JP2018135499A - Liquid crystal sealant and cured product thereof, and liquid crystal display panel, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition which has high curability so that it can be cured with a small amount of light, and is suitable for use as, for example, a liquid crystal sealant.SOLUTION: A liquid crystal sealant is provided at a wiring part of a liquid crystal display panel, with the wiring part having an aperture ratio of 50% or less, and seals a liquid crystal layer. The liquid crystal sealant contains a curable compound A having an ethylenic unsaturated double bond in the molecule, a photopolymerization initiator B, and an ammonium salt C of a quaternary organic boron anion represented by the formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal sealant and a cured product thereof, a liquid crystal display panel, and a method for manufacturing the same.

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

  The liquid crystal display panel can be manufactured, for example, by a liquid crystal dropping method. Production of a liquid crystal display panel by a liquid crystal dropping method is as follows: (1) A liquid crystal sealing agent is applied to the inner edge of a transparent substrate to form a frame for filling with liquid crystal; (2) Liquid crystal is dropped into the frame; (3) After superposing two substrates under high vacuum while the liquid crystal sealant is in an uncured state, (4) curing the liquid crystal sealant.

  Thus, in the liquid crystal dropping method, photocuring or thermosetting is performed in a state where the uncured liquid crystal sealing agent and the liquid crystal are in contact with each other. Accordingly, the liquid crystal sealant is required to have high curability in order to reduce elution into the liquid crystal. In particular, since the light does not easily reach under the substrate (light shielding portion) on which the wiring and the black matrix are formed, the liquid crystal sealant is likely to be insufficiently cured. Therefore, the liquid crystal sealant is required to have high curability that can be sufficiently cured even with a small amount of light.

  As a liquid crystal sealant used in the liquid crystal dropping method, a sealant for a liquid crystal display element including a specific thioxanthone polymerization initiator and an amine sensitizer has been proposed (for example, Patent Document 1).

  The photocurable composition has an organic boron compound (A) in which one or more naphthyl groups are bonded to a boron atom, a sensitizer (B), a triazine compound (C), and an ethylenically unsaturated bond. A photocurable composition containing an organic compound (D) (for example, Patent Document 2), a sensitizer (A), an organic boron salt (B), and a compound (C) having an ethylenically unsaturated bond. The photocurable composition containing (for example, patent document 3) is known.

International Publication No. 2015/072415 JP 2001-106712 A JP 2000-284478 A

  However, the sealing agent for liquid crystal display elements of Patent Document 1 and the photocurable compositions of Patent Documents 2 and 3 do not have sufficient curability. Therefore, when these photocurable compositions are used as, for example, a liquid crystal sealant for a liquid crystal dropping method, not only is the liquid crystal sealant hard to be cured at the light shielding portion of the substrate, but also the elution into the liquid crystal may not be suppressed. There is.

  In particular, liquid crystal display panels are becoming higher definition such as 4K and 8K. As described above, the density of wiring is increasing due to the increase in the number of pixels, and accordingly, the aperture ratio of the wiring portion (the area where 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 liquid crystal sealing agent provided in the light shielding portion is cured even in a liquid crystal display panel having such a wiring portion having a low aperture ratio and a large number of light shielding portions. Is required.

  The present invention has been made in view of the above problems, and an object thereof is to provide a photocurable resin composition having high curability that can be sufficiently cured even with a small amount of light, for example, suitable as a liquid crystal sealant. .

（式（１）中、
Ｒ_１〜Ｒ_４は、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいアルキニル基、置換されていてもよいシクロアルキル基、置換されていてもよいアラルキル基、置換されていてもよいアリール基又は置換されていてもよいヘテロアリール基であり、それぞれ同一であっても異なってもよく、且つ
Ｒ_１〜Ｒ_４の少なくとも一つは、置換されていてもよいアリール基又は置換されていてもよいヘテロアリール基であり、
Ｚ^＋は、アンモニウムカチオンである）
［２］ 前記光重合開始剤Ｂは、チオキサントン系化合物及びアントラキノン系化合物からなる群より選ばれる１以上である、［１］に記載の液晶シール剤。
［３］ 前記光重合開始剤Ｂと前記４級有機ホウ素アニオンのアンモニウム塩Ｃの含有質量比が、光重合開始剤Ｂ：４級有機ホウ素アニオンのアンモニウム塩Ｃ＝１：０．１〜１：３である、［１］又は［２］に記載の液晶シール剤。
［４］ 前記４級有機ホウ素アニオンのアンモニウム塩Ｃの含有量は、前記硬化性化合物Ａに対して０．０１〜３質量％である、［１］〜［３］のいずれかに記載の液晶シール剤。
［５］ ［１］〜［４］のいずれかに記載の液晶シール剤の硬化物。
［６］ ［１］〜［４］のいずれかに記載の液晶シール剤を用いて、一方の基板にシールパターンを形成する工程と、前記シールパターンが未硬化の状態において、前記シールパターンの領域内、又は前記一方の基板と対になる他方の基板に液晶を滴下する工程と、前記一方の基板と前記他方の基板とを、前記シールパターンを介して重ね合わせる工程と、前記シールパターンを硬化させる工程と、を含む、液晶表示パネルの製造方法。
［７］ 前記シールパターンを硬化させる工程は、前記シールパターンに光を照射して前記シールパターンを硬化させる工程を含む、［６］に記載の液晶表示パネルの製造方法。
［８］ 一対の基板と、前記一対の基板の間に配置された枠状のシール部材と、前記一対の基板の間の前記シール部材で囲まれた空間に充填された液晶層とを含み、前記シール部材が、［１］〜［４］のいずれかに記載の液晶シール剤の硬化物である、液晶表示パネル。
［９］ 前記シール部材が配置された配線部の開口率が５０％以下である、［８］に記載の液晶表示パネル。 [1] A liquid crystal sealant that is disposed in the wiring portion of the liquid crystal display panel having a wiring portion with an aperture ratio of 50% or less and seals the liquid crystal layer, and has an ethylenically unsaturated double bond in the molecule. A liquid crystal sealant comprising a curable compound A having, a photopolymerization initiator B, and an ammonium salt C of a quaternary organic boron anion represented by the following formula (1).

