JP6109636B2 - Photocurable resin composition - Google Patents

Description

  The present invention relates to a photocurable resin composition and a cured product obtained by irradiating the photocurable resin composition with active energy rays. The photocurable resin composition and the cured product are particularly useful as a sealant.

  Photocurable resin compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members, and the like.

  For example, in the following Patent Documents 1 to 4, various photocurable resin compositions are disclosed, but the photocurable resin composition is useful as an adhesive for electronic devices and semiconductor devices. Volume resistivity and water absorption resistance were not sufficient.

JP 2006-213872 A JP 2008-074928 A JP 2008-106231 A JP 2008-258429 A

  Accordingly, an object of the present invention is to provide a photocurable resin composition that is excellent in curability and water absorption resistance and has a high volume resistance value.

（式中、Ｒ^１は水素原子、ハロゲン原子で置換されていてもよい直鎖または分岐鎖の炭素原子数１〜４のアルキル基、又は、ハロゲン原子を表し、ｎは０〜１０の数である。） That is, the photocurable resin composition of the present invention comprises (1) a mixture containing a compound represented by the following general formula (I) and a compound represented by the following general formula (II) as a cationically polymerizable organic substance. 100 parts by mass, (2) 0.001 to 10 parts by mass of an energy ray sensitive cationic polymerization initiator,
Furthermore, (1) the compound represented by the following general formula (III) is contained as a cationically polymerizable organic substance.

(In the formula, R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, or a halogen atom, and n is a number from 0 to 10. is there.)

（式中、Ｚ^１は、単結合、又は、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−で中断されていてもよい直鎖または分岐鎖の炭素原子数１〜４のアルキレン基を表し、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子、ハロゲン原子、又は、ハロゲン原子で置換されていてもよい直鎖または分岐鎖の炭素原子数１〜４のアルキル基を表し、ａ及びｂは、それぞれ独立に、０〜１０の数であり、ｐは、０〜５の数である。）

Wherein Z ¹ represents a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms which may be interrupted by —CO—O— or —O—CO—, and R ² and R ³ each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, and a and b are Each is independently a number from 0 to 10, and p is a number from 0 to 5.)

In the photocurable resin composition of the present invention, the (2) energy ray-sensitive cationic polymerization initiator is [A] ^{r +} [B] _s ^t- (where r is an integer of 1 to 4, and t is 1). An integer of ˜4, s is a coefficient for keeping the charge neutral.) And a salt of a cation and an anion.

  The sealing agent of this invention consists of one of the said photocurable resin compositions, It is characterized by the above-mentioned.

  The cured product of the present invention is obtained by curing any of the above photocurable resin compositions.

  Since the photocurable resin composition of the present invention is excellent in curability and water absorption resistance and has a high volume resistance value, it is particularly useful as a sealant application. Since it has high water absorption resistance, it can be expected to have excellent solder resistance and can be suitably used for electronic equipment and semiconductor applications.

  Hereinafter, the photocurable resin composition of the present invention and the sealant comprising the photocurable resin composition will be described in detail.

  The (1) cationically polymerizable organic substance used in the present invention is a compound that is polymerized by an energy ray-sensitive cationic polymerization initiator activated by light irradiation or a compound that causes a crosslinking reaction. It is a mixture containing the compound represented and the compound represented by (II). Furthermore, it is preferable that the compound represented by general formula (III) is also included. A suitable content ratio of each compound is a compound represented by the general formula (I): a compound represented by the general formula (II) = 3: 1 to 1: 3, more preferably 2 in terms of molar ratio. : 1-1: 1. Further, when the compound represented by the general formula (III) is included, it is preferably a molar ratio (total of the compound represented by the general formula (I) and the compound represented by the general formula (II)). : Compound represented by formula (III) = 5: 1 to 1: 5, more preferably 4: 1 to 1: 1.

