TW201823277A - Photocurable resin composition and sealing agent for electronic component - Google Patents

Abstract

The present invention relates to a resin composition which is cured by irradiation with light such as ultraviolet light or visible light, and which is highly sensitive to light and sufficiently cured even by low energy light. The photocurable resin composition of the present invention comprises an oxime compound having a furan structure in the molecule of component (A), and a curable compound (B).

Description

   Photocurable resin composition and sealant for electronic parts   

The present invention relates to a photocurable resin composition used in a sealant for electronic parts. More specifically, the present invention relates to a photocurable resin composition containing a compound having a specific structure in a molecule. Since this photocurable resin composition has good sensitivity and low outgassing even for low-energy light, it is extremely useful as a sealant for electronic parts, and particularly as a sealant for displays.

The photocurable resin composition is widely used in electronic sealant applications such as display sealants, solar cell sealants, and semiconductor sealants. Examples of the display sealant include a liquid crystal sealant, an organic EL display sealant, and a touch panel adhesive. In terms of the commonality of these materials, they are required to have excellent hardenability, and at the same time have the characteristics of less gas generation and no damage to the display element.

However, a disadvantage of the photocurable resin composition is that a curing reaction does not proceed in a portion where light is not irradiated, and a usable portion is limited.

In particular, a liquid crystal sealant (hereinafter referred to as a "sealant") for a liquid crystal dropping method is not irradiated with light due to a wiring portion of an array substrate of a liquid crystal display element and a black matrix of a color filter substrate. The light-shielding portion of the liquid crystal sealant causes a problem of poor display near the sealing portion than before. That is, due to the existence of the light-shielding portion, the primary hardening by the light becomes insufficient, and a large amount of unhardened components remain in the liquid crystal sealant. When the secondary hardening step by heat is performed in this state, as a result, dissolution of the unhardened component in the liquid crystal due to heat is caused, and there is a problem that display defects near the sealing portion are caused.

In order to solve this problem, various studies are being conducted to improve thermal reactivity. Regarding the light-shielding portion, an attempt has been made to suppress liquid crystal contamination by rapidly reacting a liquid crystal sealant that is sufficiently hardened by light at a low temperature. For example, Patent Documents 1 and 2 disclose methods using a thermal radical polymerization initiator. In addition, Patent Documents 3 to 5 disclose methods using a polycarboxylic acid as a hardening accelerator.

However, in order for the thermal radical polymerization initiator to efficiently generate free radicals, the molecular weight must be a relatively small degree. Although the low-molecular compound is easily dissolved in the liquid crystal and has excellent reactivity, the thermal radical polymerization initiator itself will Causes liquid crystal contamination.

In addition, when using a polycarboxylic acid, there is a possibility that the moisture resistance reliability may be impaired, and it may not be used depending on the application.

As described above, although the development of a liquid crystal sealant is being actively carried out, a liquid crystal sealant having excellent light-shielding portion hardening properties and low liquid crystal contamination properties has not yet been realized.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2004-126211

[Patent Document 2] Japanese Patent Laid-Open No. 2009-8754

[Patent Document 3] International Publication No. 2007/138870

[Patent Document 4] Japanese Patent Laid-Open No. 2008-15155

[Patent Document 5] Japanese Patent Laid-Open No. 2009-139922

The present invention relates to a resin composition that is hardened by irradiation with ultraviolet or visible light, and proposes a resin composition that has high sensitivity to light and can be sufficiently hardened even by low-energy light. This photocurable resin composition has high hardenability in a portion where light is not sufficiently radiated, and has sufficient hardenability even if it is irradiated with low-energy light in consideration of damage to other members. Therefore, it can be used as an adhesive for electronic parts. Agents, especially sealants for displays.

As a result of intensive studies by the present inventors, it was found that a photocurable resin composition containing an oxime compound having a furan structure in a molecule is very excellent as a photoradical polymerization initiator system, that is, it has a low-energy light irradiation. The present invention has been sufficiently hardened.

In the present specification, "(meth) acrylic acid" means "acrylic and / or methacrylic acid", and "(meth) acrylfluorenyl" means "acrylfluorenyl and / or methyl" Propionyl. " In addition, the "liquid crystal sealing agent for liquid crystal dropping method" may be abbreviated as "liquid crystal sealing agent" or "sealant."

That is, the present invention relates to the following [1] to [19].

[1] A photocurable resin composition containing an oxime compound having a furan structure in the component (A) and a curable compound (B).

[2] The photocurable resin composition according to the item [1], wherein the component (A) is an oxime compound having a dibenzofuran skeleton.

[3] The photocurable resin composition according to the item [1] or [2], wherein the component (A) is an oxime compound having a diphenylsulfide structure.

[4] The photocurable resin composition according to any one of the items [1] to [3], wherein the component (A) is a compound represented by the following formula (A-1).

[5] The photocurable resin composition according to any one of the items [1] to [4], wherein the component (B) is the component (B-1) (meth) acrylic compound.

