CN115996959A - Thioxanthone compound, photopolymerization initiator, curable resin composition, composition for display element, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents
Thioxanthone compound, photopolymerization initiator, curable resin composition, composition for display element, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element Download PDFInfo
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- CN115996959A CN115996959A CN202180043468.7A CN202180043468A CN115996959A CN 115996959 A CN115996959 A CN 115996959A CN 202180043468 A CN202180043468 A CN 202180043468A CN 115996959 A CN115996959 A CN 115996959A
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- Prior art keywords
- liquid crystal
- meth
- display element
- curable resin
- crystal display
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 112
- 239000011342 resin composition Substances 0.000 title claims abstract description 91
- -1 Thioxanthone compound Chemical class 0.000 title claims abstract description 85
- 239000003999 initiator Substances 0.000 title claims abstract description 52
- 239000000565 sealant Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title description 6
- 239000004020 conductor Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 239000010419 fine particle Substances 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000011109 contamination Methods 0.000 abstract description 20
- 238000003860 storage Methods 0.000 abstract description 13
- 230000009257 reactivity Effects 0.000 abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 104
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- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- AMJYHMCHKZQLAY-UHFFFAOYSA-N tris(2-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound O=C=NC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)N=C=O)OC1=CC=CC=C1N=C=O AMJYHMCHKZQLAY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- Chemical & Material Sciences (AREA)
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Abstract
The present invention provides a thioxanthone compound having excellent reactivity with long wavelength light, and relates to a photopolymerization initiator containing the thioxanthone compound, a curable resin composition containing the photopolymerization initiator and having excellent storage stability and light shielding portion curability, a composition for a display element using the curable resin composition, a sealant for a liquid crystal display element using the curable resin composition and having excellent low liquid crystal contamination properties, a vertically conductive material using the sealant for a liquid crystal display element, and a liquid crystal display element.
Description
Technical Field
The present invention relates to thioxanthone compounds. The present invention also relates to a photopolymerization initiator containing the thioxanthone compound, a curable resin composition containing the photopolymerization initiator, a composition for a display element using the curable resin composition, and a sealant for a liquid crystal display element using the curable resin composition. The present invention also relates to a vertical conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.
Background
In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display cell, a liquid crystal dropping method called a dropping method using a curable resin composition for photo-thermal curing as disclosed in patent document 1 and patent document 2 as a sealant has been used from the viewpoints of shortening the tact time and optimizing the amount of liquid crystal used.
In the dropping process, first, a frame-like seal pattern is formed by dispensing on one of the 2 transparent substrates with electrodes. Next, in a state where the sealing agent is not cured, minute droplets of liquid crystal are dropped onto the entire inner surface of the frame of the transparent substrate, and the other transparent substrate is immediately bonded thereto, and the sealing portion is pre-cured by irradiation with light such as ultraviolet rays. Then, the liquid crystal is heated and cured in a main manner during the liquid crystal annealing, and a liquid crystal display element is manufactured. When the substrates are bonded under reduced pressure, a liquid crystal display device can be manufactured with extremely high efficiency, and the dropping process has been the mainstream of a method for manufacturing a liquid crystal display device.
However, in modern mobile devices with liquid crystal panels such as mobile phones and portable game machines, miniaturization of the devices is the most required task. As a method of downsizing the device, for example, a liquid crystal display portion is narrowed, and a sealing portion is arranged below a black matrix (hereinafter, also referred to as a narrow frame design).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2001-133794
Patent document 2: international publication No. 02/092718
Patent document 3: japanese patent laid-open No. 2017-125033
Patent document 4: international publication No. 2017/130594
Disclosure of Invention
Problems to be solved by the invention
In the narrow frame design, the sealant is disposed directly under the black matrix, and therefore, light irradiated when the sealant is photo-cured is blocked when the dropping process is performed. In the future, when the frame is narrowed or the liquid crystal material is changed, there is a concern that the uncured sealant component dissolves out into the liquid crystal and causes liquid crystal contamination even in the case of the sealant which has no problem in the past. Therefore, a sealant having a low liquid crystal contamination property and further excellent properties is demanded.
In addition, although ultraviolet irradiation is generally performed as a method of photocuring a sealing agent, particularly in a liquid crystal dropping process, the sealing agent is cured after dropping liquid crystal, and thus there is a problem in that the liquid crystal is easily degraded by ultraviolet irradiation. Therefore, in order to prevent deterioration of liquid crystal due to ultraviolet rays, an operation of performing photo-curing by using a long wavelength in a visible light region through a cut-off filter or the like is performed. As a method of photocuring the sealant with light of a long wavelength, a method of using a sensitizer having high sensitivity to light of a long wavelength in combination with a photopolymerization initiator is considered. For example, patent documents 3 and 4 disclose curable resin compositions in which a photopolymerization initiator and a sensitizer are combined and blended. However, when these curable resin compositions are used as a sealant for liquid crystal display elements, there is a concern that the total amount of photopolymerization initiator and sensitizer becomes large in order to sufficiently perform photocuring with light having a long wavelength, and contamination of liquid crystal or deterioration of storage stability occurs.
The purpose of the present invention is to provide a thioxanthone compound that has excellent reactivity with light of a long wavelength. The present invention also provides a photopolymerization initiator containing the thioxanthone compound, a curable resin composition containing the photopolymerization initiator and having excellent storage stability and light shielding portion curability, a composition for a display element using the curable resin composition, and a sealant for a liquid crystal display element using the curable resin composition and having excellent low liquid crystal contamination. The present invention also provides a vertical conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.
Solution for solving the problem
The present invention is a thioxanthone compound represented by the following formula (1).
