CN115004093A - Photothermally curable resin composition, liquid crystal sealing agent comprising same, liquid crystal display panel, and method for producing same - Google Patents
Photothermally curable resin composition, liquid crystal sealing agent comprising same, liquid crystal display panel, and method for producing same Download PDFInfo
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- CN115004093A CN115004093A CN202180011019.4A CN202180011019A CN115004093A CN 115004093 A CN115004093 A CN 115004093A CN 202180011019 A CN202180011019 A CN 202180011019A CN 115004093 A CN115004093 A CN 115004093A
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- China
- Prior art keywords
- liquid crystal
- resin composition
- curable resin
- compound
- seal pattern
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 97
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 96
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 86
- 238000007789 sealing Methods 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 146
- 239000000758 substrate Substances 0.000 claims abstract description 70
- 239000010419 fine particle Substances 0.000 claims abstract description 52
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 238000013007 heat curing Methods 0.000 claims abstract description 19
- 150000001993 dienes Chemical class 0.000 claims abstract description 18
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 17
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- 239000004945 silicone rubber Substances 0.000 claims abstract description 7
- 238000001723 curing Methods 0.000 claims description 49
- -1 aromatic vinyl compound Chemical class 0.000 claims description 32
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- 239000011256 inorganic filler Substances 0.000 claims description 15
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
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- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 39
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- 239000002245 particle Substances 0.000 description 19
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 11
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
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- JYKHAJGLEVKEAA-UHFFFAOYSA-N 2-(hydroxymethyl)anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CO)=CC=C3C(=O)C2=C1 JYKHAJGLEVKEAA-UHFFFAOYSA-N 0.000 description 2
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- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- 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
Abstract
The present invention addresses the problem of providing a photothermal curable resin composition that, when used as a liquid crystal sealing agent, can form a sealing member having high adhesion to various substrates. The photothermal curable resin composition for solving the above problems contains a curable compound (A) having an ethylenically unsaturated double bond in the molecule, a photopolymerization initiator (B), a latent heat curing agent (C), and organic fine particles (D). The organic fine particles (D) have an outer shell portion and a core portion, and the core portion contains at least one of a conjugated diene rubber and a silicone rubber containing a structural unit derived from a conjugated diene.
Description
Technical Field
The present invention relates to a photothermal curable resin composition, a liquid crystal sealing agent containing the same, a liquid crystal display panel, and a method for producing the same.
Background
As image display panels for various electronic devices such as mobile phones and personal computers, display panels of liquid crystal, organic EL, and the like are widely used. For example, a liquid crystal display panel has: 2 transparent substrates having electrodes provided on the surfaces thereof; a frame-shaped sealing member sandwiched therebetween; and a liquid crystal material sealed in a region surrounded by the sealing member.
Here, the sealing member is required to have high adhesion to the substrate. If the sealing member is peeled off from the substrate, liquid crystal leakage or the like occurs, and a display failure of an image occurs. Therefore, conventionally, a liquid crystal sealing agent used for forming a sealing member contains a compound having a hydrophilic group (for example, a silane coupling agent) and the hydrophilic group in the sealing member is chemically bonded to a hydrophilic group present on the surface of a substrate, thereby improving the adhesion.
Patent document 1 proposes that core-shell particles be contained in a liquid crystal sealing agent for forming a sealing member. Specifically, there is described core-shell-structured fine particles (F-351, manufactured by Aica Kogyo Co., Ltd.) in which the core is polybutylacrylate and the shell is polymethyl methacrylate.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 2005-15757
Disclosure of Invention
Problems to be solved by the invention
In the liquid crystal display panel, alignment films are generally disposed on the surfaces of a pair of substrates, respectively, and liquid crystals are aligned in a desired direction. In addition, in a conventional liquid crystal display panel, a liquid crystal sealant is generally applied to the outside of an alignment film disposed on a substrate to form a sealing member. Therefore, the adhesion between the substrate and the sealing member may be improved, and the adhesion between the sealing member and the substrate may be improved by adding a silane coupling agent or the like as described above.