(In the formula (1),
R _{1 to} R ₄ are an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkyl group, and optionally substituted. An aralkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group, which may be the same or different, and at least one of R _{1 to} R ₄ is substituted. An aryl group which may be substituted or a heteroaryl group which may be substituted,
Z ⁺ is an ammonium cation)
[2] The liquid crystal sealant according to [1], wherein the photopolymerization initiator B is one or more selected from the group consisting of a thioxanthone compound and an anthraquinone compound.
[3] The mass ratio of the photopolymerization initiator B and the ammonium salt C of the quaternary organic boron anion is such that the photopolymerization initiator B: the ammonium salt C of the quaternary organic boron anion C = 1: 0.1 to 1: 3. The liquid crystal sealant according to [1] or [2], which is 3.
[4] The liquid crystal according to any one of [1] to [3], wherein the content of the ammonium salt C of the quaternary organic boron anion is 0.01 to 3% by mass with respect to the curable compound A. Sealing agent.
[5] A cured product of the liquid crystal sealant according to any one of [1] to [4].
[6] A step of forming a seal pattern on one substrate using the liquid crystal sealant according to any one of [1] to [4], and a region of the seal pattern in an uncured state of the seal pattern A step of dropping the liquid crystal on the other substrate which is paired with the one substrate, a step of superposing the one substrate and the other substrate through the seal pattern, and curing the seal pattern And a liquid crystal display panel manufacturing method.
[7] The method of manufacturing a liquid crystal display panel according to [6], wherein the step of curing the seal pattern includes a step of curing the seal pattern by irradiating the seal pattern with light.
[8] including a pair of substrates, a frame-shaped sealing member disposed between the pair of substrates, and a liquid crystal layer filled in a space surrounded by the sealing member between the pair of substrates, A liquid crystal display panel, wherein the seal member is a cured product of the liquid crystal sealant according to any one of [1] to [4].
[9] The liquid crystal display panel according to [8], wherein the opening ratio of the wiring portion in which the seal member is disposed is 50% or less.

  According to the present invention, it is possible to provide a photocurable resin composition having high curability that can be sufficiently cured even with a small amount of light, for example, suitable as a liquid crystal sealant.

1. Photocurable resin composition The photocurable resin composition of the present invention comprises a curable compound A, a photopolymerization initiator B, and an ammonium salt C of a quaternary organoboron anion, and if necessary, thermosetting. Compound D, thermosetting agent E, and other component F may further be included.

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) acryloyl groups per molecule is 1 or 2 or more. The compound having a (meth) acryloyl group in the molecule may be a monomer, an oligomer or a polymer. (Meth) acryloyl group means acryloyl group or methacryloyl group, and (meth) acrylate means acrylate or methacrylate.

  Examples of compounds having one (meth) acryloyl group in one molecule include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid 2-hydroxyethyl ester. Alkyl esters are included.

  Examples of compounds having two or more (meth) acryloyl groups in one molecule include di (meth) acrylates such as polyethylene glycol, propylene glycol, and polypropylene glycol; di (meth) tris (2-hydroxyethyl) isocyanurate Acrylate; Di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol; Diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A Di (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane; diol or tri (meth) acrylate of triol; Di (meth) acrylate of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate; trimethylolpropane tri (meth) acrylate, or Pentaerythritol tri (meth) acrylate or oligomer thereof; poly (meth) acrylate of dipentaerythritol; tris (acryloxyethyl) isocyanurate; caprolactone-modified tris (acryloxyethyl) isocyanurate; caprolactone-modified tris (methacryloxyethyl) ) Isocyanurate; polyacrylate or polymethacrylate of alkyl-modified dipentaerythritol; polyacrylate of caprolactone-modified dipentaerythritol Hydroxypivalate neopentyl glycol diacrylate or dimethacrylate; caprolactone-modified hydroxypivalate neopentyl glycol di (meth) acrylate; ethylene oxide-modified phosphate acrylate or dimethacrylate; ethylene oxide-modified alkylated phosphate (meta ) Acrylate; neopentyl glycol, trimethylolpropane, pentaerythritol oligo (meth) acrylate and the like.

  The curable compound A may further have an epoxy group in the molecule. The number of epoxy groups per molecule is 1 or 2 or more. If the curable compound A further has not only a (meth) acryloyl group but also an epoxy group in the molecule, the photocurable resin composition containing the curable compound A can be provided with photocurability and thermosetting. Thereby, the sclerosis | hardenability of hardened | cured material can be improved.

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

  The epoxy compound to be reacted may be a polyfunctional epoxy compound having two or more epoxy groups in the molecule, and suppresses the decrease in the adhesiveness of the cured product of the photocurable resin composition due to excessive increase in the crosslinking density. In view of this, a bifunctional epoxy compound is preferable. Examples of bifunctional epoxy compounds include bisphenol type epoxy compounds (bisphenol A type, bisphenol F type, 2,2′-diallyl bisphenol A type, bisphenol AD type, hydrogenated bisphenol type, etc.), biphenyl type epoxy compounds, And naphthalene type epoxy compounds. Of these, bisphenol A type and bisphenol F type bisphenol type epoxy compounds are preferred from the viewpoint of good coating properties. The bisphenol type epoxy compound has advantages such as excellent coating properties as compared with the biphenyl ether type epoxy compound.

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

  You may combine the compound A1 which has a (meth) acryloyl group in a molecule | numerator, and does not have an epoxy group, and the compound A2 which has a (meth) acryloyl group and an epoxy group in a molecule | numerator. Thereby, when the photocurable resin composition further contains an epoxy compound as the thermosetting compound D, the epoxy compound, and the compound A1 having a (meth) acryloyl group in the molecule and not having an epoxy group, Can improve the compatibility. The content mass ratio between the compound A2 and the compound A1 can be, for example, A2 / A1 = 1 / 0.4 to 1 / 0.6.

