TW201730221A - Display element sealing agent, liquid crystal sealing agent and cured product thereof, and liquid crystal display panel and method for producing same - Google Patents

Abstract

The purpose of the present invention is to provide a photocurable resin composition which exhibits high curability that enables sufficient curing even when the quantity of light is small and which is suitable for use as, for example, a display element sealing agent. This display element sealing agent contains a curable compound A having an ethylenically unsaturated double bond in the molecule, a photopolymerization initiator B and an ammonium salt C of a quaternary organic boron anion represented by formula (1). (In formula (1), R1 to R4 may be the same as, or different from, each other and each denote an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkyl group, an optionally substituted aralkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group, with at least one of R1 to R4 being an optionally substituted aryl group or an optionally substituted heteroaryl group, and Z+ denotes an ammonium cation).

Description

Display element sealant, liquid crystal sealant and cured product thereof, liquid crystal display panel and method of manufacturing same

The present invention relates to a display element encapsulant, a liquid crystal encapsulant, and a cured product thereof, and a liquid crystal display panel and a method of fabricating the same.

In recent years, display panels such as liquid crystals or organic electroluminescence (EL) have been widely used as image display panels of various electronic devices typified by mobile phones or personal computers. For example, the liquid crystal display panel includes two transparent substrates provided with electrodes on the surface, a frame-shaped sealing member sandwiched between the two transparent substrates, and liquid crystal enclosed in a region surrounded by the sealing member.

The liquid crystal display panel can be manufactured, for example, by a liquid crystal dropping process. The liquid crystal display panel manufactured by the liquid crystal dropping process is manufactured by: (1) applying a liquid crystal sealing agent to the inner edge of the transparent substrate to form a frame for filling the liquid crystal, and (2) dropping the inside of the frame. Liquid crystal, (3) When the liquid crystal sealing agent is in an uncured state, the two substrates are superposed under high vacuum, and (4) the liquid crystal sealing agent is cured.

As described above, in the liquid crystal dropping process, photo hardening or thermal hardening is performed in a state where the uncured liquid crystal sealing agent is in contact with the liquid crystal. Therefore, in order to reduce elution into the liquid crystal, the liquid crystal sealing agent is required to have high hardenability. In particular, it is difficult for light to reach under the substrate (light-shielding portion) in which the wiring or the black matrix is formed, and thus the curing of the liquid crystal sealing agent is likely to be insufficient. Therefore, the liquid crystal sealing agent is required to have high hardenability which is sufficiently hardened even when the amount of light is small.

A liquid crystal display element sealing agent containing a specific thioxanthone-based polymerization initiator and an amine-based sensitizer has been proposed as a liquid crystal sealing agent used in a liquid crystal dropping process (for example, Patent Document 1).

Further, as the photocurable composition, an organoboron compound (A) containing one or more naphthalene groups bonded to a boron atom, a sensitizer (B), a triazine compound (C), and ethylene are known. A photocurable composition of the organic compound (D) having an unsaturated bond (for example, Patent Document 2), or a sensitizer (A), an organic boron salt (B), and a compound having an ethylenically unsaturated bond (C) A photocurable composition (for example, Patent Document 3). Prior art literature

Patent Document 1: International Publication No. 2015/072415 Patent Document 2: Japanese Patent Laid-Open No. 2001-106712 (Patent Document 3: Japanese Patent Laid-Open Publication No. 2000-284478)

[Problems to be Solved by the Invention] The sealing agent for liquid crystal display elements of Patent Document 1 or the photocurable composition of Patent Documents 2 and 3 do not have sufficient curability. Therefore, when the photocurable composition is used as, for example, a liquid crystal sealing agent for a liquid crystal dropping process, not only the curing of the liquid crystal sealing agent but also the dissolution of the liquid crystal sealing agent is not sufficient, and the dissolution into the liquid crystal cannot be suppressed. After that.

Especially in the liquid crystal display panel, 4K, 8K and the like are developed with high definition. As described above, the increase in the density of the wiring is increased due to the increase in the number of pixels. As a result, the aperture ratio of the wiring portion (the region in which the wiring is formed) of the liquid crystal display panel tends to decrease. Since the liquid crystal sealing agent is usually disposed in the wiring portion, the opening ratio of the wiring portion is low, and in the liquid crystal display panel having a large number of light shielding portions, it is also required to cure the liquid crystal sealing agent provided in the light shielding portion.

The present invention has been made in view of the above-described problems, and it is an object of the invention to provide a photocurable resin composition which is excellent in curability and can be sufficiently cured, for example, as a display element sealing agent. [Means for solving the problem]

[1] A display element sealing agent comprising: a curable compound A having an ethylenically unsaturated double bond in a molecule; a photopolymerization initiator B; and a quaternary organoboron anion represented by the following formula (1) Ammonium salt C; [Chemical 1] (In the formula (1), R ₁ to R ₄ are a substitutable alkyl group, a substituted alkenyl group, a substituted alkynyl group, a substitutable cycloalkyl group, a substitutable aralkyl group, The aryl group or the substituted heteroaryl group which may be substituted may be the same or different, and at least one of R ₁ to R ₄ may be a substituted aryl group or a substituted heteroaryl group, and Z ⁺ is Ammonium cation). [2] The display element sealing agent according to [1], wherein the photopolymerization initiator B is at least one selected from the group consisting of a thioxanthone compound and an anthraquinone compound. [3] The display element encapsulant according to [1] or [2], wherein a mass ratio of the photopolymerization initiator B to the ammonium salt C of the quaternary organoboron anion is a photopolymerization initiator B: ammonium salt of the fourth-order organoboron anion C = 1:0.1 to 1:3. [4] The display element sealant according to any one of [1] to [3] wherein the content of the ammonium salt C of the quaternary organoboron anion is 0.01% by mass based on the curable compound A ~3 mass%. [5] A liquid crystal sealing agent comprising the display element sealing agent according to any one of [1] to [4]. [6] A cured product which is a cured product of the liquid crystal sealing agent according to [5]. [7] The liquid crystal sealing agent according to the above [5], which is used for sealing the liquid crystal layer of the liquid crystal display panel in which the opening ratio of the wiring portion in which the liquid crystal sealing agent is disposed is 50% or less. [8] A method of manufacturing a liquid crystal display panel, comprising: a step of forming a seal pattern on one of the substrates using the liquid crystal sealant according to [5]; and in a state where the seal pattern is not hardened, a step of dropping liquid crystal on a region of the seal pattern or another substrate paired with the one of the substrates; and stacking the one of the substrates and the other substrate by the seal pattern; And a step of hardening the seal pattern. [9] The method of manufacturing a liquid crystal display panel according to [8], wherein the step of hardening the seal pattern comprises the step of irradiating the seal pattern with light to harden the seal pattern. [10] A liquid crystal display panel comprising: a pair of substrates; a frame-shaped sealing member disposed between the pair of substrates; and a space surrounded by the sealing member filled between the pair of substrates The liquid crystal layer, and the sealing member is a cured product of the liquid crystal sealing agent as described in [5]. [11] The liquid crystal display panel according to [10], wherein an opening ratio of the wiring portion in which the sealing member is disposed is 50% or less. [Effects of the Invention]

According to the present invention, it is possible to provide a photocurable resin composition which is excellent in curability and can be sufficiently cured even when the amount of light is small, for example, as a display element sealing agent.