[6] The photocurable resin composition according to any one of the items [1] to [5], wherein the component (B) is the component (B-1) (meth) acrylic compound and the component (B-2) ) A mixture of epoxy compounds.

[7] The photocurable resin composition according to any one of the items [1] to [6], further containing a component (C) organic filler.

[8] The photocurable resin composition according to the item [7], wherein the component (C) is selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and polysiloxane fine particles. One or more organic fillers in a group.

[9] The photocurable resin composition according to any one of the above [1] to [8], further containing a component (D) inorganic filler.

[10] The photocurable resin composition according to any one of the above [1] to [9], further containing a component (E) silane coupling agent.

[11] The photocurable resin composition according to any one of the items [1] to [10], further containing a component (F) thermosetting agent.

[12] The photocurable resin composition according to the item [11], wherein the component (F) is an organic acid hydrazide compound.

[13] The photocurable resin composition according to any one of the items [1] to [12], further containing a component (G) a hydrogen-drawing type photoradical polymerization initiator.

[14] The photocurable resin composition according to any one of the items [1] to [13], further containing a component (H) thermal radical polymerization initiator.

[15] A sealant for electronic parts, which uses the curable resin composition according to any one of the items [1] to [14].

[16] An electronic component using a hardened material obtained by hardening the electronic component adhesive according to the above item [15].

[17] A sealant for a liquid crystal display unit, which uses the photocurable resin composition according to any one of [1] to [14].

[18] A liquid crystal sealant using the photocurable resin composition according to any one of [1] to [14].

[19] A liquid crystal display unit, which uses the sealant for liquid crystal display unit or liquid crystal sealant described in the above item [17] or [18].

Since the photocurable resin composition of the present invention exhibits sufficient hardenability even with low-energy light, it is very useful as a sealant for an electronic part having a light-shielding portion or an electronic part that must be hardened by visible light.

[(A) An oxime compound having a furan structure in the molecule]

The photocurable resin composition of the present invention contains (A) an oxime compound having a furan structure in the molecule (hereinafter also simply referred to as "component (A)"). The compound is very sensitive to low-energy light and functions as a photoradical polymerization initiator.

The furan structure may be the furan ring itself or other ring-condensed rings, for example, it may also include a skeleton such as benzofuran and isobenzofuran. Those containing a benzofuran skeleton are preferred.

Moreover, you may have another substituent in a furan structure. Examples of the substituent include a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 aryl group, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, and a cyano group.

As the C1-C10 alkyl group, a C1-C6 alkyl group is preferred, and an alkyl group having a linear, branched, or cyclic structure such as methyl, ethyl, propyl, butyl, pentyl, and hexyl is used. A methyl group is preferred, with methyl, ethyl, butyl and tertiary butyl being particularly preferred. As the C1-C10 alkoxy group, a C1-C6 alkoxy group is preferred. The alkoxy group has a linear, branched or cyclic structure such as methoxy, ethoxy, propoxy, butoxy. An oxy group is preferred, with methoxy, ethoxy and propoxy being particularly preferred. The C1-C10 aryl group is preferably a phenyl group.

The furan structure is preferably bonded to a phenyl sulfide (diphenyl sulfide) structure, a diphenyl ether structure, or a fluorene structure through a carbonyl group.

Examples of the organic group bonded to the oxime group include a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 aryl group, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, and a cyano group. It is preferably the same as described above.

This compound can be synthesized in accordance with Japanese Patent Application Publication No. 2016-531926. The compound can also be obtained from the market under the trade name of IRGACURE OXE 04, for example.

The component (A) may be used alone or as a mixture of two or more kinds. In the photocurable resin composition of the present invention, the blending amount of the component (A) is usually 0.1 to 7 mass%, preferably 0.2 to 5 mass%, and more preferably the total amount of the photo curable resin composition. 0.3 to 3% by mass.

[(B) hardening compound]

The photocurable resin composition of the present invention contains a curable compound as a component (B) (hereinafter also simply referred to as "component (B)").

The component (B) is not particularly limited as long as it is a compound that is hardened by light, heat, and the like, and (B-1) (meth) acrylic compound is preferred.

(Herein, "(meth) acrylic acid" means "acrylic acid" and / or "methacrylic acid". The same applies hereinafter). Examples of the component (B-1) include (meth) acrylic acid esters. Compounds, epoxy (meth) acrylate compounds, and the like.

