The range is 000 to 10 × 10 ⁴ . The oxirane oxygen concentration based on the epoxy-containing group is 0.5 to 10 wt.
%, More preferably 1.0 to 5.0 wt%.

Specific examples of the epoxy-containing group represented by the general formula (1) contained in the acrylic resin used in the present invention are preferably epoxy-containing groups represented by the following chemical formulas (21) to (25).

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

Next, the thermosetting resin composition of the present invention will be described. The thermosetting resin composition of the present invention is characterized by containing an acrylic resin having an epoxy-containing group represented by the general formula (1) and a functional group capable of reacting with the epoxy group of the general formula (1). To do. There are various functional groups as the functional group capable of reacting with the epoxy group of the general formula (1),
Practically, a carboxyl group, a silanol group, a hydrolyzable alkoxysilane group, a hydroxyl group or the like is desirable. It is preferable to introduce these functional groups into the acrylic resin having the epoxy-containing group represented by the general formula (1), but the present invention is not limited to this, and a compound having these functional groups may be used as a curing agent separately. You may add in the composition which consists of acrylic resin which has an epoxy containing group shown by Formula (1). Further, when the thermosetting resin composition of the present invention is used for a coating material or the like, a one-pack type or a two-pack type can be used. The following describes the case of introducing a functional group capable of reacting with an epoxy group into the acrylic resin component, but the polymerizable monomer used for them is
In addition to being polymerized and introduced into the acrylic resin component, it may be added as a curing agent as described above before curing the thermosetting resin composition of the present invention.

The case where a "carboxyl group" is used for the curing reaction as the functional group capable of reacting with the epoxy group of the general formula (1) will be described. The polymerizable monomer that can be used to introduce a carboxyl group into the acrylic resin having an epoxy-containing group represented by the general formula (1) is an acrylic resin exemplified as the α, β-unsaturated monomer. Acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid and other carboxyl group-containing polymerizable monomers, and fumaric acid, maleic acid, itaconic acid and other unsaturated carboxylic anhydrides as alcohol half ester The body etc. can be used. In addition to the use of these carboxyl group-containing polymerizable monomers, unsaturated carboxylic acid anhydrides are copolymerized with acrylic resin production raw material monomers, and then alcohols and hydroxyl group-containing resins are used to form half-esters. It is also possible. Further, β-hydroxyethyl (meth) acrylate or a polymerizable monomer obtained by adding caprolactone to β-hydroxyethyl (meth) acrylate (PCL FA-1, PCL FM-1 manufactured by Daicel Chemical Co., Ltd.),
4-hydroxybutyl (meth) acrylate, (meth)
A carboxyl group obtained by adding an acid anhydride to a polymerizable monomer containing a hydroxyl group, such as a polymerizable monomer to which ethylene oxide or propylene oxide of acrylic acid is added (Blenmer PP, Blemmer PE manufactured by NOF CORPORATION) A containing monomer can also be used. The acid anhydrides that can be used here include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and head acid anhydride (of phthalic anhydride containing chlorine. Derivative), hymic acid anhydride, adipic acid anhydride, azelaic acid anhydride, sebacic acid anhydride, or derivatives thereof. Such a monomer having a terminal carboxyl group can be obtained by mixing and heating a polymerizable monomer having a hydroxyl group and an acid anhydride in the range of 60 ° C. to 150 ° C. in the presence of a polymerization inhibitor. It can be easily synthesized.

The thermosetting resin composition of the present invention contains an acrylic resin component having an epoxy-containing group represented by the general formula (1), which is contained as a structural unit for introducing it. The content of the monomer represented by 2) is preferably in the range of 1 to 80 wt% in the acrylic resin component, and the content of the structural unit of the carboxyl group-containing unsaturated monomer that reacts with this is The range of 5 to 60 wt% is desirable. The molar ratio of the epoxy group to the carboxyl group is in the range of 1 / 0.01 to 1/100, preferably 1 / 0.01.
The range of 0.1 to 1/10 is desirable.

