JPH0632970A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition which exhibits good storage stability at ordinary temperature, is excellent in curability, and gives a cured material excellent in heat resistance and electrical characteristics. CONSTITUTION:A compound having at least one vinyl group and one epoxy group in the molecule is reacted with at least one of a polybasic acid anhydride, a polybasic acid, an acid-terminated polymer and a carboxylated polymer, and a compound having at least one active hydrogen atom to give a vinylic resin, which is then epoxidized to produce an epoxy resin. This epoxy resin is mixed with an organoaluminum compound and an organosilicon compound having hydroxyl group(s) or hydrolyzable group(s) directly attached to the silicon atom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition which is a cured product having good storage stability at room temperature, excellent curability, heat resistance and electrical properties.

In curing an epoxy resin, for example, a curing agent such as (A) polyamine, acid anhydride or phenol, or (B) a curing catalyst typified by a BF3 complex or a tertiary amine compound is used as an epoxy resin. Addition is usually done. In the case of (A),
When polyamine is used, it has the disadvantage that the composition cannot be stored for a long time because of its high reactivity with the epoxy resin, and when an acid anhydride is used, it requires heating at high temperature for a long time. There are drawbacks.

On the other hand, in the case of (B), when the BF3 complex is used, it can be cured at a relatively low temperature, but on the other hand, it has the drawback that the cured resin has poor electrical and mechanical properties at high temperatures. . Further, when a tertiary amine is used, the curing reaction requires a high temperature and there are problems in work such as skin irritation.

In addition, when the epoxy resin is cured, it has been attempted to add a metal chelate compound as a latent curing catalyst. However, in this case, 20
Not only a high temperature of 0 ° C. or more is required, but also a relatively large amount of the above-mentioned chelate compound is about 5%, and it is difficult to form a cured resin layer having various properties due to poor solubility and dispersibility. There is an inconvenience.

From this point of view, the use of an organic aluminum compound and an organic silicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom as an epoxy curing catalyst is disclosed in JP-A-56-2319, 56-. 462
5, 57-53522, 57-133122, etc.

However, epoxy resins which can be cured with these catalysts include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate [Ceroxide 202 manufactured by Daicel Chemical Industries, Ltd.].
1, so-called alicyclic epoxy represented by UCC ERL-4221] is preferable. The epi-bis type epoxy resin and novolac epoxy resin produced from ordinary epichlorohydrin and bisphenol A or novolac phenol have a drawback that the curing speed is slow.

Further, since the alicyclic epoxy resin up to now is a liquid resin having a low viscosity, the application range of the obtained photocurable resin composition is narrowed and it is mainly used as a liquid coating agent. .

On the other hand, the epoxy resin utilizes its characteristics to make use of electrical fields such as printed circuit boards, resist inks, LED encapsulation, semiconductor encapsulation, resistors and encapsulation of capacitors, paints, adhesives and solders. Widely used in the ink field such as resist ink. Further improvements in heat resistance and electrical properties are desired in these various fields.

[0009]

As a result of intensive studies in view of the above situation, the use of an organosilicon compound gives a cured product having excellent heat resistance and electrical characteristics, and provides a suitable organoaluminum compound and organosilicon compound. It was found that an epoxy resin composition having a so-called latent property, which is stable at room temperature, can be obtained by using the compound, and the present invention has been completed.

[0010]

That is, the present invention relates to "(a) (a) a compound having at least one vinyl group and one epoxy group in one molecule, and (b) a polybasic acid anhydride,
It has a vinyl group obtained by reacting at least one of a polybasic acid, an acid terminal polymer, and a polymer containing a carboxylic acid group with (c) at least one compound having one or more active hydrogens. A thermosetting resin comprising an epoxy resin obtained by further epoxidizing the resin, and (b) an organic aluminum compound (c) an organosilicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom. Resin composition ".

Next, the present invention will be described in more detail.

