JPH0476370B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a photocurable resin composition. More specifically, the present invention relates to a photocurable epoxy resin composition that provides a cured product with excellent electrical properties, heat resistance, and weather resistance. [Prior Art] In recent years, ultraviolet curable resins that are cured by irradiation with ultraviolet light are solvent-free and low-pollution. Curing speed is extremely fast and product productivity is high. Since it cures as a 100% solid content, the volume change before and after curing is extremely small. No heat loss through the material or thermal effects on the material. Due to these characteristics, it is used in various fields. Among them, the process of photo-curing epoxy resin is important for the heat resistance, glossiness, and
It takes advantage of its adhesion, water resistance, and other properties.
It is also expected to have a wide range of applications. This photocurable epoxy resin is made by adding a photodecomposition type catalyst to an epoxy resin. It is already known that onium salts such as 3M's FC-508 and General Electric's UVE-1014 are used as catalysts. However, the catalyst components of these catalysts become ionic impurities, and when used in electrical equipment, the electrical properties may be affected or corrosion may occur. Therefore, an epoxy photocuring catalyst characterized by being composed of an aluminum compound and a silica compound that generates silanol groups when irradiated with light was proposed in Japanese Patent Application Laid-open No.
57-125212, JP-A-59-138220, etc. Epoxy resins that can be cured with these catalysts include 3,4-epoxycyclomethyl-3',4'-
Epoxycyclohexacarboxylate (Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., manufactured by UCC)
So-called alicyclic epoxy resins, such as ERL-4221), are preferred. Epibis type epoxy resins and novolac epoxy resins manufactured from ordinary epichlorohydrin and bisphenol A or novolac phenol have slow curing speeds and are not used. In addition, since conventional fat-reduced epoxy resins are liquid resins with low viscosity, the range of application of the resulting photocurable resin compositions is narrow, and they are mainly used as liquid coating agents. On the other hand, epoxy resin is widely used in the electrical field such as printed circuit boards, IC encapsulation, LED encapsulation, resistor, and capacitor encapsulation, as well as in the paint field, adhesive field, and ink field such as solder resist ink, due to its properties. It is being The emergence of photocurable epoxy resins is desired in these various fields, but each application requires a low-viscosity liquid, a high-viscosity liquid, and a solid epoxy resin, which require different molding methods. [Problems to be Solved by the Invention] In view of this situation, the inventors of the present invention have made extensive studies, and by using a new epoxy resin having a cyclohexane skeleton proposed in Japanese Patent Application No. 59-014859, various molding methods have been achieved. The present inventors have discovered that it is possible to obtain a photocurable resin composition that has properties depending on the method and provides a cured product with excellent electrical properties, weather resistance, and heat resistance. [Structure of the Invention] That is, the present invention is characterized in that it consists of (a) an epoxy resin represented by the general formula (), (b) an aluminum compound, and (c) a silicon compound that produces a silanol group when irradiated with light. Photocurable resin composition However, R ₁ is an organic compound residue having 1 active hydrogen. n1, n2...nl are 0 or integers from 1 to 100, and the sum thereof is from 1 to 100. l represents an integer from 1 to 100. A is an oxycyclohexane skeleton having a substituent, and is represented by the following formula. X is