Specific examples of the (meth) acrylic acid ester compound include N-acryloxyethyl hexahydrophthalimide, acrylic acid oxymorpholine, and 2-hydroxypropyl (meth) acrylate , 4-hydroxybutyl (meth) acrylate, cyclohexane-1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate Phenyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol Polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isoamyl (meth) acrylate, tribromophenoxyethyl (meth) acrylate, ( Dicyclopentyl methacrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecanedimethanol (meth) acrylate, bisphenol A polyethoxydi (Meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F Ethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ginseng (acryloxyethyl) isotricyanate ( tris (acryloxyethylisocyanurate)), neopentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dinepentaerythritol penta (meth) acrylate, trinepentaerythritol hexa (Meth) acrylates, trinepentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, Ε-caprolactone of di (trimethylolpropane) tetra (meth) acrylate, ester of neopentyl glycol and hydroxytrimethylacetic acid, or ester of neopentyl glycol and hydroxytrimethylacetic acid Monomers such as diacrylates of ester adducts. Preferred examples thereof include N-propenyloxyethylhexahydrophthalimide, phenoxyethyl (meth) acrylate, and dicyclopentenyloxy (meth) acrylate.

The epoxy (meth) acrylate compound can be obtained by a well-known method by reacting an epoxy compound with (meth) acrylic acid. The epoxy compound used as a raw material is not particularly limited, and an epoxy compound having two or more functions is preferred. Examples include resorcinol diglycidyl ether, bisphenol A type epoxy compounds, and bisphenol F type. Epoxy compounds, bisphenol S epoxy compounds, phenol novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, bisphenol F novolac epoxy compounds, grease Cyclic epoxy compounds, aliphatic chain epoxy compounds, epoxypropyl ester epoxy compounds, epoxypropylamine epoxy compounds, hydantoin type epoxy compounds, isotricyanate type Epoxy compounds, phenol novolak epoxy compounds having a triphenylmethane skeleton, and difunctional propyl ethers of difunctional phenols such as catechol and resorcinol, and diepoxys of difunctional alcohols Propyl etherate, and halides and hydrides thereof. Among these, bisphenol A type epoxy compounds and resorcinol diglycidyl ether are preferred from the viewpoint of liquid crystal contamination. The ratio of the epoxy group to the (meth) acrylfluorenyl group is not limited, and can be appropriately selected from the viewpoint of process suitability. In addition, a partially epoxy (meth) acrylate in which a part of the epoxy group is acrylated can be suitably used. The ratio of acrylates at this time is preferably about 30 to 70%.

The component (B-1) may be used alone or as a mixture of two or more types. When the component (B-1) is used in the photocurable resin composition of the present invention, it is usually 5 to 50% by mass, and preferably 5 to 30% by mass, based on the total amount of the photocurable resin composition.

[(B-2) epoxy compound]

As an aspect of the present invention, it is more preferable that the component (B) further contains (B-2) an epoxy compound.

The epoxy compound is not particularly limited, and it is preferably a bifunctional or more epoxy compound, and examples thereof include resorcinol diglycidyl ether, bisphenol A type epoxy resin, and bisphenol F type epoxy resin. Resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, alicyclic Epoxy resin, aliphatic chain epoxy resin, epoxypropyl ester epoxy resin, epoxypropylamine epoxy resin, hydantoin type epoxy resin, isotricyanate type epoxy resin Resins, phenol novolac epoxy resins with a triphenylmethane skeleton, and difunctional propyl ethers of difunctional phenols such as catechol and resorcinol, and dipropylene propyl of difunctional alcohols Etherates, and their halides, hydrides, etc. Among these, bisphenol A epoxy resin and resorcinol diglycidyl ether are preferred from the viewpoint of liquid crystal contamination.

The component (B-2) may be used alone or as a mixture of two or more types. When the component (B-2) is used in the photocurable resin composition of the present invention, it is usually 5 to 50% by mass, preferably 5 to 30% by mass, based on the total amount of the photocurable resin composition.

In the photocurable resin composition of the present invention, the blending amount of the component (B) is usually 10 to 80% by mass, and preferably 20 to 70% by mass, based on the total amount of the photocurable resin composition. The same applies when the component (B-1) and the component (B-2) are mixed and used.

[(C) Organic filler]

The photocurable resin composition of the present invention may contain an organic filler as a component (C) (hereinafter also simply referred to as "component (C)"). Examples of the organic filler include urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and polysiloxane fine particles. The polysiloxane particles are preferably KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), TORAFIL ^RTM E-5500, 9701, EP-2001 (manufactured by Dow Corning Toray), and are preferably used as a methylamine. Ester fine particles, preferably JB-800T, HB-800BK (Gensang Industrial Co., Ltd.), as styrene fine particles, RABALON ^RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (Mitsubishi Chemical Corporation) Is preferred), and as the styrene olefin fine particles, SEPTON ^RTM SEPS2004 and SEPS2063 are preferred.

These organic fillers can be used alone or in combination of two or more. Moreover, you may use 2 or more types as a core-shell structure. Among these, acrylic fine particles and polysiloxane fine particles are preferred.

When using the above-mentioned acrylic fine particles, an acrylic rubber having a core-shell structure composed of two types of acrylic rubbers is preferred, and a core layer of n-butyl acrylate and a shell layer of methyl methacrylate are particularly preferred. It is sold under the trade name Zefiakku ^RTM F-351 by Aica Industries Co., Ltd.