The compound having one epoxy group and one or more vinyl groups in one molecule used in the present invention has the general formula (IV) << i is an integer of 1 to 5, R ¹ and R ⁴ are hydrogen atoms or alkyl groups having 1 to 50 carbon atoms or substituted phenyl groups,
R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 50 carbon atoms, and R ² and R ³ may be wrapped around a ring. Examples of the compound represented by (IV) are the compounds shown below.

4-vinylcyclohexene-1-oxide, 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide, limonene monoxide, trivinylcyclohexane monoxide, divinylbenzene monoxide, butadiene mono Oxide and 1,2-epoxy-
Examples include compounds represented by (I) such as 9-decene, compounds represented by (II) such as allyl glycidyl ether, and compounds such as glycidyl styryl ether.

Further, the following compounds can also be used.

[0015]

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4] These may be used alone or in combination of two or more.

If necessary, ethylene oxide,
Propylene oxide, cyclohexene oxide, styrene oxide, monoepoxides such as α-olefin epoxide, vinyl cyclohexene dioxide, 3,4-
A diepoxide such as epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate may be used together with the compound having one epoxy group and one or more vinyl groups in one molecule.

The polybasic acid anhydrides or polybasic acids used in the present invention include aromatic polybasic acids and acid anhydrides thereof, and aliphatic polybasic acids and acid anhydrides thereof. Examples of aromatic polybasic acids and acid anhydrides thereof include phthalic anhydride, isophthalic acid, terephthalic acid and trimellitic anhydride. Further, as the aliphatic polybasic acid and its acid anhydride, tetrahydrophthalic acid, 4-methylhexahydrophthalic acid, hexahydrophthalic acid, adipic acid,
Maleic acid and their acid anhydrides, fumaric acid, sebacic acid, dodecane diacid, and the like.

The acid-terminated polymer used in the present invention includes polyethylene glycol and polypropylene glycol.
Acid-terminated polyesters, acid-terminated polyesters, acid-terminated polybutadienes, acids obtained by reacting polybasic acids with poly (tetramethylene glycol), poly (butylene glycol), polycyclohexene glycol, polyvinyl cyclohexene glycol, etc. Examples include terminal polycaprolactone.

Further, an acrylic copolymer having a carboxylic acid group can be used instead of the acid terminal polymer, and it contains a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, and a carboxylic acid group. These polymers may be used alone or in combination of two or more.

Next, the compounds having active hydrogen used in the present invention include alcohols, phenols, carboxylic acids, amines, thiols, hydroxyl group-terminated polymers, and hydroxyl group-containing polymers. Examples include coalescing.

The alcohols are monovalent, divalent, trivalent or higher, and include, for example, methanol and ethanol.
Alcohol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, hexanediol, glycerin, butanol, trimethylolethane, trimethylolpropane, penta Examples thereof include erythritol, diglycerol, triglycerol and the like. In addition, neopentyl glycol, neopentyl glycol ester of hydroxyhyvalic acid, dipentaerythritol, 1,4-cyclohexanedimethanol, trimethylpentanediol, 1,3,5-tris (2 -Hydroxyethyl) cyanuric acid, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A and the like can also be used.

Examples of the phenols include phenol, cresol, catechol, pyrogallol, hydroquinone,
Hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, phenol Resin and cresol-novolak resin.

The hydroxyl group-terminated polymer used in the present invention includes polyethylene glycol and polypropylene glycol.
Polyether polyols such as poly (tetramethylene glycol), poly (butylene glycol), poly (cyclohexene glycol) and poly (vinylcyclohexene glycol)
And hydroxyl-terminated polyesters, hydroxyl-terminated polybutadienes, hydroxyl-terminated polycaprolactones, and polycarbonate diols. Further, an acrylic copolymer having a hydroxyl group or the like can be used instead of the hydroxyl group-terminated polymer.

As carboxylic acids, formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane diacid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid. Acid, terephthalic acid, etc.

Further, compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid and oxycaproic acid, can also be mentioned.

The amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine,
Octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, ethano-
Lumin, etc.