However, in recent years, a liquid crystal display panel is required to have a narrow frame. Therefore, it is required to form a sealing member or the like by applying a liquid crystal sealing agent also to the region where the alignment film is disposed. However, in recent years, the alignment film has high hydrophobicity and the number of hydrophilic groups is small. That is, the amount of groups that can covalently bond to hydrophilic groups in the liquid crystal sealant is small. Therefore, it is difficult for the conventional liquid crystal sealing agent to sufficiently improve the adhesion strength between the sealing member obtained by applying the liquid crystal sealing agent and the substrate on which the alignment film is disposed. For example, there are problems as follows: if a load is applied to the liquid crystal display panel from the outside, they are peeled off at the interface of the sealing member and the substrate, and the like. Further, even when the liquid crystal sealing agent containing particles as described in patent document 1 is used, it is difficult to improve the adhesion between the substrate and the sealing member.
The present invention has been made in view of the above problems. The purpose is to provide a photo-thermal curable resin composition and the like which can form a sealing member having high adhesion to various substrates when used as a liquid crystal sealing agent, for example.
Means for solving the problems
The present invention provides the following photothermal curable resin composition and a liquid crystal sealing agent comprising the same.
[1] A photothermally curable resin composition comprising a curable compound (A) having an ethylenically unsaturated double bond in the molecule, a photopolymerization initiator (B), a latent heat curing agent (C), and organic fine particles (D), wherein the organic fine particles (D) have a shell portion and a core portion, and the core portion comprises at least one of a conjugated diene rubber and a silicone rubber containing a structural unit derived from a conjugated diene.
[2] The photothermal curable resin composition according to [1], wherein the organic fine particles (D) are composed of the outer shell portion and the core portion, the core portion contains a conjugated diene rubber containing a structural unit derived from a conjugated diene and an aromatic vinyl compound, and the outer shell portion contains a polymer having 1 or more structures selected from the group consisting of a methyl methacrylate structure, a styrene structure, an acrylonitrile structure, and a glycidyl structure.
[3] The photothermally curable resin composition according to [1] or [2], further comprising an inorganic filler (E).
[4] The photothermal curable resin composition according to any one of [1] to [3], wherein the content of the organic fine particles (D) is 5 to 17% by mass.
[5] The photothermal curable resin composition according to any one of [1] to [4], wherein the latent heat curing agent (C) is at least 1 curing agent selected from the group consisting of organic acid dihydrazide-based heat latent curing agents, amine adduct-based heat latent curing agents, and polyamine-based heat latent curing agents.
[6] A liquid crystal sealing agent comprising the photothermal curable resin composition according to any one of the above [1] to [5 ].
The invention provides a method for manufacturing a liquid crystal display panel and a liquid crystal display panel obtained by the method.
[7] A method of manufacturing a liquid crystal display panel, comprising: a step of forming a seal pattern by applying the liquid crystal sealant according to the above [6] to the alignment film of one of a pair of substrates each having the alignment film; dropping a liquid crystal on the first substrate in a region of the seal pattern or on the second substrate in a state where the seal pattern is not cured; a step of laminating the first substrate and the second substrate with the seal pattern interposed therebetween; and curing the seal pattern.
[8] The method of manufacturing a liquid crystal display panel according to [7], wherein in the step of curing the seal pattern, the seal pattern is cured by irradiating light to the seal pattern.
[9] The method of manufacturing a liquid crystal display panel according to item [8], wherein the light irradiated to the seal pattern includes light in a visible light region.
[10] The method of manufacturing a liquid crystal display panel according to [8] or [9], wherein the seal pattern irradiated with the light is further heated in the step of curing the seal pattern.
[11] A liquid crystal display panel, comprising: a pair of substrates each having an alignment film; a frame-shaped sealing member disposed between the alignment films of the pair of substrates; and a liquid crystal layer filled in a space surrounded by the sealing member between the pair of substrates, the sealing member being a cured product of the liquid crystal sealing agent described in [6 ].
Effects of the invention
According to the photothermal curable resin composition of the present invention, when used as a liquid crystal sealing agent, a sealing member capable of firmly bonding a pair of substrates to each other can be obtained.
Detailed Description
1. Photothermal curable resin composition
The photothermal curable resin composition of the present invention contains a curable compound (A) having an ethylenically unsaturated double bond in the molecule, a photopolymerization initiator (B), a latent heat curing agent (C), and specific organic fine particles (D).
As described above, in the conventional photothermal curable resin composition (liquid crystal sealing agent), adhesion between a cured product (sealing member) and a substrate is generally improved by chemical bonding. However, this method cannot sufficiently cope with a case where an alignment film is disposed on a substrate, and adhesion to the substrate is not sufficiently obtained depending on the type of the substrate.
