CN110536908B - Photocurable composition and adhesive for electronic component - Google Patents

Photocurable composition and adhesive for electronic component Download PDF

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Publication number
CN110536908B
CN110536908B CN201880025666.9A CN201880025666A CN110536908B CN 110536908 B CN110536908 B CN 110536908B CN 201880025666 A CN201880025666 A CN 201880025666A CN 110536908 B CN110536908 B CN 110536908B
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liquid crystal
photocurable composition
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meth
acrylate
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CN110536908A (en
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远岛隆行
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C08K5/25—Carboxylic acid hydrazides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells

Abstract

The invention provides a photocurable composition, and an adhesive for electronic parts, an electronic part, an adhesive for liquid crystal display units, a liquid crystal sealant and a liquid crystal display unit using the photocurable composition, wherein the photocurable composition comprises: a compound having an oxime ester structure and a thioxanthone structure in a molecule.

Description

Photocurable composition and adhesive for electronic component
Technical Field
The present invention relates to a photocurable composition, and an adhesive for electronic components, an electronic component, an adhesive for liquid crystal display cells, a liquid crystal sealing agent, and a liquid crystal display cell using the photocurable composition.
Background
Photocurable compositions have been widely used in the following applications: the adhesive is used for electronic parts such as a sealing agent for a display, a sealing agent for a solar cell, and a semiconductor sealing agent. Examples of the sealant for display include: liquid crystal display sealants, organic Electroluminescence (EL) display sealants, touch panel adhesives, and the like. These display sealing agents are required to have the following properties: on the one hand, excellent curability, and on the other hand, little outgassing and no damage to the display module.
However, since the photocurable composition does not undergo a curing reaction in a portion which cannot be reached by light, there is a limitation on the portion which can be used.
In particular, in a liquid crystal sealing agent for a liquid crystal dropping method (hereinafter, also simply referred to as "liquid crystal sealing agent"), a problem of occurrence of a display defect in the vicinity of a sealing portion is more serious than in the past because a light shielding portion is generated by a line portion of an array substrate of a liquid crystal display module and a black matrix portion of a color filter substrate, and light does not reach the liquid crystal sealing agent. If the light is not sufficiently transmitted to the liquid crystal layer for primary curing due to the presence of the light-shielding portion, a large amount of uncured components remain in the liquid crystal sealing agent. When the heat treatment is performed to the secondary curing step in this state, the uncured component is promoted to be dissolved in the liquid crystal by the heat, and a display failure occurs in the vicinity of the sealing portion.
In order to solve the problems to be solved, various studies have been made to improve the thermal reactivity of the liquid crystal sealant. In other words, the following attempts are being made: in the light shielding portion, the liquid crystal sealing agent which is not sufficiently cured by light is allowed to react rapidly from a low temperature, thereby suppressing liquid crystal contamination. For example: patent documents 1 and 2 disclose a method using a thermal radical polymerization initiator. Further, patent documents 3 to 5 disclose a method of using a polycarboxylic acid as a curing accelerator.
However, in order to efficiently generate radicals from a thermal radical polymerization initiator, a thermal radical polymerization initiator having a molecular weight as small as a certain degree is required, but a low molecular weight compound is easily dissolved in liquid crystal and has excellent reactivity, but the contamination of liquid crystal by the thermal radical polymerization initiator itself is problematic. Further, when a polycarboxylic acid is used, there is a possibility that the moisture resistance reliability is impaired, and the polycarboxylic acid may not be used depending on the application.
As described above, although the liquid crystal sealing agent has been developed very actively, a liquid crystal sealing agent having excellent curability of a light shielding portion on the one hand and low contamination of liquid crystal on the other hand has not been realized yet.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-126211
Patent document 2: japanese laid-open patent publication No. 2009-8754
Patent document 3: international publication No. 2007/138870
Patent document 4: japanese laid-open patent publication No. 2008-15155
Patent document 5: japanese patent laid-open publication No. 2009-139922
Disclosure of Invention
The purpose of the present invention is to provide a photocurable composition which can be cured by irradiation with light such as ultraviolet light or visible light, has high sensitivity to light, and can be sufficiently cured even by low-energy light.
As a result of an investigation conducted by the present inventors, the present invention as described in the following [1] to [15] was completed by finding that: a compound having both an oxime ester structure and a thioxanthone (thioxanthone) structure in its molecule is excellent as a dehydrogenation type photoinitiator and a decomposition type initiator, and has sufficient curability even when irradiated with light of low energy.
In the present specification, "(meth) acrylic" means "acrylic acid and/or methacrylic acid", "meth (acrylate)" means "acrylate and/or methacrylate", and "(meth) acryloyl" means "acryloyl and/or methacryloyl".
[1] A photocurable composition comprising: a compound having an oxime ester structure and a thioxanthone structure in a molecule.
[2] The photocurable composition according to [1], which comprises a curable compound.
[3] The photocurable composition according to [2], wherein the curable compound is a (meth) acrylic compound.
[4] The photocurable composition according to [2], wherein the curable compound is a mixture of a (meth) acrylic compound and an epoxy compound.
[5] The photocurable composition according to any one of [1] to [4], which contains an organic filler.
[6] The photocurable composition according to [5], wherein the organic filler is at least 1 selected from the group consisting of polyurethane fine particles, acrylic fine particles, styrene olefin fine particles and silicone fine particles.
[7] The photocurable composition according to any one of [1] to [6], which contains an inorganic filler.
[8] The photocurable composition according to any one of [1] to [7], which contains a silane coupling agent.