As the thiols, methyl mercaptan,
Mercapto such as ethyl mercaptan, propyl mercaptan, phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol ester of mercaptopropionic acid, for example, ethylene glycol dimercaptopropionic acid ester, trimethylolpropane trimercaptopropionic acid, pentaerythritol- Examples include rupentamercaptopropionic acid and the like.

Further, as the compound having active hydrogen, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate.
, Cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin,
Polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, polytetramethylene glycol, and the like.

The compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples thereof include allyl alcohol, acrylic acid, methacrylic acid,
2-hydroxyethyl methacrylate, 3-cyclohexene methanol, tetrahydrophthalic acid and the like.

Any compound having these active hydrogens can be used, and two or more kinds thereof may be mixed.

The epoxy resin used in the present invention includes the compound (a) having at least one vinyl group and one epoxy group in the above molecule, a polybasic acid anhydride, a polybasic acid, and an acid terminal polymer. , And at least one selected from the polymer (b) containing a carboxylic acid group and at least one selected from the compound (c) having active hydrogen to obtain a resin having a vinyl group.

Next, the desired resin is obtained by further epoxidizing the vinyl group portion of the resin having vinyl groups with an epoxidizing agent.

The charging ratio of the starting materials (a), (b), and (c) is 1 to 99 parts by weight of (a), preferably 30 to 80 parts, and 99 to 1 parts by weight of (b). Parts, preferably 20 to 70 parts, and 0 to 99 parts by weight of (c), preferably 0 to 30 parts. The component (c) may not be used depending on the case. When the component (c) is not used,
It is necessary to control the molecular weight while detecting the dehydration amount by controlling the reaction time, the degree of reduced pressure, the reaction temperature, and the like.

When the amount of component (a) used is relatively small, the epoxy group content in the target epoxy resin is small. The molar ratio of component (a) / component (b) is 0.
It is 4 to 5.0, preferably 0.5 to 3.0.

When the ratio of the component (a) is increased, the ratio of the terminal to be a hydroxyl group is increased, and when the terminal of the hydroxyl group and the terminal of the carboxyl group are present, all the terminals are hydroxyl groups as the dehydration reaction proceeds.

On the contrary, when the ratio of the component (b) is increased, the ratio of the terminal to be the carboxyl group is increased, and in the case where the hydroxyl group end and the carboxyl group end are present, all the terminals become the carboxyl group as the dehydration reaction proceeds. Become. However,
When the ratio of the component (a) increases, a part of the component (a) remains unreacted and remains. Further, when the ratio of the component (b) becomes unnecessarily large, the component (b) remains without reacting.

In the reaction for synthesizing the resin having a vinyl group, a catalyst for promoting the ring-opening reaction of the epoxy group with a carboxyl group and, if necessary, a catalyst for promoting the (dehydration) esterification reaction may be used in combination. Good.

The catalyst for promoting the ring-opening reaction that can be used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0.1 to 5.0 relative to the epoxy compound.
It is recommended to use the weight percent. This ring-opening reaction is 50 to 200 ° C.
Done in.

Examples of the catalyst for promoting the dehydration esterification reaction that can be used in the present invention include Sn compounds such as tin octylate and dibutyltin laurate, and Ti compounds such as tetrabutyl titanate.

The catalyst for promoting the dehydration esterification reaction used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0 to 1000 p for the reaction system.
It is better to use pm. This ring-opening reaction is 180-240 ° C
Done in.

The ring-opening reaction of the epoxy group with the carboxyl group and the dehydration esterification reaction may be carried out in sequence, but a method in which the reaction temperature is raised stepwise in accordance with the progress of the reaction after the raw materials and the catalyst are charged in a lump. desirable.

The resin having a cyclic olefin or vinyl group thus synthesized is reacted with an epoxidizing agent to synthesize the resin having an epoxy group of the present invention. As peracids,
Examples thereof include hydroperoxides.

Examples of peracids include formic acid, peracetic acid, perbenzoic acid and trifluoroperacetic acid. Of these, peracetic acid is industrially produced in large quantities and is available at low cost.
It is also a preferred epoxidizing agent because of its high stability.