【formula】

R ₂ is any one of H, an alkyl group, a carboalkyl group, and a carboaryl group,

The resin represented by the formula () contains one or more of the following formulas. )”. Next, the present invention will be explained in detail. In the novel epoxy resin represented by the formula () of the present invention, R1 is an organic residue having active hydrogen, and examples of the precursor organic substance having active hydrogen include alcohols, phenols, carboxylic acids, and amines. and thiols. The alcohol may be a monohydric alcohol or a polyhydric alcohol. For example, methanol, ethanol, propanol, butanol, pentanol, hexanol,
Aliphatic alcohols such as octanol, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1.3 butanediol, 1.4 butanediol, pentanediol, 1.6 hexanediol, neo Examples include polyhydric alcohols such as pentyl glycol, neopentyl glycol oxybivalic acid ester, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol. Examples of phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, phenolic resin, cresol novolak resin, etc. be. Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecanoic acid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. There is. Also included are compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid. Examples of amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylene. Examples include diamine, diethylenetriamine, triethylenetetramine, and ethanolamine. Examples of thiols include mercapto compounds such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol esters of mercaptopionic acid, such as ethylene glycol dimercaptopropionic acid ester, and trimethylolpropane trimercaptopropionic acid. , pentaerythritol pentamercaptopopic acid, and the like. In addition, as compounds 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-malein Examples include acid copolymer resins, alkyd resins, polyester polyol resins, polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, and polytetramethylene glycols. In addition, the compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, and tetrahydrophthalic acid. be. The unsaturated double bonds of these compounds may also have an epoxidized structure. In the general formula (), n ₁ , n ₂ ...nl are 0 or 1 to 100, and the sum is 1 to 100, but 100
Above that, the resin will have a high melting point and will be difficult to handle.
In reality, it is not something that can be used. l is an integer from 1 to 100. Among the substituents X of A in formula (),

Contains at least one [formula] Although it is essential

The more [formula] there are, the better. Delicious. especially

[Formula] is preferably as small as possible. That is, in the present invention, the substituent X is

[Formula] is the main one. On average, one molecule of epoxy resin used in the present invention contains

It is preferable to use a compound having two or more of the formulas from the viewpoint of increasing the crosslinking density when cured.
Specifically, the novel epoxy resin represented by formula (1) of the present invention is a polyether obtained by ring-opening polymerization of 4-vinylcyclohexene-1-oxide using an organic compound having active hydrogen as an initiator. It can be produced by epoxidizing a resin, that is, a polycyclohexene oxide polymer having a vinyl group side chain, with an oxidizing agent such as a peracid. 4-vinylcyclohexene-1-oxide can be obtained by partially epoxidizing vinylcyclohexene obtained by dimerization of butadiene with peracetic acid. It is preferable to use a catalyst when polymerizing 4-vinylcyclohexene-1-oxide in the presence of active hydrogen. Catalysts include amines such as methylamine, ethylamine, propylamine, and piperazine; organic basic acids such as pyridines and imidazoles; organic acids such as formic acid, acetic acid, and propionic acid; inorganic acids such as sulfuric acid and hydrochloric acid; and sodium methylate. Alcoholates of alkali metals such as KOH, alkalis such as NaOH, Lewis acids such as BF ₃ , ZnCl ₂ , AlCl ₃ , SnCl ₄ or their complexes, organometallic compounds such as triethylaluminum, diethylzinc, etc. be able to. These catalysts can be used in an amount of 0.01 to 10%, preferably 0.1 to 5%, based on the reactants. Reaction temperature is -70~200℃, preferably -30℃
~100℃. The reaction can also be carried out using a solvent. A solvent containing active hydrogen cannot be used. That is, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic solvents such as benzene, toluene, and xylene, as well as ethers, aliphatic hydrocarbons, esters, and the like can be used. Now, in order to epoxidize the polycyclohexene oxide polymer having a vinyl group side chain synthesized in this way to produce an epoxy resin of the formula () of the present invention, peracids, hydroperoxides,
Either can be used. As peracids, performic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid, etc. can be used. Among these, peracetic acid is a particularly preferred epoxidizing agent because it is industrially available at low cost and has high stability. Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide,
Cumene peroxide etc. can be used. A catalyst can be used during epoxidation, if necessary. For example, in the case of a peracid, an alkali such as soda carbonate or an acid such as sulfuric acid may be used as a catalyst. In the case of hydroperoxides, the catalytic effect can also be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. . The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature depending on the equipment and physical properties of the raw materials. Depending on the conditions of the epoxidation reaction, olefin bonds can be epoxidized and substituents in the raw materials can be

[Formula] and generated substituents

[Formula] causes a side reaction with an epoxidizing agent, etc., resulting in a modified substituent, which is included in the target compound. Substituent in target compound

