WO2018225543A1

WO2018225543A1 - Compound and photocurable composition using same

Info

Publication number: WO2018225543A1
Application number: PCT/JP2018/020225
Authority: WO
Inventors: 隆行遠島
Original assignee: 日本化薬株式会社
Priority date: 2017-06-06
Filing date: 2018-05-25
Publication date: 2018-12-13
Also published as: JPWO2018225543A1; TW201902886A

Abstract

Provided is a compound represented by formula (1) and a photocurable composition using the compound. In formula (1): R1 and R2 each independently represent a hydrogen atom, a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, a (C1-C8) alkyl group, or a (C1-C8) alkoxy group; R3 represents a (C1-C8) alkyl group or a (C1-C8) alkoxy group; and R4 represents a hydrogen atom, a (C1-C8) alkyl group, a (C2-C8) alkenyl group, an aryl group, or a heteroaryl group. In formula (1), R2 and R3 may be bonded to each other and form a cyclic structure. In formula (1), R3 groups may also be bonded and form a dimer.

Description

Compound and photocurable composition using the same

The present invention relates to a compound and a photocurable composition using the compound.

Photo-curable compositions are widely used in adhesive applications for electronic parts such as display sealants, solar cell sealants, and semiconductor sealants. Examples of the display sealant include a liquid crystal display sealant, an organic EL display sealant, and a touch panel adhesive. These sealants for display are required to have excellent curability and low outgassing and do not damage the display element.

However, since the photocurable composition does not undergo a curing reaction in a portion where light does not reach, there is a limit to the portion that can be used.

In particular, in the liquid crystal sealing agent for the liquid crystal dropping method, a light-shielding portion where light does not strike the liquid crystal sealing agent is generated due to the wiring portion of the array substrate of the liquid crystal display element and the black matrix portion of the color filter substrate. Has become more serious than before. If the primary curing by light becomes insufficient due to the presence of the light shielding portion, a large amount of uncured components remain in the liquid crystal sealant. When the process proceeds to the secondary curing step by heat in this state, the dissolution of the uncured component in the liquid crystal is promoted by the heat, causing a display defect near the seal.

Thus, in order to secure the sensitivity in a place where light is difficult to reach and only light of very low energy enters, it is very important to increase the sensitivity of the photopolymerization initiator.

In order to solve this problem, for example, an oxime ester type photopolymerization initiator as in Patent Document 1 has been developed.

JP-T-2016-53926

The present invention provides a compound that generates radicals by irradiation with light such as ultraviolet light and visible light, has high sensitivity to light, and exhibits sufficient reactivity even with low energy light, and a photocurable composition using the compound. For the purpose.

As a result of intensive studies, the present inventors have found that a compound having a specific structure has very excellent reactivity, that is, sufficient reactivity even when irradiated with light of low energy. The present invention described in [13] to [13] has been completed.
In the present specification, “(meth) acryl” means “acryl and / or methacryl”, “(meth) acrylate” means “acrylate and / or methacrylate”, and “(meth) acryloyl”. "Means" acryloyl and / or methacryloyl ".

[1] A compound represented by the following formula (1).

[In Formula (1), R ₁ and R ₂ are each independently a hydrogen atom, a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, (C1-C8 ) Represents an alkyl group or (C1-C8) alkoxy group, R ₃ represents a (C1-C8) alkyl group or (C1-C8) alkoxy group, R ₄ represents a hydrogen atom, (C1-C8) alkyl group, (C2-C8) represents an alkenyl group, an aryl group, or a heteroaryl group. R ₂ and R ₃ may be bonded to each other to form a cyclic structure. Further, R ₃ may be bonded to each other to form a dimer. ]
[2] The compound according to [1], wherein in formula (1), R ₁ and R ₂ are both hydrogen atoms.
[3] The compound according to [1] or [2], wherein in the formula (1), R ₄ is a methyl group.
[4] A photocurable composition containing the compound according to any one of [1] to [3].
[5] The photocurable composition according to [4], which contains a curable compound.
[6] The photocurable composition according to [5], wherein the curable compound is a (meth) acrylic compound.
[7] The photocurable composition according to [5], wherein the curable compound is a mixture of a (meth) acrylic compound and an epoxy compound.
[8] The photocurable composition according to any one of [4] to [7], which contains an organic filler.
[9] The photocurable composition according to [8], wherein the organic filler is at least one organic filler selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. .
[10] The photocurable composition according to any one of [4] to [9], which contains an inorganic filler.
[11] The photocurable composition according to any one of [4] to [10], which contains a silane coupling agent.
[12] The photocurable composition according to any one of [4] to [11], which contains a thermosetting agent.
[13] The photocurable composition according to [12], wherein the thermosetting agent is an organic acid hydrazide compound.