The hydroper oxides include hydrogen peroxide, tertiary butyl hydroper oxide, cumene per oxide and the like.

In the epoxidation, a catalyst can be used if necessary.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. In the case of hydroperoxides, a mixture of tungstic acid and caustic soda is used with hydrogen peroxide, an organic acid is used with hydrogen peroxide, or molybdenum hexacarbonyl is used in combination with tert-butyl hydroperoxide. A catalytic effect can be obtained.

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the physical properties of the equipment and raw materials. The reaction temperature range that can be used is determined depending on the reactivity of the epoxidizing agent used, and the preferable epoxidizing agent, peracetic acid, is preferably 0 to 70 ° C. The reaction is slow below 0 ° C,
At 70 ° C, decomposition of peracetic acid occurs. Further, in the tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate system, which is an example of hydroperoxide, 20 ° C. to 150 ° C. is preferable for the same reason. The solvent can be used for the purpose of reducing the viscosity of the raw material and stabilizing it by diluting the epoxidizing agent. In the case of peracetic acid, aromatic compounds, ethers, esters and the like can be used.

The charged molar ratio of the epoxidizing agent to the unsaturated bond can be changed according to the purpose such as the amount of the unsaturated bond to be left. When a compound having a large number of epoxy groups is intended, the epoxidizing agent is preferably added in an equimolar amount or more with respect to the unsaturated group. However, it is usually disadvantageous that the amount exceeds 2 times the molar amount in view of economical efficiency and side reactions, and in the case of peracetic acid, the molar ratio is preferably 1 to 1.5 times. After the completion of the predetermined reaction, the target epoxy resin (a) can be taken out from the reaction solution by a usual chemical industrial means such as concentration.

On the other hand, both the organic aluminum compound (b) and the organic silicon compound (c) used in the present invention function as a curing catalyst.

Specific examples of the organoaluminum compound include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum, isopropoxydiethoxyaluminum, trisbutoxyaluminum, trisacetoxyaluminum, trissteara. -Aluminum, trisbutyrate aluminum, trispropionate aluminum, trisisopropionate aluminum, trisacetylacetonate aluminum, tristrifluoroacetylacetonate aluminum, trishexafluoroacetylacetonate aluminum, tris Ethyl acetoacetate aluminum, trissalicyl aldehyde aluminum Arm, tris diethylmalonate la - DOO aluminum, tris propyl aceto acetamide - DOO aluminum, tris butyl aceto acetamide - DOO aluminum,
Tris-dipivaloylmethanatoaluminum, diacetylacetonato-dipivaloylmethanatoaluminum,

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[0051]

[Chemical 10]

[0052]

[Chemical 11]

[0053]

[Chemical 12]

[0054]

[Chemical 13]

[0055]

[Chemical 14] The organosilicon compound (c) having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom includes organosilane and organosiloxane.

[0056] "However, Hy is a substituent that produces an OH group or by hydrolysis OH group, R ^45p, R ^46q, and R
^47r may be the same or different and have 1 to 5 carbon atoms.
Represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an acyl group and the like, and p, q and r are 0 ≦ p,
q represents an integer satisfying the conditions of r ≦ 3, 1 ≦ p + q + r ≦ 3] In the above formula, examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an isopropyl group, and n.
-Propyl group, n-butyl group, t-butyl group, sec-
Butyl group, n-pentyl group, methoxy group, ethoxy group,
Examples of the chloromethyl group and the like, as the aryl group,
For example, a phenyl group, a tolyl group, a naphthyl group, an anthranyl group, etc., an aralkyl group, for example, a benzyl group, a phenethyl group, etc., and an alkenyl group, for example, a vinyl group, an allyl group, a propenyl group. Examples of the acyl group include an acetyl group and a benzoyl group, and an alkyl group having 1 to 5 carbon atoms, an aryl group, an aralkyl group, an alkenyl group and an acyl group are halogen. It may have a substituent such as an atom, a nitro group, a cyano group or a methoxy group.