[Formula] Substituent

[Formula] and the ratio of the three modified substituents are determined by the type of epoxidizing agent, the molar ratio of olefin bonds in the epoxidizing agent, and reaction conditions. For example, when the epoxidizing agent is peracetic acid, the modified substituents mainly have the structure shown below, and are generated from acetic acid adsorbed by the generated epoxy group. The target compound can be taken out from the reaction mixture by ordinary chemical industrial means such as concentration. The epoxy resin obtained in the above manner may be mixed with a normal fat-reduced epoxy resin, EP-vis type epoxy resin, novolak epoxy resin, etc., and used. The aluminide compound, which is the second essential component of the present invention, is an organoaluminum lead compound in which an alkoxy group, phenoxy group, acyloxy group, β-diketonate group, o-carbonylphenolate group, etc. are bonded to an aluminum atom. It is preferable that Here, the alkoxy group preferably has 1 to 10 carbon atoms, and examples include methoxy, ethoxy, isopropoxy, putoxy, and pentoxy; examples of the phenoxy group include phenoxy group, o-
Examples include methylphenoxy group, o-methoxyphenoxy group, p-itrophenoxy group, 2,6-dimethylphenoxy group, etc.; Examples of acyloxy group include acetate, propionate, isopropionate, butyrate, stearate, and ethyl acetate. Ligands include acetate, propylacetoacetate, butylacetoacetate, diethyl malate, dipivaloyl methanate; examples of β-diketonate groups include acetylacetonate, trifluoroacetylacetonate, hexa fluoroacetylacetonate,

Examples of the o-carbonylphenolate group include salicylaldehydate. Specific examples of such aluminum compounds include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum, isopropoxydiethoxyaluminum, trisputoxyaluminum, tris Aluminum acetoxy, aluminum trisstearate, aluminum trisbutyrate, aluminum trispropionate, aluminum trisisopropionate, aluminum aluminum trisacetylacetonate, aluminum aluminum trifluoroacetylacetonate, aluminum aluminum trishexafluoroacetylacetonate, aluminum trisethyl acetate Aluminum acetate, Aluminum trissalicylaldehydate, Aluminum trisdiethylmalolato, Aluminum trispropylacetoacetate, Aluminum trisbutylacetoacetate, Aluminum trisdipivaloylmethanato, Aluminum diacetylacetonate dipivaloylmethanato