In the thermosetting resin composition, a quaternary compound such as benzyltriethylammonium chloride or bromide, tetramethylammonium chloride or bromide is used as a catalyst for the reaction between the epoxy group and the carboxyl group of the general formula (1). Ammonium salts, tin-based catalysts such as dimethyltin bis (methylmalate), dimethyltin bis (ethylmalate), dimethyltin bis (butylmalate), dibutyltin bis (butylmalate), or phosphorus compounds such as triphenylphosphine, tetraphenylphosphonium chloride or bromide. Is preferably contained as a catalyst. The catalyst amount is a weight ratio to the acrylic resin component of the composition,
1 ppm to 1%, preferably 10 ppm to 3,000
It is preferably in the range of 0 ppm.

Next, the case where a "hydroxyl group" is used in the curing reaction as a functional group capable of reacting with the epoxy group of the general formula (1) will be described. The epoxy group of the general formula (1) is
The reactivity of the cationic polymerization is higher than that of a compound having a glycidyl group such as glycidyl meta-acryl and the curing reaction by the hydroxyl group and the cationic polymerization catalyst is possible. The polymerizable monomer that can be used for introducing a hydroxyl group into the acrylic resin as a functional group capable of reacting with the epoxy group of the general formula (1) is an α, β-unsaturated monomer. Examples of β-hydroxyethyl (meth) acrylate or polymerizable monomers obtained by adding caprolactone to β-hydroxyethyl (meth) acrylate (PCL FA-1, PCL FM manufactured by Daicel Chemical Co., Ltd.)
-1), 4-hydroxybutyl (meth) acrylate,
Examples of the polymerizable monomer include a hydroxyl group-containing polymerizable monomer such as a polymerizable monomer to which ethylene oxide or propylene oxide of (meth) acrylic acid is added (Blenmer PP, Blemmer PE manufactured by NOF CORPORATION).

In the thermosetting resin composition, amine-based, alkaline-based and acid-based catalysts used for curing the epoxy resin are used as catalysts for the reaction between the epoxy group and the hydroxyl group of the general formula (1). It can be preferably used. As such a catalyst, imidazoles such as 4-methylimidazole,
Tertiary amines such as tris (dimethylamino) phenol, N, N-dimethylbenzylamine, KOH, NaOH
Inorganic alkalis such as and alcoholates such as sodium alcoholate can be used. Examples of the acid-based catalyst include phosphoric acid, phosphoric acid esters that accelerate the cationic polymerization catalytic reaction, or acidic phosphoric acid group-containing (meth) acrylate, oxalic acid, succinic acid, trimellitic acid, p-toluenesulfonic acid. It is desirable to contain a highly acidic catalyst such as The amount of these catalysts is preferably in the range of 1 ppm to 10%, and more preferably 10 ppm to 2% as the polymerization ratio of the composition to the acrylic resin component. 1 ppm
If it is less than 10%, the curing acceleration effect is poor, and if it is 10% or more, the physical properties of the coating film deteriorate.

The thermosetting resin composition of the present invention contains an acrylic resin component having an epoxy-containing group represented by the general formula (1), which is contained as a structural unit for introducing it. The content of the monomer shown in 2) is preferably in the range of 1 to 80 wt% in the acrylic resin component, and the content of the structural unit of the hydroxyl group-containing polymerizable monomer that reacts with this is , 5 to 60 wt% is desirable. Further, the molar ratio of the epoxy group and the hydroxyl group is preferably in the range of 1 / 0.01 to 1/100, particularly 1 / 0.1 to 1/10.

In the thermosetting resin composition of the present invention, a compound containing a silanol group or a hydrolyzable alkoxysilyl group is used in combination as a copolymerizable monomer of the acrylic resin to further form a coating film. Physical properties can be improved. Examples of such a compound containing a hydrolyzable alkoxysilyl group include β- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
A silane coupling agent such as γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropylmethyldiethoxysilane is added as a crosslinking component, or an alkoxysilyl group-containing resin represented by the general formula (4) described later. It is also possible to introduce an alkoxysilyl group into the thermosetting resin composition by using. The content of these hydrolyzable alkoxysilyl groups is preferably 5 to 50% by weight in the acrylic resin component.