1. Photocurable resin composition The photocurable resin composition of the present invention contains a curable compound A, a photopolymerization initiator B, and an ammonium salt C of a quaternary organoboron anion, and may further contain a thermosetting compound as needed. D, thermal hardener E and other components F.

1-1. Curable Compound A The curable compound A contained in the photocurable resin composition of the present invention is a compound having an ethylenically unsaturated double bond in the molecule. The compound having an ethylenically unsaturated double bond in the molecule is preferably a compound having a (meth)acryloyl group in the molecule. The number of (meth)acryl fluorenyl groups per molecule is 1 or more. The compound having a (meth) acrylonitrile group in the molecule may be any of a monomer, an oligomer or a polymer. The (meth)acrylonyl group means an acryloyl group or a methacryloyl group, and the (meth)acrylate means an acrylate or a methacrylate.

Examples of the compound having one (meth)acryl fluorenyl group in one molecule include methyl (meth)acrylate, ethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate (methyl). ) alkyl acrylate.

Examples of the compound having two or more (meth)acrylonium groups in one molecule include di(meth)acrylate such as polyethylene glycol, propylene glycol or polypropylene glycol; and tris(2-hydroxyethyl) isocyanurate a di(meth) acrylate of an ester; a di(meth) acrylate of a diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol; a di(meth)acrylate of a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A; added to 1 mole of trimethylolpropane a di- or tri-(meth) acrylate of a triol obtained by using more than 3 moles of ethylene oxide or propylene oxide; adding 4 moles or more of ethylene oxide to 1 mole of bisphenol A or Di(meth)acrylate of diol obtained from propylene oxide; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; trimethylolpropane tri(meth)acrylate Or oligomer thereof; pentaerythritol tri(meth)acrylate or oligomer thereof; poly(meth)acrylate of dipentaerythritol; tris(propyleneoxyethyl)isocyanurate; caprolactone Modified isocyanuric acid three (C醯oxyethyl) ester; caprolactone modified tris(methacryloxyethyl) isocyanurate; polyacrylate or polymethacrylate of alkyl modified dipentaerythritol; caprolactone Polyacrylate or polymethacrylate modified with dipentaerythritol; hydroxytrimethylacetic acid neopentyl glycol diacrylate or dimethacrylate; caprolactone modified hydroxytrimethylacetic acid neopentyl glycol di Methyl) acrylate; ethylene oxide modified phosphoric acid acrylate or dimethacrylate; ethylene oxide modified alkylated phosphoric acid (meth) acrylate; neopentyl glycol, trimethylolpropane, An oligomeric (meth) acrylate of pentaerythritol or the like.

The curable compound A may also have an epoxy group in the molecule. The number of epoxy groups per molecule is 1 or more. When the curable compound A has not only a (meth) acrylonitrile group but also an epoxy group in the molecule, photocurability and thermosetting property can be imparted to the photocurable resin composition containing the curable compound A. . Thereby, the hardenability of the cured product can be improved.

The compound having a (meth) acrylonitrile group and an epoxy group in the molecule may, for example, be a glycidyl (meth)acrylate obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of a basic catalyst. .

When the epoxy compound to be reacted is a polyfunctional epoxy compound having two or more epoxy groups in the molecule, the adhesion density of the cured product of the photocurable resin composition is suppressed to be excessively high. From the viewpoint of lowering, a difunctional epoxy compound is preferred. Examples of the difunctional epoxy compound include: a bisphenol type epoxy compound (bisphenol A type, bisphenol F type, 2,2'-diallyl bisphenol A type, bisphenol type AD, and hydrogenated bisphenol) Type, etc.), a biphenyl type epoxy compound, and a naphthalene type epoxy compound. Among them, from the viewpoint of good coatability, a bisphenol A type and a bisphenol F type bisphenol type epoxy compound are preferable. The bisphenol type epoxy compound has an advantage of being excellent in coatability as compared with a biphenyl ether type epoxy compound.

The compound having a (meth)acryloyl group and an epoxy group in the molecule may be one type or a combination of two or more types.

The compound A1 having a (meth)acrylinyl group in the molecule and having no epoxy group may be combined with the compound A2 having a (meth)acryloyl group and an epoxy group in the molecule. When the photocurable resin composition further contains an epoxy compound as the thermosetting compound D, the epoxy compound and the compound having a (meth)acryl fluorenyl group and no epoxy group in the molecule can be improved. A1 compatibility. The mass ratio of the compound A2 to the compound A1 can be, for example, A2/A1 = 1/0.4 to 1/0.6.

The content of the compound A2 having a (meth) acrylonitrile group and an epoxy group in the molecule is not particularly limited, and may be, for example, 30% by mass or more based on the total of the curable compound A.

The weight average molecular weight of the curable compound A is preferably from about 310 to about 1,000. The weight average molecular weight of the curable compound A can be measured, for example, by polystyrene conversion by gel permeation chromatography (GPC).

The content of the curable compound A is preferably 40% by mass to 80% by mass, and more preferably 50% by mass to 75% by mass based on the photocurable resin composition.

1-2. Compound B The photopolymerization initiator B contained in the photocurable resin composition of the present invention is not particularly limited, and may be a self-cleaving type photopolymerization initiator or a dehydrogenation type photopolymerization. Starting agent.

Examples of the self-cleaving type photopolymerization initiator include a benzoalkyl ketone compound (for example, 2,2-dimethoxy-1,2-diphenylethane-1-one (BASF) Benzyl dimethyl ketal, 2-methyl-2-morpholinyl (4-thiomethylphenyl) propane-1-one, etc. (BASF) manufactured by IRGACURE 651) α-Aminophenylalkyl ketone, 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184, manufactured by BASF), etc., manufactured by IRGACURE 907) a hydroxyphenylalkyl ketone or the like, a fluorenyl phosphine oxide-based compound (for example, 2,4,6-trimethylbenzoin diphenylphosphine oxide, etc.), a titanocene-based compound (for example, bis(η5-2, 4) -cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, etc., acetophenone-based compound (for example, diethoxygen) Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2- Methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2- Morpholinyl (4-thiocarbamate Phenylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane, etc., benzamidine compound (for example , benzoic acid methyl ester, etc.), benzoin ether compounds (for example, benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.) and oxime ester compounds (for example, 1,2-octanedione-1-[4- (phenylthio)-2-(O-benzylidene fluorene)] (IRGACURE OXE01 manufactured by BASF), ethyl ketone-1-[9-ethyl-6-( 2-Methylbenzylidene)-9H-carbazol-3-yl]-1-(0-ethenylhydrazine) (IRGACURE OXE02, manufactured by BASF).