Specific examples of such silicon compounds include, for example, triphenylmethoxysilane, diphenyldimethoxysilane, triphenylethoxysilane, diphenylmethylmethoxysilane, phenylvinylmethylmethoxysilane, diphenyldiethoxysilane, tri (para). (Methoxyphenyl) methoxysilane, triacetylmethoxysilane, diphenylethylethoxysilane, diphenylpropylethoxysilane, diphenylmethylacetoxysilane, diphenyldipropionyloxysilane, diphenylmethyltriphenylacetoxysilane,
Tri (paranitrophenyl) methoxysilane, phenyldivinylpropoxysilane, 2-futenyldiphenylmethoxysilane, di (2-pentenyl) phenylethoxysilane, phenyldipropylmethoxysilane, tri (paramethoxyphenyl) ethoxysilane, paramethylbenzyl Trimethoxysilane, trifluoroacetyltrimethoxysilane, di (parachlorophenyl) diethoxysilane, triethylmethoxysilane, trimethylmethoxysilane, tripropylmethoxysilane, tributylethoxysilane, tributylacetoxysilane, Phenyldiethoxysilane, tri (paramethoxyphenyl) methoxysilane, triacetylmethoxysilane, diphenylethylethoxysilane, diphenylpropylethoxysilane, diphenylmethylacetoxysilane, diphenyldipropionyloxysilane, diphenylmethyltriphenylacetoxysilane, tri (para) Nitrophenyl) methoxysilane, phenyldivinylpropoxysilane, 2-phenyldiphenylmethoxysilane, di (2-pentenyl) phenylethoxysilane, phenyldipropylmethoxysilane, tri (paramethoxyphenyl) ethoxysilane, paramethylbenzyltrimethoxysilane , Trifluoroacetyltrimethoxysilane, di (parachlorophenyl) diethoxysilane, triethylmethoxysilane, Methyl methoxy silane, tripropyl silane, tributyl silane, tributyl acetoxysilane,

The organosiloxane is represented by the following formula.

[0059] << However, R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , and R ⁵³
May be the same or different and can be changed to each group at the same time, and an OH group, a hydrolyzable group, and a carbon number of 1 to 5
, An alkyl group, an aryl group, an aralkyl group, an alkenyl group, an acyl group, and an organosiloxane residue represented by the following formula And so on. In particular, at least one of the structural units is OH
It contains at least one of a group and a hydrolyzable group. In addition, n2 is an integer of 0 or more >> In the above formula, examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, and a t-butyl group. Group, sec-butyl group, n-pentyl group, methoxy group, ethoxy group, chloromethyl group and the like, the aryl group, for example, phenyl group, tolyl group, naphthyl group, anthranyl group, and the like,
Examples of the aralkyl group include benzyl group and phenethyl group, and examples of the alkenyl group include
Examples thereof include a vinyl group, an allyl group, a propenyl group, and a phenyl group. Examples of the acyl group include an acetyl group and a benzoyl group. An alkyl group having 1 to 5 carbon atoms, an aryl group, an aralkyl group, The alkenyl group and the acyl group may have a substituent such as a halogen atom, a nitro group, a cyano group and a methoxy group.

Among the above-mentioned organosiloxanes, the degree of polymerization is 50 or less and the OH group equivalent or hydrolyzable group equivalent is 10
Those having an OH group equivalent of 5 or less are suitable for the present invention.
It is preferably 0 to 500.

Specific examples of such an organosiloxane include 1,3-dimethoxy-1,3-dimethyl-1,3-diphenyldisiloxane and 1,5-diethoxy-1,3,5-trimethyl-. 1,3,5-triphenyltrisiloxane, 1,7-dimethoxy-1,3
5,7-Tetramethyl-1,3,5,7-tetraphenyltetrasiloxane, 1,3-dimethoxytetraphenyldisiloxane, 1,5-dimethoxy-3,3-dimethyl-1,1,5,5- Tetraphenyltrisiloxane,
1,3,5-trimethoxypentaphenyltrisiloxane, 1,5-dimethoxyhexa (p-methoxyphenyl) trisiloxane,

[0062]

[Chemical 15] And hydrolysis products thereof, and Q1-
3037 (Methoxy group content 18% by weight, Toshiba Silicon
And SH6018 (OH equivalent of about 400, Toray Silicone Co., Ltd.) and the like, which are available under the trade names.