R ¹ in the above general formula (I), R ² and R ³ in the above general formula (II) can be a straight or branched chain carbon atom having 1 to 4 carbon atoms which may be substituted with a halogen atom Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, chloroethyl, fluoroethyl, 1-chloropropyl, 2-chloropropyl, 1-chlorobutyl, 2-chlorobutyl and the like. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Alkylene in a linear or branched alkylene group having 1 to 4 carbon atoms which may be interrupted by —CO—O— or —O—CO—, which Z ¹ in formula (II) may take Examples of the group include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene and the like.

A commercial item can also be used as a compound represented by the said general formula (I) and (II).
Examples of the compound represented by the general formula (I) include XD-1000, XD-1000-L, XD-1000-2L (manufactured by Nippon Kayaku Co., Ltd.), Epicron HP-7200, Epicron HP-7200H, Epicron HP- 7200HH, Epicron HP-7200HHH, Epicron HP-7200L (manufactured by DIC), Tactix556, Tactix71756 (manufactured by Huntsman Advanced Materials), and the like.
Examples of the compound represented by the general formula (II) include jER YL-6571, jER YL-6663, jER YX-8000, jER YX-8034, jER YX-8040 (manufactured by Mitsubishi Chemical Corporation), Epicron EXA-7015 ( DIC), Eponex DRH-151, Eponex DRH-1510, Eponex 510 (manufactured by Shell Chemical), Denacol EX-252 (manufactured by Nagase ChemteX), Adeka Resin EP-4080, Adeka Resin EP-4080E, Adeka Resin EP-4080S (Made by ADEKA) etc. are mentioned.

  As the above (1) cationic polymerizable organic substance, an aromatic epoxy resin, an alicyclic epoxy resin or an aliphatic epoxy resin other than the compounds represented by the general formulas (I) to (III) may be used. it can.

  Specific examples of the aromatic epoxy resin include polyhydric phenol having at least one aromatic ring or polyglycidyl ether of an alkylene oxide adduct thereof, such as bisphenol A, bisphenol F, or further alkylene oxide added thereto. Examples thereof include glycidyl ethers and epoxy novolac resins of the above compounds.

  Specific examples of the alicyclic epoxy resin include cyclohexene oxide obtained by epoxidizing a polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. A cyclopentene oxide containing compound is mentioned. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Metageo Sun, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4 -Epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propanedicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, epoxyhexahydrophthalic acid Examples thereof include di-2-ethylhexyl, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane and the like.

  Specific examples of the aliphatic epoxy resin include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and the like. As typical compounds, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, dipentaerythritol One or more glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin Polyglycidyl ether of polyether polyol, diglycidyl ester of aliphatic long-chain dibasic acid obtained by adding an alkylene oxide of And the like. In addition, monoglycidyl ethers of higher aliphatic alcohols, phenols, cresols, butylphenols, polyether alcohol monoglycidyl ethers obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy Examples include octyl stearate, butyl epoxy stearate, epoxidized soybean oil, and epoxidized polybutadiene.

  In the above (1) cationically polymerizable organic substance, the use ratio of the epoxy resin other than the compounds represented by the general formulas (I) to (III) is not particularly limited, and is generally within the range not impairing the object of the present invention. What is necessary is just to use at a normal usage rate. For example, the amount of the epoxy resin other than the compounds represented by the above general formulas (I) to (III) is preferably 0 to 40 parts by mass, more preferably 100 parts by mass of the cationically polymerizable organic substance (1). Is 0-30 parts by mass.

The energy beam sensitive cationic polymerization initiator (2) used in the present invention may be any compound that can release a substance that initiates cationic polymerization by irradiation with energy rays. Preferably, it is a double salt that is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof. Typical examples of such compounds include the following general formula: [A] ^{r +} [B] _s ^t- (where r is an integer of 1 to 4, t is an integer of 1 to 4, s is a neutral charge) Cation and anion salts represented by the formula (1).

Here, the cation [A] ^{r +} is preferably onium, and the structure thereof can be represented by, for example, the following general formula [(R ⁷ ) _a Q] ^{r +} .