Examples of the dehydrogenation type photopolymerization initiator include: a benzophenone-based compound (for example, benzophenone, methyl phthaloylbenzoate-4-phenylbenzophenone, 4, 4'). -dichlorobenzophenone, hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, benzoated benzophenone, 3,3',4,4'- Tetrakis(butyl carbonyl peroxide) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, etc., thioxanthone-based compounds (for example, thioxanthone, 2-chlorothiazepinone (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-chloro-4-propoxythiazinone, 1-chloro-4-ethoxythiazinone (Lambson Limited) ) manufactured by Speedcure CPTX), 2-isopropyloxaxanone (Speedcure ITX manufactured by Lambson Limited), 4-isopropylthioxanthone, 2,4-Dimethylthioxanthone, 2,4-diethylthiaxanone (Speedcure DETX manufactured by Lambson Limited), 2,4-dichlorosulfide A fluorenone or a quinone compound (for example, 2-methyl hydrazine, 2-ethyl hydrazine, 2-third Base, 1-chloropurine, etc., 2-hydroxyindole (2-Hydroxyanthraquinone manufactured by Tokyo Chemical Industry Co., Ltd.), 2,6-dihydroxyindole (manufactured by Tokyo Chemical Industry Co., Ltd.) 2,6-dihydroxy fluorene (Anthraflavic Acid), 2-hydroxymethyl hydrazine (2-(Hydroxymethyl)anthraquinone) manufactured by Pure Chemical Co., Ltd.), and benzophenone Lanthanide compounds.

The absorption wavelength of the photopolymerization initiator B is not particularly limited, and it is easy to obtain high curability by being combined with the ammonium salt C of the quaternary organoboron anion. Therefore, it is preferred to absorb light having a wavelength of 360 nm or more. Starter B. Among them, a photopolymerization initiator B which absorbs light having a wavelength of 360 nm to 780 nm is more preferable, and a photopolymerization initiator B which absorbs light having a wavelength of 360 nm to 430 nm is preferable.

Examples of the photopolymerization initiator B that absorbs light having a wavelength of 360 nm or more include a phenylalkylketone-based compound, a fluorenylphosphine oxide-based compound, a titanocene-based compound, an oxime ester-based compound, and a thioxanthone-based compound. The compound or an anthraquinone compound is preferably a thioxanthone compound or an anthraquinone compound.

The molecular weight of the photopolymerization initiator B is preferably, for example, 200 or more and 5,000 or less. When the molecular weight is 200 or more, it is difficult to cause elution into the liquid crystal. When the molecular weight is 5,000 or less, the compatibility with the curable compound A can be improved, and thus sufficient curability can be easily obtained. The molecular weight of the photopolymerization initiator B is more preferably 230 or more and 3,000 or less, and still more preferably 230 or more and 1,500 or less.

The molecular weight of the photopolymerization initiator B can be "relative molecular mass" of the molecular structure of the detected main peak when performing high performance liquid chromatography (HPLC) under the following conditions. Find it by form.

Specifically, a photopolymerization initiator B was dissolved in tetrahydrofuran (THF) to prepare a sample solution, and subjected to high performance liquid chromatography (HPLC) measurement under the following measurement conditions. Then, the area percentage of the detected peak (the ratio of the area of each peak to the total area of all the peaks) was determined, and the presence or absence of the main peak was confirmed. The main peak is the peak of the highest intensity among all the peaks detected by the characteristic detection wavelength (for example, 400 nm for the thioxanthone compound) (the highest peak of the peak height) . (HPLC measurement conditions) Device: AcquityTM UPLC H-Class system manufactured by Waters Column: Acquity UPLC BEH C18, 2.1 mm ID×100 Mm Particle size: 1.7 μm Mobile phase: A: Acetonitrile B: 5 mM ammonium acetate aqueous solution A/B=60/40 (0 minutes to 4 minutes) 95/5 (4 minutes to 9 minutes) 95/5 (9 minutes~ 10 minutes) Flow rate: 0.4 mL/min Photo-Diode Array (PDA) detector: Measurement wavelength: 190 nm to 500 nm

The relative molecular mass corresponding to the peak apex of the detected main peak can be determined by Liquid Chromatography Mass Spectrometry (LC/MS). (LC/MS measurement conditions) Device: manufactured by Waters, AcquityTM H-Class system/SQ detector (Detector) Column: Acquity UPLC BEH C18, 2.1 mm ID × 100 mm Particle size: 1.7 μm Mobile phase: A: Acetonitrile B: 5 mM ammonium acetate solution A/B=60/40 (0 min to 4 min) 95/5 (4 min ~ 9 Minutes) 95/5 (9 minutes to 10 minutes) Flow rate: 0.4 mL/min Ionization: Electrospray Ionization (ESI), positive/negative ion measurement PDA detector: Measurement wavelength: 190 nm to 500 nm

The photopolymerization initiator B may be one type or a combination of two or more types.

The content of the photopolymerization initiator B is preferably from 0.01% by mass to 10% by mass based on the curable compound A. When the content of the photopolymerization initiator B is 0.01% by mass or more, sufficient photocurability is easily obtained. When the content of the photopolymerization initiator B is 10% by mass or less, the elution into the liquid crystal is small, so that contamination of the liquid crystal is easily reduced. The content of the photopolymerization initiator B is more preferably from 0.1% by mass to 5% by mass, even more preferably from 0.1% by mass to 3% by mass, even more preferably from 0.1% by mass to 2.5% by mass, based on the curable compound A.

The structure of the photopolymerization initiator B contained in the photocurable resin composition can be obtained by high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC/MS) and nuclear magnetic resonance (Nuclear Magnetic Resonance, The NMR measurement or the infrared (IR) measurement is combined to determine. For example, when a thioxanthone-based compound is used as the photopolymerization initiator B, it can be carried out in the following order. 1) A solution obtained by dissolving a photocurable resin composition in tetrahydrofuran (THF) is centrifuged by a centrifugal separator to precipitate a particle component such as cerium oxide particles or thermoplastic resin particles. The obtained solution was filtered by a filter to remove the particle component, and a sample liquid was obtained. 2) The sample liquid obtained in the above 1) was subjected to high performance liquid chromatography (HPLC) measurement. The measurement method and conditions of HPLC are the same as the measurement methods and conditions of HPLC in the measurement of the molecular weight. Then, in the HPLC assay, the determination of the thioxanthone skeleton by liquid chromatography mass spectrometry (LC/MS) corresponds to the peak apex of the main peak detected by a characteristic detector with a wavelength of 400 nm. The relative molecular mass and composition. The measurement method and conditions of LC/MS are the same as the measurement methods and conditions of LC/MS in the measurement of the molecular weight. 3) The sample solution obtained in the above 1) is subjected to NMR measurement or IR measurement. Thereby, the chemical structure of the thioxanthone-based compound was determined.

1-3. Ammonium salt of quaternary organoboron anion C The ammonium salt C of the quaternary organoboron anion activates the photopolymerization initiator B and also functions as a sensitizer which contributes to the hardening reaction. The ammonium salt C of the quaternary organoboron anion preferably contains a ring having (4n+2) (n is an integer of 0 or more) π electrons. The ring having (4n+2) π electrons is preferably an aromatic hydrocarbon ring or an aromatic hetero ring, and more preferably an aromatic hydrocarbon ring. The ammonium salt C of the quaternary organoboron anion containing an aromatic hydrocarbon ring or an aromatic heterocyclic ring absorbs light in a wider wavelength range and is therefore easily activated.