[9] The photocurable composition according to any one of [1] to [8], which contains a thermal curing agent.
[10] The photocurable composition according to [9], wherein the thermal curing agent is an organic hydrazide compound.
[11] An adhesive for electronic parts, which uses the photocurable composition according to any one of [1] to [10 ].
[12] An electronic component bonded with a cured product obtained by curing the adhesive for electronic components according to [11 ].
[13] An adhesive for liquid crystal display cells, which uses the photocurable composition according to any one of [1] to [10 ].
[14] A liquid crystal sealing agent using the photocurable composition according to any one of [1] to [10 ].
[15] A liquid crystal display cell bonded with the liquid crystal display cell adhesive according to [13] or the liquid crystal sealing agent according to [14 ].
The photocurable composition of the present invention has high curability in a portion which cannot be sufficiently reached by light, and has sufficient curability even when low-energy light is irradiated in consideration of damage to other members, and therefore, the photocurable composition is useful as a sealant for electronic components or an adhesive for electronic components, which is used for manufacturing electronic components having a light shielding portion and electronic components which must be cured by visible light, particularly, a sealant for displays.
Detailed Description
< Photocurable composition >
[ Compound having an oxime ester structure and a thioxanthone structure in a molecule ]
The photocurable composition of the present embodiment contains: a compound having both an oxime ester structure and a thioxanthone structure in a molecule (hereinafter, also referred to as a "specific compound"). This specific compound functions as a photopolymerization initiator, and its sensitivity to low-energy light is very high. The specific compound may be used alone in 1 kind, or 2 or more kinds may be used in combination.
The oxime ester structure of the specific compound is, for example, a structure represented by the following formula (1).
Figure BDA0002237218690000041
In the above formula (1), R1Represents (C1-C8) alkyl or (C1-C8) alkoxy, R2Represents a hydrogen atom, a (C1-C8) alkyl group, a (C2-C8) alkenyl group, an aryl group, or a heteroaryl group.
In the above formula (1), R is1The (C1-C8) alkyl group in (1) includes, for example: the linear, branched or cyclic unsubstituted alkyl group is preferably a linear alkyl group. Specific examples thereof include: a straight-chain alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and cyclic alkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl. The (C1-C8) alkyl group may be a cyclic alkyl group bonded to a chain alkyl group such as 3-cyclopentylpropyl group. Among these, from the viewpoint of compatibility between the curable compound and the solvent, (C1-C3) alkyl is preferred, and specific examples thereof include: methyl, ethyl, n-propyl, preferably methyl.
In the above formula (1), R is1The (C1-C8) alkoxy group in (C) may, for example: the linear or branched unsubstituted alkoxy group is preferably a linear alkoxy group. Specific examples thereof include: linear alkoxy groups such as methoxy, ethoxy, n-propoxy, and n-butoxy; branched alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy and tert-butoxy. Among these, methoxy is preferred.
In the above formula (1), R1Methyl is preferred.
In the above formula (1), R2The (C1-C8) alkyl group in (A) includes preferred ones, all represent the same as R mentioned above1The (C1-C8) alkyl group in (A) has the same meaning.
In the above formula (1), R is2The (C2-C8) alkenyl group in (C) may, for example: a linear or branched unsubstituted alkenyl group. Specific examples thereof include: vinyl, 1-propenyl, 2-propenyl, and the like.
In the above formula (1), R is2Examples of the aryl and heteroaryl in (1) include: phenyl, pyridyl, thienyl, and the like. The aryl group and the heteroaryl group may be substituted with at least 1 substituent selected from the group consisting of a carboxyl group, a sulfo group, a hydroxyl group, an acetylamino group, a halogen atom, a cyano group, a nitro group, an aminosulfonyl group, an alkyl group, an alkoxy group and the like. Examples of the aryl group and the heteroaryl group having such a substituent include a 4-nitrophenyl group.
In the above formula (1), R2Preferably a hydrogen atom or a methyl group.
In the formula (1), the bonding position may be a position bonded to the thioxanthone structure represented by the following formula (2), and when the thioxanthone structure is bonded via another bonding group, the bonding position may be a position bonded to the bonding group. Examples of the bonding group include: alkylene (alkylene), alkylidene (alkylene), alkylene oxide (alkylene oxide) groups, and the like.
The thioxanthone structure of the specific compound is represented by the following formula (2).
Figure BDA0002237218690000051
In the formula (2), the bonding position may be a position to bond to the oxime ester structure represented by the formula (1), and when bonding to the oxime ester structure is performed via another bonding group, the bonding position may be a position to bond to the bonding group. Examples of the bonding group include: alkylene, alkylidene, epoxyalkyl, and the like.
The thioxanthone structure represented by the above formula (2) may have other substituents in addition to the oxime ester structure represented by the above formula (1). As other substituents, there may be exemplified: carboxyl group, sulfo group, hydroxyl group, acetamido group, halogen atom, cyano group, nitro group, aminosulfonyl group, (C1-C8) alkyl group, (C1-C8) alkoxy group and the like.
When the thioxanthone structure represented by the above formula (2) has another substituent, the substituent may be the same as R in the above formula (1)1Bonded to form a ring structure.
Specific examples of the specific compound include the following compound numbers 1 to 20. However, the present invention is not limited to these examples. Among the compounds of compound numbers 1 to 20, the compounds of compound numbers 1 to 17 and 20 are preferred, and the compound number 1 is preferred.
Figure BDA0002237218690000071
Among the specific compounds, for example: the compounds of compound No. 1 and compound No. 20 can be synthesized by the method described in synthesis example 1 described below.