Examples of the polysiloxane fine particles include organic polysiloxane crosslinked powders and linear dimethyl polysiloxane crosslinked powders. Examples of the composite silicone rubber include a silicone resin (for example, a polyorganosilsesquioxane resin) coated on the surface of the silicone rubber. Among these fine particles, particularly preferred is a silicone rubber having a linear dimethyl polysiloxane crosslinked powder or a silicone resin coated with a linear dimethyl polysiloxane crosslinked powder. Rubber particles. These may be used alone or in combination of two or more. In addition, the shape of the rubber powder is preferably a sphere having a small viscosity and stickiness after the addition. When the component (C) is used in the photocurable resin composition of the present invention, the total amount of the photocurable resin composition is usually 5 to 50% by mass, preferably 5 to 40% by mass.

[(D) Inorganic filler]

The photocurable resin composition of the present invention may contain an inorganic filler as a component (D) (hereinafter also simply referred to as a component (D)). Examples of the inorganic filler contained in the present invention include silicon oxide, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, and oxidation. Aluminum, magnesium oxide, zirconia, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc. Preferable examples include fused silica, crystalline silica, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, aluminum hydroxide, calcium silicate, and aluminum silicate. Of these, silica, alumina, and talc are preferred. These inorganic fillers may be used by mixing two or more kinds.

If the average particle diameter of the inorganic filler is too large, it may cause defects such as failure to form a gap smoothly when the upper and lower glass substrates are bonded when manufacturing a liquid crystal display unit with a narrow gap, so it is appropriate to be 2000 nm or less, and preferably 1000 nm or less , More preferably 300 nm or less. The preferable lower limit is about 10 nm, and more preferably about 100 nm. The particle size can be measured using a laser diffraction / scattering type particle size distribution measuring device (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).

In the photocurable resin composition of the present invention, when an inorganic filler is used, the total amount of the photocurable resin composition is usually 5 to 50% by mass, preferably 5 to 40% by mass. When the content of the inorganic filler is less than 5% by mass, the bonding strength to the glass substrate is low and the moisture resistance reliability is also deteriorated. Therefore, the reduction in the bonding strength after moisture absorption may increase. When the content of the inorganic filler is more than 50% by mass, the content of the filler may be too large, and it may be difficult to collapse and the gap of the liquid crystal cell may not be formed.

[(E) Silane coupling agent]

The photocurable resin composition of the present invention is capable of adding a silane coupling agent as a component (E) to improve adhesion strength and moisture resistance (hereinafter also simply referred to as "component (E)").

Examples of the component (E) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyl Diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl Group) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-hydrothiopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride , 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and the like. Since these silane coupling agents are sold under the trade names of KBM series, KBE series, etc. by Shin-Etsu Chemical Industry Co., Ltd., they can be easily obtained from the market. When the component (E) is used in the photocurable resin composition of the present invention, it is preferably 0.05 to 3% by mass based on the total amount of the photocurable resin composition.

[(F) Thermal hardener]

The photocurable resin composition of the present invention may contain a thermosetting agent as a component (F) (hereinafter also simply referred to as "component (F)"). The component (F) reacts nucleophilically by a non-shared electron pair or an anion in the molecule, and examples thereof include polyamines, polyphenols, and organic acid hydrazine compounds. But it is not limited by these. Among these, an organic acid hydrazine compound can be suitably used. Examples include dihydrazine terephthalate, dihydrazine isophthalate, dihydrazine isophthalate, 2,6-naphthoate dihydrazine, 2,6-pyridine dihydrazine, 1, 2, 4 -Benzyltriazine, 1,4,5,8-naphthoic acid tetramethylhydrazine, pyromelitic acid tetramethylhydrazine and the like. In addition, in the case of an aliphatic hydrazine compound, for example, formamidine, acetazine, propionic acid hydrazide, dihydrazine oxalate, dihydrazine malonate, and dihydrazine succinate , Dihydrazine glutarate, Dihydrazine adipate, Dihydrazide pimelate, Dihydrazide sebacate, 1,4-cyclohexanedihydrazine, Dihydrazide tartrate, Dihydrazide malate , Imino diacetic acid dihydrazine, N, N'-hexamethylene bis-hemicarbazide, trimethylhydrazine citrate, trimethylhydrazine nitrogen acetate, trimethylhydrazine cyclohexanetricarboxylic acid, 1,3 -Hydantoin skeletons such as bis (hydrazinocarbonylethyl) -5-isopropylhydantoin, preferably those having a hyaluronate skeleton (hydantoin ring) Carbon skeleton substituted with isopropyl), a dihydrazine compound, ginseng (1-hydrazinocarbonylmethyl) isotricyanate, ginseng (2-hydrazinocarbonylethyl) isotricyanate, Ginseng (1-hydrazinocarbonylethyl) isotricyanate, ginseng (3-hydrazinocarbonylpropyl) isotricyanate, bis (2-hydrazinocarbonylethyl) isotricyanate Wait. In terms of the balance between hardening reactivity and latentity, dihydrazide isophthalate, dihydrazine malonate, dihydrazine adipate, and (1-hydrazinocarbonylmethyl) heterotrimers are preferred. Cyanate, ginseng (1-hydrazinocarbonylethyl) isotricyanate, ginseng (2-hydrazinocarbonylethyl) isotricyanate, ginseng (3-hydrazinocarbonylpropyl) isotricyanate Polycyanate, particularly preferred is ginseng (2-hydrazinocarbonylethyl) isotricyanate.