The case where a "silanol group" or a hydrolyzable "alkoxysilanol group" as a functional group capable of reacting with the epoxy group of the general formula (1) is used as a copolymerization monomer of an acrylic resin will be described. The epoxy group of the general formula (1) has higher reactivity of cationic polymerization as compared with a compound having a glycidyl group such as glycidyl metaacreyl,
A curing reaction using a cationic polymerization catalyst with a silanol group or a hydrolyzable alkoxysilane group is also possible.
As the polymerizable monomer that can be used for introducing the silanol group or the hydrolyzable alkoxysilanol group into the acrylic resin, the compound represented by the general formula (4) can be used.

[0039]

[Chemical 15]

Specifically, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxy. Propylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane,
γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxybutylphenyldiethoxysilane, γ- (meth) acryloxybutylphenyldipropoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropylphenylmethylmethoxysilane, γ-
(Meth) acryloxypropylphenylmethylethoxysilane and compounds having the following structural formulas can be used. In the following formula, Ph is a phenyl group (C ₆ H
₅ ), Bu is a butyl group (C ₄ H ₉ ), and R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms.

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

[0045]

[Chemical 20]

[0046]

[Chemical 21]

Examples of the compound having the structure represented by the general formula (4) in which the portion A is a carbonyloxyphenylene group include the following compounds. In the formula, P
h represents a phenyl group, R ₁ represents hydrogen or an alkyl group having 1 to 4 carbon atoms.

[0048]

[Chemical formula 22]

[0049]

[Chemical formula 23]

[0050]

[Chemical formula 24]

[0051]

[Chemical 25]

[0052]

[Chemical formula 26]

[0053]

[Chemical 27]

A hydrolyzable alkoxysilanol group or silanol group-containing monomer contained as a structural unit of an acrylic resin having an epoxy-containing group represented by the general formula (1) in a thermosetting resin composition, and a general formula The content ratio of the structural unit of the monomer represented by (2) is 1 / 0.1 to 1/1000, preferably 1 / 0.25 to 1/100 by weight ratio with respect to the entire acrylic resin. It is a range. When the content of the structural unit of the epoxy group-containing polymerizable monomer represented by the general formula (2) is larger than this range, the curability of the composition tends to be poor, and when it is smaller than this range, the weather resistance and the mechanical properties are poor. The physical properties of the coating film, such as physical properties, deteriorate, and problems such as a decrease in the curing rate of the coating film and the occurrence of curing shrinkage are likely to occur.

In this thermosetting resin composition, the cationic polymerization catalyst reaction is promoted as a catalyst for the reaction of the epoxy group of the general formula (1) with the silanol group and the hydrolyzable alkoxysilanol group, and a suitable pot life is obtained. A known aluminum chelate, titanium chelate or zirconium chelate compound catalyst that gives Among these chelate compounds, a chelate compound containing a compound capable of forming keto or enol tautomerism as a ligand forming a stable chelate ring is desirable. Examples of the compound capable of forming keto and enol tautomerism include β-diketones (acetylacetone etc.), acetoacetic acid esters (methyl acetoacetate etc.), malonates (ethyl malonate etc.), and a hydroxyl group at the β-position. It is possible to use a ketone having a group such as diacetone alcohol, an aldehyde having a hydroxyl group at the β-position (such as salicylaldehyde), an ester having a hydroxyl group at the β-position (methyl salicylate), and the like. In particular, it is preferable to use acetoacetic acid esters and β-diketones.

The aluminum chelate compound comprises the aluminum alcoholate represented by the general formula (18) and the above-mentioned compound capable of forming a keto or enol tautomer in an amount of about 3 mol or less per 1 mol of the aluminum alcoholate. It can be prepared by mixing in a ratio and heating if necessary.

[0057]

[Chemical 28]

The aluminum alcoholates represented by the general formula (18) include aluminum trimethoxide,
Aluminum triethoxide, aluminum tri-n-
Examples include propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-sec-butoxide, aluminum tri-tert-butoxide and the like. Among these, it is preferable to use aluminum triisopropoxide, aluminum tri-sec-butoxide, aluminum tri-n-butoxide and the like.