The specific compound generates radicals by irradiation with light such as ultraviolet light or visible light, has high sensitivity to light, and exhibits sufficient reactivity even with low-energy light. In addition, it has good thermal stability, low volatility, good storage stability, and good solubility, and is also suitable for photopolymerization in the presence of air (oxygen). Therefore, the specific compound is useful as a photopolymerization initiator for polymerizing a curable compound capable of radical polymerization.
The content of the specific compound in the total amount of the photocurable composition is usually 0.001 to 10% by mass, preferably 0.002 to 5.0% by mass, more preferably 0.1 to 3.0% by mass. When the content of the specific compound is 0.001% by mass or more, the photocurable composition tends to be sufficiently photopolymerizable. On the other hand, if the content of the specific compound is 10% by mass or less, the amount of unreacted compound can be reduced. As a result, the following situation tends to be suppressed: the light resistance and storage stability of the photocurable composition are deteriorated; and, when the photocurable composition is used as a sealant for a display module, it adversely affects display characteristics.
[ photopolymerization initiator ]
The photocurable composition of the present embodiment may further contain another photopolymerization initiator in addition to the specific compound. The other photopolymerization initiator is not particularly limited as long as it is a compound capable of initiating a chain polymerization reaction by generating a radical, an acid, a base, or the like by irradiation with ultraviolet rays or visible light.
Specific examples of other photopolymerization initiators include: benzil dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methyl propiophenone, 2-methyl [4- (methylthio) phenyl group]-2- (N-morpholinyl) -1-propane, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl disulfide, and the like. Examples of commercially available products include: IRGACURERTM 651、184、2959、127、907、396、379EG、819、784、754、500、OXE01、OXE02，DAROCURERTM 1173，LUCIRINRTMTPO (manufactured by BASF corporation); SEIKUOLRTMZ, BZ, BEE, BIP, BBI (manufactured by Seiko Chemicals Co., Ltd.), etc. In the present specification, the superscript "RTM" means a registered trademark.
Among these, from the viewpoint of improving the curability of the photocurable composition by light absorption of a wide range of wavelengths, the maximum absorption wavelength (. lamda.max) in the wavelength region of 200 to 300nm is preferableA photopolymerization initiator having an absorbance of 400 or more, more preferably 500 or more at the maximum absorption wavelength (. lamda.max) in the wavelength region of 200 to 300nm, still more preferably 1500 or more at the maximum absorption wavelength (. lamda.max) in the wavelength region of 200 to 300 nm. Examples of the photopolymerization initiator having an absorption intensity of 500 or more at a maximum absorption wavelength (λ max) in a wavelength region of 200 to 300nm include: IRGACURERTM651. 184, 2959 (trade name). Further, examples of the photopolymerization initiator having an absorption intensity of 1500 or more at a maximum absorption wavelength (λ max) in a wavelength region of 200 to 300nm include: IRGACURERTM2959 (trade name).
In addition, from the viewpoint of preventing outgassing, the photopolymerization initiator is preferably one having a molecular weight of 150 to 1000. Also, from the viewpoint of preventing outgassing, the photopolymerization initiator preferably has a (meth) acryloyl group in the molecule, and for example: the reaction product of 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one. This compound can be produced by the method described in international publication No. 2006/027982.
When the photocurable composition of the present embodiment contains another photopolymerization initiator, the content of the other photopolymerization initiator in the total amount of the photocurable composition is preferably 0.001 to 10% by mass, more preferably 0.1 to 5.0% by mass.
[ photo-initiation assistant ]
The photocurable composition of the present embodiment may contain a photoinitiator aid such as a tertiary amine for further improving curability. The tertiary amine is not particularly limited, and examples thereof include: ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N-dimethylbenzylamine, and the like. Further, 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 be suitably used.
When the photocurable composition of the present embodiment contains a photoinitiator aid, the content of the photoinitiator aid in the total amount of the photocurable composition is preferably 0.005 to 20 mass%, more preferably 0.01 to 10 mass%.
[ curable Compound ]
The photocurable composition of the present embodiment preferably contains a curable compound. The curable compound is not particularly limited as long as it can be cured by light, heat, or the like, and is preferably a (meth) acrylic compound such as a (meth) acrylate compound or an epoxy (meth) acrylate compound. The (meth) acrylic acid-based compound may be used alone in 1 kind, or 2 or more kinds may be used in combination.
Examples of the (meth) acrylate compound 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, phenylpolyethoxy (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, orthophenylphenol monoethoxy (meth) acrylate, orthophenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromophenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and mixtures thereof, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris ((meth) acryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane hexa (meth) acrylate, propylene glycol (meth) acrylate, and/or propylene glycol (meth) acrylate, propylene glycol (meth) acrylate, and/or propylene glycol (meth) acrylate, Trimethylolpropane (poly) ethoxytri (meth) acrylate, bis (trimethylolpropane) tetra (meth) acrylate, diacrylate of an ester of neopentyl glycol and hydroxytrimethylacetic acid, diacrylate of an epsilon-caprolactone adduct of an ester of neopentyl glycol and hydroxytrimethylacetic acid, and the like. Among these, N-acryloyloxyethylhexahydrophthalimide, phenoxyethyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate are preferable.