In contrast, the photothermal curable resin composition of the present invention includes organic fine particles (D) having an outer shell portion and a core portion, and the core portion of the organic fine particles (D) includes either a conjugated diene rubber containing a structural unit derived from a conjugated diene or a silicone rubber. When the photothermal curable resin composition contains such organic fine particles (D), residual stress generated when the photothermal curable resin composition is applied and cured is relaxed by the core portions of the organic fine particles (D). Therefore, stress is not easily applied between the substrate and the cured product. That is, even if an alignment film or the like is disposed on the substrate, peeling between the substrate and the photothermal curable resin composition (sealing member) is less likely to occur. Even when a load is applied to a liquid crystal display panel or the like including a cured product (sealing member) of the photothermal curable resin composition, the organic fine particles (D) can disperse the load. Therefore, stress is less likely to act on the interface between the sealing member and the substrate, and peeling of these is suppressed.
The components in the photothermal curable resin composition of the present invention will be described in detail below.
1-1 curable Compound (A)
The curable compound (a) may be a compound having an ethylenically unsaturated double bond in the molecule. The curable compound (a) may be any of a monomer, an oligomer, or a polymer. Examples of the curable compound (a) include compounds having a (meth) acryloyl group in the molecule. The number of (meth) acryloyl groups in the compound having a (meth) acryloyl group per 1 molecule may be 1, or 2 or more. In the present specification, the term (meth) acryloyl refers to acryloyl or methacryloyl, or both. The description of (meth) acrylate refers to acrylate or methacrylate, or both. Further, the description of "(meth) acryl-" means "acryl-" or "methacryl-", or both of them.
Examples of the curable compound (a) containing 1 (meth) acryloyl group in 1 molecule include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
Examples of the curable compound (a) having 2 or more (meth) acryloyl groups in 1 molecule include: di (meth) acrylates derived from polyethylene glycol, propylene glycol, polypropylene glycol, and the like; di (meth) acrylate from tris (2-hydroxyethyl) isocyanurate; di (meth) acrylate derived from a diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol; di (meth) acrylate derived from diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol a; di-or tri (meth) acrylate derived from triol obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane; di (meth) acrylate derived from diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of bisphenol a; tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate; trimethylolpropane tri (meth) acrylate, or an oligomer thereof; pentaerythritol tri (meth) acrylate or an oligomer thereof; poly (meth) acrylates of dipentaerythritol; tris (acryloyloxyethyl) isocyanurate; caprolactone-modified tris (acryloyloxyethyl) isocyanurate; caprolactone-modified tris (methacryloyloxyethyl) isocyanurate; poly (meth) acrylates of alkyl-modified dipentaerythritol; caprolactone-modified poly (meth) acrylates of dipentaerythritol; hydroxypivalic acid neopentyl glycol di (meth) acrylate; caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate; ethylene oxide-modified phosphoric acid (meth) acrylate; ethylene oxide-modified alkylated phosphoric acid (meth) acrylates; neopentyl glycol, trimethylolpropane, oligomeric (meth) acrylates of pentaerythritol, and the like.
The curable compound (a) may further have an epoxy group in the molecule. The number of epoxy groups per 1 molecule may be 1, or 2 or more. When the curable compound (a) has not only a (meth) acryloyl group but also an epoxy group in a molecule, the photothermal curable resin composition may be cured by heat. That is, both photocuring and thermal curing may be used. When the photothermal curable resin composition has photocurability and thermosetting properties, the photothermal curable resin composition can be efficiently cured in a short time.
Examples of the compound having a (meth) acryloyl group and an epoxy group in a molecule include glycidyl (meth) acrylate obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a basic catalyst.
The epoxy compound that reacts with (meth) acrylic acid may be a polyfunctional epoxy compound having 2 or more epoxy groups in the molecule, and is preferably a 2-functional epoxy compound from the viewpoint of suppressing the decrease in the adhesiveness of the cured product of the photothermal curable resin composition due to an excessively high crosslinking density. Examples of the 2-functional epoxy compound include bisphenol type epoxy compounds (bisphenol A type, bisphenol F type, 2' -diallylbisphenol A type, bisphenol AD type, hydrogenated bisphenol type, and the like), biphenyl type epoxy compounds, and naphthalene type epoxy compounds. Among them, bisphenol type epoxy compounds of bisphenol a type and bisphenol F type are preferable from the viewpoint that the coating property of the photothermal curable resin composition is easily improved. The curable compound (a) derived from the bisphenol epoxy compound has advantages such as superior coating properties to the curable compound (a) derived from the biphenyl ether epoxy compound.