The compound of the present invention generates radicals by irradiation with light such as ultraviolet light and visible light, has high sensitivity to light, and exhibits sufficient reactivity even with low energy light. For this reason, the photocurable composition using the compound of the present invention is used as a sealant used for manufacturing an electronic component having a light-shielding portion or an electronic component that needs to be cured by visible light, particularly as a sealant for a display. Useful.

<Compound>
The compound according to this embodiment has a structure represented by the following formula (1).

In the above formula (1), R ₁ and R ₂ are each independently a hydrogen atom, carboxy group, sulfo group, hydroxy group, acetylamino group, halogen atom, cyano group, nitro group, sulfamoyl group, (C1-C8 ) Represents an alkyl group or (C1-C8) alkoxy group, R ₃ represents a (C1-C8) alkyl group or (C1-C8) alkoxy group, R ₄ represents a hydrogen atom, (C1-C8) alkyl group, (C2-C8) represents an alkenyl group, an aryl group, or a heteroaryl group. R ₂ and R ₃ may be bonded to each other to form a cyclic structure. Further, R ₃ may be bonded to each other to form a dimer.

R ₁ and R ₂ are substituted at any position of the thioxanthone skeleton.

Examples of the (C1-C8) alkyl group in R ₁ and R ₂ in the above formula (1) include a linear, branched, or cyclic unsubstituted group, and a linear one is preferable. Specific examples include linear groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-hentyl group, n-hexyl group, n-heptyl group, n-octyl group; isopropyl group Branched chain groups such as isobutyl group, sec-butyl group and tert-butyl group; cyclic groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group; The (C1-C8) alkyl group may be a group in which a chain alkyl group and a cyclic alkyl group are bonded, such as a 3-cyclopentylpropyl group. Among these, a methyl group and an n-propyl group are preferable, and a methyl group is more preferable.

Examples of the (C1-C8) alkoxy group in R ₁ and R ₂ in the above formula (1) include a linear or branched unsubstituted group, and a linear group is preferable. Specific examples include linear groups such as methoxy group, ethoxy group, n-propoxy group and n-butoxy group; branched chain groups such as isopropoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group. And the like. Among these, a methoxy group is preferable.

The (C1-C8) alkyl group or (C1-C8) alkoxy group in R ₃ in the above formula (1), including preferred ones, includes the (C1-C8) alkyl group or (C1-C8) in R ₁ and R ₂ above. C8) Represents the same meaning as the alkoxy group.

The (C1-C8) alkyl group in R ₄ in the above formula (1) has the same meaning as the (C1-C8) alkyl group in R ₁ and R ₂ including the preferable one.

Examples of the (C2-C8) alkenyl group for R ₄ in the above formula (1) include linear or branched unsubstituted groups. Specific examples include vinyl group, 1-propenyl group, 2-propenyl group and the like.

Examples of the aryl group and heteroaryl group in R ₄ in the above formula (1) include a phenyl group, a pyridyl group, and a thienyl group. The aryl group and heteroaryl group are substituted with at least one substituent such as a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, an alkyl group, and an alkoxy group. Also good. Examples of those having such a substituent include a 4-nitrophenyl group.

As a preferable combination of R ₁ to R ₄ in the above formula (1), R ₁ is a hydrogen atom or a (C1-C4) alkyl group, R ₂ is a hydrogen atom or a (C1-C4) alkyl group, And a combination in which R ₃ is a (C1-C8) alkyl group and R ₄ is a methyl group, an aryl group, or a heteroaryl group. R ₁ and R ₂ are preferably both hydrogen atoms. R ₄ is preferably a methyl group. A more preferable combination of R ₁ to R ₄ in the above formula (1) includes a combination in which R ₁ is a hydrogen atom, R ₂ is a hydrogen atom, R ₃ is a methyl group, and R ₄ is a methyl group.

Specific examples of the compound according to this embodiment include, for example, the following compound numbers 1 to 20. However, it is not limited to these.

Among the compounds according to this embodiment, for example, the compound of Compound No. 1 can be synthesized by the method described in Synthesis Example 2 of Example 1 described later, and the compound of Compound No. 1 is the compound of Example 1 described later. It can be synthesized by the method described in Synthesis Example 3.