[ chemical formula 1]
In the formula (1), X represents a structure represented by the following formula (2-1), (2-2) or (2-3), R 1 Each independently of the other and represents a hydrogen atom, a methyl group, an ethyl group or a nitro group, R 2 Each independently and represents a hydrogen atom, a methyl group, an ethyl group or a nitro group.
[ chemical formula 2]
In the formulae (2-1), (2-2) and (2-3), R 3 Represents a structure containing a hetero atom and an aromatic ring, and represents a bonding position.
The present invention will be described in detail below.
The present inventors have studied to improve the curability of a light shielding portion by blending a photopolymerization initiator having excellent reactivity with light having a long wavelength into a curable resin composition. However, in the case of using such a photopolymerization initiator, the storage stability of the obtained curable resin composition may be deteriorated, or liquid crystal contamination may occur in the case of using the obtained curable resin composition as a sealant for a liquid crystal display element. Accordingly, the present inventors have studied on the use of a thioxanthone compound having a specific structure as a photopolymerization initiator. As a result, it has been found that a curable resin composition having all of excellent storage stability, light shielding portion curability, and low liquid crystal contamination in the case of being used as a sealant for a liquid crystal display element can be obtained, and the present invention has been completed.
In the present specification, the term "long wavelength" refers to light having a wavelength of 400nm or more.
The thioxanthone compound of the present invention is represented by the above formula (1).
In the formula (1), X represents a structure represented by the formula (2-1), (2-2) or (2-3), and R in the formulas (2-1), (2-2) and (2-3) 3 Represents a structure comprising a heteroatom and comprising an aromatic ring. By making R as described above 3 The thioxanthone compound of the present invention has a structure including a heteroatom and an aromatic ring, and thus the conjugation of the thioxanthone skeleton is expanded, whereby the thioxanthone compound is excellent in reactivity to light of a long wavelength. As a result, when the thioxanthone compound of the present invention is used as a photopolymerization initiator in a curable resin composition, the light shielding portion of the curable resin composition is excellent in curability. In particular, R is preferable in view of more excellent reactivity with light having a long wavelength 3 The R is more preferable in view of the fact that the electron density is high and the low liquid crystal contamination property is more excellent when used in a sealant for a liquid crystal display element because of the structure represented by the following formula (3-1), (3-2), (3-3), (3-4), (3-5), (3-6), (3-7) or (3-8) 3 The structure represented by the following formula (3-1), (3-2), (3-3), (3-4) or (3-5) is more preferably the structure represented by the following formula (3-1).
[ chemical formula 3]
In the formulae (3-1) to (3-8), the bond position is represented. In the formulae (3-1) to (3-8), hydrogen atoms other than those contained in the OH groups of the formulae (3-2) and (3-3) may be substituted.
In the above formula (1), R 1 Each independently of the other and represents a hydrogen atom, a methyl group, an ethyl group or a nitro group, R 2 Each independently and represents a hydrogen atom, a methyl group, an ethyl group or a nitro group. Among them, from the viewpoint of solubility to a curable resin to be described later, at least 1R in the formula (1) is preferable 1 Is methyl or ethyl, and at least 1R in the above formula (1) 2 Is methyl or ethyl.
The thioxanthone compound of the present invention has a preferable lower limit of 500 and a preferable upper limit of 1000. When the molecular weight is within this range, the thioxanthone compound of the present invention is used as a photopolymerization initiator in a sealant for a liquid crystal display element, and thus the low liquid crystal contamination is more excellent. The thioxanthone compound of the present invention has a more preferable lower limit of 550 and a more preferable upper limit of 800.
In the present specification, the "molecular weight" is a molecular weight determined from a structural formula of a compound having a specific molecular structure, and may be expressed by using a number average molecular weight for a compound having a wide distribution of polymerization degrees and a compound having no specific modified site. In the present specification, the "number average molecular weight" is a value obtained by measuring by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converting the obtained product into polystyrene. Examples of the column used for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa electric company).
The thioxanthone compound of the present invention is suitable for use as a photopolymerization initiator. Photopolymerization initiators containing the thioxanthone compounds of the present invention are also one of the present invention.
The curable resin composition containing the curable resin and the photopolymerization initiator of the present invention is also one of the present invention.
Since the photopolymerization initiator of the present invention has excellent reactivity with light having a long wavelength, when the curable resin composition of the present invention is used for a sealant for a liquid crystal display element, the content of the photopolymerization initiator of the present invention is reduced within a range in which the curability of a light shielding portion can be maintained, thereby making it possible to further improve the low liquid crystal contamination property of the sealant for a liquid crystal display element.
The content of the photopolymerization initiator of the present invention in the curable resin composition of the present invention is preferably 0.05 parts by weight, and the upper limit is preferably 3 parts by weight, based on 100 parts by weight of the curable resin. The light shielding portion of the curable resin composition obtained by setting the content of the photopolymerization initiator of the present invention to 0.05 parts by weight or more is more excellent in curability. When the content of the photopolymerization initiator of the present invention is 3 parts by weight or less, the resulting curable resin composition is more excellent in storage stability and is more excellent in low liquid crystal contamination property when the curable resin composition is used as a sealant for a liquid crystal display element. The more preferable lower limit of the content of the photopolymerization initiator of the present invention is 0.1 part by weight, and the more preferable upper limit is 2 parts by weight.
The curable resin composition of the present invention may contain a photopolymerization initiator other than the photopolymerization initiator of the present invention within a range that does not hinder the object of the present invention.
Examples of the other photopolymerization initiator include a benzophenone compound, an acetophenone compound, an acylphosphine oxide compound, a titanocene compound, an oxime ester compound, a benzoin ether compound, and a thioxanthone compound other than the photopolymerization initiator of the present invention.