The titanium chelate compound has the general formula (1
9) a titanium alcoholate represented by the above-mentioned keto,
The compound capable of forming the enol tautomer is titanium 1
It can be prepared by mixing in a ratio of about 4 mol or less with respect to mol and heating if necessary.

[0060]

[Chemical 29]

Examples of the titanates represented by the general formula (19) include tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate and tetra-tert-butyl. There are titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate and the like, among which tetraisopropyl titanate and tetra-n-
Butyl titanate, tetra-tert-butyl titanate and the like are preferable. For compounds where m is an integer greater than or equal to 1, tetraisobutyl titanate, tetra-tert
-Butyl titanate, tetraisopropyl titanate,
A dimer to an 11-mer of tetra-n-butyl titanate is preferable.

The zirconium chelate compound comprises a zirconium compound represented by the general formula (20) and a compound capable of forming a keto or enol tautomer in a ratio of about 4 mol to 1 mol of the zirconium compound. It can be prepared by mixing at a ratio not higher than this and heating if necessary.

[0063]

[Chemical 30]

The zirconates represented by the general formula (20) include tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate and tetra-sec.
-Butyl zirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, tetra-tert-pentyl zirconate, tetra-tert
-Hexyl zirconate, tetra-n-heptyl zirconate, tetra-n-octyl zirconate, tetra-
There are n-stearyl zirconates and the like, and among them, especially tetraisopropyl zirconate, tetra-n-propyl zirconate, tetraisobutyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert- Butyl zirconate and the like are preferred. Further, for the compound in which m is an integer of 1 or more, tetraisopropyl zirconate, tetra-n
-Propyl zirconate, tetra-n-butyl zirconate, tetraisobutyl zirconate, tetra-sec
-Butyl zirconate and tetra-tert-butyl zirconate dimers to 11-mers are preferable, and a constitutional unit in which these zirconates are associated with each other may be contained.

Among the above, particularly preferable chelate compounds in the present invention are diisopropylate ethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum and tris (isopropylacetoacetate). Aluminum, tris (n-butylacetoacetate) aluminum, isopropoxybisethylacetoacetate aluminum, diisopropoxyethylacetoacetate aluminum, tris (acetylacetonate) aluminum, tris (ethylacetonate) aluminum, diisopropylate ethylacetonate Aluminum, monoacetylacetonate, bis (ethylacetonate) aluminum, monoethylacetoacetate bis Acetylacetonate) aluminum, tris (isopropylate) aluminum, tris (sec-butylate) aluminum, di-isopropylate mono -sec- butoxy aluminum, tris (acetylacetonate) aluminum chelate compounds such as aluminum. Further, titanium chelate compounds such as diisopropoxy bis (ethylacetoacetate), diisopropoxy bis (acetylacetate) and diisopropoxy bis (acetylacetone) titanate are preferable. In addition, tetrakis (acetylacetone)
Zirconium chelate compounds such as zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetonato) zirconium and tetrakis (ethylacetoacetate) zirconium can be preferably used. In the present invention, any one kind or a mixture of several kinds of the aluminum chelate compound, the zirconium chelate compound and the titanium chelate compound may be used.

The amount of the chelate compound added is 0.01 to 100 parts by weight based on the total amount of the acrylic resin.
The range of 30 parts by weight is preferable, and more preferably 0.05.
To 15 parts by weight, more preferably 0.5 to
It is in the range of 10 parts by weight. If the amount of the catalyst is less than 0.01 parts by weight, the cross-linking curability tends to decrease, and conversely, if the amount of the catalyst is more than 30 parts by weight, the curing catalyst remaining in the cured product may reduce the water absorption and weather resistance of the coating film. It can cause worsening.

When the thermosetting resin composition according to the present invention is used in a paint or the like, a melamine-formaldehyde resin and / or an isocyanate or a blocked isocyanate may be used in combination in order to increase the crosslinking density. Two or more kinds of functional groups capable of reacting with the epoxy group of the general formula (1) may be used at the same time, and are preferable.