The epoxy (meth) acrylate compound is obtained by reacting an epoxy compound with (meth) acrylic acid in a known manner. The epoxy compound used as a raw material is not particularly limited, and an epoxy compound having a 2-or more-functional group is preferable. Examples of the 2-or more-functional epoxy compound include: resorcinol diglycidyl ether, bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol a novolac 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, phenol novolac type epoxy compounds having a triphenol methane skeleton, diglycidyl etherate of difunctional phenols (catechol, resorcinol, etc.), diglycidyl etherate of difunctional alcohols, halides or hydrides thereof, and the like. Among these, when the photocurable composition of the present embodiment is used as a liquid crystal sealing agent, a bisphenol a type epoxy compound and resorcinol diglycidyl ether are preferable from the viewpoint of liquid crystal staining property. The ratio of the epoxy group to the (meth) acryloyl group in the epoxy (meth) acrylate compound is not particularly limited, and may be appropriately selected from the viewpoint of process suitability.
The photocurable composition of the present embodiment preferably contains an epoxy compound in addition to the (meth) acrylic compound (excluding the (meth) acrylic compound). The epoxy compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The epoxy compound is not particularly limited, and an epoxy compound having 2 or more functions is preferable. Examples of the 2-or more-functional epoxy compound include: resorcinol diglycidyl ether, bisphenol a epoxy resin, bisphenol F epoxy 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, glycidyl ester epoxy resin, glycidyl amine epoxy resin, hydantoin epoxy resin, isocyanurate epoxy resin, phenol novolac epoxy resin having a triphenol methane skeleton, diglycidyl etherate of difunctional phenol (catechol, resorcinol, etc.), diglycidyl etherate of difunctional alcohol, halide or hydride thereof, and the like. Among these, when the photocurable composition of the present embodiment is used as a liquid crystal sealing agent, a bisphenol a type epoxy resin and resorcinol diglycidyl ether are preferable from the viewpoint of liquid crystal staining properties.
When the photocurable composition of the present embodiment contains a curable compound, the content of the curable compound in the total amount of the photocurable composition is usually 10 to 80% by mass, preferably 20 to 70% by mass.
When the photocurable composition of the present embodiment contains an epoxy compound, the content of the epoxy compound in the total amount of the photocurable composition is usually 5 to 50% by mass, preferably 5 to 30% by mass.
[ organic Filler ]
The photocurable composition of the present embodiment may contain an organic filler. The organic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
As the organic filler, there may be exemplified: polyurethane fine particles, acrylic fine particles, styrene olefin fine particles, and silicone fine particles. As the silicone fine particles, preferred are: KMP-594, KMP-597, and KMP-598 (trade name, manufactured by shin-Etsu chemical industries, Ltd.); torayfilRTME-5500, 9701, and EP-2001 (trade name, manufactured by Dow Corning Toray Co., Ltd.). As the polyurethane fine particles, preferred are: JB-800T, HB-800BK (trade name, manufactured by Kogyo Co., Ltd.). As the fine styrene particles, preferred are: RABALONRTMT320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C and SJ6300C (trade name, manufactured by Mitsubishi chemical corporation). As the styrene olefin fine particles, preferred are: SEPTONRTMSEPS2004 and SEPS2063 (trade name, manufactured by KURARAY Co., Ltd.). These organic fillers may be core-shell structured organic fillers using 2 or more materials.
Among these organic fillers, acrylic fine particles and silicone fine particles are preferable.
The acrylic fine particles are preferably an acrylic rubber having a core-shell structure composed of 2 kinds of acrylic rubbers, and more preferably acrylic fine particles having a core layer of n-butyl acrylate and a shell layer of methyl methacrylate. Acrylic fine particles having a core layer of n-butyl acrylate and a shell layer of methyl methacrylate, which are commercially available from AICA industries, Inc. as ZEFIACRTMF-351 (trade name).
Further, examples of the fine silicone particles include: organopolysiloxane crosslinked powder, linear dimethylpolysiloxane crosslinked powder, composite silicone rubber obtained by coating silicone rubber with a silicone resin (for example, polysilsesquioxane resin), and the like. Among these silicone fine particles, preferred are: silicone rubber of a linear dimethylpolysiloxane crosslinked powder, or composite silicone rubber fine particles of a linear dimethylpolysiloxane crosslinked powder coated with a silicone resin. The rubber powder is preferably spherical in shape, and the viscosity of the rubber powder after addition thereof is less increased.
When the photocurable composition of the present embodiment contains an organic filler, the content of the organic filler in the total amount of the photocurable composition is usually 5 to 50% by mass, preferably 5 to 40% by mass.
[ inorganic Filler ]
The photocurable composition of the present embodiment may contain an inorganic filler. The inorganic filler may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the inorganic filler include: silicon oxide, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, or the like; preferred examples are: particles of fused silica, crystalline silica, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, and the like; particles of silica, alumina, talc, etc. are preferable.
The average particle diameter of the inorganic filler is preferably 2000nm or less, more preferably 1000nm or less, and further preferably 300nm or less. The average particle diameter of the inorganic filler is set to 2000nm or less, and there is a tendency that, for example, the following: when the photocurable composition of the present embodiment is used as a liquid crystal sealant for a liquid crystal dropping method to produce a liquid crystal cell having a narrow gap, the gap can be smoothly formed when the upper and lower glass substrates are bonded to each other. The lower limit is preferably about 10nm, and more preferably about 100 nm. The particle diameter can be measured using a laser diffraction/scattering particle size distribution analyzer (dry type) (LMS-30, manufactured by SEISHIN corporation, Ltd.).