In the quaternary organoboron anion, at least one of the rings having (4n+2) π electrons is preferably bonded to a boron atom. The ammonium salt C of the quaternary organoboron anion is preferably represented by the following formula (1). [Chemical 2]

R ₁ to R ₄ of the formula (1) are a substitutable alkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted cycloalkyl group, a substituted aralkyl group, and a Substituted aryl or substituted heteroaryl. R ₁ to R ₄ may be the same or different.

The alkyl group in the alkyl group which may be substituted is an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a decyl group and the like. The alkenyl group in the alkenyl group which may be substituted is an alkenyl group having 2 to 20 carbon atoms, and examples thereof include a vinyl group, a propenyl group, a butenyl group and the like. The alkynyl group in the substituted alkynyl group is an alkynyl group having 2 to 20 carbon atoms, and examples thereof include an ethynyl group, a propynyl group and the like. The cycloalkyl group in the cycloalkyl group which may be substituted is a cycloalkyl group having 5 to 20 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group and the like. The aralkyl group in the optionally substituted aralkyl group is an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group and the like. The aryl group in the aryl group which may be substituted is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group and the like. The heteroaryl group in the optionally substituted heteroaryl group is a heteroaryl group having 3 to 20 carbon atoms, and examples thereof include a pyridyl group and the like.

The substituent which the alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, the aralkyl group, the aryl group or the heteroaryl group may have is not particularly limited, and is preferably an electron-donating group. The electron donating group may be difficult to delocalize the electron density of the quaternary organoboron anion. The ammonium salt of the quaternary organoboron anion is difficult to exist stably. Therefore, when the ammonium salt C of the quaternary organoboron anion having an electron-donating group receives energy from the photopolymerization initiator B, it is considered that the dissociation is relatively easy, and the curing reaction of the curable compound A is easily started. Examples of the electron-donating group include an alkyl group such as a methyl group, an ethyl group, a propyl group or a tributyl group, an alkoxy group such as a methoxy group, and a hydroxyl group.

Wherein at least one (preferably 2, more preferably 3) of R ₁ to R ₄ is a substitutable aryl group or a substituted heteroaryl group, more preferably a substitutable aryl group. The ammonium salt C of the quaternary organoboron anion containing an aromatic hydrocarbon ring or an aromatic hetero ring easily absorbs light in a wider wavelength range, and thus is easily activated. In addition, as the number of aromatic hydrocarbon rings or aromatic heterocyclic rings contained in the ammonium salt C of the quaternary organoboron anion increases, the absorption wavelength is more likely to be further shifted to the longer wavelength side, and the activation is easier.

Examples of the quaternary organoboron anion include: n-butyltriphenylborate, n-octyltriphenylborate, n-dodecyltriphenylborate, dibutyltriphenylborate, Tributyltriphenylborate, benzyltriphenylborate, n-butyltris(4-methylphenyl)borate, n-butyltris(2-tolyl)borate, n-butyl tris(4- Tert-butylphenyl)borate, n-butyltrinaphthylborate, n-butyltris(3-methylnaphthyl)borate, tetra-n-butylborate, di-n-butyldiphenyl Borate, tetrabenzyl borate, and the like.

Z ⁺ of the formula (1) is an ammonium cation. The ammonium cation is preferably a tetraalkylammonium cation. Examples of the tetraalkylammonium cation include a tetramethylammonium cation, a tetraethylammonium cation, a tetra-n-butylammonium cation, a tetraoctylammonium cation, and the like.

The molecular weight of the ammonium salt C of the quaternary organoboron anion is, for example, preferably from 350 to 900. When the molecular weight of the ammonium salt C of the quaternary organoboron anion is 350 or more, it is difficult to elute into the liquid crystal, and thus it is easy to reduce liquid crystal contamination. When the molecular weight of the ammonium salt C of the quaternary organoboron anion is 900 or less, the compatibility with the curable compound A is hardly impaired, and it is easy to uniformly disperse. The ammonium salt C of the quaternary organoboron anion has a molecular weight of preferably from 450 to 800. The molecular weight of the ammonium salt C of the quaternary organoboron anion can be determined in the same manner as described above.

The content of the ammonium salt C of the quaternary organoboron anion is preferably 0.01% by mass to 10% by mass based on the curable compound A. When the content of the ammonium salt C of the quaternary organoboron anion is 0.01% by mass or more, the photopolymerization initiator B can be sufficiently activated, so that sufficient curability can be easily obtained. When the content of the ammonium salt C of the quaternary organoboron anion is 10% by mass or less, the curability is not impaired and elution into the liquid crystal is less likely to occur. The content of the ammonium salt C of the quaternary organoboron anion is more preferably 0.1% by mass to 5% by mass, even more preferably 0.1% by mass to 3% by mass, even more preferably 0.1% by mass to 2.5% by mass, based on the curable compound A. .

The structure of the ammonium salt C of the quaternary organoboron anion contained in the photocurable resin composition can be confirmed in the same manner as the method of confirming the structure of the photopolymerization initiator B contained in the photocurable resin composition. .

The content of the photopolymerization initiator B and the ammonium salt C of the quaternary organoboron anion is preferably a photopolymerization initiator B: an ammonium salt C of a quaternary organoboron anion C = 1:0.05 to 1:3. When the mass ratio of the photopolymerization initiator B to the ammonium salt C of the quaternary organoboron anion is within the above range, sufficient curability is easily obtained even when the amount of light is small. The mass ratio of the photopolymerization initiator B to the ammonium salt C of the quaternary organoboron anion is more preferably the photopolymerization initiator B: the ammonium salt of the quaternary organoboron anion C=1:0.1 to 1:3, and further preferably It is 1:0.1 to 1:2.

In the present invention, by combining the photopolymerization initiator B with the ammonium salt C of the quaternary organoboron anion, high hardenability can be obtained even when the amount of light is small. Although the reason is not clear, it is estimated as follows. That is, the photopolymerization initiator B is excited by absorbing the irradiated light, and its energy is shifted to the ammonium salt C of the quaternary organoboron anion. The hardening reaction of the curable compound A is promoted by using the ammonium salt C of the activated quaternary organoboron anion as a starting point. At the same time, the hardening reaction starting from the excited photopolymerization initiator B itself is also promoted. Therefore, it is considered that the combination of the photopolymerization initiator B and the ammonium salt C of the quaternary organoboron anion can synergistically improve the hardenability.

In the photopolymerization initiator B, the thioxanthone compound or the ruthenium compound has a relatively low reactivity in the visible light range, and is easily combined with the ammonium salt C of the quaternary organoboron anion even in the visible light range. The hardenability.