The component (F) may be used alone or as a mixture of two or more kinds. When the component (F) is used in the photocurable resin composition of the present invention, the total amount of the photocurable resin composition is usually 0.1 to 10% by mass, and preferably 1 to 10% by mass.

[(G) Hydrogen-extracting type photoradical polymerization initiator]

The photocurable resin composition of the present invention may further contain a hydrogen-extraction type photoradical polymerization initiator as a component (G) (hereinafter also simply referred to as "component (G)"). The so-called hydrogen-extracting type photoradical polymerization initiator is a polymerization initiator that extracts hydrogen from other molecules and generates free radicals by irradiation with ultraviolet or visible light. The mechanism of free radical generation is as follows: (A) The cracking type photoradical polymerization initiator is different. In the present invention, by containing the component (G) and generating radicals coexisting with different mechanisms, it is possible to further improve photoreactivity.

The hydrogen-extraction type photoradical polymerization initiator is not particularly limited, and examples thereof include diphenyl ketone, acridone, 2-ethylanthraquinone, 2-chlorothioanthrone, and 2-isopropyl Anthraquinone, 2,4-diethylthioanthrone and the like. In addition, for example, a thiaanthrone compound having a reactive group in the molecule described in International Publication 2012/011220 can be suitably used.

In the photocurable resin composition of the present invention, when the component (G) is used, the total amount of the photocurable resin composition is usually 0.001 to 5% by mass, preferably 0.002 to 5% by mass.

[(H) Thermal radical polymerization initiator]

The photocurable resin composition of the present invention can contain a (H) thermal radical polymerization initiator (hereinafter also simply referred to as "component (H)") to improve the curing speed and curability.

The thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction. Examples include organic peroxides, azo compounds, benzoin compounds, and benzoin. Ethyl ether compounds, acetophenone compounds, tetraphenyl-1,2-ethylene glycol (Benzopinacole), and the like can be suitably used. For example, in terms of organic peroxides, Kayamek ^RTM A, M, R, L, LH, SP-30C, Perkadox CH-50L, BC-FF, Cadox B-40ES, Perkadox 14, Trigonox ^RTM 22-70E, 23- C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester ^RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl ^RTM B, Perkadox 16, Kayacarbon ^RTM BIC -75, AIC-75 (made by Kayaku Akzo Co., Ltd.), Permek ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, TMH, C, V, 22, MC, Percure ^RTM AH, AL , HB, Perbutyl ^RTM H, C, ND, L, Percumyl ^RTM H, D, Perloyl ^RTM IB, IPP, Perocta ^RTM ND (manufactured by Nippon Oil Co., Ltd.), etc. can be obtained as commercially available products.

As for the azo compound, VA-044, 086, V-070, VPE-0201, VSP-1001 (manufactured by Wako Pure Chemical Industries, Ltd.) can be obtained as commercially available products.

The content of the component (H) is in the total amount of the photocurable resin composition, preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass, and particularly preferably 0.001 to 3% by mass.

The photocurable resin composition of the present invention can be further formulated with additives such as a hardening accelerator such as organic acid and imidazole, a radical polymerization inhibitor, a pigment, a leveling agent, an antifoaming agent, and a solvent, as necessary.

[Hardening accelerator]

Examples of the curing accelerator include organic acids and imidazole.

Examples of the organic acid include organic carboxylic acids and organic phosphoric acids, and organic carboxylic acids are preferred. Specific examples include aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, diphenyl ketone tetracarboxylic acid, and furan dicarboxylic acid, succinic acid, and hexane. Diacid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, ginseng (2-carboxymethyl) isocyanurate, ginseng (2-carboxyethyl) iso Cyanurate, ginseng (2-carboxypropyl) isocyanurate, bis (2-carboxyethyl) isocyanurate, etc.

Examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-tri , 2,4-diamino-6 (2'-undecylimidazole (1 ')) ethyl-s-tri , 2,4-diamino-6 (2'-ethyl-4-methylimidazole (1 ')) ethyl-s-tri , 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-tri / Isotricyanic acid adduct, 2-methylimidazole isotricyanic acid 2: 3 adduct, 2-phenylimidazole isotricyanic acid adduct, 2-phenyl-3,5 -Dimethylolimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, etc. .

In the photocurable resin composition of the present invention, when a curing accelerator is used, the total amount of the photocurable resin composition is usually 0.1 to 10% by mass, preferably 1 to 5% by mass.