Further, R ⁷ is an organic group having 1 to 60 carbon atoms and optionally containing any number of atoms other than carbon atoms. a is an integer of 1 to 5. The a R ^{7 s} are independent and may be the same or different. In addition, at least one of R ⁷ is preferably an organic group as described above having an aromatic ring. For example, it may be substituted with an alkyl group, alkoxy group, hydroxy group, hydroxyalkoxy group, halogen atom, benzyl group, thiophenoxy group, 4-benzoylphenylthio group, 2-chloro-4-benzoylphenylthio group, etc. A phenyl group is mentioned. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{r +} is q, the relationship r = a−q needs to be established (however, N = N is treated as a valence of 0).

Further, the anion [B] ^t- is preferably a halide complex, and the structure thereof can be represented by, for example, the following general formula, [LX _b ] ^t- .

Further, here, L is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is a halogen atom or a phenyl group which may be substituted with a halogen atom or an alkoxy group. b is an integer of 3-7. Further, when the valence of L in the anion [B] ^t− is p, it is necessary that the relationship t = b−p holds.

Specific examples of the anion [LX _b ] ^t- of the above general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ) ⁻ , Examples include hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like.

Moreover, the thing of the structure represented by the following general formula, [LXb _-1 (OH)] ^t- can also be preferably used for the anion [B] ^t- . L, X, and b are the same as described above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate anion. , Trinitrobenzenesulfonate anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.

  In the present invention, among these onium salts, it is particularly effective and preferable to use the following aromatic onium salts (a) to (c). Among these, one of them can be used alone, or two or more of them can be mixed and used.

  (I) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, and the like.

  (B) Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, and tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt.

  (C) Triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4, 4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4,4′-bis [di ( β-hydroxyethoxy) phenylsulfonio] phenylsulfide-bis-hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonylio] f Phenylsulfide-bis-hexafluorophosphate, 4- [4 ′-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4 ′-(benzoyl) phenylthio] phenyl-di Triarylsulfonium salts such as-(4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate and diphenyl-4 A triarylsulfonium salt such as a mixture of thiophenoxyphenylsulfonium hexafluoroantimonate and 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate.

Other preferable examples include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-arene complexes such as hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and silanols such as triphenylsilanol The mixture of these can be mentioned.

  Among these, from the viewpoint of practical use and photosensitivity, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex.

  The use ratio of the (2) energy ray-sensitive cationic polymerization initiator to the (1) cationic polymerizable organic substance is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention. Preferably, (1) the energy-sensitive cationic polymerization initiator is 0.001 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the cationically polymerizable organic substance. If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as the water absorption rate and the strength of the cured product may be adversely affected.

The photocurable resin composition of the present invention preferably contains a silane coupling agent.
Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane Any (meth) acrylic acid ester functional alkoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Epoxy-functional alkoxysilanes such as (3,4-epoxycyclohexyl) propyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ- Aminofunctional alkoxysilanes such as aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium alkoxides such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium geo Titanium chelates such as tyroxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, zirconium tributoxy monostearate, etc. Zirconium acylates, isocyanate silanes such as methyl triisocyanate silane, and the like can be used.

  Although the usage-amount of the said silane coupling agent is not specifically limited, Preferably, it is the range of 1-20 mass parts with respect to 100 mass parts of whole quantity of the solid substance in a photocurable resin composition.

A thixotropic agent can be used for the photocurable resin composition of the present invention as necessary.
Examples of the thixotropic agent include ultrafine silica, anhydrous silica, colloidal silica, aluminum stearate, surface-treated bentonite, hydrogenated castor oil, and the like.

  Although the usage-amount of the said thixotropic agent is not specifically limited, Preferably, it is the range of 1-20 mass parts with respect to 100 mass parts of whole quantity of the solid substance in a photocurable resin composition.