The compound according to this embodiment generates radicals by irradiation with ultraviolet light or visible light, has high sensitivity to light, and exhibits sufficient reactivity even with low energy light. It also has good thermal stability, low volatility, good storage stability, and good solubility and is suitable for photopolymerization in the presence of air (oxygen). Therefore, the compound according to the present embodiment is useful as a photopolymerization initiator for polymerizing a curable compound capable of radical polymerization.

<Photocurable composition>
[Compound represented by the above formula (1)]
The photocurable composition which concerns on this embodiment contains the compound represented by the said Formula (1). The compound represented by the above formula (1) may be used alone or in combination of two or more.

The content of the compound represented by the above formula (1) is usually 0.001 to 10% by mass, preferably 0.002 to 5.0% by mass in the total amount of the photocurable composition. Preferably, the content is 0.1 to 3.0% by mass. When the content of the compound represented by the above formula (1) is 0.001% by mass or more, photopolymerization of the photocurable composition tends to proceed sufficiently. On the other hand, an unreacted compound decreases that the content rate of the compound represented by the said Formula (1) is 10 mass% or less. As a result, deterioration of light resistance and storage stability of the photocurable composition and adverse effects on display characteristics when the photocurable composition is used as a sealant for display elements tend to be suppressed.

[Photopolymerization initiator]
The photocurable composition concerning this embodiment may contain other photoinitiators other than the compound denoted by the above-mentioned formula (1). The other photopolymerization initiator is not particularly limited as long as it is a compound that generates a radical, an acid, a base, or the like by irradiation with ultraviolet light or visible light and initiates a chain polymerization reaction.

Specific examples of other photopolymerization initiators include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [ 4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl disulfide and the like. Examples of commercially available ^{^{products, IRGACURE RTM 651,184,2959,127,907,396,379EG, 819,784,754,500, OXE01}} , OXE02, DAROCURE RTM 1173, LUCIRIN RTM TPO ( manufactured by BASF); Seikuoru ^RTM Z, BZ, BEE, BIP, BBI (manufactured by Seiko Chemical Co., Ltd.); In the present specification, the superscript “RTM” means a registered trademark.

Among these, a photopolymerization initiator having a maximum absorption wavelength (λmax) absorbance of 400 or more in a wavelength region of 200 to 300 nm from the viewpoint of enhancing light curability of a photocurable composition by utilizing light absorption in a wide range of wavelengths. More preferable is a photopolymerization initiator having an absorbance at a maximum absorption wavelength (λmax) in the wavelength region of 200 to 300 nm of 500 or more, and an absorbance at a maximum absorption wavelength (λmax) in the wavelength region of 200 to 300 nm is more than 1500. Some photoinitiators are more preferred. Examples of the photopolymerization initiator having an absorbance at the maximum absorption wavelength (λmax) in the wavelength region of 200 to 300 nm of 500 or more include IRGACURE ^RTM 651, 184, and 2959. Examples of the photopolymerization initiator having an absorbance at the maximum absorption wavelength (λmax) in the wavelength region of 200 to 300 nm of 1500 or more include IRGACURE ^RTM 2959.

The photopolymerization initiator preferably has a molecular weight of 150 to 1000 from the viewpoint of preventing outgassing. Similarly, from the viewpoint of preventing outgassing, those having a (meth) acryl group in the molecule are preferable, for example, 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy The reaction product with 2-methyl-1-propan-1-one is preferably used. This compound can be produced by the method described in International Publication No. 2006/027982.

When the photocurable composition according to this embodiment contains other photopolymerization initiator, the content is preferably 0.001 to 10% by mass in the total amount of the photocurable composition, More preferably, the content is 1 to 5.0% by mass.

[Photoinitiator]
The photocurable composition according to the present embodiment may contain a photoinitiation assistant such as a tertiary amine in order to further improve the curability. The tertiary amines include, but are not limited to, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and the like. Moreover, a high molecular weight compound in which a plurality of tertiary amines are branched with a polyhydric alcohol or the like in one molecule can also be used as appropriate.

When the photocurable composition according to this embodiment contains a photoinitiator auxiliary, the content is preferably 0.005 to 20% by mass in the total amount of the photocurable composition, 0.01 More preferably, it is ˜10% by mass.

[Curable compound]
The photocurable composition according to this embodiment preferably contains a curable compound. Although it will not specifically limit as a sclerosing | hardenable compound if it is a compound hardened | cured by light, heat | fever, etc., (meth) acrylic compounds, such as a (meth) acrylic ester compound and an epoxy (meth) acrylate compound, are preferable. A (meth) acryl compound may be used individually by 1 type, and may use 2 or more types together.