[Anti-radical polymerization inhibitor]

The above-mentioned radical polymerization inhibitor is not particularly limited as long as it is a compound that prevents polymerization by reacting with a radical generated from a photoradical polymerization initiator, a thermal radical polymerization initiator, or the like, and examples thereof include quinones, Piperidine, hindered phenol, and nitroso. Specific examples include naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxide, 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxide, 2,2,6,6, -tetramethyl-4-methoxypiperidine-1-oxide, 2 , 2,6,6-Tetramethyl-4-phenoxypiperidine-1-oxide, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, p-benzoquinone, butylated hydroxyl Anisyl ether, 2,6-di-tertiary-butyl-4-ethylphenol, 2,6-di-tertiary-butylcresol, stearyl β- (3,5-di-tertiary-butyl-4 -Hydroxyphenyl) propionate, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-thiobis-3-methyl-6-th Tributylphenol), 4,4'-butylenebis (3-methyl-6-third butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3 -Third-butyl-4-hydroxy-5-methylphenyl) propanyloxy] ethyl], 2,4,8,10-tetraoxaspiro [5,5] undecane, [- Methylene-3- (3 ', 5'-di-third-butyl-4'-hydroxyphenylpropionate) methane, 1,3,5-ginseng (3', 5'-bis-third Butyl-4'-hydroxybenzyl) -sec-tri -2,4,6- (1H, 3H, 5H) trione, p-methoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-nitrosophenylhydrogenamine aluminum Salt, trade name Adk Stab LA-81, trade name Adk Stab LA-82 (manufactured by ADEKA Co., Ltd.), and the like are not limited thereto. Among these, naphthoquinone-based, hydroquinone-based, and nitroso-based A preferred radical polymerization inhibitor is naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, Polystop 7300P (made by Bodong Co., Ltd.) , Polystop 7300P (made by Bodong Co., Ltd.) is the best.

The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and particularly preferably 0.01 to 0.2% by mass in the total amount of the photocurable resin composition of the present invention. .

As an example of obtaining the photocurable resin composition of the present invention, the following method is exemplified. First, in the component (B) (the components (B-1) and (B-2) are used as a mixture), the component (A) and the optional component (G) are heated and dissolved. Next, after cooling to room temperature, the components (C), (D), (E), (F), (H), antifoaming agents, leveling agents, solvents, etc. are added as needed, by using a well-known mixture A device such as a three-roll mill, a sand mill, a ball mill, or the like is uniformly mixed and filtered using a metal screen, whereby the liquid crystal sealant of the present invention can be manufactured.

The photocurable resin composition system of the present invention is very useful as a sealant for electronic parts. The electronic component sealant includes, but is not limited to, a flexible printed wiring board adhesive, a TAB adhesive, a semiconductor adhesive, and various display adhesives, which are adhesives for electronic components.

Moreover, in the sealing compound for liquid crystal display units, the photocurable resin composition system of this invention is very useful especially as a liquid crystal sealing compound. Examples of the liquid crystal display unit when the resin composition of the present invention is used as a liquid crystal sealant are as follows.

A liquid crystal display unit manufactured using the sealant for a liquid crystal display unit of the present invention is one in which a pair of substrates having predetermined electrodes formed on the substrate are arranged oppositely at a predetermined interval, and the surroundings are sealed with the liquid crystal sealant, and the gap is sealed in LCD made. The type of the enclosed liquid crystal is not particularly limited. Here, the substrate refers to a combination of substrates having a light-transmitting combination on at least one of glass, quartz, plastic, and silicon. As a method for producing the liquid crystal sealant, a spacer (gap control material) such as glass fiber is added to the liquid crystal sealant, and then the liquid crystal sealant is applied to one of the pair of substrates using an applicator or a screen printing device, as necessary. Temporary hardening is performed at 80 to 120 ° C. Subsequently, the liquid crystal is dropped to the inside of the dam of the liquid crystal sealant, and the other glass substrate is laminated in a vacuum to form a gap. After the gap is formed, the liquid crystal display unit of the present invention can be obtained by curing at 90 to 130 ° C for 1 to 2 hours. In the case of using a photothermal combination type, the liquid crystal sealant portion is irradiated with ultraviolet rays using an ultraviolet ray irradiator to harden the light. The ultraviolet irradiation amount is preferably 500 to 6000 mJ / cm ² , and more preferably 1,000 to 4000 mJ / cm ² . Subsequently, if necessary, the liquid crystal display unit of the present invention can be obtained by curing at 90 to 130 ° C for 1 to 2 hours. The liquid crystal display unit of the present invention obtained in this way has no display failure due to liquid crystal contamination and has excellent adhesion and humidity resistance reliability. Examples of the spacer include glass fibers, silica beads, and polymer beads. The diameter varies depending on the purpose, and is usually 2 to 8 μm, preferably 4 to 7 μm. The usage amount is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, and more preferably about 0.9 to 1.5 parts by mass with respect to 100 parts by mass of the liquid crystal sealant of the present invention.