Specific examples of the above-mentioned other photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 1,2- (dimethylamino) -2- ((4-methylphenyl) methyl) -1- (4- (4-morpholinyl) phenyl) -1-butanone, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 1- (4- (phenylthio) phenyl) -1, 2-octanedione 2- (O-benzoyl oxime), 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, and the like.
The other photopolymerization initiator may be used alone, or 2 or more kinds may be used in combination.
The curable resin composition of the present invention contains a curable resin.
The curable resin preferably contains a (meth) acrylic compound, more preferably contains a (meth) acrylic compound and an epoxy compound.
In the present specification, the "(meth) acrylic" means acrylic or methacrylic, the "(meth) acrylic compound" means a compound having a (meth) acryloyl group, and the "(meth) acryloyl group" means an acryloyl group or a methacryloyl group.
Examples of the (meth) acrylic compound include a (meth) acrylate compound, an epoxy (meth) acrylate, and a urethane (meth) acrylate. Among them, epoxy (meth) acrylate is preferable. From the viewpoint of reactivity, the (meth) acrylic compound preferably has 2 or more (meth) acryloyl groups in 1 molecule.
In the present specification, the term "(meth) acrylate" means an acrylate or a methacrylate, and the term "epoxy (meth) acrylate" means a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.
Examples of the monofunctional compound in the (meth) acrylate compound include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylcarbitol (meth) acrylate, 2-trifluoroethyl (meth) acrylate, 2, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, and the like.
Examples of the 2-functional compound in the (meth) acrylate compound include: 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate neopentyl glycol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) acrylate, and the like.
Examples of the compound having 3 or more functions among the (meth) acrylate compounds include: trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acryloxyethyl phosphate, di (trimethylolpropane) tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Examples of the epoxy (meth) acrylate include: and those obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
Examples of the epoxy compound that is a raw material for synthesizing the epoxy (meth) acrylate include: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2' -diallyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide addition bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, thioether type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound, o-cresol novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound, biphenyl novolac type epoxy compound, naphthol novolac type epoxy compound, glycidyl amine type epoxy compound, alkyl polyol type epoxy compound, rubber modified type epoxy compound, glycidyl ester compound, and the like.
Examples of commercial products of the bisphenol A type epoxy compound include jER828EL and jER1004 (both manufactured by Mitsubishi chemical corporation), EPICLON EXA-850CRP (manufactured by DIC corporation), and the like.
Examples of commercial products of the bisphenol F type epoxy compound include jER806 and jER4004 (both manufactured by Mitsubishi chemical corporation).
Examples of commercial products of the bisphenol S type epoxy compound include EPICLON EXA1514 (manufactured by DIC Co.).
Examples of the commercial products of the 2,2' -diallylbisphenol A type epoxy compound include RE-810NM (manufactured by Japanese chemical Co., ltd.).
Examples of commercial products of the hydrogenated bisphenol type epoxy compound include EPICLON EXA7015 (manufactured by DIC Co.).
Examples of commercial products obtained by adding propylene oxide to bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
Examples of commercial products of the resorcinol-type epoxy compound include EX-201 (manufactured by Nagase ChemteX Co., ltd.).
Examples of commercial products of the biphenyl epoxy compounds include jER YX-4000H (manufactured by mitsubishi chemical company).
Examples of commercial products of the above-mentioned thioether-type epoxy compounds include YSLV-50TE (NIPPON STEEL Chemical & Material Co.) and the like.
Examples of commercial products of the diphenyl ether type epoxy compounds include YSLV-80DE (NIPPON STEEL Chemical & Material Co.) and the like.
Examples of commercial products of the dicyclopentadiene type epoxy compound include EP-4088S (manufactured by ADEKA Co., ltd.).
Examples of the commercial products of the naphthalene type epoxy compound include EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Co.).
Examples of the commercial products of the phenol novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Co., ltd.).
Examples of the commercial products of the o-cresol novolac type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Co., ltd.).
Examples of commercial products of the dicyclopentadiene phenol type epoxy compound include EPICLON HP7200 (manufactured by DIC Co.).
Examples of commercial products of the biphenyl novolac type epoxy compounds include NC-3000P (manufactured by Japanese chemical Co., ltd.).
Examples of the commercial products of the naphthol novolac type epoxy compounds include ESN-165S (NIPPON STEEL Chemical & Material Co.).
Examples of commercial products of the glycidylamine-type epoxy compounds include jor 630 (manufactured by mitsubishi chemical Co., ltd.), epicalon 430 (manufactured by DIC corporation), tetra-X (manufactured by mitsubishi gas chemical Co., ltd.), and the like.
Examples of commercial products of the alkyl polyol type epoxy compound include ZX-1542 (NIPPON STEEL Chemical & Material Co., ltd.), EPICLON 726 (DIC Co., ltd.), epoligo 80MFA (co-Rong chemical Co., ltd.), denacol EX-611 (Nagase ChemteX Co., ltd.), and the like.
Examples of commercial products of the rubber-modified epoxy compound include YR-450, YR-207 (both NIPPON STEEL Chemical and Material Co., ltd.), epolead PB (DAICEL Co., ltd.), and the like.
Examples of the commercial products of the above glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Co., ltd.).
Examples of other commercially available products of the epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (both manufactured by NIPPON STEEL Chemical & Material Co., ltd.), XAC4151 (manufactured by Asahi chemical Co., ltd.), jER1031, jER1032 (both manufactured by Mitsubishi chemical Co., ltd.), EXA-7120 (manufactured by DIC Co., ltd.), TEPIC (manufactured by Nissan chemical Co., ltd.), and the like.