  Although content in particular of compound A2 which has a (meth) acryloyl group and an epoxy group in a molecule is not restrict | limited, For example, it may be 30 mass% or more with respect to the sum total of the curable compound A.

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

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

1-2. Photoinitiator B
The photopolymerization initiator B contained in the photocurable resin composition of the present invention is not particularly limited, but may be a self-cleavage type photopolymerization initiator or a hydrogen abstraction type photopolymerization initiator. Also good.

  Examples of self-cleaving photopolymerization initiators include alkylphenone compounds (eg, benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651 manufactured by BASF), 2- Α-aminoalkylphenone such as methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (IRGACURE 907 manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184 manufactured by BASF) α-hydroxyalkylphenone, etc.), acylphosphine oxide compounds (eg 2,4,6-trimethylbenzoindiphenylphosphine oxide, etc.), titanocene compounds (eg bis (η5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenol E) titanium, etc.), acetophenone compounds (for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) ) Propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, etc.), phenylglyoxylate compounds (eg methylphenylglyoxyester), 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-benzoyloxime)] (IRGACURE OXE01 manufactured by BASF), ethanone-1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) (such as IRGACURE OXE02 manufactured by BASF).

  Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone compounds (for example, benzophenone, methyl-4-phenylbenzophenone, o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-). Methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, etc.), thioxanthone compounds (for example, thioxanthone, 2-chlorothioxanthone (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-chloro-4-propoxythioxanthone, 1-chloro-4-ethoxythioxanthone (Lambson Limited Speedcure CPTX), 2-isopropylxanthone (Lambson Limited S eedcure ITX), 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone (Speedcure DETX manufactured by Lambson Limited), 2,4-dichlorothioxanthone, anthraquinone compounds (for example, 2-methylanthraquinone, 2-ethyl Anthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2-hydroxyanthraquinone (2-Hydroxyanthraquinone, manufactured by Tokyo Chemical Industry Co., Ltd.), 2,6-dihydroxyanthraquinone (Anthraflavic Acid, manufactured by Tokyo Chemical Industry Co., Ltd.), 2-hydroxymethyl Anthraquinone (2- (Hydroxymethyl) anthraquinone manufactured by Junsei Kagaku) etc.) and benzylic compounds are included.

  Although the absorption wavelength of the photopolymerization initiator B is not particularly limited, it is easy to obtain high curability by combining with the ammonium salt C of a quaternary organoboron anion, so that the photopolymerization initiator absorbs light having a wavelength of 360 nm or more. B is preferred. Among these, photopolymerization initiator B that absorbs light having a wavelength of 360 to 780 nm is more preferable, and photopolymerization initiator B that absorbs light having a wavelength of 360 to 430 nm is more preferable.

  Examples of the photopolymerization initiator B that absorbs light having a wavelength of 360 nm or more include alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, thioxanthone compounds, and anthraquinone compounds. Are thioxanthone compounds and anthraquinone compounds.

  The molecular weight of the photopolymerization initiator B is preferably, for example, 200 or more and 5000 or less. If the molecular weight is 200 or more, elution into the liquid crystal may be difficult to occur. When the molecular weight is 5000 or less, the compatibility with the curable compound A can be improved, so that sufficient curability is easily obtained. The molecular weight of the photopolymerization initiator B is more preferably 230 or more and 3000 or less, and further preferably 230 or more and 1500 or less.

  The molecular weight of the photopolymerization initiator B can be obtained as the “relative molecular mass” of the molecular structure of the main peak detected when high performance liquid chromatography (HPLC) is performed under the following conditions.

Specifically, a photopolymerization initiator B is dissolved in THF (tetrahydrofuran) to prepare a sample solution, and high performance liquid chromatography (HPLC) measurement is performed under the following measurement conditions. Then, the area percentage of the detected peak (ratio of the area of each peak to the sum of the areas of all peaks) is obtained, and the presence or absence of the main peak is confirmed. The main peak refers to a peak having the highest intensity (peak having the highest peak height) among all peaks detected at a detection wavelength characteristic of each compound (for example, 400 nm for a thioxanthone compound).
(HPLC measurement conditions)
Equipment: Acquity TM UPLC H-Class system made 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 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4mL / min
PDA detector: Measurement wavelength: 190-500nm

The relative molecular mass corresponding to the peak apex of the detected main peak can be measured by liquid chromatography mass spectrometry (LC / MS).
(LC / MS measurement conditions)
Equipment: Acquity TM H-Class system / SQ Detector made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile
B: 5 mM ammonium acetate aqueous solution
A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4 mL / min Ionization: ESI (electrospray ionization), positive / negative ion measurement
PDA detector: Measurement wavelength: 190-500nm

  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 0.01 to 10% by mass with respect to 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, since the elution into the liquid crystal is small, it is easy to reduce the contamination of the liquid crystal. The content of the photopolymerization initiator B is more preferably 0.1 to 5% by mass with respect to the curable compound A, further preferably 0.1 to 3% by mass, and 0.1 to 2%. It is particularly preferable that the content be 5% by mass.

The structure of the photopolymerization initiator B contained in the photocurable resin composition is specified by combining high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC / MS) with NMR measurement or IR measurement. be able to. For example, when a thioxanthone compound is used as the photopolymerization initiator B, the following procedure can be used.
1) A solution in which a photocurable resin composition is dissolved in tetrahydrofuran (THF) is centrifuged by a centrifugal separator to precipitate particle components such as silica particles and thermoplastic resin particles. The obtained solution is filtered through a filter to remove the particle component, thereby obtaining a sample solution.
2) The sample solution obtained in 1) is subjected to high performance liquid chromatography (HPLC) measurement. The HPLC measurement method and conditions are the same as the HPLC measurement method and conditions in the above-described molecular weight measurement.
Next, in HPLC measurement, the relative molecular mass and composition formula of the main peak detected by a detector with a wavelength of 400 nm characteristic of the thioxanthone skeleton are measured by liquid chromatography mass spectrometry (LC / MS). To do. The LC / MS measurement method and conditions are the same as the LC / MS measurement method and conditions in the aforementioned molecular weight measurement.
3) The NMR measurement or IR measurement is performed on the sample solution obtained in 1) above. Thereby, the chemical structure of the thioxanthone compound is specified.