When the photocurable composition of the present embodiment contains an inorganic filler, the content of the inorganic filler in the total amount of the photocurable composition is usually 5 to 50% by mass, preferably 5 to 40% by mass. When the content of the inorganic filler is 5% by mass or more, the adhesion strength to the glass substrate can be improved, and the moisture resistance reliability can also be improved, so that the decrease in adhesion strength after moisture absorption tends to be suppressed. When the content of the inorganic filler is 50% by mass or less, for example, the following tendency is exhibited: when the photocurable composition of the present embodiment is used as a liquid crystal sealant for a liquid crystal dropping method to produce a liquid crystal cell, the inorganic filler is easily crushed and can be smoothly performed.
[ silane coupling agent ]
The photocurable composition of the present embodiment may contain a silane coupling agent in order to improve the adhesive strength and moisture resistance. The silane coupling agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the silane coupling agent include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, N-phenyltrimethoxysilane, N- (2-aminopropyl) ethyl) 3-aminopropyltrimethoxysilane, N- (2-aminopropyl) trimethoxysilane, N- (2-aminoethylmethyl) ethyl) 3-aminopropyltrimethoxysilane, N- (2-glycidyloxypropyltrimethoxysilane, N- (2-ethylmethyl) ethyl) 3-glycidyloxypropyltrimethoxysilane, N- (2-ethylmethyl) ethyl) methyl-hydroxysilane, N- (2-hydroxyben-ethyl) 3-glycidyloxypropyltrimethoxysilane, N- (2-glycidyloxypropyltrimethoxysilane, N-vinyltrimethoxysilane, or a mixture of one or a mixture of a compound of formula, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and the like. These silane coupling agents are commercially available from shin-Etsu chemical industries, Inc. in KBM series, KBE series, etc., and thus can be easily obtained from the market.
When the photocurable composition of the present embodiment contains a silane coupling agent, the content of the silane coupling agent in the total amount of the photocurable composition is preferably 0.05 to 3% by mass.
[ Heat curing agent ]
The photocurable composition of the present embodiment may contain a thermal curing agent. The heat-curing agent may be used alone in 1 kind, or in combination of 2 or more kinds.
The thermal curing agent undergoes nucleophilic reaction by a lone pair of electrons or an intramolecular anion, and examples thereof include: polyamines, polyphenols, organic hydrazide compounds, and the like. Among these, organic hydrazide compounds are preferably used.
Among the organic hydrazide compounds, examples of the aromatic hydrazide compound include: terephthaloyl hydrazine, isophthaloyl hydrazine, 2, 6-naphthalene carboxylic acid dihydrazide, 2, 6-pyridine dihydrazide, 1,2, 4-benzene trihydrazide, 1,4,5, 8-naphthoic acid tetrahydrazide, pyromellitic hydrazide, etc. Among the organic hydrazide compounds, the aliphatic hydrazide compounds include, for example: formylhydrazine, acethydrazide, propionohydrazide, oxalohydrazide, malonohydrazide, succinohydrazide, glutarohydrazide, adipyl, pimeloyl dihydrazide, sebacohydrazide, 1, 4-cyclohexanedihydrazide, tartrazinedihydrazide, apple dihydrazide, iminodiacetic hydrazide, N '-hexamethylene bis-semicarbazide (N, N' -hexamethylenehydrazide), citratrihydrazide, nitrilotriacetic hydrazide, cyclohexanetrihydrazide; dihydrazide compounds having a hydantoin skeleton (skeleton in which the carbon atom of the hydantoin ring is replaced with an isopropyl group), such as 1,3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin (1,3-bis (hydrazinocarbonyl) -5-isopropylhydantoin); tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate, and the like.
Among the organic hydrazide compounds, preferred are isophthaloyl hydrazide, malonoyl hydrazide, adipoyl hydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, and tris (3-hydrazinocarbonylpropyl) isocyanurate, from the viewpoint of a balance between curing reactivity and latency, and more preferred is tris (2-hydrazinocarbonylethyl) isocyanurate.
When the photocurable composition of the present embodiment contains a thermal curing agent, the content of the thermal curing agent in the total amount of the photocurable composition is usually 0.1 to 10% by mass, preferably 1 to 5% by mass.
[ thermal radical polymerization initiator ]
The photocurable composition of the present embodiment may contain a thermal radical polymerization initiator in order to improve the curing speed and curability. The thermal radical polymerization initiator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The thermal radical polymerization initiator is not particularly limited as long as it is a compound capable of generating radicals by heating and starting a chain polymerization reaction, and examples thereof include: organic peroxides, azo compounds, benzoin ether compounds, acetophenone compounds, benzopinacol (benzopinacol), and the like, and benzopinacol is preferably used.
As organic compoundsCommercially available products of peroxides, such as: kayamekRTM A、M、R、L、LH、SP-30C，Perkadox CH-50L、BC-FF，Cadox B-40ES，Perkadox 14，TrigonoxRTM 22-70E、23-C70、121、121-50E、121-LS50E、21-LS50E、42、42LS，KayaesterRTM P-70、TMPO-70、CND-C70、OO-50E、AN，KayabutylRTM B，Perkadox 16，KayacarbonRTMBIC-75, AIC-75 (trade name, manufactured by Akzo Co., Ltd.); PERMEKRTM N、H、S、F、D、G，PERHEXARTM H、HC、TMH、C、V、22、MC，PERCURERTMAH，PERBUTYLRTM H、C、ND、L，PERCUMYLRTM H、D，PEROYLRTM IB、IPP，PEROCTARTMND (trade name, manufactured by Nichigan oil Co., Ltd.) and the like.