The curable compound (a) may contain only one kind of the above-mentioned compound, or may contain two or more kinds thereof. The curable compound (a) is particularly preferably a compound (a1) having a (meth) acryloyl group and no epoxy group in the molecule, and a compound (a2) having a (meth) acryloyl group and an epoxy group in the molecule. For example, when another curable compound (for example, an epoxy compound) described later is further contained in the photothermal curable resin composition, the compatibility between the compound (a1) and the epoxy compound may be low. On the other hand, when the compound having an epoxy group (a2) is used, the compatibility of each component in the photothermal curable resin composition is improved. In addition, in general, when the photothermographic curable resin composition is used for a liquid crystal sealing agent, a hydrophobic compound (e.g., an epoxy compound) is more likely to elute into a liquid crystal than a hydrophilic compound, but by combining the compound (a1) and the compound (a2), elution of the epoxy compound into the liquid crystal is more likely to be suppressed. The content mass ratio of the compound (a2) to the compound (a1) is preferably 1/0.4 to 1/0.6 as a2/a 1.
The content of the compound (a2) having a (meth) acryloyl group and an epoxy group in the molecule is not particularly limited, and is preferably 30% by mass or more, for example, based on the total amount of the curable compound (a).
In any of the above curable compounds (a), the weight average molecular weight is preferably about 310 to 1000. The weight average molecular weight of the curable compound (a) can be measured in terms of polystyrene by Gel Permeation Chromatography (GPC), for example.
The content of the curable compound (a) is preferably 40 to 80% by mass, and more preferably 50 to 75% by mass, based on the total amount of the photothermal curable resin composition. When the amount of the curable compound (a) is within this range, the strength of the obtained cured product (e.g., sealing member) is increased, and the adhesion between the substrate and the cured product (sealing member) can be improved.
1-2 photo polymerization initiator (B)
The photopolymerization initiator is not particularly limited as long as it is a compound capable of, for example, radical polymerization of the curable compound (a) by irradiation with light. For example, the photopolymerization initiator may be a self-cleavage type photopolymerization initiator or a hydrogen abstraction type photopolymerization initiator.
Examples of the self-cleavage type photopolymerization initiator include: alkylphenone-based compounds (e.g., benzildimethyl ketal such as 2, 2-dimethoxy-1, 2-diphenylethane-1-one (IRGACURE 651 manufactured by BASF Co., Ltd.); α -aminoalkylphenones such as 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1-one (IRGACURE 907 manufactured by BASF Co., Ltd.); α -hydroxyalkylphenones such as 1-hydroxycyclohexylphenylketone (IRGACURE 184 manufactured by BASF Co., Ltd.), acylphosphine oxide-based compounds (e.g., 2,4, 6-trimethylbenzoin diphenylphosphine oxide), titanocene-based compounds (e.g., bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, etc.)), Acetophenone-based compounds (e.g., diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-mercaptomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, etc.), benzoyl formate-based compounds (e.g., methyl phenylglyoxylate (methyl phenylglyoylester), etc.), Benzoin ether compounds (e.g., benzoin methyl ether, benzoin isopropyl ether, etc.), and oxime ester compounds (e.g., 1, 2-octanedione-1- [4- (phenylsulfanyl) -2- (O-benzoyl oxime) ] (IRGACURE OXE01, BASF Co., Ltd.), ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (0-acetyl oxime) (IRGACURE OXE02, BASF Co., Ltd.).
Examples of the hydrogen abstraction-type photopolymerization initiator include: benzophenone-based compounds (e.g., benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4 ' -dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4 ' -methyl-diphenylsulfide, acrylated benzophenone, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3 ' -dimethyl-4-methoxybenzophenone, etc.), thioxanthone-based compounds (e.g., thioxanthone, 2-chlorothioxanthone (manufactured by Tokyo chemical industries), 1-chloro-4-propoxythioxanthone, 1-chloro-4-ethoxythioxanthone (Speedcure CPTX manufactured by Lambson Limited), 2-isopropylxanthone (Speedcure ITX manufactured by Lambson Limited), 4-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-Diethylthioxanthone (DETX) (Speedcure DETX manufactured by Lambson Limited), 2, 4-dichlorothioxanthone, etc.), anthraquinone compounds (e.g., 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertbutylanthraquinone, 1-chloroanthraquinone, 2-Hydroxyanthraquinone (2-Hydroxyanthone manufactured by Tokyo Kagaku K.), 2, 6-dihydroxyanthraquinone (Anthraflavic Acid manufactured by Tokyo Kagaku K.), 2-hydroxymethylanthraquinone (2- (Hydroxymethyl) anthone manufactured by pure chemical Co., Ltd.), etc.), and benzil compounds. The photothermal curable resin composition may contain only one kind of photopolymerization initiator (B), or may contain two or more kinds of photopolymerization initiators (B).