1-3.Ammonium salt C of quaternary organoboron anion C
The ammonium salt C of the quaternary organic boron anion activates the photopolymerization initiator B and can itself function as a sensitizer that contributes to the curing reaction. The ammonium salt C of the quaternary organic boron anion preferably has 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 and an aromatic heterocyclic ring, and more preferably an aromatic hydrocarbon ring. The ammonium salt C of a quaternary organoboron anion containing an aromatic hydrocarbon ring or an aromatic heterocycle is likely to be activated because it can absorb light in a wider wavelength region.

In the quaternary organic boron anion, it is preferable that at least one of the rings having (4n + 2) π electrons is bonded to a boron atom. Such an ammonium salt C of a quaternary organic boron anion is preferably represented by the following formula (1).

R _{1 to} R _{4 in} Formula (1) are an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkyl group, and a substituted group. An aralkyl group which may be substituted, an aryl group which may be substituted, or a heteroaryl group which may be substituted. 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, and a decyl group. . 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 an ethylenyl group, a propenyl group, and a butenyl group. The alkynyl group in the alkynyl group which may be substituted is an alkynyl group having 2 to 20 carbon atoms, and examples thereof include an ethynyl group and a propynyl group. 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 and a cyclohexyl group. The aralkyl group in the aralkyl group which may be substituted is an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group. 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, and an anthracenyl group. 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.

  The substituent that the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aralkyl group, aryl group or heteroaryl group may have is not particularly limited, but is preferably an electron-donating group. The electron donating group can make it difficult to delocalize the electron density of the quaternary organoboron anion. Such ammonium salts of quaternary organic boron anions are unlikely to exist stably. Therefore, it is considered that the ammonium salt C of the quaternary organoboron anion having an electron donating group is relatively easily dissociated when receiving energy from the photopolymerization initiator B, so that the curing reaction of the curable compound A is likely to start. . Examples of the electron donating group include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a t-butyl group, an alkoxy group such as a methoxy group, a hydroxyl group, and the like.

However, at least one (preferably two, more preferably three) of R _{1 to} R _{4 is} an optionally substituted aryl group or an optionally substituted heteroaryl group, more preferably a substituted group. An aryl group which may be substituted. The ammonium salt C of a quaternary organoboron anion containing an aromatic hydrocarbon ring or an aromatic heterocycle is easily activated because it easily absorbs light in a wider wavelength region. Also, the greater the number of aromatic hydrocarbon rings or aromatic heterocycles contained in the ammonium salt C of the quaternary organic boron anion, the easier it is for the absorption wavelength to shift to the longer wavelength side and for activation.

  Examples of quaternary organoboron anions include n-butyltriphenylborate, n-octyltriphenylborate, n-dodecyltriphenylborate, sec-butyltriphenylborate, t-butyltriphenylborate, benzyltriphenylborate, n-butyltri (4-tolyl) borate, n-butyltri (2-tolyl) borate, n-butyltri (4-t-butylphenyl) borate, n-butyltrinaphthylborate, n-butyltri (3-methylnaphthyl) borate , Tetra-n-butyl borate, di-n-butyl diphenyl borate, tetrabenzyl borate and the like.

Z ^{+ in} 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, and a tetraoctylammonium cation.

  The molecular weight of the ammonium salt C of the quaternary organic boron anion is preferably 350 to 900, for example. When the molecular weight of the ammonium salt C of the quaternary organic boron anion is 350 or more, it is difficult to elute into the liquid crystal, so that the liquid crystal contamination is easily reduced. When the molecular weight of the ammonium salt C of the quaternary organic boron anion is 900 or less, the compatibility with the curable compound A is not easily lost, and it is easily dispersed uniformly. The molecular weight of the quaternary organic boron anion ammonium salt C is more preferably 450 to 800. The molecular weight of the ammonium salt C of the quaternary organic boron anion can be measured in the same manner as described above.

  The content of the ammonium salt C of the quaternary organic boron anion is preferably 0.01 to 10% by mass with respect to the curable compound A. When the content of the ammonium salt C of the quaternary organic boron anion is 0.01% by mass or more, the photopolymerization initiator B can be sufficiently activated, so that sufficient curability is easily obtained. When the content of the ammonium salt C of the quaternary organic boron anion is 10% by mass or less, elution into the liquid crystal is difficult to occur without impairing the curability. The content of the ammonium salt C of the quaternary organic boron anion is more preferably 0.1 to 5% by mass, still more preferably 0.1 to 3% by mass with respect to the curable compound A. It is particularly preferably 1 to 2.5% by mass.

  The structure of the ammonium salt C of the quaternary organic boron anion contained in the photocurable resin composition should be confirmed in the same manner as the method for confirming the structure of the photopolymerization initiator B contained in the photocurable resin composition described above. Can do.

  The content ratio by mass of the photopolymerization initiator B and the ammonium salt C of the quaternary organic boron anion is: photopolymerization initiator B: ammonium salt of the quaternary organic boron anion C = 1: 0.05 to 1: 3. preferable. When the content mass ratio of the photopolymerization initiator B and the ammonium salt C of the quaternary organic boron anion is within the above range, sufficient curability can be easily obtained even with a small amount of light. The content ratio by mass of the photopolymerization initiator B and the ammonium salt C of the quaternary organic boron anion is: photopolymerization initiator B: ammonium salt C of the quaternary organic boron anion C = 1: 0.1 to 1: 3. More preferably, it is 1: 0.1 to 1: 2.