In the photocurable resin composition of the present invention, a thermal polymerization initiator can be used as necessary.
Thermal polymerization initiator is a compound that generates a cationic species or Lewis acid by heating, such as a salt of sulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; diethylenetriamine, triethylenetriamine, tetraethylenepenta Polyalkylpolyamines such as min; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine; m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone Aromatic polyamines such as; such polyamines; phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, etc. Polyepoxy addition-modified products produced by reacting various kinds of epoxy resins such as glycidyl ethers or glycidyl esters of carboxylic acids in a conventional manner; such organic polyamines as phthalic acid, isophthalic acid, dimer acid, etc. An amidation modified product produced by reacting carboxylic acids with a conventional method; at least one aldehyde reaction in the nucleus of polyamines and aldehydes such as formaldehyde and phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. Mannich-modified products produced by reacting phenols having sex sites by a conventional method; polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelain Acid, sebacic acid, Decanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecane Aliphatic dicarboxylic acids such as diacids, hydrogenated dimer acids and dimer acids; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid , Tricarboxylic acids such as trimesic acid and trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid) acid anhydrides; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, etc. .

  A commercial item can also be used as said thermal polymerization initiator, for example, Adeka Opton CP77, Adeka Opton CP66 (made by ADEKA), CI-2638, CI-2624 (made by Nippon Soda Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI -80L, Sun-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.

  The amount of the thermal polymerization initiator used is not particularly limited, but is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of solids in the photocurable resin composition, When using a thermal polymerization initiator, it is preferable to heat at 130 to 180 ° C. for 20 minutes to 1 hour when the photocurable resin composition of the present invention is cured.

  In the photocurable resin composition of the present invention, a solvent capable of dissolving or dispersing each of the components (1) to (5) as necessary, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, Ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol can be added.

  The photocurable resin composition of the present invention is applied on a supporting substrate such as glass, metal, paper, plastic, etc. by a known means such as a roll coater, a curtain coater, various printing, and immersion. Moreover, after applying on a support substrate such as a film, it can be transferred onto another support substrate, that is, used as a dry film, and the application method is not limited.

  In addition, as long as the effects of the present invention are not impaired, other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, dyes and other colorants, photosensitizers and antifoaming agents as necessary. , Thickeners, surfactants, leveling agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antistatic agents, flow regulators, adhesion promoters, etc. Resin additives and the like can be added.

  The photocurable resin composition of the present invention is cured by irradiation with active energy rays. Examples of active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are the most economical. preferable. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.

  Specific applications of the photocurable resin composition of the present invention include glasses, optical materials represented by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, Insulating varnish, insulating sheet, laminate, printed circuit board, semiconductor device, LED package, liquid crystal inlet, organic EL, optical element, electrical insulation, electronic component, separation membrane, etc., Molding material, putty, glass fiber impregnating agent, sealant, passivation film for semiconductors and solar cells, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, projection TV, etc. Lens parts of lens sheets such as Fresnel lens sheets and lenticular lens sheets used for screens, or backers using such sheets Optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, casting agents for optical modeling, etc. Examples of substrates that can be applied as coating agents include metals, wood, rubber, plastics , Glass, ceramic products and the like.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

  Hereinafter, the photocurable resin composition of the present invention and the cured product obtained by curing the photocurable resin composition will be specifically described with reference to examples, evaluation examples, and comparative examples. In Examples and Comparative Examples, “part” means “part by mass”.

[Examples 1 to 18, Comparative Examples 1 to 4, Reference Example 1]
Resins were sufficiently mixed in the formulations shown in [Table 1] to [Table 5] below to obtain photocurable resin compositions of Examples, Comparative Examples, and Reference Examples. Light obtained by pasting a polyimide tape at a height of 200 μm around a glass substrate having a size of 120 × 120 × 1.3 mm, and performing mold release treatment with a die-free (fluorine-based mold release agent; manufactured by Daikin Industries). A curable resin composition was applied. The glass substrate which gave the mold release process was piled up. On both surfaces of the glass substrate was irradiated with ultraviolet light at an energy amount of 2000 mJ / cm ² by gauge 4000 mJ / cm ² using a high pressure mercury lamp. The film was heated in an oven at 175 ° C. for 30 minutes and post-cured. It took out from the glass substrate after cooling, and peeled the resin cured film from the glass substrate.