Further, as a commercial product of the azo compound, there can be exemplified: VA-044, 086, V-070, VPE-0201, VSP-1001 (trade name, manufactured by Wako pure chemical industries, Ltd.), and the like.
When the photocurable composition of the present embodiment contains a thermal radical polymerization initiator, the thermal radical polymerization initiator is usually 0.0001 to 10% by mass, preferably 0.0005 to 5% by mass, more preferably 0.001 to 3% by mass, of the total amount of the photocurable composition.
[ other ingredients ]
The photocurable composition of the present embodiment may contain additives such as a curing accelerator, a radical polymerization inhibitor, a pigment, an antifoaming agent, and a solvent, as required.
(curing accelerators)
Examples of the curing accelerator include: organic acids, imidazole compounds, and the like.
Examples of the organic acid include: organic carboxylic acids, organic phosphoric acids, etc., and organic carboxylic acids are preferred. Specifically, for example: 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.
As the imidazole compound, there can be exemplified: 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-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 Triazine, 2, 4-diamino-6- (2 '-methylimidazole (1')) ethyl-s-triazine isocyanuric acid adduct, 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 of the present embodiment contains a curing accelerator, the content of the curing accelerator in the total amount of the photocurable composition is usually 0.1 to 10% by mass, preferably 1 to 5% by mass.
(radical polymerization inhibitor)
The radical polymerization inhibitor is not particularly limited as long as it is a compound capable of inhibiting the progress of polymerization by reacting with radicals generated from a photo radical polymerization initiator, a thermal radical polymerization initiator, and the like, and examples thereof include: quinone, piperidine, hindered phenol, nitroso and other radical polymerization inhibitors. Specific examples thereof include: naphthoquinone, 2-hydroxynaphthoquinone, 2-menadione, 2-methoxynaphthoquinone, 2,6, 6-tetramethylpiperidine-1-oxide (2,2,6,6-tetramethylpiperidine-1-oxyl), 2,6, 6-tetramethyl-4-hydroxypiperidine-1-oxide, 2,6, 6-tetramethyl-4-methoxypiperidine-1-oxide, 2,6, 6-tetramethyl-4-phenoxypiperidine-1-oxide, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, p-benzoquinone, butylated hydroxyanisole, 2, 6-di (tert-butyl) -4-ethylphenol, 2, 6-di (tert-butyl) cresol, 2, 6-tetramethyl-4-phenoxypiperidine-1-oxide, hydroquinone, 2-methylhydroquinone, 2,6, 6-tetramethylpiperidine-1-oxide, and mixtures thereof, Stearyl β - (3, 5-di (tert-butyl) -4-hydroxyphenyl) propionate, 2 '-methylenebis (4-ethyl-6-tert-butylphenol), 4' -thiobis (3-methyl-6-tert-butylphenol), 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 (tert-butyl) -4' -hydroxyphenyl) propionate ] methane, n-butyl-ethyl-methyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, n-butyl-ethyl-methyl-2, 4-methyl-6-tert-butylphenol, n-butyl-4-hydroxyphenyl) propionate ] methane, n-butyl-ethyl-methyl-2, 4-butyl-6-tert-butyl-phenyl-butyl-2, 4-butyl-6-hydroxy-phenyl-propionate, n-butyl-ethyl-methyl-ethyl-methyl-2, n-butyl-ethyl-2, 5-ethyl-methyl-ethyl-4-methyl-ethyl-2, 4-butyl-ethyl-4-phenyl-ethyl-2, 4-methyl-ethyl-propyl-2, 4-ethyl-2, 4-ethyl-4-one, or a, 1,3, 5-tris (3 ', 5 ' -di (tert-butyl-4 ' -hydroxybenzyl) -sec-triazine-2, 4,6- (1H,3H,5H) trione ], P-methoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-nitrosophenylhydroxylamine, trade name ADEKA STAB LA-81, trade name ADEKA STAB LA-82 (both manufactured by ADEKA Co., Ltd.), and the like, among these, naphthoquinone-based, hydroquinone-based, nitroso-based, piperidine-based radical polymerization inhibitors are preferable, naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2, 6-di (tert-butyl) P-cresol, POLYSTOP7300P (manufactured by Bo Dong Co., Ltd.) is more preferable, and POLYSTOP7300P (manufactured by Bo Dong Co., Ltd.) is still more preferable.
When the photocurable composition of the present embodiment contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor in the total amount of the photocurable composition is usually 0.0001 to 1% by mass, preferably 0.001 to 0.5% by mass, and more preferably 0.01 to 0.2% by mass.
[ viscosity of Photocurable composition ]
The photocurable composition of the present embodiment preferably has a viscosity of 150 to 500 pas, more preferably 200 to 500 pas, at 25 ℃. In particular, when the photocurable composition of the present embodiment is used as a liquid crystal sealing agent, the viscosity of the photocurable composition at 25 ℃ is preferably 250 to 400 pas, more preferably 280 to 320 pas. When the viscosity is 250Pa · s or more, the cell formation tends to be facilitated by suppressing the occurrence of liquid crystal penetration. The viscosity is set to 400 pas or less, and the liquid crystal sealing agent tends to be easily applied.
[ method for preparing Photocurable composition ]
As an example of a method for preparing the photocurable composition according to the present embodiment, the following method can be exemplified. First, the specific compound is dissolved in the curable compound by heating. Then, after cooling to room temperature, an organic filler, an inorganic filler, a silane coupling agent, a thermosetting agent, a thermal radical polymerization initiator, a defoaming agent, a leveling agent, a solvent, and the like are added as necessary. Then, the photocurable composition of the present embodiment can be prepared by mixing the components uniformly using a known mixing device such as a three-roll mill, a sand mill, or a ball mill, and filtering the mixture with a metal sieve.