The absorption wavelength of the photopolymerization initiator (B) is not particularly limited, and for example, it is preferably a photopolymerization initiator (B) that absorbs light having a wavelength of 360nm or more. Among them, the photopolymerization initiator (B) which absorbs light in the visible light region is more preferable, the photopolymerization initiator (B) which absorbs light having a wavelength of 360 to 780nm is further preferable, and the photopolymerization initiator (B) which absorbs light having a wavelength of 360 to 430nm is particularly preferable.
Examples of the photopolymerization initiator (B) which absorbs light having a wavelength of 360nm or more include an alkylphenone-based compound, an acylphosphine oxide-based compound, a titanocene-based compound, an oxime ester-based compound, a thioxanthone-based compound, and an anthraquinone-based compound, and an oxime ester-based compound is preferable.
The structure of the photopolymerization initiator (B) can be determined by combining High Performance Liquid Chromatography (HPLC) and liquid chromatography mass spectrometry (LC/MS), with NMR measurement or IR measurement.
The molecular weight of the photopolymerization initiator (B) is preferably 200 to 5000, for example. If the molecular weight is 200 or more, the photopolymerization initiator (B) is less likely to be eluted into the liquid crystal when the photothermal curable resin composition is used as a liquid crystal sealant. On the other hand, if the molecular weight is 5000 or less, the compatibility with the curable compound (a) increases, and the photo-thermal curable resin composition tends to have good curability. The molecular weight of the photopolymerization initiator (B) is more preferably 230 to 3000, and still more preferably 230 to 1500.
The molecular weight of the photopolymerization initiator (B) can be determined as the "relative molecular mass" of the molecular structure of the main peak detected by High Performance Liquid Chromatography (HPLC).
Specifically, a sample solution in which the photopolymerization initiator (B) was dissolved in THF (tetrahydrofuran) was prepared, and measurement was performed by High Performance Liquid Chromatography (HPLC). Then, the percentage of the area of the detected peak (the ratio of the area of each peak to the total of the areas of all peaks) was obtained, and the presence or absence of the main peak was checked. The main peak is a peak having the highest intensity (peak having the highest height) among all peaks detected at a detection wavelength characteristic to each compound (for example, 400nm in the case of a thioxanthone-based compound). The relative molecular Mass corresponding to the peak top of the main peak detected can be determined by Liquid Chromatography Mass Spectrometry (LC/MS).
The amount of the photopolymerization initiator (B) is preferably 0.01 to 10% by mass relative to the curable compound (A). When the amount of the photopolymerization initiator (B) is 0.01% by mass or more relative to the curable compound (a), the curability of the photothermal curable resin composition is easily improved. When the content of the photopolymerization initiator (B) is 10% by mass or less, the photopolymerization initiator (B) is less likely to be eluted into the liquid crystal when the photothermal curable resin composition is used for a liquid crystal sealing agent. The content of the photopolymerization initiator (B) is more preferably 0.1 to 5% by mass, still more preferably 0.1 to 3% by mass, and particularly preferably 0.1 to 2.5% by mass, relative to the curable compound (a).
1-3 latent heat-curing agent (C)
The latent heat-curing agent (C) is a compound represented by the following formula: a compound which does not cure the thermosetting compound (a) and other curable compounds described later under ordinary storage conditions (room temperature, visible light, etc.), but cures these compounds when heat is applied. If the photothermal curable resin composition contains the latent heat curing agent (C), the photothermal curable resin composition can be thermally cured. The latent heat-curing agent (C) is preferably a curing agent capable of curing an epoxy compound (hereinafter, also referred to as "epoxy curing agent").
From the viewpoint of improving the viscosity stability of the photothermal curable resin composition and not impairing the moisture resistance of the cured product, the melting point of the epoxy curing agent is preferably 50 ℃ to 250 ℃, more preferably 100 ℃ to 200 ℃, and still more preferably 150 ℃ to 200 ℃.