The number average molecular weight of the acrylic resin contained in the thermosetting composition of the present invention is 1,000 to 1
It is preferably in the range of 0,000, more preferably 2,
It is in the range of 000 to 50,000. Molecular weight is 100
If it is 0 or less, sufficient mechanical properties of the coating film cannot be obtained,
When it is 100,000 or more, the viscosity becomes extremely high and the workability becomes poor, and when a coating composition having an appropriate viscosity is prepared, the nonvolatile content becomes low and the practicality becomes poor.

Further, the thermosetting composition of the present invention may contain another compound having an epoxy group and having a molecular weight of 3,000 or less. These low molecular weight epoxy compounds are useful as a reactive diluent and are effective in reducing the viscosity of the thermosetting resin composition. The compounding amount of these epoxy compounds is 1 to 80 wt% in the resin component of the thermosetting resin composition.
%, Preferably 5 to 60 wt%. If it is 1% or less, the effect of reducing the viscosity is insufficient, and if it is 80% or more, the physical properties of the coating film deteriorate. Further, the thermosetting resin composition of the present invention can also contain a component having a molecular weight of 1,500 or less containing an oxirane ring as a reactive diluent, whereby the organic solvent released during curing of the coating film It is possible to significantly reduce the amount. As such a low molecular weight epoxy compound, a bifunctional alicyclic compound (eg, Daicel Chemical's Celoxide 2021, 2080 series), a polyfunctional alicyclic epoxy compound (eg, Daicel Chemical's Epolide GT series), or 1,9 -Epoxy monomers containing various glycidyl groups such as nonane diepoxide, alkoxysilane compound of 1,9-nonane monoepoxyside, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, cyclohexane dimethanol diglycidyl ether, etc. Can be preferably used.

[0070]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In the following, “parts” means parts by weight.

(Synthesis Example 1) Stirrer, Dimroth cooler,
Xylene 150 was placed in a 2 liter glass reaction flask equipped with a thermometer, a dropping funnel and a nitrogen introducing tube.
Parts, 150 parts of propylene glycol monomethyl ether acetate, and 3 parts of perbutyl O (manufactured by NOF CORPORATION) as an initiator, and then methyl methacrylate 20
0 part, methacrylic acid 85 parts, epoxy group-containing monomer (the following formula) 200 parts, styrene 100 parts, 2-ethylhexyl methacrylate 50 parts, caprolactone-added hydroxyethyl methacrylate (manufactured by Daicel Chemical Industries, PCL
FM-1) 50 parts of the mixture, and separately from these monomers, a mixture of 150 parts of xylene, 150 parts of propylene glycol monomethyl ether acetate, and 4 parts of perbutyl O (manufactured by NOF Corporation) as an initiator. The temperature was set to 80 ° C., the mixture was added dropwise over about 2 hours with stirring, and the mixture was aged for 3 hours. The reaction product resin has a solid content concentration of 53.
%, The average molecular weight was 6,500, the oxirane oxygen concentration in terms of solid content was 2.2%, and the acid value was 81 mgKOH / g.

[0072]

[Chemical 31]

(Synthesis Example 2) Stirrer, Dimroth cooler,
Xylene 150 was placed in a 2 liter glass reaction flask equipped with a thermometer, a dropping funnel and a nitrogen introducing tube.
Parts, 150 parts of propylene glycol monomethyl ether acetate, and 3 parts of perbutyl O (manufactured by NOF CORPORATION) as an initiator, and then methyl methacrylate 10
0 part, methacrylic acid 105 parts, epoxy group-containing monomer (the following formula) 200 parts, styrene 150 parts, n-butyl methacrylate 50 parts, caprolactone-added hydroxyethyl methacrylate (manufactured by Daicel Chemical Industries, PCL FM
-1) A mixture of 50 parts, and, in addition to these monomers, 150 parts of xylene, 150 parts of propylene glycol monomethyl ether acetate, and perbutyl O as an initiator.
A mixture of 4 parts (manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise over about 2 hours while stirring at a flask temperature of 80 ° C., and further 3
Aged for hours. The reaction product resin had a solid content concentration of 52%, an average molecular weight of 6,500, an oxirane oxygen concentration of 2.7% in terms of solid content, and an acid value of 103 mgKOH / g.