< uses of Photocurable compositions >
The photocurable composition of the present embodiment is very useful as a sealing agent for electronic components or an adhesive for electronic components. Examples of the electronic component sealant or the electronic component adhesive include: an adhesive for flexible printed wiring boards, an adhesive for Tape Automated Bonding (TAB), an adhesive for semiconductors, various adhesives for displays, and the like, but are not limited thereto.
The photocurable composition of the present embodiment is very useful as an adhesive for liquid crystal display cells, and particularly as a liquid crystal sealing agent. The following shows an example of a liquid crystal display cell when the photocurable composition of the present embodiment is used as a liquid crystal sealing agent.
A liquid crystal display unit manufactured using an adhesive for liquid crystal display units is formed by forming predetermined electrodes on substrates of a pair of substrates, arranging the pair of substrates in opposition to each other at a predetermined interval, sealing the periphery with a liquid crystal sealant, and sealing liquid crystal in the gap. The type of the liquid crystal to be sealed is not particularly limited. The substrate is composed of the following combination of substrates: is made of glass, quartz, plastic, organic silicon, etc., and at least one of the substrates has light-transmitting property.
The method of manufacturing the liquid crystal display unit is, for example, as follows.
First, a spacer (gap control material) is added to the liquid crystal sealant. Examples of the spacer include: glass fibers, silica beads, polymer beads, and the like. The diameter of the spacer is different depending on the purpose, and is usually 2 to 8 μm, preferably 4 to 7 μm. The amount of the spacer used is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, more preferably 0.9 to 1.5 parts by mass, based on 100 parts by mass of the liquid crystal sealing agent.
Then, after applying the liquid crystal sealing agent to one of the pair of substrates by using a dispenser, a screen printing apparatus, or the like, the liquid crystal sealing agent is temporarily cured at 80 to 120 ℃ as required. Then, liquid crystal was dropped inside the bank of the liquid crystal sealant, and another glass substrate was stacked in vacuum to form a gap. After the gap is formed, the liquid crystal display unit can be obtained by curing the liquid crystal display unit at 90 to 130 ℃ for 1 to 2 hours. When the liquid crystal sealing material is used in a photothermal combination type, the liquid crystal sealing material is irradiated with ultraviolet rays using an ultraviolet ray irradiation apparatus to be photo-cured. The ultraviolet irradiation dose is 500-6000 mJ/cm2Preferably, the concentration is 1000 to 4000mJ/cm2Preferably. Then, curing the cured product at 90 to 130 ℃ for 1 to 2 hours as required to obtain a liquid crystal display unit. The liquid crystal display cell obtained in the above manner is free from display failure due to contamination of liquid crystal, and is excellent in adhesion and moisture resistance reliability.
The photocurable composition of the present embodiment is very suitable for the following applications: an electronic component designed to have a light shielding portion, or an adhesive that needs to be cured by low-energy light such as visible light. Preferable are, for example: a liquid crystal display sealant, an organic EL sealant, and a touch panel adhesive used under the line light-shielding portion.
[ examples ]
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. Unless otherwise specified, "%" in this document is based on mass.
< Synthesis example 1>
[ Synthesis of 2-acetylthioxanthone ]
Figure BDA0002237218690000191
2-acetylthioxanthone is synthesized according to the synthetic sequence described in the prior art (Material Technology, Vol.27, No.6(2009), pp.242-251).
[ Synthesis of TX-OXE (Compound No. 1) ]
Figure BDA0002237218690000201
A200 mL four-necked reaction vessel was equipped with a thermometer and cooling tube and nitrogen flow was started at a flow rate of 30 mL/min. 2-acetylthioxanthone (0.50g), hydroxylamine hydrochloride (0.20g), and N, N-dimethylformamide (60mL) were charged into a reaction vessel, and a reaction was carried out at 80 ℃ for 4 hours. After 50mL of water was added to stop the reaction, the mixture was extracted with methyl isobutyl ketone (200mL) and washed 3 times with 50mL of water. The solvent was removed using an evaporator to obtain the oxime of 2-acetylthioxanthone (TX-OX/yellow solid). The yellow solid (crude crystals) obtained here was used directly for the oxime esterification reaction.
Figure BDA0002237218690000202
A200 mL four-necked reaction vessel was equipped with a thermometer and cooling tube and nitrogen flow was started at a flow rate of 30 mL/min. The total amount of TX-OX, acetic anhydride (0.24g), and butyl acetate (30mL) were charged in a reaction vessel, and the reaction was carried out at 90 ℃ for 5 hours. After 50mL of water was added to stop the reaction, the mixture was extracted with methyl isobutyl ketone (200mL) and washed 3 times with 50mL of water. 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 0.35g of an oxime ester of 2-acetylthioxanthone (TX-OXE/yellow solid) (yield of 2-stage reaction: 57%).
1H-NMR(400MHz，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 of TX-OXE-2 (Compound No. 20) ]
Figure BDA0002237218690000211
A200 mL four-necked reaction vessel was equipped with a thermometer and cooling tube and nitrogen flow was started at a flow rate of 30 mL/min. TX-OX (0.5g), benzoyl chloride (0.52g), triethylamine (0.47g), and tetrahydrofuran (30mL) were charged in a reaction vessel, and a reaction was carried out at 55 ℃ for 8 hours. After 30mL of water was added to stop the reaction, the precipitated solid was separated by filtration. The yellow solid obtained here was recrystallized from dimethyl sulfoxide and water to obtain 0.28g of an oxime ester of 2-acetylthioxanthone (TX-OXE-2/yellow solid) (yield: 40%).