Examples of the epoxy curing agent include organic acid dihydrazide-based heat latent curing agents, imidazole-based heat latent curing agents, dicyandiamide-based heat latent curing agents, amine adduct-based heat latent curing agents, and polyamine-based heat latent curing agents.
Examples of the organic acid dihydrazide-based heat latent curing agent include adipic acid dihydrazide (melting point 181 ℃ C.), 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin (melting point 120 ℃ C.), 7, 11-octadecadienyl-1, 18-dicarbonhydrazide (melting point 160 ℃ C.), dodecanedioic acid dihydrazide (melting point 190 ℃ C.), and sebacic acid dihydrazide (melting point 189 ℃ C.), and the like.
Examples of the imidazole-based heat latent curing agent include 2, 4-diamino-6- [2 '-ethylimidazolyl- (1') ] -ethyltriazine (melting point 215 to 225 ℃ C.), 2-phenylimidazole (melting point 137 to 147 ℃ C.), and the like.
Examples of the dicyandiamide-based heat latent curing agent include dicyandiamide (melting point 209 ℃ C.) and the like.
The amine adduct-based heat latent curing agent is a heat latent curing agent comprising an adduct compound obtained by reacting an amine compound having catalytic activity with an arbitrary compound. Examples of the amine adduct-based heat latent curing agent include Ajinomoto Fine-Techno Co., product of Inc. (melting point 110 ℃ C.), Ajinomoto Fine-Techno Co., product of Inc., Amicure PN-23 (melting point 100 ℃ C.), Ajinomoto Fine-Techno Co., product of Inc. (melting point 115 ℃ C.), Amicone PN-31 (melting point 115 ℃ C.), Ajinomoto Fine-Techno Co., product of Inc., Amicure PN-H (melting point 115 ℃ C.), Ajinomoto Fine-Techno Co., product of Inc. (melting point 120 ℃ C.), and Amiconto Fine-Techno Co., product of Inc. (melting point 131 ℃ C.), and the like.
The polyamine-based heat latent curing agent is a heat latent curing agent having a polymer structure obtained by reacting an amine with an epoxy, and examples thereof include Adeka Harden EH4339S (softening point 120-130 ℃ C.) manufactured by ADEKA, and Adeka Harden EH4357S (softening point 73-83 ℃ C.) manufactured by ADEKA.
Among the above, from the viewpoints of availability, compatibility with other components, and the like, an organic acid dihydrazide-based heat latent curing agent, an amine adduct-based heat latent curing agent, or a polyamine-based heat latent curing agent is preferable. The latent heat-curing agent (C) may contain only one epoxy curing agent, or may contain two or more epoxy curing agents.
The content of the latent heat-curing agent (C) is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 5 to 20% by mass, based on the total amount of the photothermal curable resin composition. The photothermal curable resin composition of the present invention can be prepared into a liquid curable resin composition. The one-pack curable resin composition is excellent in workability because it does not require mixing of a base and a curing agent at the time of use.
The content of the latent heat-curing agent (C) is preferably 3.8 to 75% by mass, more preferably 3.8 to 50% by mass, and still more preferably 5 to 40% by mass, based on the curable compound (a). When the content of the latent heat-curing agent (C) is 3.8% by mass or more relative to the curable compound (a), the curability of the curable compound (a) during heating can be easily improved. On the other hand, if the content is 75% by mass or less, the liquid crystal is less likely to be contaminated with the latent heat-curing agent (C) when the photothermal curable resin composition is used for a liquid crystal sealing agent.
1-4. organic microparticles (D)
The organic fine particles (D) may be particles having an outer shell portion and a core portion, and the core portion may contain a conjugated diene rubber or a silicone rubber. Here, the core portion is a region located near the center of the organic fine particle (D) and giving a desired elasticity to the organic fine particle (D). On the other hand, the outer shell portion is a layer region disposed on the outermost surface side of the organic fine particles (D) as compared with the core portion, and is a layer for improving compatibility between the organic fine particles (D) and other components in the photothermal curable resin composition. The outer shell portion may cover the core portion completely or only a part of the core portion, but when the outer shell portion covers the core portion completely, the affinity of the organic fine particles (D) with other components can be improved, and the dispersibility of the organic fine particles (D) can be improved.