1-4. Thermosetting Compound D The thermosetting compound D is preferably an epoxy compound having an epoxy group in the molecule. However, the thermosetting compound D is different from the curable compound A. The thermosetting compound D is more preferably an epoxy compound having no (meth) acrylonitrile group in the molecule. The epoxy compound may be any of a monomer, an oligomer or a polymer. When the photocurable resin composition is used as a liquid crystal sealing agent, for example, the solubility and diffusibility of the liquid crystal are low, and not only the display characteristics of the obtained liquid crystal panel can be improved, but also the moisture resistance of the cured product can be improved. Sex.

The epoxy compound may be an aromatic epoxy compound having a weight average molecular weight of 500 to 10,000, preferably 1,000 to 5,000. The weight average molecular weight of the epoxy compound can be measured by gel permeation chromatography (GPC) in terms of polystyrene.

Examples of the aromatic epoxy compound include aromatic diols represented by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, and the like, and ethylene glycol, propylene glycol, and alkanediol. A modified diol, an aromatic polyglycidyl ether compound obtained by reaction with epichlorohydrin; a novolak resin derived from phenol or cresol and formaldehyde, a polyalkenyl phenol or a copolymer thereof A polyphenol type represented by the reaction, a novolac type polyglycidyl ether compound obtained by a reaction with epichlorohydrin, a glycidyl ether compound of a xylylene phenol resin, or the like. Among them, preferred are: cresol novolak type epoxy compound, phenol novolak type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, trisphenol methane type epoxy compound, trisphenol B An alkyl type epoxy compound, a trisphenol type epoxy compound, a dicyclopentadiene type epoxy compound, a diphenyl ether type epoxy compound, and a biphenyl type epoxy compound. The epoxy compound may be one type or a combination of two or more types.

The epoxy compound may be in the form of a liquid or a solid. In terms of easily improving the moisture resistance of the cured product, a solid epoxy compound is preferred. The softening point of the solid epoxy compound is preferably 40 ° C or more and 150 ° C or less.

The content of the thermosetting compound D is preferably from 3.8% by mass to 50% by mass, and more preferably from 5% by mass to 30% by mass based on the curable compound A. When the content of the thermosetting compound D is 3.8 mass% or more with respect to the curable compound A, it is easy to further improve the moisture resistance of the cured product or the adhesion strength to the glass substrate, and if it is 50% by mass or less, the production is performed. The compatibility with the curable compound A is easily and further improved.

The content of the thermosetting compound D is preferably from 3% by mass to 20% by mass based on the photocurable resin composition. When the content of the thermosetting compound D with respect to the photocurable resin composition is 3% by mass or more, the moisture resistance of the cured product is easily improved, and when it is 20% by mass or less, the photocurable resin composition can be suppressed. Excessive increase in the viscosity of the object. The content of the thermosetting compound D is more preferably from 3% by mass to 15% by mass, even more preferably from 4% by mass to 15% by mass, based on the photocurable resin composition.

1-5. Thermal Hardener E The heat hardener E is a compound which hardens the thermosetting compound D under normal storage conditions (at room temperature, under visible light, etc.), but cures the compound when heated. The photocurable resin composition containing the thermosetting agent E is excellent in storage stability and excellent in thermosetting property. The heat hardener E is preferably an epoxy hardener.

The epoxy resin hardener preferably has a melting point of 50 ° C or more, from the viewpoint of improving the viscosity stability of the photocurable resin composition and not impairing the moisture resistance of the cured product, depending on the heat curing temperature. 250 ° C or less, more preferably 100 ° C or more and 200 ° C or less, and further preferably 150 ° C or more and 200 ° C or less.

Examples of the epoxy hardener include an organic acid diterpene thermal latent curing agent, an imidazole thermal latent curing agent, an amine adduct thermal latent curing agent, and a polyamine thermal latent curing agent.

Examples of the organic acid diterpene thermal latent hardener include: diammonium adipate (melting point 181 ° C), 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin (melting point 120 ° C), 7,11-octadecane-1,18-dicarbonyl oxime (melting point 160 ° C), dodecanedioic acid dihydrazide (melting point 190 ° C), and diterpene sebacate肼 (melting point 189 ° C) and so on. Examples of the imidazole-based thermal latent curing agent include: 2,4-diamino-6-[2'-ethylimidazolyl-(1')]-ethyltriazine (melting point: 215 ° C to 225 ° C), And 2-phenylimidazole (melting point: 137 ° C to 147 ° C). The amine addition product thermal latent curing agent is a thermal latent curing agent containing an addition compound obtained by reacting a catalyst-based amine compound with any compound, and examples thereof include: Ajinomoto fine chemistry ( Amicure PN-40 (melting point 110 ° C) manufactured by Ajinomoto Fine-Techno Co., Ltd., Amicure PN-23 (melting point 100 ° C) manufactured by Ajinomoto Fine Chemicals Co., Ltd., Amicure PN-31 (melting point: 115 ° C) manufactured by Ajinomoto Fine Chemicals Co., Ltd., Amicure PN-H (melting point 115 ° C) manufactured by Ajinomoto Fine Chemicals Co., Ltd. Amicure MY-24 (melting point 120 ° C) manufactured by Ajinomoto Fine Chemicals Co., Ltd., and Amicure MY-H (melting point 131 ° C) manufactured by Ajinomoto Fine Chemicals Co., Ltd. Wait. The polyamine thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine with an epoxy, and examples thereof include: Adico hardening manufactured by ADEKA Co., Ltd. Adeka Hardener EH4339S (softening point: 120 ° C to 130 ° C), and Adeka Hardener EH4357S (softening point: 73 ° C to 83 ° C) manufactured by ADEKA Co., Ltd. The epoxy hardener may be used alone or in combination of two or more.

The content of the thermosetting agent E is preferably from 3.8 to 75% by mass, more preferably from 3.8 to 50% by mass, even more preferably from 10 to 40% by mass, based on the curable compound A. When the content of the thermosetting agent E is 3.8% by mass or more with respect to the curable compound A, the thermosetting property of the curable compound A is likely to be improved, and when it is 50% by mass or less, contamination of the liquid crystal is easily suppressed.

The content of the thermosetting agent E is preferably from 3% by mass to 30% by mass, more preferably from 3% by mass to 20% by mass, even more preferably from 5% by mass to 20% by mass, based on the photocurable resin composition. The photocurable resin composition containing the thermosetting agent E can be a one-liquid curable resin composition. Since the one-liquid curable resin composition does not need to be mixed with a hardener at the time of use, it is excellent in workability.

The total content of the thermosetting compound D and the thermosetting agent E is preferably from 6% by mass to 50% by mass, more preferably from 6% by mass to 35% by mass, even more preferably 6% by mass, based on the photocurable resin composition. ～30% by mass.

1-6. Other components F 1-6-1. Thermoplastic resin particles The photocurable resin composition of the present invention may further contain thermoplastic resin particles as needed. The thermoplastic resin particles include a thermoplastic resin having a softening point temperature of from 50 ° C to 120 ° C, preferably from 70 ° C to 100 ° C, measured by a ring and ball method, and may have a number average particle diameter of from 0.05 μm to 5 μm, preferably 0.1 μm. ~3 μm. The photocurable resin composition containing such thermoplastic resin particles can alleviate the shrinkage stress generated in the cured product. In addition, when the number average particle diameter is equal to or less than the upper limit, it is possible to prevent the coating stability from being lowered by the thermoplastic resin particles when forming a sealing member having a small line width. The number average particle size can be determined using a dry particle size distribution meter.