[0074]

[Chemical 32]

(Synthesis Example 3) Stirrer, Dimroth cooler,
Xylene 150 was placed in a 2 liter glass reaction flask equipped with a thermometer, a dropping funnel and a nitrogen introducing tube.
Parts, 150 parts of propylene glycol monomethyl ether acetate, and 3 parts of perbutyl O (manufactured by NOF CORPORATION) as an initiator, and then methyl methacrylate 10
0 part, methacrylic acid 105 parts, epoxy group-containing monomer R>
(Formula) 200 parts, styrene 150 parts, n-butyl methacrylate 50 parts, caprolactone-added hydroxyethyl methacrylate (PCL FM- manufactured by Daicel Chemical Industries, Ltd.)
1) A mixture of 50 parts, and separately from these monomers, 150 parts of xylene, 150 parts of propylene glycol monomethyl ether acetate, and perbutyl O as an initiator.
A mixture of 4 parts (manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise over about 2 hours while stirring at a flask temperature of 80 ° C., and further 3
Aged for hours. The reaction product resin had a solid content concentration of 50%, an average molecular weight of 6,500, an oxirane oxygen concentration converted to solid content of 2.8%, and an acid value of 105 mgKOH / g.

[0076]

[Chemical 33]

(Synthesis Example 4) Stirrer, Dimroth cooler,
Xylene 150 was placed in a 2 liter glass reaction flask equipped with a thermometer, a dropping funnel and a nitrogen introducing tube.
Parts, butyl acetate 150 parts, perbutyl O as an initiator
After charging 3 parts (manufactured by Nippon Oil & Fats Co., Ltd.), 200 parts of methyl methacrylate, an epoxy group-containing monomer (the following formula) 150
Parts, styrene 100 parts, γ-trimethoxysilylpropyl methacrylate 203 parts, caprolactone-added hydroxyethyl methacrylate (PCL manufactured by Daicel Chemical Industries, Ltd.
FM-1) a mixture of 100 parts, and a mixture of 150 parts of xylene, 150 parts of butyl acetate and 4 parts of perbutyl O (manufactured by NOF Corporation) as an initiator at a flask temperature of 80 apart from these monomers. The mixture was added dropwise with stirring at about 2 hours for about 2 hours and aged for 3 hours. The reaction product resin is
The solid content concentration was 47%, the average molecular weight was 7,500, and the oxirane oxygen concentration in terms of solid content was 3.4%.

[0078]

[Chemical 34]

(Synthesis example 5) Stirrer, Dimroth condenser,
Xylene 150 was placed in a 2 liter glass reaction flask equipped with a thermometer, a dropping funnel and a nitrogen introducing tube.
Parts, butyl acetate 150 parts, perbutyl O as an initiator
After charging 3 parts (manufactured by Nippon Oil & Fats Co., Ltd.), 200 parts of methyl methacrylate, an epoxy group-containing monomer (the following formula) 150
Parts, styrene 100 parts, γ-trimethoxysilylpropyl methacrylate 203 parts, caprolactone-added hydroxyethyl methacrylate (PCL manufactured by Daicel Chemical Industries, Ltd.
FM-1) a mixture of 100 parts, and a mixture of 150 parts of xylene, 150 parts of butyl acetate and 4 parts of perbutyl O (manufactured by NOF Corporation) as an initiator at a flask temperature of 80 apart from these monomers. The mixture was added dropwise with stirring at about 2 hours for about 2 hours and aged for 3 hours. The reaction product resin is
The solid content concentration was 50%, the average molecular weight was 7,500, and the oxirane oxygen concentration converted to solid content was 3.4%.