Examples include [Formula]. These aluminum compounds may be used alone or in a mixed system of two or more, and the amount added is 0.001 to 10% by weight relative to the epoxy resin.
%, preferably in the range of 1-5%. If the amount is less than 0.001% by weight, sufficient curing properties of the lining film will not be obtained, and if it exceeds 10% by weight, not only will the cost increase, but moisture resistance will tend to decrease. The third essential component of the composition of the present invention is a silicon compound that generates silanol groups upon irradiation with light.
As such a silicon compound, a silicon compound having any one of a peroxysilane group, an o-nitrobenzyloxy group, and an α-ketosilyl group is preferable. Among these silicon compounds, those having a peroxysilane group have the following formula: (R1)n-Si(O-O-
R2) 4-n (wherein R1 and R2 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group; n is 0 to (represents an integer of 3). In the above formula, examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, t-butyl group, sec-butyl group, and n-pentyl group. , methoxy group, ethoxy group, chloromethyl group;
Examples of the aryl group include phenyl group, raftyl group, anthranyl group, and benzyl group; C1-C5 alkyl group and aryl group include substituents such as halogen atom, nitro group, cyano group, and methoxy group. It may have. A specific example of such a silicon compound is the following formula: Examples include compounds shown in the following. Moreover, those having an o-nitrobenzyloxy group have the following formula: (In the formula, R1, R2, and R3 may be the same or different, and each represents a hydrogen atom; a halogen atom; a vinyl group; an allyl group; an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms; Alkoxy group of number 1 to 10: unsubstituted or substituted aryl group; aryloxy group; siloxy group, R4 is a hydrogen atom; unsubstituted or substituted alkyl group having 1 to 10 carbon atoms; phenyl group; substituted phenyl group Representation, R5,
R6, R7, and R8 may be the same or different, and each is a hydrogen atom; a nitro group; a cyano group;
hydroxy group; mercapto group; halogen atom; acetyl group; allyl group; alkyl group having 1 to 5 carbon atoms; alkoxy group having 1 to 5 carbon atoms; unsubstituted or substituted aryl group;
p, q, r are 0≦p, q, r≦3, 1≦p+q+
Represents an integer that satisfies the condition r≦3. ) is a compound represented by Examples of unsubstituted or substituted alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, t-butyl group, pentyl group, chloromethyl group, chloroethyl group, fluoromethyl group, cyanomethyl group, etc. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-
Examples include propoxy group and n-butoxy group. Examples of unsubstituted or substituted aryl groups include phenyl group, p-methoxyphenyl group, p-chlorophenyl group, p-trifluoromethylphenylvinylmethylphenyl (o-nitrobenzyloxy)
Silane, t-butylmethylphenyl(o-nitrobenzyloxy)silane, triethyl(o-nitrobenzyloxy)silane tri(2-chloroethyl)-o-nitrobenzyloxysilane, tri(p-trifluoromethylphenyl) -o-nitrobenzyloxysilane,
Trimethyl[α-(o-nitrophenyl)-o-nitrobenzyloxy]silane, dimethylphenyl[α-(o-nitrophenyl)-o-nitrobenzyloxy]silane, methylphenyldi[α-(o
-nitrophenyl)-o-nitrobenzyloxy]
Silane, triphenyl(α-ethyl-o-nitrobenzyloxy)silane, trimethyl(3-methyl-2-nitrobenzyloxy)silanedimethylphenyl(3,4,5-trimethoxy-2-nitrobenzyloxy)silane, triphenyl (4,
5,6-trimethoxy-2-nitropenzyloxy)silane, diphenylmethyl (5-methyl-4
-methoxy-2-nitrobenzyloxy)silane triphenyl(4,5-dimethyl-2-nitrobenzyloxy)silane, vinylmethylphenyl(4,5-dichloro-2-nitrobenzyloxy)
Silane, triphenyl(2,6-dinitrobenzyloxy)silane, diphenylmethyl(2,4-
nitrobenzyloxy)silane, triphenyl(3-methoxy-2-nitrobenzyloxy)silane, vinylmethylphenyl(3,4-dimethoxy-2-nitrobenzyloxy)silane, dimethyldi(o-nitrobenzyloxy)silane, methylphenyldi (o-nitrobenzyloxy)silane, vinylphenyldi(o-nitrobenzyloxy)silane, t-butylphenyldi(o-nitrobenzyloxy)silane, diethyldi(o-nitrobenzyloxy)silane, 2-chloroethylphenyldi(o- nitrobenzyloxy)silane, diphenyldi(o-nitrobenzyloxy)silane, diphenyldi(3-
methoxy-2-nitrobenzyloxy)silane,
Diphenyldi(3,4-dimethoxy-2-nitrobenzyloxy)silane, Diphenyldi(2,6
-dinitrobenzyloxy)silane, diphenyldi(2,4-dinitrobenzyloxy)silane,
Methyltri(o-nitrobenzyloxy)silane, phenyltri(o-nitrobenzyloxy)
Silane, p-bis(o-nitrobenzyloxydimethylsilyl)benzene 1,1,3,3-tetraphenyl-1,3-di(o-nitrobenzyloxy)siloxane, 1,
1,3,3,5,5-hexaphenyl-1,5-
Examples include di(o-nitrobenzyloxy)siloxane and silicon compounds produced by the reaction of SICl-containing silicone resin with o-nitrobenzyl alcohol. Finally, those with an α-ketosilyl group have the following formula: (In the formula, l, m, and n represent the numbers 0, 1, 2, and 3, and l+n+m does not exceed 3; R1,
R2, R3, and R4 may be the same or different, and each has a carbon number of 1 to 10, such as an alkyl group, an aryl group, an allyl group, a hydrocarbon group such as a vinyl group,
Aryloxy group, represents an alkoxy group having 1 to 10 carbon atoms, and these are halogen atoms, NO ₂ , CN,