Examples of the thermoplastic resin particles include fine particles obtained by suspension polymerization of a resin containing an epoxy group and a double bond group and a monomer capable of undergoing radical polymerization. Examples of the resin containing an epoxy group and a double bond group include a resin obtained by reacting a bisphenol F type epoxy resin and methacrylic acid in the presence of a tertiary amine. Examples of the monomer which can be subjected to radical polymerization include butyl acrylate, glycidyl methacrylate, and divinylbenzene.

1-6-2. Filler The photocurable resin composition of the present invention may further contain a filler as needed. The viscosity of the photocurable resin composition containing the filler, the strength of the cured product, and the linear expansion property and the like may be good.

Examples of the filler include: calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum niobate, zirconium silicate, iron oxide, titanium oxide, titanium nitride, aluminum oxide (alumina), zinc oxide, Inorganic fillers such as cerium oxide, potassium titanate, kaolin, talc, glass beads, sericite, activated clay, bentonite, aluminum nitride, and tantalum nitride. Among them, cerium oxide and talc are preferred.

The shape of the filler may be a fixed shape such as a spherical shape, a plate shape, or a needle shape, or may be an indefinite shape. In the case where the filler is spherical, the average primary particle diameter of the filler is preferably 1.5 μm or less, and the specific surface area is preferably from 0.5 m ² /g to 20 m ² /g. The average primary particle diameter of the filler can be measured by a laser diffraction method described in JIS Z8825-1. The specific surface area of the filler can be measured by the Brunauer-Emmett-Teller method (BET method) described in JIS Z8830.

The photocurable resin composition of the present invention may further include a thermal radical polymerization initiator, a coupling agent such as a decane coupling agent, an ion trapping agent, an ion exchanger, a leveling agent, a pigment, a dye, and a plasticizer. And additives such as defoamers.

Examples of the decane coupling agent include: vinyl trimethoxy decane, γ-(meth) propylene methoxy propyl trimethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidyloxy Propyltriethoxydecane, and the like. The content of the decane coupling agent may be from 0.01% by mass to 5% by mass based on the photocurable resin composition. When the content of the decane coupling agent is 0.01% by mass or more, the cured product of the photocurable resin composition tends to have sufficient adhesiveness.

The photocurable resin composition of the present invention may further include a spacer or the like for adjusting a gap of the liquid crystal display panel.

The total content of the other components F is preferably from 1% by mass to 50% by mass based on the photocurable resin composition. When the total content of the other components F is 50% by mass or less, the viscosity of the photocurable resin composition is unlikely to increase excessively, and coating stability is hard to be impaired.

1-7. Physical Properties of Photocurable Resin Composition The E-type viscometer of the photocurable resin composition of the present invention preferably has a viscosity at 25 ° C and 2.5 rpm of from 200 Pa·s to 450 Pa·s, more preferably It is 300 Pa·s to 400 Pa·s. When the viscosity is within the above range, the coatability of the photocurable resin composition by the dispenser becomes good.

The photocurable resin composition of the present invention can be used, for example, as a sealant. The sealing agent is preferably a display element sealing agent used for sealing a display element such as a liquid crystal display element, an organic EL element, or a light emitting diode (LED) element. The display element sealing agent is preferably a liquid crystal sealing agent, and more preferably a liquid crystal sealing agent for a liquid crystal dropping process.

2. Display Element Panel and Method of Manufacturing the Same The display element panel of the present invention includes a pair of substrates, a display element disposed between the pair of substrates, and a sealing member that seals the display elements. The sealing member can be made into a cured product of the display element sealing agent of the present invention. The display element sealing agent of the present invention contains the photocurable resin composition of the present invention.

Examples of the display element include a liquid crystal display element, an organic EL element, an LED element, and the like. Among them, the liquid curable resin composition of the present invention is preferably a liquid crystal display element because it can satisfactorily suppress liquid crystal contamination.

In other words, the liquid crystal display panel of the present invention includes a pair of substrates, a frame-shaped sealing member disposed between the pair of substrates, and a space surrounded by the frame-shaped sealing member filled between the pair of substrates. Liquid crystal layer (liquid crystal display element). The sealing member can be made into a cured product of the liquid crystal sealing agent of the present invention. The liquid crystal sealing agent of the present invention contains the photocurable resin composition of the present invention.

Both of the substrates are transparent substrates. The material of the transparent substrate may be glass or polycarbonate, polyethylene terephthalate, polyether oxime or polymethyl methacrylate (PMMA).

A matrix-shaped thin film transistor (TFT), a color filter, a black matrix, or the like may be disposed on a surface of one of the pair of substrates. An alignment film may be further disposed on the surface of the substrate. The alignment film contains a known organic alignment agent or inorganic alignment agent.

The display mode of the liquid crystal display panel is not particularly limited, and may be Twisted Nematic (TN), Vertical Alignment (VA), In Plane Switching (IPS), and polymer stable alignment. Any of the modes (Polymer-Sustained Alignment, PSA).

The aperture ratio (opening ratio defined by the following formula) of the wiring portion in the region in which the sealing member is disposed is not particularly limited, and may be, for example, 50% or less. The aperture ratio (%) of the wiring portion = the area of the opening portion of the wiring portion in the region where the sealing member is disposed, the area of the wiring portion in the region where the sealing member is disposed, and the area of the wiring portion × 100 (%). The outer peripheral portion of the panel has a region in which wiring is formed, and the area of the wiring portion refers to the sum of the area of the opening and the area of the light shielding portion.

The light shielding portion is an area in which a black matrix or wiring is disposed. The width of the light shielding portion may be, for example, 40 μm to 200 μm.

The liquid crystal display panel is manufactured using the liquid crystal sealing agent of the present invention. The manufacturing method of the liquid crystal display panel generally has a liquid crystal dropping process and a liquid crystal injection process, but the liquid crystal display panel of the present invention is preferably manufactured by a liquid crystal dropping process.

The manufacturing method of the liquid crystal display panel by the liquid crystal dropping process comprises: 1) a step of forming a sealing pattern of the liquid crystal sealing agent of the present invention on one of the substrates; 2) a state in which the sealing pattern is uncured, on the substrate a step of dropping liquid crystal in a region surrounded by the seal pattern or another substrate facing the region surrounded by the seal pattern; 3) a step of overlapping one of the substrates with the other substrate via a seal pattern; And 4) a step of hardening the seal pattern.

In the step of 2), the state in which the sealing pattern is not cured means that the curing reaction of the liquid crystal sealing agent does not proceed to the gelation point. Therefore, in the step of 2), in order to suppress the dissolution of the liquid crystal sealing agent in the liquid crystal, the sealing pattern may be light-irradiated or heated to be semi-hardened.