The organic fine particles (D) may contain another layer between the shell portion and the core portion, but are preferably composed of the shell portion and the core portion from the viewpoint of ease of production of the organic fine particles (D). Whether or not the organic fine particles (D) have an outer shell portion and a core portion can be determined by, for example, a Transmission Electron Microscope (TEM) or the like after curing the photothermal curable resin composition by light and heat.
The core portion may contain at least one of a conjugated diene rubber and a silicone rubber, but may contain both. The core portion may contain components other than these rubbers within a range not impairing the object and curing of the present invention.
The conjugated diene rubber may contain a structural unit derived from a conjugated diene alone, or may be a copolymer of a conjugated diene and a vinyl monomer copolymerizable with the conjugated diene.
Examples of the conjugated diene include isoprene, 1, 3-butadiene, 2-chloro-1, 3-butadiene, 2-methyl-1, 3-butadiene, chloroprene and the like. The conjugated diene rubber may contain only one type of constituent unit derived from a conjugated diene, or may contain two or more types of constituent units derived from a conjugated diene. The amount of the structural unit derived from the conjugated diene in the conjugated diene rubber is preferably 50 to 100% by mass based on the total amount of all the structural units.
On the other hand, examples of the vinyl monomer copolymerizable with the conjugated diene include: aromatic vinyl monomers such as styrene, α -methylstyrene, monochlorostyrene and dichlorostyrene; vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl halide monomers such as vinyl chloride and vinyl bromide; vinyl acetate; olefin monomers such as ethylene, propylene, butylene, and isobutylene; and polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. The conjugated diene rubber may contain only one kind of structural unit derived from these vinyl monomers, or may contain two or more kinds of structural units derived from these vinyl monomers. The amount of the structural unit derived from the vinyl monomer in the conjugated diene rubber is preferably 0 to 50% by mass based on the total amount of all the structural units.
Specific examples of the conjugated diene rubber include diene rubbers such as Natural Rubber (NR), Isoprene Rubber (IR), Butadiene Rubber (BR), Styrene Butadiene Rubber (SBR), Styrene Isoprene Butadiene Rubber (SIBR), ethylene propylene diene rubber (EPDM), Chloroprene Rubber (CR), and acrylonitrile butadiene rubber (NBR).
On the other hand, examples of the silicone rubber include rubbers obtained by polymerizing a silicone-based monomer, copolymers of a silicone-based monomer and a vinyl monomer copolymerizable with the silicone-based monomer, and the like.
Examples of the silicone-based monomer include silicone monomers having 2 alkyl groups and/or aryl groups such as dimethylsiloxane, diethylsiloxane, methylphenylsiloxane, diphenylsiloxane, dimethylsiloxane-diphenylsiloxane, and the like; siloxane monomers having 1 alkyl or aryl group, and the like. On the other hand, the vinyl monomer copolymerizable with the silicone-based monomer is the same as the above-mentioned vinyl monomer copolymerizable with the conjugated diene.
Among the above, the core portion of the organic fine particles (D) preferably contains a conjugated diene rubber, more preferably contains a structural unit derived from a conjugated diene and an aromatic vinyl compound (the aromatic vinyl monomer described above), and particularly preferably contains a Styrene Butadiene Rubber (SBR).
The amount of the core part in the entire organic fine particles (D) is preferably 60 to 90% by mass, and more preferably 80 to 90% by mass. When the ratio of the core portion in the organic fine particles (D) is in the above range, sufficient elasticity can be obtained in a cured product of the photothermal curable resin composition. For example, the adhesive strength between the sealing member obtained from the curable resin composition and the substrate of the liquid crystal display panel is sufficiently increased. The content of the core portion in the organic fine particles (D) can be measured by, for example, an absorbance ratio of a spectrum of infrared spectroscopic analysis.
The shape of the core portion is not particularly limited, but is preferably spherical from the viewpoint of, for example, making the particle diameter uniform.
On the other hand, the outer shell portion of the organic fine particle (D) is not particularly limited as long as it has affinity with the core portion and can improve dispersibility of the organic fine particle (D) in the photothermal curable resin composition. The outer shell portion may be a polymer of a (meth) acrylate monomer, a vinyl monomer. Such an outer shell portion can be formed, for example, by forming the core portion and then polymerizing a (meth) acrylate monomer or a vinyl monomer around the core portion.
Examples of the (meth) acrylate ester monomer include: alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate; aromatic ring-containing (meth) acrylates such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; glycidyl (meth) acrylates such as glycidyl (meth) acrylate and glycidyl alkyl (meth) acrylate; alkoxyalkyl (meth) acrylates; allyl alkyl (meth) acrylates such as allyl (meth) acrylate and allyl alkyl (meth) acrylate; polyfunctional (meth) acrylates such as monoethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate; and so on.