Examples of (meth) acrylic ester compounds include N-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, 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-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy (meta ) Acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromo Enyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, pe Taerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylolpropane tri (meta) ) Acrylate, trimethylolpropane polyethoxytri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ester diacrylate of neopentyl glycol and hydroxypivalic acid, ε-caprolactone of ester of neopentyl glycol and hydroxypivalic acid Examples thereof include diacrylates of adducts. Among these, N-acryloyloxyethyl hexahydrophthalimide, phenoxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate are preferable.

The epoxy (meth) acrylate compound can be obtained by a known method by reacting an epoxy compound with (meth) acrylic acid. Although it does not specifically limit as an epoxy compound used as a raw material, The epoxy compound more than bifunctional is preferable. Examples of the bifunctional or higher functional epoxy compound include resorcin diglycidyl ether, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolak type Epoxy compounds, bisphenol F novolac type epoxy compounds, alicyclic epoxy compounds, aliphatic chain epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, hydantoin type epoxy compounds, isocyanurate type epoxy compounds, triphenolmethane skeleton Phenol novolac-type epoxy compounds having di- and diglycidyl ethers of bifunctional phenols (catechol, resorcinol, etc.) Things, difunctional alcohols diglycidyl ethers of, and the like thereof halide or hydrogenated product. Among these, when the photocurable composition according to the present embodiment is used as a liquid crystal sealant, bisphenol A type epoxy compounds and resorcin diglycidyl ether are preferable from the viewpoint of liquid crystal contamination. The ratio of the epoxy group and the (meth) acryloyl group in the epoxy (meth) acrylate compound is not particularly limited, and is appropriately selected from the viewpoint of process compatibility.

The photocurable composition according to this embodiment preferably contains an epoxy compound (excluding the (meth) acrylic compound) in addition to the (meth) acrylic compound. An epoxy compound may be used individually by 1 type, and may use 2 or more types together.

The epoxy compound is not particularly limited, but a bifunctional or higher functional epoxy compound is preferable. Examples of the bifunctional or higher functional epoxy compound include resorcin diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type Epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, triphenolmethane skeleton Phenol novolac epoxy resin containing diglycidyl etherified products of bifunctional phenols (catechol, resorcinol, etc.), difunctional alcohols Glycidyl etherified product, and the like thereof halide or hydrogenated product. Among these, when the photocurable composition according to the present embodiment is used as a liquid crystal sealant, bisphenol A type epoxy resin and resorcin diglycidyl ether are preferable from the viewpoint of liquid crystal contamination.

When the photocurable composition according to this embodiment contains a curable compound, the content thereof is usually 10 to 80% by mass, preferably 20 to 70% by mass, based on the total amount of the photocurable composition. is there.
When the photocurable composition according to this embodiment contains an epoxy compound, the content is usually 5 to 50% by mass, preferably 5 to 30% by mass, based on the total amount of the photocurable composition. It is.

[Organic filler]
The photocurable composition according to the present embodiment may contain an organic filler. An organic filler may be used individually by 1 type, and may use 2 or more types together.

Examples of the organic filler include urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. Examples of the silicone fine particles include KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.); Trefill ^RTM E-5500, 9701, EP-2001 (manufactured by Toray Dow Corning Co., Ltd.). preferable. As urethane fine particles, JB-800T and HB-800BK (manufactured by Negami Industrial Co., Ltd.) are preferable. As the styrene fine particles, Lavalon ^RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, and SJ6300C (manufactured by Mitsubishi Chemical Corporation) are preferable. As the styrene olefin fine particles, Septon ^RTM SEPS 2004 and SEPS 2063 (manufactured by Kuraray Co., Ltd.) are preferable. These organic fillers may be core-shell organic fillers using two or more materials.

Among these organic fillers, acrylic fine particles and silicone fine particles are preferable.

As the acrylic fine particles, an acrylic rubber having a core-shell structure composed of two kinds of acrylic rubber is preferable, and the core layer is preferably n-butyl acrylate and the shell layer is more preferably methyl methacrylate. Acrylic fine particles whose core layer is n-butyl acrylate and whose shell layer is methyl methacrylate are sold by Aika Kogyo Co., Ltd. as Zefiac ^RTM F-351.

Silicone fine particles include organopolysiloxane cross-linked powder, linear dimethylpolysiloxane cross-linked powder, and a composite silicone rubber in which a silicone resin (for example, polyorganosilsesquioxane resin) is coated on the surface of the silicone rubber. Etc. Among these silicone fine particles, preferred is a silicone rubber of a linear dimethylpolysiloxane crosslinked product powder, or a composite silicone rubber fine particle of a silicone resin-coated linear dimethylpolysiloxane crosslinked product powder. The shape of the rubber powder is preferably a sphere with little increase in viscosity after addition.