  In the present invention, by combining the photopolymerization initiator B and the ammonium salt C of the quaternary organic boron anion, high curability can be obtained even with a small amount of light. The reason is not clear, but is presumed as follows. That is, the photopolymerization initiator B absorbs the irradiated light and excites it, and its energy moves to the ammonium salt C of the quaternary organic boron anion. The curing reaction of the curable compound A proceeds from the activated ammonium salt C of the quaternary organoboron anion. At the same time, the curing reaction starting from the excited photopolymerization initiator B itself proceeds. Therefore, it is considered that the curability is enhanced synergistically by combining the photopolymerization initiator B and the ammonium salt C of the quaternary organic boron anion.

  Among photopolymerization initiators B, thioxanthone compounds and anthraquinone compounds have relatively low reactivity in the visible light region, but when combined with the ammonium salt C of a quaternary organoboron anion, sufficient curing is also possible in the visible light region. It is easy to get sex.

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) acryloyl group in the molecule. The epoxy compound may be any of a monomer, an oligomer or a polymer. Epoxy compounds, for example, have low solubility and diffusibility in liquid crystal when using a photocurable resin composition as a liquid crystal sealant, and not only improve the display characteristics of the resulting liquid crystal panel, but also the moisture resistance of the cured product. Can increase sex.

  The epoxy compound may be an aromatic epoxy compound having a weight average molecular weight of 500 to 10000, preferably 1000 to 5000. The weight average molecular weight of the epoxy compound can be measured in terms of polystyrene by gel permeation chromatography (GPC).

  Examples of aromatic epoxy compounds include the reaction of aromatic diols typified by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, etc., and diols modified with ethylene glycol, propylene glycol, alkylene glycol, and epichlorohydrin. Aromatic polyvalent glycidyl ether compound obtained by the above; novolak type obtained by reaction of novolak resin derived from phenol or cresol and formaldehyde, polyphenols typified by polyalkenylphenol and copolymers thereof, and epichlorohydrin Polyvalent glycidyl ether compounds; xylylene phenol resin glycidyl ether compounds and the like are included. Among them, cresol novolac type epoxy compound, phenol novolac type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, triphenolmethane type epoxy compound, triphenolethane type epoxy compound, trisphenol type epoxy compound, dicyclopentadiene type Epoxy compounds, diphenyl ether type epoxy compounds and biphenyl type epoxy compounds are preferred. The epoxy compound may be one type or a combination of two or more types.

  The epoxy compound may be liquid or solid. A solid epoxy compound is preferable from the viewpoint of easily improving the moisture resistance of the cured product. The softening point of the solid epoxy compound is preferably 40 ° C. or higher and 150 ° C. or lower.

  It is preferable that content of the thermosetting compound D is 3.8-50 mass% with respect to the curable compound A, and it is more preferable that it is 5-30 mass%. When the content of the thermosetting compound D with respect to the curable compound A is 3.8% by mass or more, the moisture resistance of the cured product and the adhesive strength to the glass substrate can be further easily increased. Sometimes compatibility with the curable compound A tends to be even better.

  It is preferable that content of the thermosetting compound D is 3-20 mass% with respect to a 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 has An excessive increase in viscosity can be suppressed. As for content of the thermosetting compound D, it is more preferable that it is 3-15 mass% with respect to a photocurable resin composition, and it is further more preferable that it is 4-15 mass%.

1-5. Thermosetting agent E
The thermosetting agent E is a compound that does not cure the thermosetting compound D under normal storage conditions (room temperature, under visible light, etc.), but cures the compound when given heat. The photocurable resin composition containing the thermosetting agent E is excellent in storage stability and thermosetting. The thermosetting agent E is preferably an epoxy curing agent.

  The melting point of the epoxy curing agent is 50 ° C. or more and 250 ° C. or less, although it depends on the thermosetting temperature from the viewpoint of enhancing the viscosity stability of the photocurable resin composition and not impairing the moisture resistance of the cured product. The temperature is preferably 100 ° C. or higher and 200 ° C. or lower, and more preferably 150 ° C. or higher and 200 ° C. or lower.

  Examples of the epoxy curing agent include organic acid dihydrazide thermal latent curing agent, imidazole thermal latent curing agent, amine adduct thermal latent curing agent, and polyamine thermal latent curing agent.

  Examples of organic acid dihydrazide thermal latent curing agents include adipic acid dihydrazide (melting point 181 ° C.), 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (melting point 120 ° C.), 7,11-octa Decadiene-1,18-dicarbohydrazide (melting point 160 ° C.), dodecanedioic acid dihydrazide (melting point 190 ° C.), sebacic acid dihydrazide (melting point 189 ° C.) and the like. Examples of imidazole-based thermal latent curing agents include 2,4-diamino-6- [2′-ethylimidazolyl- (1 ′)]-ethyltriazine (melting point: 215 to 225 ° C.) and 2-phenylimidazole (melting point) 137-147 ° C.) and the like. The amine adduct thermal latent curing agent is a thermal latent curing agent comprising an addition compound obtained by reacting an amine compound having catalytic activity with an arbitrary compound, and examples thereof include Ajinomoto Fine Techno Co., Ltd. ) Amicure PN-40 (melting point 110 ° C.), Ajinomoto Fine Techno Co., Ltd. Amicure PN-23 (melting point 100 ° C.), Ajinomoto Fine Techno Corp. Amicure PN-31 (melting point 115 ° C.) Amicure PN-H (melting point 115 ° C) manufactured by Ajinomoto Fine Techno Co., Ltd. Amycure MY-24 (melting point 120 ° C), Amicure MY-H (melting point 131 ° C) manufactured by Ajinomoto Fine Techno Co. It is. The polyamine thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine and an epoxy. Examples thereof include Adeka Hardener EH4339S (softening point 120 to 130, manufactured by ADEKA Corporation). ° C), and ADEKA Corporation ADEKA HARDNER EH4357S (softening point 73-83 ° C). The epoxy curing agent may be only one kind or a combination of two or more kinds.

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

  The content of the thermosetting agent E is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and 5 to 20% by mass with respect to the photocurable resin composition. Further preferred. The photocurable resin composition containing the thermosetting agent E can be a one-component curable resin composition. The one-component curable resin composition is excellent in workability because it is not necessary to mix the main agent and the curing agent in use.