The photocurable resin composition of the present invention is very suitable for use in an electronic part having a design with a light-shielding portion or a sealant that must be hardened by low-energy light such as visible light. For example, a liquid crystal sealant, a sealant for organic EL, and an adhesive for touch panels are used under the wiring light-shielding portion.

    [Example]    

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to the examples. In addition, unless otherwise specified, "part" and "%" in this text are quality standards.

[Synthesis example 1]

In accordance with Japanese Patent Application Publication No. 2016-531926, a compound represented by the following formula (A-1) was synthesized as the following component as a component (A).

Diphenyl sulfide was added to aluminum chloride in dichloromethane at 0 ° C. Next, chloroacetamyl chloride was added at 0 ° C, and the mixture was stirred at room temperature for 2 hours to obtain a mixture. Aluminum chloride and 4-methylpentamyl chloride were added to the mixture at 0 ° C and stirred overnight to obtain a reaction mixture. After the reaction mixture was poured into ice water, the organic layer was extracted with dichloromethane. The organic layer was dried and concentrated with magnesium sulfate, and the residue was purified by a column chromatography to obtain a compound of the following formula (2) as a white powder.

The compound of the formula (2) was added to acetone, potassium carbonate and salicylaldehyde were added, and the mixture was stirred under reflux for 3 hours. The reaction mixture was warmed to room temperature, water and acidified by adding HCl solution. The precipitate was recovered by filtration and dried to obtain a compound of the following formula (3).

The obtained compound of the above formula (3) was added to ethyl acetate, and hydroxylammonium chloride and pyridine were further added. The mixture was stirred at reflux for 3 hours. The reaction mixture was warmed to room temperature and then poured into water. The organic layer was extracted with ethyl acetate, and dried over magnesium sulfate. After concentration, the crude product was purified by a column chromatography to obtain a compound of the following formula (4) as a pale yellow solid.

The compound of the formula (4) was added to ethyl acetate, and then acetamidine chloride and 111 mg of triethylamine were added, followed by stirring at room temperature for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. After concentration, the crude product was recrystallized with ethyl acetate / hexane to obtain the compound of the above formula (A-1) as a pale yellow solid.

[Example 1, Comparative Example 1]

The two components (B) were mixed at the ratio shown in Table 1 below. The component (A) of Synthesis Example 1 was heated and dissolved at 90 ° C, and then cooled to room temperature, and the components (C), (D), and ( E), (F), and (H) were stirred and then dispersed by a three-roll mill and filtered using a metal screen (635 screen) to prepare Examples 1 and 2 of the photocurable resin composition. In addition, Comparative Example 1 was prepared by changing the component (A) using the component (O).

[Tg (UV + thermal hardening)]

The photo-curable resin composition produced in Example 1 and Comparative Example 1 was sandwiched between polyethylene terephthalate (PET) films to form a film having a thickness of 100 μm, and then a metal halide lamp ( After being irradiated with 3000 mJ / cm ² (100 mW / cm ^{2 for} 30 seconds), it was put into an oven at 120 ° C. for 60 minutes to be cured. After curing, the PET film was peeled to obtain a sealant cured film, which was then cut into an elongated shape of 50 mm × 5 mm as a test piece. The test piece was measured in a tensile mode of a dynamic viscoelasticity measuring device (DMS-6100: manufactured by SII Nano Technology Co., Ltd.) under the conditions of a frequency of 10 Hz and a temperature rise of 3 ° C / min. The loss coefficient Tan δ is obtained from the ratio of the loss modulus to the storage modulus (JIS K 7244-1), and the temperature at which the obtained loss coefficient Tan δ is the maximum value is taken as the glass transition temperature. . The results are shown in Table 1.

[Tg (Vis + thermosetting)]

The photocurable resin composition produced in Example 1 and Comparative Example 1 was sandwiched between polyethylene terephthalate (PET) films to form a film having a thickness of 100 μm, and then a metal halide lamp was used for the film. (Made by USHIO Electric Co., Ltd.) After being irradiated with visible light of 3000 mJ / cm ² (100 mW / cm ^{2 for} 30 seconds), it was placed in an oven at 120 ° C. for 60 minutes to be cured. After curing, the PET film was peeled to obtain a sealant cured film, which was then cut into an elongated shape of 50 mm × 5 mm as a test piece. The test piece was measured in a tensile mode of a dynamic viscoelasticity measuring device (DMS-6100: manufactured by SII Nano Technology Co., Ltd.) under the conditions of a frequency of 10 Hz and a temperature rise of 3 ° C / min. The loss coefficient Tan δ was obtained from the ratio of the loss modulus to the storage modulus (JIS K 7244-1), and the temperature at which the obtained loss coefficient Tan δ was the maximum was set as the glass transition temperature. The results are shown in Table 1.