The above-mentioned organosilane and organopolysiloxane compounds may be used either individually or in combination of two or more.

The amounts of the organic aluminum compound (b) and the organic silicon compound (c) having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom are different depending on the kind of the epoxy compound used, but it cannot be generally stated. Generally, 0.001 to 100 parts by weight of epoxy compound
It is 10 parts by weight, preferably 0.01 to 5 parts by weight. At this time, it is preferable to mix and use the organic silicon compound such that the silanol-containing hydroxyl group or the hydrolyzable group is 1 equivalent or more, and further 1 to 5 equivalent per 1 mol of the organic aluminum compound. .

In the method of the present invention, in addition to the above curing catalyst, a generally used acid anhydride curing agent can be blended if necessary. Examples of such acid anhydride curing agents include phthalic anhydride, maleic anhydride,
Hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhymitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride and the like can be mentioned.

Since both the organic aluminum compound and the organosilicon compound of the present invention begin to show activity at about 80 ° C., the curing temperature may be 30 to 200 ° C., preferably 80 to 180 ° C. Note that this curing reaction does not need to be carried out in a closed system unlike the conventional organometallic compound catalysts, and it is sufficient to carry out in the air.

In the present invention, a filler such as silica, a pigment, a dye or the like may be added if necessary.

[0068]

INDUSTRIAL APPLICABILITY The epoxy resin of the present invention is not only suitable for casting, impregnation, system formation, etc. as a so-called useless formulation by selecting the type and composition ratio of the epoxy resin, but also has a low boiling point such as dioxane and tetrahydrofuran. It also dissolves in solvents. Therefore, it can be easily impregnated into glass cloth, paper, etc., so that it can be used for forming a laminated plate. Also powder coating,
It can also be used in solder-resist ink and the like. (Below margin)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C09D 163/00 PHZ 8830-4J PKB 8830-4J

Claims (11)

[Claims] 1. (a) (a) a compound having at least one vinyl group and one epoxy group in one molecule, (b) a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, And a resin having a vinyl group obtained by reacting at least one kind of a polymer having a carboxylic acid group with (c) at least one kind of a compound having one or more active hydrogens, and further obtained by epoxidation. Thermosetting resin composition, comprising: (b) an organic aluminum compound; and (b) an organosilicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom. 2. The thermosetting resin composition according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is 4-vinylcyclohexene-1-oxide. 3. The compound having one or more vinyl groups and one epoxy group in one molecule is 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide. 1. The thermosetting resin composition of 1. 4. The thermosetting resin composition according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is limonene monoxide. 5. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following general formula (I): The thermosetting resin composition according to claim 1, which is a compound represented by << n is an integer of 0 to 30 >>. 6. A compound having one or more vinyl group and one epoxy group in one molecule is represented by the following general formula (II): The thermosetting resin composition according to claim 1, which is a compound represented by << n1 and n2 are integers from 0 to 30 >>. 7. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following general formula (III): The thermosetting resin composition according to claim 1, which is a compound represented by << Ph is a substituted phenyl group >>. 8. A compound having one or more active hydrogens,
The thermosetting resin composition according to claim 1, which is an alcohol, a hydroxyl group-terminated polymer, or a polymer containing a hydroxyl group. 9. The thermosetting resin composition according to claim 1, wherein the acid-terminated polymer is an acid-terminated polyester. 10. The thermosetting resin composition according to claim 8, wherein the hydroxyl group terminated polymer is a hydroxyl group terminated polyester. 11. The thermosetting resin composition according to claim 8, wherein the hydroxyl-terminated polymer is a hydroxyl-terminated polyether.