  The total content of the thermosetting compound D and the thermosetting agent E is preferably 6 to 50% by mass, more preferably 6 to 35% by mass, with respect to the photocurable resin composition. More preferably, it is 30 mass%.

1-6. Other ingredients F
1-6-1. Thermoplastic resin particles
The photocurable resin composition of the present invention may further contain thermoplastic resin particles as necessary. The thermoplastic resin particles include a thermoplastic resin having a softening point temperature measured by the ring and ball method of 50 to 120 ° C., preferably 70 to 100 ° C., and a number average particle diameter of 0.05 to 5 μm, preferably 0.8. It may be 1 to 3 μm. The photocurable resin composition containing such thermoplastic resin particles can relieve the shrinkage stress generated in the cured product. Moreover, when the number average particle diameter is set to the upper limit value or less, it is possible to prevent the coating stability from being lowered by the thermoplastic resin particles when forming a seal member having a thin line width. The number average particle size can be measured with 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 with a monomer capable of 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 radically polymerizable monomers 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 necessary. A photocurable resin composition containing a filler may have good viscosity, strength of a cured product, linear expansion, and the like.

  Examples of fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, titanium nitride, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, Inorganic fillers such as kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride are included. Of these, silicon dioxide and talc are preferable.

The shape of the filler may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or may be an irregular shape. When 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 0.5 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 BET method described in JIS Z8830.

  The photo-curable resin composition of the present invention is optionally combined with a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a plasticizer, and a quenching agent. An additive such as a foaming agent may be further included.

  Examples of the silane coupling agent include vinyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and the like. Content of a silane coupling agent may be 0.01-5 mass% with respect to a photocurable resin composition. When the content of the silane 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 for adjusting the gap of the liquid crystal display panel.

  The total content of other components F is preferably 1 to 50% by mass with respect to 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 hardly excessively increased, and the coating stability is hardly impaired.

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

  The photocurable resin composition of the present invention can be used as, for example, a sealing agent. The sealing agent is preferably a display element sealing agent used for sealing display elements such as liquid crystal display elements, organic EL elements, and LED elements. The display element sealant is particularly preferably a liquid crystal sealant, and more preferably a liquid crystal sealant for a liquid crystal dropping method.

2. Display element panel and manufacturing method thereof The display element panel of the present invention includes a pair of substrates, a display element disposed between the pair of substrates, and a seal member for sealing the display element. The seal member can be a cured product of the display element sealant of the present invention. The display element sealing agent of the present invention is composed of the photocurable resin composition of the present invention.

  Examples of display elements include liquid crystal display elements, organic EL elements, LED elements, and the like. Among these, a liquid crystal display element is preferable because the photocurable resin composition of the present invention can satisfactorily suppress liquid crystal contamination.

  That is, the liquid crystal display panel of the present invention includes a space surrounded by a pair of substrates, a frame-shaped seal member disposed between the pair of substrates, and a frame-shaped seal member between the pair of substrates. A filled liquid crystal layer (liquid crystal display element). The seal member can be a cured product of the liquid crystal sealant of the present invention. The liquid crystal sealing agent of the present invention comprises the photocurable resin composition of the present invention.

  Each of the pair of substrates is a transparent substrate. The material of the transparent substrate can be glass or plastic such as polycarbonate, polyethylene terephthalate, polyethersulfone and PMMA.

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

  The display method of the liquid crystal display panel is not particularly limited, and may be any of TN method (Twisted Nematic), VA method (Visual Alignment), IPS method (In Plane Switching), PSA method (Polymer-Stained Alignment) and the like. .

The aperture ratio (the aperture ratio defined by the following formula) of the wiring portion in the region where the seal member is disposed is not particularly limited, but may be, for example, 50% or less.
Opening ratio of wiring part (%) = area of wiring part opening in area where seal member is arranged / area of wiring part in area where seal member is arranged × 100 (%)
The wiring portion is a region where wiring is formed (in the outer peripheral portion of the liquid crystal display panel). The area of the wiring portion is the area of the opening that forms the wiring portion and the light shielding that forms the wiring portion. It is the sum of the areas of the parts.

  The light shielding portion is a region where a black matrix and wiring are arranged. The width of the light shielding portion may be 40 to 200 μm, for example.

  The liquid crystal display panel is manufactured using the liquid crystal sealant of the present invention. Generally, there are a liquid crystal dropping method and a liquid crystal injecting method as a method for manufacturing a liquid crystal display panel, but the liquid crystal display panel of the present invention is preferably manufactured by a liquid crystal dropping method.

The manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is
1) forming a seal pattern of the liquid crystal sealant of the present invention on one substrate;
2) dropping the liquid crystal in a region surrounded by the seal pattern of the substrate or a region of the other substrate facing the region surrounded by the seal pattern in a state where the seal pattern is uncured;
3) a step of superimposing one substrate and the other substrate through a seal pattern;
4) curing the seal pattern.

  In the step 2), the uncured state of the seal pattern means a state in which the curing reaction of the liquid crystal sealant has not progressed to the gel point. For this reason, in the step 2), in order to suppress dissolution of the liquid crystal sealant in the liquid crystal, the seal pattern may be semi-cured by light irradiation or heating.

  In the step 4), only curing by light irradiation may be performed, but after curing by light irradiation, curing by heating may be performed. That is, the step 4) includes a step of irradiating the seal pattern with light to cure the seal pattern; when the liquid crystal sealant further includes the aforementioned thermosetting agent (E), the seal pattern irradiated with light A step of heating and curing may be further included. Since the liquid crystal sealant can be cured in a short time by curing by light irradiation, dissolution in the liquid crystal can be suppressed. By combining curing by light irradiation and curing by heating, damage to the liquid crystal layer due to light can be reduced compared to the case of only curing by light irradiation.