In the step of 4), only hardening by light irradiation may be performed, but after hardening by light irradiation, hardening by heating may be performed. That is, the step of 4) includes the step of irradiating the seal pattern with light to harden the seal pattern; and in the case where the liquid crystal sealant further comprises the heat hardener (E), it may further include performing the light-irradiated seal pattern. The step of heating to harden it. By curing by light irradiation, the liquid crystal sealing agent can be hardened in a short time, so that dissolution in the liquid crystal can be suppressed. By combining hardening by light irradiation and hardening by heating, damage to the liquid crystal layer by light can be reduced as compared with the case of hardening by only light irradiation.

The light to be irradiated is not particularly limited, and is preferably light having a wavelength of from 370 nm to 450 nm. The reason for this is that the light of the wavelength causes less damage to the liquid crystal or the driving electrode. A known light source that emits ultraviolet light or visible light can be used for the irradiation of light. In the case of illuminating visible light, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, or the like can be used.

The light irradiation energy may be any energy that can harden the curable compound A. The photohardening time depends on the composition of the liquid crystal sealing agent, but is, for example, about 10 minutes.

The heat hardening temperature depends on the composition of the liquid crystal sealing agent, but is, for example, 120 ° C, and the heat hardening time is about 2 hours.

Since the liquid crystal sealing agent of the present invention contains the photopolymerization initiator B and the ammonium salt C of the quaternary organoboron anion, it exhibits high hardenability even when the amount of light is small. Therefore, when the liquid crystal display panel is manufactured, the liquid crystal sealing agent of the present invention can be sufficiently cured even in the light shielding portion such as the wiring of the substrate or the underside of the black matrix. Further, since the liquid crystal sealing agent of the present invention exhibits high curability, the unhardened component does not easily remain, and the elution of the photopolymerization initiator B or the ammonium salt C of the quaternary organoboron anion into the liquid crystal can be reduced.

In particular, liquid crystal materials used in liquid crystal display panels that can cope with high response speed, high contrast, high viewing angle, and high image quality, such as VA, PSA, and IPS, are susceptible to external factors, and are sealed by liquid crystals. The composition of the UV or liquid crystal sealing agent at the time of hardening of the agent and the deterioration of the performance of the liquid crystal material. In addition, the high density of the liquid crystal display panel, that is, the increase in the number of pixels, increases the density of the wiring. As a result, the aperture ratio of the wiring portion in which the liquid crystal sealing agent is disposed is lowered (the light shielding portion is increased).

On the other hand, since the liquid crystal sealing agent of the present invention has high photocurability, even if it is a portion that is shielded by a black matrix or the like (a portion where light does not directly reach, a light-shielding portion), it is hardened by photohardening. . For example, when light having a wavelength of 400 nm or more is irradiated for 20 seconds at an irradiation intensity of 100 mW/cm ² , it is preferable to be hardened from the end portion to 45 μm or more. As described above, the light-shielding portion is also photocured, whereby deterioration of the liquid crystal due to the uncured component of the liquid crystal sealing agent can be suppressed. Therefore, the liquid crystal sealing agent of the present invention is suitable for sealing the liquid crystal layer of the liquid crystal display panel in which the opening ratio of the wiring portion of the liquid crystal sealing agent is 50% or less. Example

Hereinafter, the present invention will be described in more detail with reference to examples. The scope of the invention is not to be construed as limited by the embodiments.

1. Material (curable compound A) A-1: methacrylic acid-modified bisphenol F-type epoxy resin (95% partial methacrylate) obtained in Synthesis Example 1 (Synthesis Example 1) 160 g Liquid bisphenol F type epoxy resin (YDF-8170C, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent: 160 g/eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, as a catalyst 0.2 g of triethanolamine and 81.7 g of methacrylic acid were added to the flask, and the mixture was sent to dry air and reacted at 90 ° C for 5 hours while stirring under reflux. The obtained compound was washed 20 times with ultrapure water to obtain a methacrylic acid modified bisphenol F type epoxy resin (curable compound A-1). GPC analysis of the resin revealed a weight average molecular weight of 792.

A-2: Acrylic modified bisphenol F type epoxy resin (50% partial acrylate) obtained in Synthesis Example 2 (Synthesis Example 2) First, 500 ml equipped with a stirrer, a gas introduction tube, a thermometer, and a condenser In a four-necked flask, 175 g of bisphenol F-type epoxy resin (YDF-8170C, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent of 160 g/eq), 37 g of acrylic acid, and 0.2 g of contact were mixed. The triethanolamine of the medium and 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor were heated and stirred at 110 ° C for 12 hours while blowing dry air. The obtained reaction product was repeatedly subjected to a washing treatment 12 times with ultrapure water to obtain an acrylic modified bisphenol F type epoxy resin (curable compound A-2). The resin was analyzed by HPLC or NMR, and as a result, a bisphenol F-type epoxy resin modified with acrylonitrile acid was 50% of an epoxy group. Further, GPC analysis of the resin revealed a weight average molecular weight of 692.

Polyethylene glycol diacrylate: Light Acrylate 14EG-A, manufactured by Kyoeisha Chemical Co., Ltd. (refer to the following formula, molecular weight 600) [Chem. 3]

(Photopolymerization initiator B) Omnipol-TX, manufactured by IGM resin (IGM Resins) (refer to the following formula, thioxanthone-based compound) [Chemical 4] IRUGACURE OXE01, manufactured by BASF (refer to the following formula, oxime ester compound) [Chemical 5] 2-(Hydroxymethyl)anthracene, manufactured by Pure Chemical Co., Ltd. (refer to the following formula, lanthanide compound) [Chem. 6]

(Ammonium salt C of quaternary organoboron anion) P3B, manufactured by Showa Denko Co., Ltd. (refer to the following formula, melting point: 140 ° C to 144 ° C) [Chem. 7] N3B, manufactured by Showa Denko Co., Ltd. (refer to the following formula, melting point is 140 ° C ~ 141 ° C) [Chem. 8]

(thermosetting compound D) Epoxy resin: manufactured by Mitsubishi Chemical Corporation, jER resin 1004, softening point 97 ° C

(Heat hardener E) Dioxane adipate: manufactured by Nippon Kasei Co., Ltd., ADH, melting point 177 ° C ~ 184 ° C

(Other components F) Ceria particles: manufactured by Nippon Shokubai Chemical Co., Ltd., S-100 Thermoplastic resin particles: manufactured by Aica Industries, F351, softening point 120 ° C, average particle diameter 0.3 μm γ - Glycidoxypropyltrimethoxydecane: manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403

2. Preparation and evaluation of photocurable resin composition

(Example 1) 420 parts by mass of the curable compound A-1 obtained in Synthesis Example 1 and 200 parts by mass of polyethylene glycol II as a curable compound A were used in a three-roll mill. Acrylate (Light Acrylate 14EG-A, manufactured by Kyoeisha Chemical Co., Ltd.), 10 parts by mass of Omnipol-TX (IGM Resins) as photopolymerization initiator B 10 parts by mass of P3B (manufactured by Showa Denko Co., Ltd.), and 50 parts by mass of epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER resin 1004) of the ammonium salt C of the fourth-order organic boron anion, 90 parts by mass of diammonium adipate (ADH manufactured by Nippon Kasei Co., Ltd.) and 130 parts by mass of cerium oxide particles (manufactured by Nippon Shokubai Chemical Co., Ltd., S-100) as a filler 70 parts by mass of F351 (manufactured by Aica Industries Co., Ltd.) as a thermoplastic resin particle, and 20 parts by mass of γ-glycidoxypropyltrimethoxydecane as a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM) -403 Mixed thoroughly to obtain a photocurable resin composition.