Examples of the commercial products of the epoxy (meth) acrylates include epoxy (meth) acrylates manufactured by DAICEL ALLNEX, epoxy (meth) acrylates manufactured by new chemical industry, epoxy (meth) acrylates manufactured by co-company chemical industry, and epoxy (meth) acrylates manufactured by Nagase ChemteX.
Examples of the epoxy (meth) acrylate produced by Daicel ALLNEX include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, and EBECRYL RDX 63182.
Examples of the epoxy (meth) acrylate include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.
Examples of the Epoxy (meth) acrylate produced by the company of Cooperation chemical include Epoxy Ester M-600A, epoxy Ester 40EM, epoxy Ester 70PA, epoxy Ester 200PA, epoxy Ester 80MFA, epoxy Ester 3002M, epoxy Ester 3002A, epoxy Ester 1600A, epoxy Ester 3000M, epoxy Ester 3000A, epoxy Ester 200EA, epoxy Ester 400EA, and the like.
Examples of the epoxy (meth) acrylate include Denacol Acrylate DA-141, denacol Acrylate DA-314, denacol Acrylate DA-911, and the like, which are manufactured by Nagase ChemteX corporation.
The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin compound.
Examples of the isocyanate compound include: isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1, 5-naphthalene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, xylylene Diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6, 11-undecyltriacrylate, and the like.
Further, as the above isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyol with an excessive amount of an isocyanate compound can also be used.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of a diol, mono (meth) acrylate or di (meth) acrylate of a triol, and epoxy (meth) acrylate.
Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, and polyethylene glycol.
Examples of the triol include trimethylolethane, trimethylolpropane, and glycerin.
Examples of the epoxy (meth) acrylate include bisphenol a type epoxy acrylate.
Examples of the commercial products of the urethane (meth) acrylates include urethane (meth) acrylates produced by east asia synthesis, urethane (meth) acrylates produced by DAICEL ALLNEX, urethane (meth) acrylates produced by industrial company on the root, urethane (meth) acrylates produced by new chemical industry, and urethane (meth) acrylates produced by co-mingled chemical industry.
Examples of the urethane (meth) acrylate produced by the east Asia synthetic company include M-1100, M-1200, M-1210, and M-1600.
Examples of urethane (meth) acrylates manufactured by Daicel ALLNEX include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260, and the like.
Examples of urethane (meth) acrylates produced by the above-mentioned root industries include artesin UN-330, artesin SH-500B, artesin UN-1200TPK, artesin UN-1255, artesin UN-3320HB, artesin UN-7100, artesin UN-9000A, and artesin UN-9000H.
Examples of the urethane (meth) acrylate include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, and UA-W2A.
As urethane (meth) acrylate produced by the company of Cooperation, AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T and the like are mentioned, for example.
Examples of the epoxy compound include: an epoxy compound which is a raw material for synthesizing the above epoxy (meth) acrylate, a partially (meth) acrylic acid-modified epoxy compound, and the like.
In the present specification, the above-mentioned partial (meth) acrylic-modified epoxy compound means, for example: a compound having 1 or more epoxy groups and 1 or more (meth) acryloyl groups in 1 molecule, which is obtained by reacting a part of epoxy groups of an epoxy compound having 2 or more epoxy groups in 1 molecule with (meth) acrylic acid.
When the (meth) acrylic compound and the epoxy compound are contained as the curable resin or when the partially (meth) acrylic-modified epoxy compound is contained, the ratio of the (meth) acryloyl group in the total of the (meth) acryloyl groups and the epoxy groups in the curable resin is preferably 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acryloyl groups is in this range, the occurrence of liquid crystal contamination in the case of using the obtained curable resin composition as a sealant for a liquid crystal display element is suppressed, and the adhesiveness is further excellent.
The curable resin preferably has-OH groups, -NH-groups, from the viewpoint of more excellent low liquid crystal contamination in the case where the obtained curable resin composition is used as a sealant for a liquid crystal display element 2 Hydrogen-bonding units such as radicals.
The curable resin may be used alone or in combination of 2 or more.
The curable resin composition of the present invention may contain a sensitizer. The sensitizer has the function of further improving the polymerization initiation efficiency of the photopolymerization initiator and further promoting the curing reaction of the curable resin composition of the present invention.
Examples of the sensitizer include ethyl 4- (dimethylamino) benzoate, 9, 10-dibutoxyanthracene, 2, 4-diethylthioxanthone, 2-dimethoxy-1, 2-diphenylethane-1-one, benzophenone, 2, 4-dichlorobenzophenone, methyl-o-benzoate, 4 '-bis (dimethylamino) benzophenone, and 4-benzoyl-4' -methyldiphenyl sulfide.
The content of the sensitizer is preferably 0.01 parts by weight, and the content of the sensitizer is preferably 3 parts by weight, based on 100 parts by weight of the curable resin. The sensitizer effect is further exhibited by setting the content of the sensitizer to 0.01 parts by weight or more. By setting the content of the sensitizer to 3 parts by weight or less, light can be transmitted to a deep portion without excessively increasing absorption. The lower limit of the content of the sensitizer is more preferably 0.1 parts by weight, and the upper limit is more preferably 1 part by weight.
The curable resin composition of the present invention may contain a thermal polymerization initiator within a range that does not hinder the object of the present invention.
Examples of the thermal polymerization initiator include thermal polymerization initiators composed of azo compounds, organic peroxides, and the like. Among them, an initiator composed of an azo compound (hereinafter, also referred to as "azo initiator") is preferable, and an initiator composed of a polymer azo compound (hereinafter, also referred to as "polymer azo initiator") is more preferable from the viewpoint of suppressing liquid crystal contamination in the case where the obtained curable resin composition is used for a sealant for a liquid crystal display element.