It may have a substituent such as -OCH3 in the molecule. ) is a compound represented by A specific example is Compounds such as The amount of these silicon compounds added is 0.2 to 2.0% by weight, preferably 1 to 2.0% by weight, based on the epoxy resin.
It is in the range of 10% by weight. If the amount is less than 0.1% by weight, sufficient curing properties cannot be obtained, and although it is possible to use more than 20% by weight, there are problems such as high cost and decomposition products of the catalyst component. This is not preferable because there are cases. The composition of the present invention has the above three components, that is, an epoxy resin, an aluminum compound, and a silicon compound, as essential components, but it is also preferable to add various rust-preventing pigments to improve the overall rust-preventive property. preferable. Examples of the antirust pigment at this time include borates; phosphates; chromates; and molybdates. The amount added is usually 10 to 50% based on the weight of the epoxy resin. In addition, no inconvenience occurs even if various coloring dyes, pigments, or additives such as silica and alumina are blended. The composition of the present invention can be put to practical use by being cured by a method such as room temperature photocuring, heating photocuring, and after-curing after photocuring after being applied to a substrate. At this time, the wavelength of the irradiated light varies depending on the composition of the lining composition, but is usually 180 to 700 nm.
It is m. Irradiation with ultraviolet light is particularly effective. The light irradiation time varies depending on the composition of the epoxy resin, type of catalyst, light source, etc., but is usually 10 seconds to 30 seconds.
Preferably 20 seconds to 1 minute. The heating temperature for photocuring varies depending on the composition of the epoxy resin and the type of catalyst, but is usually 20 to 200°C, preferably 60 to 100°C. As a light source, a low pressure mercury lamp, a high pressure mercury lamp, a carbon arc lamp, a xenon lamp, an argon glow discharge tube, a metal halide lamp, etc. can be used. After-curing after photocuring varies depending on the composition of the epoxy resin and the type of catalyst, but is usually carried out at 50 to 200°C, preferably 100 to 180°C, for 1 to 10 hours, preferably 2 to 5 hours. . [Effect of the invention] The photocurable resin composition of the invention has excellent heat resistance,
It has electrical properties, particularly tracking resistance and arc resistance, and is characterized by low corrosion resistance to metals, making it particularly suitable for use as an electrical material. Hereinafter, the present invention will be explained in more detail with reference to Examples. Synthesis example 1 Allyl alcohol 58g (1 mol), 4-vinylcyclohexene-1-oxide 868g (7 mol)
and 4.7 g of BF ₃ etherate were mixed at 60° C. and reacted until the conversion of 4-vinylcyclohexene-1-oxide reached 98% or more as determined by gas chromatography analysis. Ethyl acetate was added to the obtained reaction crude liquid, washed with water, and then the ethyl acetate layer was immersed to obtain a viscous liquid. In the infrared absorption spectrum of the product, absorption by epoxy groups at 810 and 850 cm ^-1 observed in the raw material has disappeared, and at 1080 and 1150 cm
^-1 has an absorption due to an ether bond, and gas chromatography analysis shows that there is a trace amount of allyl alcohol in the product, but the infrared absorption spectrum shows an OH group absorption at 3450 cm ^-1 , so this compound is It was confirmed that the structure was shown by the following formula. 492 g of this compound was dissolved in ethyl acetate and charged into a reactor, to which 395 g of peracetic acid was added dropwise as an ethyl acetate solution over 2 hours. During this time, the reaction temperature was maintained at 40°C. After the completion of peracetic acid preparation, 40
It was further aged for 6 hours at °C. Ethyl acetate was added to the reaction crude liquid, and the mixture was washed with alkaline water containing 416 g of sodium carbonate, and then thoroughly washed with distilled water. The ethyl acetate layer was concentrated to obtain a viscous clear liquid. This compound has an oxirane oxygen content of 9.27%
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 cm ^-1 . Furthermore, absorption due to residual vinyl groups was observed at 1640 cm ^-1 , and 492 g of this compound was reacted with 395 g of peracetic acid in the same manner as in Synthesis Example 1 to obtain a viscous transparent liquid. This compound had an oxirane oxygen content of 9.27%, and a characteristic absorption due to the epoxy group was observed at 1260 cm ^-1 in the infrared absorption spectrum. Furthermore, absorption due to residual vinyl groups was observed at 1640 cm ^-1 , and 492 g of this compound was reacted with 395 g of peracetic acid in the same manner as in Synthesis Example 1 to obtain a viscous transparent liquid. This compound had an oxiranic acid content of 9.27%, and a characteristic absorption due to epoxy groups was observed at 1260 cm ^-1 in the infrared absorption spectrum. Furthermore, absorption due to residual vinyl groups is observed at 1640 cm ^-1 and at 3450 cm ^-1
OH group, 1730 cm ^-1