  (1) The following compounds 1-1 to 1-9 were used as the cationically polymerizable organic substance.

Compound 1-1: Epoxy equivalent: 210-280, n = 0-3

Compound 1-2: Epoxy equivalent: 210-280, n = 0-3

Compound 1-3: Epoxy equivalent: 230 to 250, p = 0 to 5

Compound 1-8: Epoxy equivalent: 230-250, p = 0-5

  (2) The following compounds 2-1 to 2-6 were used as the energy ray-sensitive cationic polymerization initiator.

＊１：下記化合物Ａ：

＊２：下記化合物Ｂ：

＊３：疎水性シリカ微粉末（平均粒径：１６ｎｍ）
＊４：親水性シリカ微粉末（平均粒径：４μｍ）

* 1: Compound A:

* 2: Compound B below:

* 3: Hydrophobic silica fine powder (average particle size: 16 nm)
* 4: Hydrophilic silica fine powder (average particle size: 4 μm)

[Examples 1 to 18, Comparative Examples 1 to 4, Reference Example]
The following evaluation was performed about the resin cured film obtained by the said Examples 1-18, Comparative Examples 1-4, and the reference example. The results are shown in the above [Table 1] to [Table 5].

(Volume resistance value)
After charging for 30 seconds, the measurement was performed using a digital ultrahigh resistance / microammeter (manufactured by Advantest Corporation: R8340A).

(Water absorption rate)
A 60 mm × 60 mm × 0.3 mm thick water absorption rate test piece (cured product) was prepared, and the test piece was kept in a constant temperature and humidity chamber (constant temperature manufactured by EYELA) based on JIS K7209 (plastic water absorption rate and boiling water absorption rate test method). Incubation was performed at 80 ° C. and 90% RH until there was no weight increase. The water absorption was calculated from the weight difference between the initial weight and the weight when the weight increased.

(Curable)
The initial calorific value at the time of light irradiation was measured using a photochemical reaction calorimeter (Optical DSC) to evaluate the curability. Each sample was 2 mg, and the light irradiation conditions were 20 mW / 30 ° C.

  From the above [Table 1] to [Table 5], it is clear that the photocurable resin composition of the present invention is excellent in curability and water absorption resistance and has a high volume resistance value. For example, as is clear from the comparison between the reference example and the comparative example 1, the comparative example 1 not including the compound represented by the general formula (II) is inferior in terms of volume resistance, water absorption resistance and curability. Met. Similarly, Comparative Example 2 was inferior in terms of volume resistance value and water absorption resistance as compared with the Reference Example.

Claims (4)

(1) As a cationically polymerizable organic substance, 100 parts by mass of a mixture containing a compound represented by the following general formula (I) and a compound represented by the following general formula (II);
(2) 0.001 to 10 parts by mass of an energy ray sensitive cationic polymerization initiator,
Further, (1) as a cationically polymerizable organic substance, a compound represented by the following general formula (III):
The photocurable resin composition characterized by containing.

(In the formula, R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, or a halogen atom, and n is a number from 0 to 10. is there.)

Wherein Z ¹ represents a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms which may be interrupted by —CO—O— or —O—CO—, and R ² and R ³ each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, and a and b are Each is independently a number from 0 to 10, and p is a number from 0 to 5.)

(2) The energy ray-sensitive cationic polymerization initiator is [A] ^{r +} [B] _s ^t- (where r is an integer of 1 to 4, t is an integer of 1 to 4, and s keeps the charge neutral. coefficient is.) a cation and a salt of the anion represented by claim 1 Symbol placement of the photocurable resin composition. A sealant comprising the photocurable resin composition according to claim 1 . A cured product obtained by curing the photocurable resin composition according to claim 1 .