1H-NMR(400MHz，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 1 and 2>
Curable compounds (B-1, B-2, B-3) shown in Table 1 below were mixed, heated at 90 ℃ to dissolve specific compound (A-1) shown in Table 1 below, and then cooled to room temperature. Then, the remaining components in table 1 below were added and stirred, and then dispersed by using a three-roll mill. Then, the mixture was filtered through a metal sieve (635 sieve) to prepare photocurable compositions of examples 1 and 2. The numerical values of the respective components in table 1 are expressed in parts by mass.
< comparative examples 1 and 2>
Photocurable compositions of comparative examples 1 and 2 were prepared in the same manner as in examples 1 and 2, except that the specific compound (A-1) was replaced with other components (O-2, O-3) shown in Table 1 below.
< evaluation >
[ degree of curing of light-blocking portion (ultraviolet irradiation) ]
To each of the photocurable compositions of examples 1 and 2 and comparative examples 1 and 2, 1 mass% of 4 μm glass fiber (manufactured by Nippon electric glass Co., Ltd.) was added to prepare a liquid crystal sealing agent. After a glass substrate was etched to set lines and pitches of 100 μm by chromium, a liquid crystal sealant was applied to the glass substrate, and black was appliedThe matrix substrate is bonded as a counter substrate. Then, from the substrate side where the line/pitch was set, at 3000mJ/cm2(100mW/cm230 seconds) was irradiated with ultraviolet rays having a wavelength of 365nm, and the degree of curing was measured with a microscope. The results are shown in table 1 below.
[ degree of curing of light-shielding portion (visible light irradiation) ]
To each of the photocurable compositions of examples 1 and 2 and comparative examples 1 and 2, 1 mass% of 4 μm glass fiber (manufactured by Nippon electric glass Co., Ltd.) was added to prepare a liquid crystal sealing agent. After a glass substrate was etched with chrome to provide lines and pitches of 100 μm, a liquid crystal sealant was applied to the glass substrate, and a black matrix substrate was bonded to form a counter substrate. Then, from the substrate side where the line/pitch was set, at 3000mJ/cm2(100mW/cm230 seconds) was irradiated with visible light having a wavelength of 405nm, and the degree of curing was measured with a microscope. The results are shown in table 1 below.
[ viscosity ]
The viscosity (Pa · s) at 25 ℃ of each of the photocurable compositions of examples 1 and 2 and comparative examples 1 and 2 was measured using an E-type viscometer (R115-type viscometer (manufactured by eastern industries, ltd)). The results are shown in table 1 below.
[ Table 1]
Figure BDA0002237218690000221
A-1: TX-OXE (synthesized in Synthesis example 1)
B-1: bisphenol A type epoxy acrylate (synthesized by the method described in Japanese patent laid-open publication No. 2016-24243)
B-2: epoxy acrylate ester of resorcinol glycidyl ether (synthesized by the method described in WO 2004/104683)
B-3: bisphenol A type partial epoxy acrylate (acrylic acid of Japanese patent laid-open publication No. 2016-24243 was reacted at 50% equivalent weight)
C-1: polymethacrylate-based organic fine particles (F-351S, manufactured by AICA industries, Ltd.)
D-1: spherical silica (manufactured by TOKUYAMA GmbH: SANSIL SSP-07M)
E-1: 3-glycidoxypropyltrimethoxysilane (Sila-Ace S-510, JNC Co., Ltd.)
F-1: sebacoyl hydrazine (SDH manufactured by Tsukak chemical Co., Ltd.)
O-1: 1,3, 5-tris (2-carboxyethyl) isocyanurate (CIC acid, product of four chemical industries, Ltd.)
O-2: diethyl thioxanthone
O-3: 1, 2-octanedione, 1- [4- (phenylthio) -,2- (O-benzoyloxime) ] (OXE-01, BASF Co.)
As shown in table 1, the photocurable compositions of examples 1 and 2 using TX-OXE as the specific compound showed better curability in the deep part (low energy irradiation part) regardless of irradiation with ultraviolet light or visible light, compared to the photocurable compositions of comparative examples 1 and 2 using compounds having similar structures. In other words, it was confirmed that the photocurable compositions of examples 1 and 2 have excellent curability by curing at low energy.

Claims (9)

1. A liquid crystal sealant comprising: a compound having an oxime ester structure and a thioxanthone structure in a molecule, and a (meth) acrylic compound, and has a viscosity of 250 to 400 pas at 25 ℃.
2. A liquid crystal sealant according to claim 1, which contains an epoxy compound.
3. A liquid crystal sealant according to claim 1 or 2, which contains an organic filler.
4. The liquid crystal sealing agent according to claim 3, wherein the organic filler is at least 1 selected from the group consisting of polyurethane fine particles, acrylic fine particles, styrene olefin fine particles, and silicone fine particles.
5. A liquid crystal sealing agent according to claim 1 or 2, which contains an inorganic filler.
6. The liquid crystal sealing agent according to claim 1 or 2, which contains a silane coupling agent.
7. A liquid crystal sealing agent according to claim 1 or 2, which contains a thermal curing agent.
8. The liquid crystal sealing agent according to claim 7, wherein the heat-curing agent is an organic hydrazide compound.
9. A liquid crystal display cell bonded using the liquid crystal sealant according to any one of claims 1 to 8.
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