When the photocurable composition according to the present embodiment contains an organic filler, the content is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the photocurable composition. .

[Inorganic filler]
The photocurable composition according to this embodiment may contain an inorganic filler. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

Examples of the inorganic filler include silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, and hydroxide. Examples include magnesium, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably fused silica, crystalline silica, silicon nitride, boron nitride, carbonic acid Examples of the particles include calcium, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, and aluminum silicate, and particles such as silica, alumina, and talc are preferable.

The average particle size of the inorganic filler is suitably 2000 nm or less, preferably 1000 nm or less, more preferably 300 nm or less. When the average particle diameter of the inorganic filler is 2000 nm or less, for example, when producing a narrow gap liquid crystal cell using the photocurable composition according to the present embodiment as a liquid crystal sealing agent for a liquid crystal dropping method, the upper and lower There is a tendency that a gap can be formed well when a glass substrate is bonded. Moreover, a preferable minimum is about 10 nm, More preferably, it is about 100 nm. The particle diameter can be measured with a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).

When the photocurable composition according to the present embodiment contains an inorganic filler, the content is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the photocurable composition. . By setting the content of the inorganic filler to 5% by mass or more, the adhesive strength to the glass substrate is improved and the moisture resistance reliability is also improved, so that a decrease in the adhesive strength after moisture absorption tends to be suppressed. When the content of the inorganic filler is 50% by mass or less, for example, when the liquid crystal cell is produced using the photocurable composition according to the present embodiment as a liquid crystal sealing agent for a liquid crystal dropping method, the inorganic filler is crushed. It tends to be easier and better.

[Silane coupling agent]
The photocurable composition according to this embodiment may contain a silane coupling agent in order to improve adhesive strength and moisture resistance. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl). Ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxy Silane 3-chloropropyl methyl dimethoxy silane, 3-chloropropyl trimethoxy silane, and the like. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. as KBM series, KBE series, etc., they are easily available from the market.

When the photocurable composition according to this embodiment contains a silane coupling agent, the content is preferably 0.05 to 3% by mass in the total amount of the photocurable composition.

[Thermosetting agent]
The photocurable composition according to this embodiment may contain a thermosetting agent. A thermosetting agent may be used individually by 1 type, and may use 2 or more types together.

The thermosetting agent reacts nucleophilically with an unshared electron pair or an anion in the molecule, and examples thereof include polyvalent amines, polyhydric phenols, and organic acid hydrazide compounds. Among these, organic acid hydrazide compounds are preferably used.

Among the organic acid hydrazide compounds, examples of the aromatic hydrazide compound include terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzenetrihydrazide, 1, Examples include 4,5,8-naphthoic acid tetrahydrazide and pyromellitic acid tetrahydrazide. Examples of the aliphatic hydrazide compound among the organic acid hydrazide compounds include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and pimelic acid dihydrazide. , Sebacic acid dihydrazide, 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N′-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1 , 3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin and the like, preferably a valine hydantoin skeleton ( Dihydrazide compounds having a skeleton in which the carbon atom of the danttoin ring is substituted with an isopropyl group), tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (1-hydrazinocarbonyl) And ethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, and bis (2-hydrazinocarbonylethyl) isocyanurate.

Among organic acid hydrazide compounds, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) are selected from the balance between curing reactivity and potential. ) Isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, and tris (3-hydrazinocarbonylpropyl) isocyanurate are preferred, and tris (2-hydrazinocarbonylethyl) isocyanurate is more preferred.

When the photocurable composition according to the present embodiment contains a thermosetting agent, the content is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the photocurable composition. %.

[Thermal radical polymerization initiator]
The photocurable composition according to this embodiment may contain a thermal radical polymerization initiator in order to improve the curing rate and curability. A thermal radical polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

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, such as organic peroxide, azo compound, benzoin compound, benzoin ether compound, acetophenone compound, benzopinacol, etc. And benzopinacol is preferably used.

Commercially available organic peroxides include Kayamek ^RTM A, M, R, L, LH, SP-30C, Parkadox CH-50L, BC-FF, Cadox B-40ES, Parkadox 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, Parkardox 16, Kayacaron ^RTM BIC-75, AIC-75 (above, manufactured by Kayaku Akzo Co., Ltd.); Permec ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, TMH, C, V, 22, MC, Pakyua ^RTM AH, AL, HB, Perbutyl ^{RTM H, C, ND, L} , Pakumi ^RTM H, D, PEROYL ^RTM IB, IPP, Perocta ^RTM ND (manufactured by NOF CORPORATION); and the like.