(Examples 2 to 9 and Comparative Examples 1 to 3) A photocurable resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 1 or Table 2 was changed.

The curability of the obtained photocurable resin composition was evaluated by the following method.

<Photocurability Evaluation 1> The photopolymerizable composition was irradiated at 1 mW/cm ² for 30 seconds using a ViscoanalySER VAR100 (manufactured by REOLOGICA INSTRUMENT) at a wavelength of 360 nm. The viscosity rise behavior at 25 ° C at ~430 nm light. In this case, the curing time until the viscosity of the photopolymerizable composition after the light irradiation is 50% of the value of the saturated viscosity value is measured. The saturated viscosity value refers to the viscosity when the photopolymerizable composition is completely cured. The shorter the hardening time, the more excellent the hardenability can be judged.

<Photocurability Evaluation 2> A substrate 1 having five black matrixes having a width of 200 μm formed on the glass substrate at intervals of 100 μm in width and a substrate 2 having a black matrix formed on the entire surface of the glass substrate were prepared. The photopolymerizable resin is applied to the substrate 1 so that the coating region after bonding the substrate 1 and the substrate 2 has a rectangular shape orthogonal to the longitudinal direction of the black matrix and the thickness after curing is 5 μm. Composition. The coated region has a length (long side) orthogonal to the longitudinal direction of the black matrix and has a length of 1500 μm, and a length parallel to the longitudinal direction of the black matrix (short side) is a rectangle having a length of 600 μm to 800 μm. shape. On the other hand, a release agent is applied onto the substrate 2. After the substrates were bonded to each other so as to overlap each of the coated surfaces, light having a wavelength of 400 nm to 480 nm was irradiated from the substrate 1 side at 100 mW/cm ^{2 for} 20 seconds to obtain a laminated panel. In the laminated panel, the aperture ratio of the region in which the liquid crystal sealing agent was disposed was 33.3%. Then, the substrate 1 is peeled off from the laminated panel. Each of the 200 μm-width black matrix portions of the obtained substrate 1 was observed with an optical microscope, and the uncured width and the cured width of the photopolymerizable resin composition were measured, and the average values of the five were determined. Whether or not hardening is judged based on observation by an optical microscope. The smaller the unhardened width, the larger the hardening width, and the more excellent the hardenability. Further, the uncured portions of the photopolymerizable resin composition of each of the black matrix portions are located at the central portion in the width direction of the black matrix, and the cured portions are located at both end portions in the width direction of the black matrix. The hardening width in the table indicates the respective widths of the two hardened portions located at both end portions in the width direction of the black matrix.

The evaluation results of Examples 1 to 9 are shown in Table 1, and the evaluation results of Comparative Examples 1 to 3 are shown in Table 2. [Table 1] [Table 2]

Table 1 and Table 2 show that the photocurable resin composition of Examples 1 to 9 containing the ammonium salt C of the quaternary organoboron anion is comparatively comparative with the ammonium salt C which does not contain the quaternary organoboron anion. In the photocurable resin composition of the first to the second examples, the curing time in the photocurability evaluation 1 was short, and the uncured width in the photocurability evaluation 2 was small, and both of them had high hardenability.

Further, according to the comparison between Example 1, Example 2, and Example 6 to Example 9, it is understood that the thioxanthone compound or the quinone compound as the photopolymerization initiator B and the ammonium of the quaternary organoboron anion are used. The photocurable resin composition of Example 1, Example 2, Example 8 and Example 9 in which the salt C is combined is compared with the oxime ester compound which is the photopolymerization initiator B and the quaternary organic boron anion. In the photocurable resin composition of Example 6 and Example 7 in which the ammonium salt C was combined, the photocurability evaluation 2 had a small unhardened width and a higher hardenability.

The present application claims priority based on Japanese Patent Application No. 2016-30785, filed on Feb. 22, 2016. The contents described in the specification of the application are all incorporated in the specification of the present application. [Industrial availability]

The present invention can provide a photocurable resin composition which is excellent in curability and can be sufficiently cured even when the amount of light is small, for example, as a display element sealing agent.

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Claims (11)

A display element sealing agent comprising: a curable compound A having an ethylenically unsaturated double bond in a molecule; a photopolymerization initiator B; and an ammonium salt of a quaternary organoboron anion represented by the following formula (1) C; (In the formula (1), R ₁ to R ₄ are a substitutable alkyl group, a substituted alkenyl group, a substituted alkynyl group, a substitutable cycloalkyl group, a substitutable aralkyl group, The aryl group or the substituted heteroaryl group which may be substituted may be the same or different, and at least one of R ₁ to R ₄ may be a substituted aryl group or a substituted heteroaryl group, and Z ⁺ is Ammonium cation). The display element sealing agent according to claim 1, wherein the photopolymerization initiator B is one or more selected from the group consisting of a thioxanthone compound and an anthraquinone compound. The display element encapsulant according to claim 1, wherein the photopolymerization initiator B and the ammonium salt C of the quaternary organoboron anion have a mass ratio of photopolymerization initiator B: four grades. The ammonium salt of the organoboron anion C = 1:0.1 to 1:3. The display element sealing agent according to claim 1, wherein the content of the ammonium salt C of the quaternary organoboron anion is 0.01% by mass to 3% by mass based on the curable compound A. A liquid crystal sealing agent comprising the display element sealing agent according to any one of claims 1 to 4. A cured product which is a cured product of a liquid crystal sealing agent as described in claim 5 of the patent application. The liquid crystal sealing agent according to claim 5, wherein the liquid crystal layer of the liquid crystal display panel in which the opening ratio of the wiring portion of the liquid crystal sealing agent is 50% or less is sealed. A method of manufacturing a liquid crystal display panel, comprising: using a liquid crystal sealing agent according to claim 5, a step of forming a sealing pattern on one of the substrates; and in a state where the sealing pattern is not hardened, a step of dropping liquid crystal on a region of the seal pattern or another substrate paired with the one of the substrates; and stacking the one of the substrates and the other substrate by the seal pattern; And a step of hardening the seal pattern. The method of manufacturing a liquid crystal display panel according to claim 8, wherein the step of hardening the seal pattern includes a step of irradiating the seal pattern with light to harden the seal pattern. A liquid crystal display panel comprising: a pair of substrates; a frame-shaped sealing member disposed between the pair of substrates; and a liquid crystal layer in a space surrounded by the sealing member filled between the pair of substrates And the sealing member is a cured product of the liquid crystal sealing agent as described in claim 5 of the patent application. The liquid crystal display panel according to claim 10, wherein an opening ratio of the wiring portion in which the sealing member is disposed is 50% or less.