[0080]

[Chemical 35]

(Synthesis example 6) Stirrer, Dimroth condenser,
Xylene 150 was placed in a 2 liter glass reaction flask equipped with a thermometer, a dropping funnel and a nitrogen introducing tube.
Parts, butyl acetate 150 parts, perbutyl O as an initiator
After charging 3 parts (manufactured by Nippon Oil & Fats Co., Ltd.), 200 parts of methyl methacrylate, epoxy group-containing monomer (the following formula) 200
Parts, styrene 100 parts, γ-trimethoxysilylpropyl methacrylate 250 parts, caprolactone-added hydroxyethyl methacrylate (PCL manufactured by Daicel Chemical Industries, Ltd.
FM-1) a mixture of 100 parts, and a mixture of 150 parts of xylene, 150 parts of butyl acetate and 4 parts of perbutyl O (manufactured by NOF Corporation) as an initiator at a flask temperature of 80 apart from these monomers. The mixture was added dropwise with stirring at about 2 hours for about 2 hours and aged for 3 hours. The reaction product resin is
The solid content concentration was 58%, the average molecular weight was 8,200, and the oxirane oxygen concentration converted to solid content was 1.9%.

[0082]

[Chemical 36]

(Synthesis Example 7) Stirrer, Dimroth cooler,
Xylene 150 was placed in a 2 liter glass reaction flask equipped with a thermometer, a dropping funnel and a nitrogen introducing tube.
Parts, butyl acetate 150 parts, perbutyl O as an initiator
After charging 3 parts (manufactured by NOF CORPORATION), 250 parts of hydroxyethyl methacrylate and 20 parts of methyl methacrylate
0 part, epoxy group-containing monomer (the following formula) 200 parts, n-butyl methacrylate 100 parts, γ-trimethoxysilylpropyl methacrylate 100 parts, caprolactone-added hydroxyethyl methacrylate (PCL FM-1 manufactured by Daicel Chemical Industries) 100 parts Separately from these monomers, 150 parts of xylene, 150 parts of butyl acetate, and 4 parts of perbutyl O (manufactured by NOF CORPORATION) as an initiator were added dropwise over about 2 hours while stirring at a flask temperature of 80 ° C. And aged for another 3 hours. The reaction product resin had a solid content concentration of 60%, an average molecular weight of 9,500, and an oxirane oxygen concentration of 1.6% in terms of solid content.

[0084]

[Chemical 37]

(Example 1: Coating coating preparation example 1) 1 part of tetrabutylammonium bromide and 100 parts of each acrylic resin synthesized in synthesis example 1 and synthesis example 2 and acrylic resin synthesized in synthesis example 3 To the above, 1 part of tetraphenylphosphonium chloride was added, and then each was diluted with a mixed solvent of xylene / butyl acetate = 1/1 to prepare a clear coating solution. Then, an electrodeposition coated plate (manufactured by Nippon Test Panel) was applied with a bar coater to obtain coating films 1, 2, and 3 and baked at 140 ° C. for 30 minutes to prepare a coating film.

(Example 2: Coating film preparation example 2) 2 parts of tris (n-propylacetoacetate) aluminum to 100 parts of the acrylic resin synthesized in Synthesis example 4; 100 parts of the acrylic resin of Synthesis example 5 to Tris 2 parts of (n-propyl acetoacetate) zirconium; 2 parts of tris (acetylacetonato) aluminum was added to 100 parts of the acrylic resin of Synthesis Example 6, and then Celoxide 2021P.
20 parts of a cycloaliphatic epoxy resin manufactured by Daicel Chemical Co., Ltd. was blended to prepare a clear coating solution. Then, apply it to the electrodeposition coated board (manufactured by Nippon Test Panel) with a bar coater, and
Baking was performed at 5 ° C. for 30 minutes to form coating films 4, 5, and 6.

Example 3: Coating film preparation example 3 0.1 part of phosphoric acid was added to 100 parts of the acrylic resin synthesized in Synthesis example 7, and 2-ethylhexyl phosphate was added to 100 parts of the acrylic resin of Synthesis example 7. Was added in an amount of 2 parts and then diluted with a mixed solvent of xylene / butyl acetate = 1/1 to prepare a clear coating solution. Then, it was applied to an electrodeposition coated plate (manufactured by Nippon Test Panel) with a bar coater and baked at 85 ° C. for 60 minutes to form coating films 7 and 8.