The thermal polymerization initiator may be used alone or in combination of 2 or more.
In the present specification, the "polymer azo compound" refers to a compound having an azo group and having a number average molecular weight of 300 or more, which generates radicals capable of curing (meth) acryloyloxy groups by heat.
The number average molecular weight of the polymer azo compound is preferably 1000 at the lower limit and 30 tens of thousands at the upper limit. When the number average molecular weight of the polymer azo compound is in this range, it is possible to prevent adverse effects on liquid crystals and to easily mix the polymer azo compound with a curable resin when the obtained curable resin composition is used as a sealant for a liquid crystal display element. The number average molecular weight of the polymer azo compound is more preferably limited to 5000, more preferably to 10 ten thousand, still more preferably to 1 ten thousand, and still more preferably to 9 ten thousand.
Examples of the polymer azo compound include: a polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via azo groups.
The polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via azo groups is preferably a polymer azo compound having a polyethylene oxide structure.
Specific examples of the polymer azo compound include a polycondensate of 4,4 '-azobis (4-cyanovaleric acid) and polyalkylene glycol, and a polycondensate of 4,4' -azobis (4-cyanovaleric acid) and polydimethylsiloxane having a terminal amino group.
Examples of the commercially available products of the polymeric azo initiator include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (both manufactured by Fuji film and Wako pure chemical industries, ltd.).
Examples of azo initiators other than polymers include V-65 and V-501 (both of Fuji photo-chemical Co., ltd.).
Examples of the organic peroxide include ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
The content of the thermal polymerization initiator is preferably 0.01 part by weight, and the upper limit is preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the thermal polymerization initiator is within this range, contamination of liquid crystal in the case where the obtained curable resin composition is used for a sealant for a liquid crystal display element is suppressed, and the storage stability and thermosetting property are further excellent. The lower limit of the content of the thermal polymerization initiator is more preferably 0.1 part by weight, and the upper limit is more preferably 5 parts by weight.
The curable resin composition of the present invention may contain a thermosetting agent.
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, and acid anhydrides. Among them, organic acid hydrazides are suitably used.
The above-mentioned thermosetting agents may be used alone or in combination of 2 or more.
Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of the commercial products of the organic acid hydrazide include organic acid hydrazides manufactured by Otsuka chemical company, and organic acid hydrazides manufactured by Ajinomoto Fine-Techno company.
Examples of the organic acid hydrazide manufactured by Otsuka chemical Co., ltd include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Techno include Amicure VDH, amicure VDH-J, amicure UDH, and Amicure UDH-J.
The content of the thermosetting agent is preferably 1 part by weight at a lower limit and 50 parts by weight at an upper limit, based on 100 parts by weight of the curable resin. By setting the content of the thermosetting agent to this range, thermosetting properties can be further improved without deteriorating the coatability and the like of the obtained curable resin composition. The more preferable upper limit of the content of the above-mentioned thermosetting agent is 30 parts by weight.
The curable resin composition of the present invention preferably contains a filler for the purpose of viscosity adjustment, further improvement of adhesion due to stress dispersion effect, improvement of linear expansion coefficient, improvement of moisture resistance of a cured product, and the like.
As the filler, an inorganic filler and an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, montmorillonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
The above fillers may be used alone or in combination of 2 or more.
The preferable lower limit of the content of the filler in 100 parts by weight of the curable resin composition of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. When the content of the filler is in this range, the effect of improving the adhesion and the like is more excellent without deteriorating the coating property and the like. The lower limit of the content of the filler is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.
The curable resin composition of the present invention may contain a silane coupling agent. The silane coupling agent mainly has a role as an adhesion promoter for favorably adhering the curable resin composition to an adherend such as a substrate.
Examples of suitable silane coupling agents include 3-aminopropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, and 3-isocyanatopropyl trimethoxysilane. These have excellent effect of improving adhesion to a substrate or the like, and can inhibit the outflow of the curable resin into liquid crystal when the obtained curable resin composition is used as a sealant for a liquid crystal display element by chemically bonding the curable resin.
The silane coupling agent may be used alone or in combination of 2 or more.
The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the curable resin composition of the present invention is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the occurrence of liquid crystal contamination is suppressed and the effect of improving the adhesion is further improved when the obtained curable resin composition is used as a sealant for a liquid crystal display element. The more preferable lower limit of the content of the above silane coupling agent is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.
The curable resin composition of the present invention may contain an opacifying agent. By containing the above-mentioned light-shielding agent, the curable resin composition of the present invention can be suitably used as a light-shielding sealant.
The curable resin composition of the present invention contains the photopolymerization initiator of the present invention having excellent reactivity with light having a long wavelength, and therefore, even when the light blocking agent is contained, the composition is excellent in curability with light having a long wavelength.
Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, a substance having high insulation is preferable, and titanium black is more preferable.
The titanium black exhibits a sufficient effect even without surface treatment, but may be used: surface-treated titanium black such as titanium black surface-treated with an organic component such as a coupling agent, and titanium black surface-coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide. Among them, titanium black treated with an organic component is preferable from the viewpoint of further improving the insulation property.
In addition, since a display element manufactured using the curable resin composition of the present invention containing the titanium black as the light shielding agent has sufficient light shielding properties, a display element having high contrast without light leakage and excellent image display quality can be realized.
Examples of the commercial products of the titanium black include 12S, 13M-C, 13R-N, 14M-C (all of them are manufactured by Mitsubishi MATERIALS Co., ltd.), and Tilack D (manufactured by Gibby formation Co., ltd.).