  The light to be irradiated is not particularly limited, but is preferably light having a wavelength of 370 to 450 nm. This is because the light having the above wavelength causes relatively little damage to the liquid crystal and the drive electrode. For light irradiation, a known light source that emits ultraviolet light or visible light can be used. For irradiation with 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 energy that can cure the curable compound A. The photocuring time is, for example, about 10 minutes although it depends on the composition of the liquid crystal sealant.

  The thermosetting temperature is 120 ° C., for example, although it depends on the composition of the liquid crystal sealant, and the thermosetting time is about 2 hours.

  Since the liquid crystal sealing agent of the present invention contains a photopolymerization initiator B and an ammonium salt C of a quaternary organic boron anion, it exhibits high curability even with a small amount of light. Therefore, when the liquid crystal display panel is manufactured, the liquid crystal sealant of the present invention can be sufficiently cured even in a light shielding portion such as a wiring on a substrate or under a black matrix. Further, since the liquid crystal sealant of the present invention exhibits high curability, it is difficult for uncured components to remain, and elution of the photopolymerization initiator B and the ammonium salt C of the quaternary organic boron anion into the liquid crystal can be reduced.

In particular, liquid crystal materials used for liquid crystal display panels that can handle high response speed, high contrast, high viewing angle, and high image quality, such as VA, PSA, and IPS, are easily affected by external factors. There is a possibility that the performance of the liquid crystal material may be deteriorated by UV at the time of curing the liquid crystal sealant and the constituent components of the liquid crystal sealant.
In addition, high definition of the liquid crystal display panel, that is, high density of wiring due to an increase in the number of pixels is progressing, and accordingly, the aperture ratio of the wiring part where the liquid crystal sealant is disposed is reduced (the light shielding part is increased). There is a tendency.

On the other hand, since the liquid crystal sealant of the present invention has high photocurability, photocuring proceeds even in a portion that is blocked by a black matrix or the like (a portion that is not directly exposed to light, a light blocking portion). Can be partially cured. For example, when light having a wavelength of 400 nm or more is irradiated at an irradiation intensity of 100 mW / cm ² for 20 seconds, it is preferable that 45 μm or more can be cured from the edge. As described above, the progress of photocuring also in the light shielding portion can suppress the deterioration of the liquid crystal due to the uncured component of the liquid crystal sealant. Therefore, the liquid crystal sealant of the present invention is suitable for sealing a liquid crystal layer of a liquid crystal display panel in which the opening ratio of the wiring portion where the liquid crystal sealant is disposed is 50% or less.

  In the following, the invention will be described in more detail with reference to examples. These examples do not limit the scope of the present invention.

1. Material (Curable Compound A)
A-1: Methacrylic acid-modified bisphenol F type epoxy resin obtained in Synthesis Example 1 (95% partially methacrylic product)
(Synthesis Example 1)
160 g of liquid bisphenol F type epoxy resin (YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, 0.2 g of triethanolamine as a catalyst, and 81.7 g of methacrylic acid was charged into the flask, dried air was fed into the flask, and the mixture was reacted at 90 ° C. with stirring under reflux for 5 hours. 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). As a result of GPC analysis of this resin, the weight average molecular weight was 792.

A-2: Acrylic acid-modified bisphenol F type epoxy resin obtained in Synthesis Example 2 (50% partially acrylated product)
(Synthesis Example 2)
First, 175 g of bisphenol F type epoxy resin (YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq) is added to a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, acrylic acid : 37 g, triethanolamine: 0.2 g as a catalyst, and hydroquinone monomethyl ether: 0.2 g as a polymerization inhibitor were mixed and heated and stirred at 110 ° C. for 12 hours while blowing dry air. The obtained reaction product was repeatedly washed with ultrapure water 12 times to obtain an acrylic acid-modified bisphenol F type epoxy resin (curable compound A-2).
As a result of analyzing this resin by HPLC and NMR, it was a bisphenol F type epoxy resin in which 50% of the epoxy groups were modified with acryloyl acid. Moreover, as a result of GPC analysis of this resin, the weight average molecular weight was 692.

Polyethylene glycol diacrylate: Light acrylate 14EG-A, manufactured by Kyoeisha Chemical Co., Ltd. (see formula below, molecular weight 600)

ＩＲＵＧＡＣＵＲＥ ＯＸＥ０１、ＢＡＳＦ社製（下記式参照、オキシムエステル系化合物）

２−（ヒドロキシメチル）アントラキノン、純正化学社製（下記式参照、アントラキノン系化合物）

(Photopolymerization initiator B)
Omnipol-TX, manufactured by IGM Resins (see formula below, thioxanthone compound)

IRUGACURE OXE01, manufactured by BASF (see formula below, oxime ester compound)

2- (Hydroxymethyl) anthraquinone, manufactured by Junsei Chemical Co., Ltd. (see formula below, anthraquinone compound)

Ｎ３Ｂ、昭和電工社製（下記式参照、融点１４０〜１４１℃）

(Ammonium salt C of quaternary organic boron anion)
P3B, manufactured by Showa Denko KK (see formula below, melting point 140-144 ° C.)

N3B, manufactured by Showa Denko KK (see formula below, melting point 140-141 ° C.)

(Thermosetting compound D)
Epoxy resin: Mitsubishi Chemical Corporation, jER1004, softening point 97 ° C

(Thermosetting agent E)
Adipic acid dihydrazide: Nippon Kasei Co., Ltd., ADH, melting point 177-184 ° C

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

2. Preparation and Evaluation of Photocurable Resin Composition (Example 1)
420 parts by mass of curable compound A-1 obtained in Synthesis Example 1 as curable compound A, 200 parts by mass of polyethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate 14EG-A), and photopolymerization initiator B 10 parts by mass of Omnipol-TX (manufactured by IGM Resins), 10 parts by mass of P3B (manufactured by Showa Denko) as the ammonium salt C of the quaternary organic boron anion, and an epoxy resin (Mitsubishi Chemical) as the thermosetting compound D 50 parts by mass, jER1004), 90 parts by mass of adipic acid dihydrazide (Nippon Kasei Co., Ltd. ADH) as thermosetting agent E, and 130 parts by mass of silica particles (S-100, manufactured by Nippon Shokubai Co., Ltd.) as fillers Part, 70 parts by mass of F351 (manufactured by Aika Kogyo) as thermoplastic resin particles, and γ-glycidoxypropyl as a silane coupling agent Trimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-403) and 20 parts by weight, were mixed in sufficient a uniform liquid using a three-roll mill, to obtain a photocurable resin composition.