Further, examples of commercially available azo compounds include VA-044, 086, V-070, VPE-0201, VSP-1001 (above, manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

When the photocurable composition according to the present embodiment contains a thermal radical polymerization initiator, the content thereof is usually 0.0001 to 10% by mass in the total amount of the photocurable composition, preferably 0.00. It is 0005 to 5% by mass, and more preferably 0.001 to 3% by mass.

[Other ingredients]
The photocurable composition concerning this embodiment may contain additives, such as a hardening accelerator, a radical polymerization inhibitor, a pigment, a leveling agent, an antifoamer, and a solvent, as needed.

(Curing accelerator)
Examples of the curing accelerator include organic acids and imidazoles.
Examples of the organic acid include organic carboxylic acid and organic phosphoric acid, and organic carboxylic acid is preferable. Specifically, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, tris (2-Carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (2-carboxypropyl) isocyanurate, bis (2-carboxyethyl) isocyanurate and the like.
Examples of imidazole compounds include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl-2. -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl-4-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-methyl) Midazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and the like.

When the photocurable composition according to this embodiment contains a curing accelerator, the content thereof is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the photocurable composition. %.

(Radical polymerization inhibitor)
The radical polymerization inhibitor is not particularly limited as long as it is a compound that prevents polymerization by reacting with radicals generated from a photo radical polymerization initiator or a thermal radical polymerization initiator, and is not limited to quinone, piperidine, hinders. Examples include radical polymerization inhibitors such as dophenol and nitroso. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethyl-4 -Hydroxypiperidine-1-oxyl, 2,2,6,6, -tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxyl, hydroquinone 2-methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearyl β- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis 4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9 -Bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxaspiro [5 5] Undecane, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenylpropionate)] methane, 1,3,5-tris (3 ′, 5′-di -T-butyl-4'-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, paramethoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N- Toro Seo aluminum salts of phenyl hydroxylamine, trade name ADK STAB LA-81, include the trade name ADK STAB LA-82 (all manufactured by Ltd. Adeka) and the like. Of these, naphthoquinone, hydroquinone, nitroso, and piperidine radical polymerization inhibitors are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, polystop 7300P ( Hakuto Co., Ltd.) is more preferable, and Polystop 7300P (Hakuto Co., Ltd.) is more preferable.

When the photocurable composition according to this embodiment contains a radical polymerization inhibitor, the content thereof is usually 0.0001 to 1% by mass, preferably 0.001 in the total amount of the photocurable composition. It is -0.5 mass%, More preferably, it is 0.01-0.2 mass%.

[Viscosity of photocurable composition]
The viscosity at 25 ° C. of the photocurable composition according to this embodiment is preferably 150 to 500 Pa · s, more preferably 200 to 500 Pa · s. In particular, when the photocurable composition according to this embodiment is used as a liquid crystal sealant, the viscosity of the photocurable composition at 25 ° C. is preferably 250 to 400 Pa · s, and more preferably 280 to 320 Pa · s. By setting the viscosity to 250 Pa · s or more, occurrence of liquid crystal insertion is suppressed, and cell formation tends to be facilitated. When the viscosity is 400 Pa · s or less, application of the liquid crystal sealant tends to be easy.

[Method for Preparing Photocurable Composition]
Examples of the method for preparing the photocurable composition according to this embodiment include the following methods. First, the compound represented by the formula (1) is heated and dissolved in the curable compound. Subsequently, after cooling to room temperature, an organic filler, an inorganic filler, a silane coupling agent, a thermosetting agent, a thermal radical polymerization initiator, an antifoaming agent, a leveling agent, a solvent, etc. are added as needed. And the photocurable composition which concerns on this embodiment can be prepared by mixing uniformly with well-known mixing apparatuses, such as a 3 roll, a sand mill, and a ball mill, and filtering with a metal mesh.

[Uses of photocurable composition, etc.]
The photocurable composition according to the present embodiment is very useful as an electronic component sealant or an electronic component adhesive. Examples of the electronic component sealant or the electronic component adhesive include, but are not limited to, flexible printed wiring board adhesives, TAB adhesives, semiconductor adhesives, various display adhesives, and the like. is not.

Also, the photocurable composition according to this embodiment is very useful as an adhesive for liquid crystal display cells, particularly as a liquid crystal sealant. An example is shown below about the liquid crystal display cell at the time of using the photocurable composition which concerns on this embodiment as a liquid-crystal sealing compound.