The preferable lower limit of the specific surface area of the titanium black is 13m 2 Per g, a preferred upper limit is 30m 2 With a lower limit of 15m being more preferred per gram 2 A more preferred upper limit is 25m 2 /g。
The preferable lower limit of the volume resistance of the titanium black is 0.5 Ω·cm, the preferable upper limit is 3 Ω·cm, the more preferable lower limit is 1 Ω·cm, and the more preferable upper limit is 2.5 Ω·cm.
The primary particle diameter of the light-shielding agent is preferably limited to 1nm at a lower limit and 5000nm at an upper limit. When the primary particle diameter of the light-shielding agent is in this range, the light-shielding property can be further improved without deteriorating the drawing property and the like of the obtained curable resin composition. The primary particle diameter of the light-shielding agent is more preferably 5nm in lower limit, more preferably 200nm in upper limit, still more preferably 10nm in lower limit, and still more preferably 100nm in upper limit.
The primary particle size of the light-shielding agent may be measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
The lower limit of the content of the light-shielding agent in 100 parts by weight of the curable resin composition of the present invention is preferably 5 parts by weight, and the upper limit is preferably 80 parts by weight. By setting the content of the light blocking agent to this range, the obtained curable resin composition can exhibit more excellent light blocking properties without deteriorating the adhesion to an adherend such as a substrate, the strength after curing, and the drawing property. The content of the light-shielding agent is more preferably 10 parts by weight, still more preferably 70 parts by weight, still more preferably 30 parts by weight, and still more preferably 60 parts by weight.
The curable resin composition of the present invention may further contain additives such as a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, a leveling agent, and a polymerization inhibitor, as required.
Examples of the method for producing the curable resin composition of the present invention include: a method of mixing the curable resin, the photopolymerization initiator, and additives such as a silane coupling agent, if necessary, using a mixer.
Examples of the mixer include a homogenizing and dispersing machine, a homogenizing and mixing machine, a universal mixer, a planetary mixer, a kneader, and a three-roll machine.
The curable resin composition of the present invention can be suitably used as a composition for a display element, and can be particularly suitably used as a sealant for a liquid crystal display element. The composition for a display element and the sealant for a liquid crystal display element each comprising the curable resin composition of the present invention are also one of the present invention.
By incorporating conductive fine particles into the sealing agent for a liquid crystal display element of the present invention, a vertically conductive material can be produced. The vertical conductive material containing the sealing agent for a liquid crystal display element and conductive fine particles of the present invention is also one of the present invention.
As the conductive fine particles, metal balls, fine particles having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, the fine particles having the conductive metal layer formed on the surface of the fine resin particles are suitable because the fine resin particles have excellent elasticity and can be electrically connected without damaging the transparent substrate or the like.
The liquid crystal display element using the sealant for a liquid crystal display element of the present invention or the vertically conductive material of the present invention is also one of the present invention.
The sealant for a liquid crystal display element of the present invention can be suitably used for manufacturing a liquid crystal display element by a liquid crystal dropping process. Examples of the method for manufacturing the liquid crystal display element of the present invention by the liquid crystal dropping method include the following methods.
First, a step of applying the sealant for a liquid crystal display element of the present invention to a substrate to form a frame-like seal pattern is performed. Next, a step of applying droplets of liquid crystal to the entire inner surface of the frame of the seal pattern in an uncured state such as a sealant for a liquid crystal display element of the present invention and immediately superposing the other substrate is performed. Then, a step of irradiating the seal pattern portion with light to photocure the sealant is performed, and by the above method, a liquid crystal display element can be obtained. By setting the light to be irradiated to light of a wavelength such as visible light, damage to the peripheral member due to the light irradiation can be alleviated, and the sealant can be sufficiently photo-cured even when the sealant is disposed in the light shielding portion. In addition, the step of curing the sealant by heating may be performed in addition to the step of photocuring the sealant.
Effects of the invention
According to the present invention, a thioxanthone compound having excellent reactivity with light having a long wavelength can be provided. Further, according to the present invention, a photopolymerization initiator containing the thioxanthone compound, a curable resin composition containing the photopolymerization initiator and having excellent storage stability and light shielding portion curability, a composition for a display element using the curable resin composition, and a sealant for a liquid crystal display element using the curable resin composition and having excellent low liquid crystal contamination properties can be provided. Further, according to the present invention, it is possible to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
Drawings
Fig. 1 is a cross-sectional view schematically showing a liquid crystal display element produced without a light shielding portion using each of the curable resin compositions obtained in examples and comparative examples.
Fig. 2 is a cross-sectional view schematically showing a liquid crystal display element produced in a state where a light shielding portion is present using each of the curable resin compositions obtained in examples and comparative examples.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(production of Compound A)
To 5.0 parts by weight of 2, 5-thiophenedicarboxylic acid in 100mL of dehydrated tetrahydrofuran, 20.0 parts by weight of 2-hydroxy-9-oxothioxanthene and 0.1 part by weight of p-toluenesulfonic acid were added, and the mixture was refluxed for 12 hours. Next, the resultant was extracted with ethyl acetate. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution and brine, and then dried over anhydrous magnesium sulfate, whereby 1.2 parts by weight of compound a (pale yellow solid) as a photopolymerization initiator of the present invention was obtained.
By passing through 1 H-NMR, GPC and FT-IR analysis revealed that the obtained compound A was a compound represented by the following formula (4).
[ chemical formula 4]
(production of Compound B)
To 5.0 parts by weight of 9-oxothioxanthene in 100mL of methylene chloride, 2.7 parts by weight of thiophene-2, 5-dicarbonyl dichloride and 3.7 parts by weight of aluminum chloride were added, and the mixture was stirred at room temperature for one hour. Next, the reaction mixture was poured into ice water, and the resultant was extracted with ethyl acetate. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution and brine, and then dried over anhydrous magnesium sulfate, whereby 4.3 parts by weight of compound B (pale yellow solid) as a photopolymerization initiator of the present invention was obtained.