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

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

<Photocurability evaluation 1>
When the photopolymerizable composition was irradiated with light having a wavelength of 360 to 430 nm at 1 mW / cm ² for 30 seconds, the viscosity increasing behavior at 25 ° C. was observed using VISCOANALYSER VAR100 (manufactured by REOLOGICA INSTRUMENT). At this time, the curing time until the viscosity of the photopolymerizable composition after light irradiation was 50% of the saturated viscosity value was measured. The saturated viscosity value is a viscosity when the photopolymerizable composition is completely cured. It can be determined that the shorter the curing time, the better the curability.

<Photocurability evaluation 2>
A substrate 1 in which five black matrices having a width of 200 μm were formed on a glass substrate at intervals of 100 μm and a substrate 2 in which a black matrix was formed on the entire surface of the glass substrate were produced. The substrate 1 is coated with the photopolymerizable resin composition so that the application area after bonding the substrate 1 and the substrate 2 becomes a rectangular shape orthogonal to the longitudinal direction of the black matrix, and the thickness after curing is 5 μm. It was applied as follows. The coating area was in the form of a rectangle having a length in the direction (long side) perpendicular to the longitudinal direction of the black matrix of 1500 μm and a length in the direction parallel to the longitudinal direction of the black matrix (short side) of 600 to 800 μm. On the other hand, a release agent was applied to the substrate 2.
After laminating these substrates so that the respective coated surfaces overlap each other, light with a wavelength of 400 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 where the liquid crystal sealant is disposed was 33.3%.
Next, the substrate 1 was peeled off from the laminated panel. Each 200 μm-wide black matrix portion of the obtained substrate 1 was observed with an optical microscope, the uncured width and the cured width of the photopolymerizable resin composition were measured, and the average value of the five was determined. Whether it was cured or not was judged by observation with an optical microscope. It can be determined that the smaller the uncured width and the larger the cured width, the better the curability.
In addition, the uncured portion of the photopolymerizable resin composition in each black matrix portion is in the central portion in the width direction of the black matrix; the cured portion is in both end portions in the width direction of the black matrix. The cured width in the table indicates the width of each of the two cured portions at both ends 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.

  From Tables 1 and 2, the photocurable resin compositions of Examples 1 to 9 containing the ammonium salt C of the quaternary organic boron anion are the light of Comparative Examples 1 to 2 not containing the ammonium salt C of the quaternary organic boron anion. It can be seen that the curing time in the photocurable evaluation 1 is shorter than that in the curable resin composition, the uncured width in the photocurable evaluation 2 is small, and both have high curability.

  Further, from the comparison of Examples 1, 2, and 6-9, Examples 1, 2, 8 and 8 in which a thioxanthone compound or an anthraquinone compound and an ammonium salt C of a quaternary organic boron anion were combined as the photopolymerization initiator B. The photocurable resin composition of No. 9 is lighter than the photocurable resin composition of Examples 6 and 7 in which the oxime ester compound and the ammonium salt C of the quaternary organic boron anion are combined as the photopolymerization initiator B. In the curability evaluation 2, it can be seen that the uncured width is small and has higher curability.

  The present invention has a high curability that can be sufficiently cured even with a small amount of light, and can provide a photocurable resin composition suitable as, for example, a liquid crystal sealant.

Claims (9)

A liquid crystal sealant that is disposed in the wiring portion of the liquid crystal display panel having a wiring portion with an aperture ratio of 50% or less and seals the liquid crystal layer,
A curable compound A having an ethylenically unsaturated double bond in the molecule;
Photopolymerization initiator B;
A liquid crystal sealing agent comprising an ammonium salt C of a quaternary organic boron anion represented by the following formula (1).

(In the formula (1),
R _{1 to} R ₄ are an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkyl group, and optionally substituted. An aralkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group, which may be the same or different, and at least one of R _{1 to} R ₄ is substituted. An aryl group which may be substituted or a heteroaryl group which may be substituted,
Z ⁺ is an ammonium cation)   The liquid crystal sealant 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 content ratio by mass of the photopolymerization initiator B and the ammonium salt C of the quaternary organic boron anion is photopolymerization initiator B: ammonium salt C of the quaternary organic boron anion C = 1: 0.1 to 1: 3. The liquid crystal sealing agent according to claim 1 or 2.   Content of the ammonium salt C of the said quaternary organoboron anion is a liquid-crystal sealing compound as described in any one of Claims 1-3 which is 0.01-3 mass% with respect to the said sclerosing | hardenable compound A.   Hardened | cured material of the liquid-crystal sealing compound as described in any one of Claims 1-4. Using the liquid crystal sealant according to any one of claims 1 to 4, a step of forming a seal pattern on one substrate;
In the uncured state of the seal pattern, dropping the liquid crystal on the other substrate that is paired with the one substrate in the region of the seal pattern;
Superimposing the one substrate and the other substrate through the seal pattern;
Curing the seal pattern;
A method for manufacturing a liquid crystal display panel, comprising:   The method of manufacturing a liquid crystal display panel according to claim 6, wherein the step of curing the seal pattern includes a step of curing the seal pattern by irradiating the seal pattern with light. A pair of substrates;
A frame-shaped sealing member disposed between the pair of substrates;
A liquid crystal layer filled in a space surrounded by the seal member between the pair of substrates,
The liquid crystal display panel in which the said sealing member is the hardened | cured material of the liquid-crystal sealing compound as described in any one of Claims 1-4.   The liquid crystal display panel according to claim 8, wherein an opening ratio of a wiring portion in which the seal member is disposed is 50% or less.