A liquid crystal display cell manufactured using an adhesive for a liquid crystal display cell has a pair of substrates each having a predetermined electrode formed on the substrate opposed to each other at a predetermined interval, and the periphery is sealed with a liquid crystal sealant, and a liquid crystal is interposed in the gap. Is enclosed. The kind of liquid crystal to be sealed is not particularly limited. The substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicone, etc. and having light transmission properties.

The manufacturing method of a liquid crystal display cell is as follows, for example.
First, a spacer (gap control material) is added to the liquid crystal sealant. Examples of the spacer include glass fiber, silica beads, and polymer beads. The diameter of the spacer varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount of use is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, more preferably about 0.9 to 1.5 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. It is.

Next, after applying a liquid crystal sealant to one of the pair of substrates using a dispenser, a screen printing apparatus, or the like, temporary curing is performed at 80 to 120 ° C. as necessary. Thereafter, the liquid crystal is dropped inside the weir of the liquid crystal sealant, and the other glass substrate is overlaid in a vacuum to create a gap. After forming the gap, the liquid crystal display cell can be obtained by curing at 90 to 130 ° C. for 1 to 2 hours. When used as a photothermal combination type, the liquid crystal sealant is irradiated with ultraviolet rays by an ultraviolet irradiator and photocured. The amount of ultraviolet irradiation is preferably 500 to 6000 mJ / cm ² , more preferably 1000 to 4000 mJ / cm ² . Thereafter, if necessary, it is cured at 90 to 130 ° C. for 1 to 2 hours to obtain a liquid crystal display cell. The liquid crystal display cell thus obtained does not have a display defect due to liquid crystal contamination, and has excellent adhesion and moisture resistance reliability.

The photocurable composition according to the present embodiment is very suitable for use in an electronic component designed to have a light-shielding portion and an adhesive application that needs to be cured with low energy light such as visible light. For example, it is suitable as a liquid crystal display sealing agent, an organic EL sealing agent, and a touch panel adhesive used under a wiring light shielding portion.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. Unless otherwise specified, “%” in the text is based on mass.

<Example 1>
[Synthesis Example 1: Synthesis of 2-acetylthioxanthone]

2-Acetylthioxanthone was synthesized according to the synthesis procedure described in the prior literature (Material Technology, Vol. 27, No. 6 (2009), pp. 242-251).

[Synthesis Example 2: Synthesis of TX-OXE (Compound No. 1)]

A thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min. 2-Acetylthioxanthone (0.50 g), hydroxylamine hydrochloride (0.20 g), and N, N-dimethylformamide (60 mL) were added to the reaction vessel and reacted at 80 ° C. for 4 hours. The reaction was stopped by adding 50 mL of water, extracted with methyl isobutyl ketone (200 mL), and washed with 50 mL of water three times. The solvent was removed using an evaporator to obtain an oxime product of 2-acetylthioxanthone (TX-OX / yellow solid). The yellow solid (crude crystals) obtained here was used for the oxime esterification reaction as it was.

A thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min. A total amount of TX-OX, acetic anhydride (0.24 g), and butyl acetate (30 mL) were added to the reaction vessel, and the reaction was carried out at 90 ° C. for 5 hours. The reaction was stopped by adding 50 mL of water, extracted with methyl isobutyl ketone (200 mL), and washed with 50 mL of water three times. The solvent was removed using an evaporator to obtain a yellow solid. The yellow solid obtained here was recrystallized from acetone and water to obtain 0.35 g of 2-acetylthioxanthone oxime ester (TX-OXE / yellow solid) (yield of two-step reaction: 57%).
¹ H-NMR (400 MHz, DMSO-d6); δ (ppm) 2.30 (s, 3H), 2.51 (s, 3H), 7.53 (ddd, 1H) 7.59-7.6 ( m, 2H), 7.64-7.68 (m, 1H), 8.25 (dd, 1H), 8.60-8.66 (m, 1H), 8.85 (d, 1H)

[Synthesis Example 3: Synthesis of TX-OXE-2 (Compound No. 20)]

A thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min. TX-OX (0.5 g), benzoyl chloride (0.52 g), triethylamine (0.47 g), and tetrahydrofuran (30 mL) were added to the reaction vessel, and the reaction was carried out at 55 ° C. for 8 hours. The reaction was stopped by adding 30 mL of water, and the precipitated solid was collected by filtration. The yellow solid obtained here was recrystallized with dimethyl sulfoxide and water to obtain 0.28 g (yield: 40%) of 2-acetylthioxanthone oxime ester (TX-OXE-2 / yellow solid).
¹ H-NMR (400 MHz, DMSO-d6); δ (ppm) 2.65 (s, 3H), 7.58-7.67 (m, 3H), 7.72-7.85 (m, 2H) 7.89-8.28 (m, 5H), 8.51 (d, 1H), 8.85 (s, 1H)

<Examples 2 and 3>
The curable compounds (B-1, B-2, B-3) shown in Table 1 below were mixed and the photopolymerization initiator (A-1) shown in Table 1 below was heated and dissolved at 90 ° C. Until cooled. Next, the remaining components in Table 1 below were added and stirred, and then dispersed in a three-roll mill. Then, the photocurable composition of Example 2 and 3 was prepared by filtering with a metal mesh (635 mesh). In addition, the numerical value of each component in Table 1 represents a mass part.