By passing through 1 H-NMR, GPC and FT-IR analysis revealed that the compound B was a compound represented by the following formula (5).
[ chemical formula 5]
(production of Compound C)
Compound C was obtained as a photopolymerization initiator of the present invention in the same way as the above "(production of compound B)", except that 2, 4-diethyl-9-oxothioxanthene was used instead of 9-oxothioxanthene.
By passing through 1 H-NMR, GPC and FT-IR analysis revealed that the obtained compound C was a compound represented by the following formula (6).
[ chemical formula 6]
(production of Compound D)
Compound D was obtained as a photopolymerization initiator of the present invention in the same way as the above "(production of compound B)", except that 2-nitro-9-oxothioxanthene was used instead of 9-oxothioxanthene.
By passing through 1 H-NMR, GPC and FT-IR analysis revealed that the obtained compound D was a compound represented by the following formula (7).
[ chemical formula 7]
(preparation of Compound E)
To 5.0 parts by weight of 9-oxothioxanthene-2-trifluoromethanesulfonate in 100mL of tetrahydrofuran was added PdCl 2 (dppf) 0.1 part by weight, K 2 PO 4 1.0 parts by weight and 2.7 parts by weight of 2-dithiophene-5-boronic acid were refluxed for 3 hours. Next, the resultant was extracted with ethyl acetate. The ethyl acetate layer was washed with a saturated aqueous sodium hydrogencarbonate solution and brine, and then dried over anhydrous magnesium sulfate, whereby 1.9 parts by weight of compound E (pale yellow solid) as a photopolymerization initiator of the present invention was obtained.
By passing through 1 H-NMR, GPC and FT-IR analysis revealed that the obtained compound E was a compound represented by the following formula (8).
[ chemical formula 8]
(preparation of Compound F)
A compound F as a photopolymerization initiator of the present invention was obtained in the same way as the above "(production of compound B)", except that furan-2, 5-dicarboxyl dichloride was used instead of thiophene-2, 5-dicarbonyl dichloride.
By passing through 1 H-NMR, GPC and FT-IR analysis revealed that the compound F was a compound represented by the following formula (9).
[ chemical formula 9]
Examples 1 to 15 and comparative examples 1 to 4
The curable resin compositions of examples 1 to 15 and comparative examples 1 to 4 were prepared by mixing the materials in the proportions shown in tables 1 to 3 using a planetary mixer (manufactured by THINKY Co., ltd., "deaeration mixing Takara Shuzo").
< evaluation >
The curable resin compositions obtained in examples and comparative examples were evaluated as follows. The results are shown in tables 1 to 3.
(storage stability)
The initial viscosity immediately after production and the viscosity after 24 hours of storage at 25℃under 50% RH atmosphere after production were measured for each of the curable resin compositions obtained in examples and comparative examples. The storage stability was evaluated by setting (viscosity after storage)/(initial viscosity) as a thickening ratio, setting the thickening ratio to be "very small" when the thickening ratio is less than 1.05, setting the thickening ratio to be 1.05 or more and less than 1.10 as "o", setting the thickening ratio to be 1.10 or more and less than 1.15 as "Δ", and setting the thickening ratio to be 1.15 or more as "x".
The viscosity of the curable resin composition was measured using an E-type viscometer (manufactured by BROOK FIELD Co., "DV-III"), at 25℃and a rotation speed of 1.0 rpm.
(photo-curing Property)
1 part by weight of spacer particles (made by water chemical industry Co., ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each curable resin composition obtained in examples and comparative examples. Then, the curable resin composition was filled into a dispensing syringe (manufactured by Musashi Engineering, company, "PSY-10E"), subjected to a defoaming treatment, and then coated on a glass substrate by a dispenser (manufactured by Musashi Engineering, company, "SHOTMASTER 300"). The glass substrate of the same size was bonded to the substrate under reduced pressure of 5Pa by a vacuum bonding apparatus. The portion of the cured resin composition of the bonded glass substrate was irradiated with 100mW/cm using a metal halide lamp 2 For 10 seconds. The light irradiation is performed by a cut-off filter (400 nm cut-off filter) that cuts off light having a wavelength of 400nm or less.
FT-IR measurement of the curable resin composition was performed using an infrared spectroscopic device (manufactured by BIORAD Co., "FTS 3000"), and the amount of change in the peak derived from the (meth) acryloyl group before and after light irradiation was measured. The case where the peak derived from (meth) acryloyl group after light irradiation was reduced by 95% or more was designated "excellent", the case where the peak derived from (meth) acryloyl group after light irradiation was reduced by 85% or more and less than 95% was designated "good", the case where the peak derived from (meth) acryloyl group after light irradiation was reduced by 80% or more and less than 85% was designated "delta", and the case where the peak derived from (meth) acryloyl group after light irradiation was reduced by less than 80% was designated "×", and photocurability was evaluated.
(Low liquid Crystal contamination)
1 part by weight of spacer particles (made by water chemical industry Co., ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each curable resin composition obtained in examples and comparative examples. Next, the curable resin composition in which the spacer fine particles were dispersed was applied to the substrate with the rubbed alignment film and the transparent electrode by using a dispenser so that the line width became 1 mm.
Next, a fine droplet of liquid crystal (manufactured by Chisso corporation, "JC-5004 LA") was applied dropwise to the tapeThe color filter substrate with the transparent electrode was immediately bonded to the entire in-frame surface of the curable resin composition on the electrode substrate. Then, the curable resin composition was irradiated with 100mW/cm by using a metal halide lamp 2 The cured product was heated at 120℃for 1 hour to obtain a liquid crystal display element. The light irradiation is performed by a cut-off filter (400 nm cut-off filter) that cuts off light having a wavelength of 400nm or less.