[Tg (UV + thermosetting) -Tg (Vis + thermosetting)]

From the above measurement results, the values of Tg (UV + thermosetting) -Tg (Vis + thermosetting) were calculated and shown in Table 1. This makes it possible to confirm the difference between the curability by UV and the curability by visible light. The smaller the difference is, the harderability to the same degree as that of UV can be achieved in visible light, and the use of hardening with visible light can be achieved.

[Light-shielding part hardening width]

Each of the liquid crystal sealants of the examples and comparative examples obtained by adding 1% by mass of 4 μm glass fibers (manufactured by Nippon Electric Glass Co., Ltd.) was applied to a line and space (line & space) provided with 100 μm by etching of chromium. ), And a black matrix substrate was bonded as the opposing substrate, and ultraviolet light was irradiated at 3000 mJ / cm ² (100 mW / cm ² and 30 seconds) from the substrate side where the wires / spacers were provided, and the curing width was measured using a microscope. The results are shown in Table 1.

A1: OE32 described in Japanese Special Table 2016-531926 (synthesized using the method of Japanese Special Table 2016-531926)

B-1-1: Bisphenol A epoxy methacrylate (using a common synthesis method and changing the acrylic acid in Japanese Laid-Open Patent Publication No. 2016-24243 to methacrylic acid)

B-1-2: Partial epoxy methacrylate of bisphenol A type (in Japanese Patent Application Laid-Open No. 2016-24243) (using a common synthesis method and changing the acrylic acid in Japanese Laid-Open Patent Application No. 2016-24243 into a synthesis example) Methacrylic acid, and react at 50% equivalent)

C-1: Polymethacrylate-based organic fine particles (manufactured by Aica Industrial Co., Ltd .: F-351S)

D-1: Spherical silica (manufactured by Tokuyama Co., Ltd .: Sunseal SSP-07M)

E-1: 3-glycidoxypropyltrimethoxysilane (made by JNC Co., Ltd .: Sila-Ace S-510)

F-1: Dihydrazine sebacate (manufactured by Otsuka Chemical Co., Ltd .: SDH)

G-1: 2-Methacryloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one Reaction product (synthesized using the method described in International Publication No. 2006/027982)

H-1: VA-086 (manufactured by Wako Pure Chemical Industries, Ltd.)

O-1: ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime) ( (OXE-02 BASF company)

As shown in Table 1, compared with the photocurable resin composition of Comparative Example 1, the photocurable resin composition of Example 1 has the same curability as ultraviolet rays even under visible light, and is deep in the light-shielding portion. (Low energy irradiation part) The hardenability is also good. That is, it can be confirmed that it has excellent hardenability by low energy.

    [Industrial availability]    

The photocurable resin composition of the present invention has high curability in a portion where light is not sufficiently irradiated, and has sufficient curability even when it is irradiated with visible light in consideration of damage to other members. Therefore, it can be used as an adhesive for electronic parts , Especially sealants for displays.

Claims (16)

    A photocurable resin composition containing an oxime compound having a furan structure in the component (A) and a curable compound in the component (B).         The photocurable resin composition according to item 1 of the scope of patent application, wherein the component (B) is the component (B-1) (meth) acrylic compound.         The photocurable resin composition according to item 1 or 2 of the scope of patent application, wherein the aforementioned component (B) is a mixture of the component (B-1) (meth) acrylic compound and the component (B-2) epoxy compound .         The photocurable resin composition according to any one of the claims 1 to 3, further comprising a component (C) organic filler.         The photocurable resin composition according to item 4 of the scope of the patent application, wherein the component (C) is selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and polysiloxane fine particles. One or more organic fillers in a group.         The photocurable resin composition according to any one of claims 1 to 5 of the patent application scope, further comprising a component (D) inorganic filler.         The photocurable resin composition according to any one of claims 1 to 6 of the patent application scope, further comprising a component (E) silane coupling agent.         The photocurable resin composition according to any one of claims 1 to 7 of the scope of patent application, further comprising a component (F) thermosetting agent.         The photocurable resin composition according to item 8 of the scope of patent application, wherein the aforementioned component (F) is an organic acid hydrazine compound.         The photocurable resin composition according to any one of claims 1 to 9 of the scope of patent application, further comprising a component (G) a hydrogen-extraction type photoradical polymerization initiator.         The photocurable resin composition according to any one of claims 1 to 10 of the scope of application for a patent, further comprising a component (H) thermal radical polymerization initiator.         A sealant for electronic parts is a hardening resin composition described in any one of claims 1 to 11 of the scope of patent application.         An electronic part is a hardened product obtained by hardening the sealant for electronic parts described in claim 12 of the scope of patent application.         A sealant for a liquid crystal display unit is a photocurable resin composition described in any one of claims 1 to 11 of the scope of patent application.         A liquid crystal sealant using the photocurable resin composition described in any one of claims 1 to 11 of the scope of patent application.         A liquid crystal display unit uses a sealant or a liquid crystal sealant for a liquid crystal display unit described in item 14 or 15 of the scope of patent application.