Example 4: Preparation of coating film example 4 100 parts of the acrylic resin synthesized in Synthesis example 7 was mixed with 0.1 part of phosphoric acid, and then 20 parts of Celoxide 2021P (Daicel Chemical's alicyclic epoxy resin). , A clear coating solution was prepared. Then, an electrodeposition coated plate (manufactured by Nippon Test Panel) was applied with a bar coater and baked at 85 ° C. for 60 minutes to form a coating film 9.

(Evaluation of coating film) Coating films 1 to 9 according to coating film preparation examples
The following coating film evaluation was performed. The results are shown in Table 1. Paint stability: After the prepared clear paint was allowed to stand at room temperature for 10 days, the presence or absence of gelation and thickening phenomenon was confirmed. Gel fraction: Peel off the dried coating film from the glass plate and extract with acetone using a Soxhlet extractor for 5 hours, and extract residue (%)
Was measured. Impact resistance: Measured with a DuPont impact tester using a 500 g weight. Scratch resistance: Cleanser (Kao: New Homing Cleanser) was applied to flannel cloth (2 cm x 2 cm) to give a coating film of 5
The retention rate of 20-degree gloss after 10 reciprocations under a load of 00 g was measured. Weather resistance: 1 at a temperature of 40 to 70 ° C. using a QUV measuring device
A cycle of irradiation for 5 minutes and condensation for 15 minutes was performed for 2,000 hours, and the degree of coating film deterioration was visually observed.

[0090]

[Table 1]

(Effect of the Invention) The thermosetting resin composition of the present invention can be suitably used for paints, adhesives and inks, because it cures rapidly at low temperature to give excellent film properties. Further, it is suitable for improving the scratch resistance of the coating film, and can be very suitably used as an automobile to which an epoxy group is applied, a paint for acid rain resistant for construction materials, and a weather resistant paint.

─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-52-77137 (JP, A) JP-A-6-184408 (JP, A) JP-A-3-172318 (JP, A) JP-A-60- 250012 (JP, A) JP 59-122557 (JP, A) JP 2-228351 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59/20 C08L 33 / 14 C09D 163/00-163/10 C09D 133/14

Claims (9)

(57) [Claims] 1. A thermosetting resin composition containing at least one acrylic resin component, wherein any of the acrylic resin components contains an epoxy-containing group represented by the general formula (1), and A thermosetting resin composition, wherein any component of the thermosetting resin composition contains a functional group capable of reacting with the epoxy group of the general formula (1). [Chemical 1] 2. The thermosetting resin composition according to claim 1, wherein any of the acrylic resin components contains a functional group capable of reacting with the epoxy group of the general formula (1). 3. The functional group capable of reacting with the epoxy group of the general formula (1) is a group selected from the group consisting of a carboxyl group, a hydroxyl group, a silanol group and a hydrolyzable alkoxysilanol group. Item 1 or 2
The thermosetting resin composition described. 4. The thermosetting resin composition according to claim 1, wherein the epoxy-containing group of general formula (1) is an epoxy-containing group represented by the following (21). . [Chemical 2] 5. The thermosetting resin composition according to claim 1, wherein the epoxy-containing group of the general formula (1) is an epoxy-containing group represented by the following (22). . [Chemical 3] 6. The thermosetting resin composition according to claim 1, wherein the epoxy-containing group of the general formula (1) is an epoxy-containing group represented by the following (23). . [Chemical 4] 7. The thermosetting resin composition according to claim 1, wherein the epoxy-containing group of the general formula (1) is an epoxy-containing group represented by the following (24). . [Chemical 5] 8. The thermosetting resin composition according to claim 1, wherein the epoxy-containing group of the general formula (1) is an epoxy-containing group represented by the following (25). . [Chemical 6] 9. A coating composition containing the thermosetting resin composition according to claim 1.