For the liquid crystal display element, 2 kinds of liquid crystal display elements (no light shielding portion) were produced in which light was completely irradiated to the curable resin composition by controlling the application position of the curable resin composition by a dispenser, and liquid crystal display elements (having a light shielding portion) in which the curable resin composition was applied to the black matrix of the color filter substrate so as to apply 50% of the line width. Fig. 1 is a cross-sectional view schematically showing a liquid crystal display element fabricated without a light shielding portion using each of the curable resin compositions obtained in examples and comparative examples, and fig. 2 is a cross-sectional view schematically showing a liquid crystal display element fabricated with a light shielding portion using each of the curable resin compositions obtained in examples and comparative examples. As shown in fig. 1, the state in which the light shielding portion is not present in the curable resin composition 1 is a state in which the curable resin composition 1 is completely irradiated with light, whereas as shown in fig. 2, the state in which the light shielding portion is present in the curable resin composition 1 is a state in which the curable resin composition 1 is in contact with the liquid crystal 3, and the light is hardly reached because the curable resin composition 1 is shielded by the black matrix 2.
After 100 hours of operation test, the obtained liquid crystal display element was visually checked to confirm that the alignment of the liquid crystal was disturbed (display unevenness) when a voltage was applied at 80 ℃ for 1000 hours.
The liquid crystal display device was evaluated for low liquid crystal contamination by marking "very good" when no display unevenness was observed at all in the liquid crystal display device, marking "good" when slight display unevenness was observed in the vicinity (peripheral portion) of the curable resin composition of the liquid crystal display device, marking "delta" when there was a significant thick display unevenness in the peripheral portion, marking "x" when the significant thick display unevenness was spread not only in the peripheral portion but also in the central portion.
The liquid crystal display elements evaluated as "verygood" and "good" are grades having no problem in practical use, the liquid crystal display element of "delta" is a grade having a possibility of causing a problem according to display design, and the liquid crystal display element of "×" is a grade not practical.
TABLE 1
TABLE 3
Industrial applicability
According to the present invention, a thioxanthone compound having excellent reactivity with light having a long wavelength can be provided. Further, according to the present invention, a photopolymerization initiator containing the thioxanthone compound, a curable resin composition containing the photopolymerization initiator and having excellent storage stability and light shielding portion curability, a composition for a display element using the curable resin composition, and a sealant for a liquid crystal display element using the curable resin composition and having excellent low liquid crystal contamination properties can be provided. Further, according to the present invention, it is possible to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
Description of the reference numerals
1. Curable resin composition
2. Black matrix
3. Liquid crystal
Claims (10)
1. A thioxanthone compound represented by the following formula (1),
in the formula (1), X represents a structure represented by the following formula (2-1), (2-2) or (2-3), R 1 Each independently of the other and represents a hydrogen atom, a methyl group, an ethyl group or a nitro group, R 2 Each independently and represents a hydrogen atom, a methyl group, an ethyl group or a nitro group,
in the formulae (2-1), (2-2) and (2-3), R 3 Represents a structure containing a hetero atom and an aromatic ring, and represents a bonding position.
2. The thioxanthone compound of claim 1, wherein the R 3 Is of the structure represented by the following formula (3-1), (3-2), (3-3), (3-4), (3-5), (3-6), (3-7) or (3-8),
in the formulae (3-1) to (3-8), the bond position is represented; in the formulae (3-1) to (3-8), hydrogen atoms other than the hydrogen atoms contained in the OH groups of the formulae (3-2) and (3-3) are optionally substituted.
3. The thioxanthone compound of claim 2, wherein the R 3 The structure is represented by the formula (3-1).
4. The thioxanthone compound according to claim 1, 2 or 3, wherein at least 1R in the formula (1) 1 Is methyl or ethyl, and at least 1R in the formula (1) 2 Is methyl or ethyl.
5. A photopolymerization initiator comprising the thioxanthone compound of claim 1, 2, 3 or 4.
6. A curable resin composition comprising a curable resin and the photopolymerization initiator according to claim 5.
7. A composition for display elements, which is prepared by using the curable resin composition according to claim 6.
8. A sealant for a liquid crystal display element, which is obtained by using the curable resin composition according to claim 6.
9. A vertically conductive material comprising the sealant for a liquid crystal display element according to claim 8 and conductive fine particles.
10. A liquid crystal display element comprising the sealant for a liquid crystal display element according to claim 8 or the vertically conductive material according to claim 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020164804 | 2020-09-30 | ||
| JP2020-164804 | 2020-09-30 | ||
| PCT/JP2021/035089 WO2022071116A1 (en) | 2020-09-30 | 2021-09-24 | Thioxanthone compound, photopolymerization initiator, curable resin composition, composition for display element, sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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| CN115996959A true CN115996959A (en) | 2023-04-21 |
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| CN202180043468.7A Pending CN115996959A (en) | 2020-09-30 | 2021-09-24 | Thioxanthone compound, photopolymerization initiator, curable resin composition, composition for display element, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7144627B2 (en) |
| KR (1) | KR20230078950A (en) |
| CN (1) | CN115996959A (en) |
| TW (1) | TW202222804A (en) |
| WO (1) | WO2022071116A1 (en) |
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- 2021-09-24 CN CN202180043468.7A patent/CN115996959A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2022071116A1 (en) | 2022-04-07 |
| WO2022071116A1 (en) | 2022-04-07 |
| TW202222804A (en) | 2022-06-16 |
| KR20230078950A (en) | 2023-06-05 |
| JP7144627B2 (en) | 2022-09-29 |
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