[Formula] This compound has the structure of general formula (1) (R1: glycidyl group or allyl group, n = average 7,
It was confirmed that the epoxy group contained a group in which a portion of acetic acid was added to an epoxy group. Synthesis Example 2 In the same manner as in Synthesis Example 1, 134 g of trimethylolpropane and 1863 g of 4-vinylcyclohexene-1-oxide were reacted to obtain a viscous liquid product. In the infrared absorption spectrum of the product, the absorption due to epoxy groups at 810 and 850 cm ^-1 observed in the raw material has disappeared, and the absorption due to ether bonds exists at 1080 and 1150 cm ^-1 , and the NMR
Analysis confirmed that this compound has a structure shown by the following formula. (Note that n ₁ , n ₂ , n ₃ have an average of 5
) Further, 573 g of this compound and 387 g of peracetic acid were reacted in the same manner as in Synthesis Example 1 to obtain a viscous transparent liquid. This compound has an oxirane oxygen content of 9.03%
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 cm ^-1 . Furthermore, 1640cm ^-1
Absorption due to residual vinyl groups is observed in 3450
OH group at cm ^-1 , 1730 cm ^-1

[Formula] This compound has a structure of the general formula () (R ₁ :trimethylolpropane residue l=3,
It was confirmed that n ₁ , n ₂ , n ₃ =5 on average, including one part of a group in which acetic acid was added to an epoxy group). Examples 1 to 6 Comparative Examples 1 to 2 Epoxy resins obtained in Synthesis Examples 1 and 2, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (Celoxide manufactured by Daicel Chemical Co., Ltd.)
2021) Epicote 828 (manufactured by Ciel Chemical Co., Ltd., bisphetol A type epoxy resin) Trisacetylacetonatoaluminum (TAAA) as an organoaluminum compound Trisethylacetoacetatoaluminum (TEAACA) As an organosilicon compound triphenyl (0-nitrobenzyloxy) Silane (TPONBS) t-butyldiphenyl (5-methyl-2-nitrobenzyloxy) silane (TBOPM) was used in the ratio shown in Table 1, and the metal halide lamp irradiation distance was 80w/cm.
A cured plate with a thickness of 2 mm was prepared by irradiating at 6.5 cm for 100 seconds, and its physical properties were measured and compared. The results are shown in Table-1.

【table】

Claims (1)

[Claims] 1. A photocurable resin comprising: (a) an epoxy resin represented by the general formula (); (b) an aluminum compound; and (c) a silicon compound that produces silanol groups when irradiated with light. Composition. However, R ₁ is an organic compound residue having 1 active hydrogen. n1, n2...nl are 0 or integers from 1 to 100, and the sum thereof is from 1 to 100. l represents an integer from 1 to 100. A is an oxycyclohexane skeleton having a substituent, and is represented by the following formula. X is [formula] R ₂ is any one of H, an alkyl group, a carboalkyl group, and a carboaryl group, and the resin represented by the formula () contains at least one group. 2. The photocurable resin composition according to claim 1, wherein the aluminum compound is an organic aluminum compound. 3 The silicon compound has a peroxysilane group, o-
The photocurable resin composition according to claim 1, which is a silicon compound having either a nitrobenzyloxy group or an α-ketosilyl group. 4. The photocurable resin composition according to claim 1, wherein the aluminum compound and the silicon compound have a blending ratio of 0.001 to 10% by weight and 0.1 to 20% by weight, respectively, based on the weight of the epoxy resin. thing.