<Comparative Examples 1 and 2>
In the same manner as in Examples 2 and 3, except that other components (O-2, O-3) shown in Table 1 below were used in place of the photopolymerization initiator (A-1), Comparative Examples 1 and 2 A photocurable composition was prepared.

<Evaluation>
[Light-shielding part curing width (UV irradiation)]
1% by mass of 4 μm glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) was added to each of the photocurable compositions of Examples 2 and 3 and Comparative Examples 1 and 2, to prepare a liquid crystal sealant. A liquid crystal sealant was applied to a glass substrate provided with 100 μm lines and spaces by etching chromium, and a black matrix substrate was bonded as a counter substrate. Next, ultraviolet light having a wavelength of 365 nm was irradiated from the substrate side provided with the line / space at an irradiation amount of 3000 mJ / cm ² (100 mW / cm ² for 30 seconds), and the curing width was measured with a microscope. The results are shown in Table 1 below.

[Light-shielding part curing width (visible light irradiation)]
1% by mass of 4 μm glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) was added to each of the photocurable compositions of Examples 2 and 3 and Comparative Examples 1 and 2, to prepare a liquid crystal sealant. A liquid crystal sealant was applied to a glass substrate provided with 100 μm lines and spaces by etching chromium, and a black matrix substrate was bonded as a counter substrate. Next, visible light having a wavelength of 405 nm was irradiated at a dose of 3000 mJ / cm ² (100 mW / cm ² for 30 seconds) from the side of the substrate on which the line / space was provided, and the curing width was measured with a microscope. The results are shown in Table 1 below.

[viscosity]
The viscosity (Pa · s) at 25 ° C. of each of the photocurable compositions of Examples 2 and 3 and Comparative Examples 1 and 2 was measured with an E-type viscometer (R115 viscometer (manufactured by Toki Sangyo Co., Ltd.)). . The results are shown in Table 1 below.

As shown in Table 1, the photocurable compositions of Examples 2 and 3 using TX-OXE as a photopolymerization initiator are the same as those of Comparative Examples 1 and 2 using a photopolymerization initiator having a similar structure. Compared with the curable composition, the curability in the deep part (low energy irradiated part) was good in both ultraviolet and visible light. That is, it was confirmed that the photocurable compositions of Examples 2 and 3 have excellent curability at low energy.

Claims

A compound represented by the following formula (1).

[In Formula (1), R 1 and R 2 are each independently a hydrogen atom, a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, (C1-C8 ) Represents an alkyl group or (C1-C8) alkoxy group, R 3 represents a (C1-C8) alkyl group or (C1-C8) alkoxy group, R 4 represents a hydrogen atom, (C1-C8) alkyl group, (C2-C8) represents an alkenyl group, an aryl group, or a heteroaryl group. R 2 and R 3 may be bonded to each other to form a cyclic structure. Further, R 3 may be bonded to each other to form a dimer. ]
The compound according to claim 1, wherein in the formula (1), R 1 and R 2 are both hydrogen atoms.
The compound according to claim 1 or 2, wherein in the formula (1), R 4 is a methyl group.
A photocurable composition containing the compound according to any one of claims 1 to 3.
The photocurable composition according to claim 4, comprising a curable compound.
The photocurable composition according to claim 5, wherein the curable compound is a (meth) acrylic compound.
The photocurable composition according to claim 5, wherein the curable compound is a mixture of a (meth) acrylic compound and an epoxy compound.
The photocurable composition according to any one of claims 4 to 7, comprising an organic filler.
The photocurable composition according to claim 8, wherein the organic filler is at least one organic filler selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles.
The photocurable composition according to any one of claims 4 to 9, which contains an inorganic filler.
The photocurable composition according to any one of claims 4 to 10, comprising a silane coupling agent.
The photocurable composition according to any one of claims 4 to 11, comprising a thermosetting agent.
The photocurable composition according to claim 12, wherein the thermosetting agent is an organic acid hydrazide compound.