On the other hand, examples of the vinyl monomer include the same monomers as those capable of copolymerizing with the conjugated diene described above.
Among them, the outer shell portion preferably contains a polymer having 1 or more structures selected from the group consisting of a methyl methacrylate structure, a styrene structure, an acrylonitrile structure, and a glycidyl structure. When the outer shell portion contains a polymer having such a structure, the above curable compound (a) and the like have good compatibility with the organic fine particles (D).
The amount of the outer shell in the entire organic fine particles (D) is preferably 10 to 40% by mass, and more preferably 10 to 20% by mass. When the ratio of the outer shell portion in the organic fine particles (D) is in the above range, the dispersibility of the organic fine particles (D) is good. The content of the outer shell portion in the organic fine particles (D) can be measured by an absorbance ratio of a spectrum of infrared spectroscopic analysis or the like.
The shape of the organic fine particles (D) is not particularly limited, but is preferably substantially spherical. The average particle diameter of the organic fine particles (D) when they are substantially spherical is preferably 0.1 to 0.8. mu.m, more preferably 0.1 to 0.6. mu.m. When the average particle diameter is within this range, a fine sealing member can be formed using the photothermal curable resin composition. The average particle diameter can be measured by image analysis by a microscopic method, specifically, an electron microscope. More specifically, the average particle diameter was determined by image analysis of the liquid crystal sealing agent and selecting 50 organic fillers having a particle diameter of 1 μm or less and measuring the particle diameter.
The content of the organic fine particles (D) is preferably 5 to 17% by mass, more preferably 7 to 16% by mass, and still more preferably 9 to 15% by mass, based on the total amount of the photothermal curable resin composition. When the amount of the organic fine particles is 5% by mass or more, the adhesion strength between the cured product (sealing member) and the substrate becomes high when the photothermal curable resin composition is used for a liquid crystal sealing agent. On the other hand, when the content of the organic fine particles (D) is 17% by mass or less, the amount of other components (for example, the curable compound (a)) becomes sufficient, and the strength of the cured product (sealing member) increases.
1-5 inorganic Filler (E)
The photothermal curable resin composition of the present invention may further contain an inorganic filler (E) if necessary. When the photothermal curable resin composition contains the inorganic filler (E), the photothermal curable resin composition is easily improved in viscosity, strength of a cured product, linear expansion property, and the like.
Examples of the inorganic filler (E) include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium nitride, aluminum oxide (alumina), zinc oxide, silica, potassium titanate, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride and the like. Among them, silica and talc are preferable.
The shape of the inorganic filler (E) may be a fixed shape such as a sphere, a plate, or a needle, or may be an irregular shape. When the inorganic filler (E) is spherical, the inorganic filler (E) preferably has an average primary particle diameter of 1.5 μm or less and a specific surface area of 0.5 to 20m 2 (ii) in terms of/g. The average primary particle diameter of the inorganic filler (E) 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 content of the inorganic filler (E) is preferably 1 to 45% by mass based on the total amount of the photothermal curable resin composition. When the content of the inorganic filler (E) is 1% by mass or more, the moisture resistance of a cured product of the photothermal curable resin composition is likely to be high, and when it is 45% by mass or less, the coating stability of the photothermal curable resin composition is unlikely to be impaired. The content of the inorganic filler (E) is more preferably 3 to 30% by mass relative to the photothermal curable resin composition.
1-6. other curable Compounds
The photothermal curable resin composition may further contain a thermosetting compound. Wherein the thermosetting compound is a compound different from the above-mentioned curable compound (A).
Examples of the thermosetting compound include epoxy compounds having an epoxy group in the molecule. The epoxy compound may be any of monomers, oligomers or polymers. When the photothermal curable resin composition contains an epoxy compound, the display characteristics of the resulting liquid crystal panel become good, and the moisture resistance of the cured product (sealing member) becomes high.
The epoxy compound particularly preferably has an aromatic ring. The weight average molecular weight of the epoxy compound is preferably 500 to 10000, more 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 the aromatic epoxy compound include: aromatic polyglycidyl ether compounds obtained by reacting aromatic diols represented by bisphenol a, bisphenol S, bisphenol F, bisphenol AD, and the like, diols obtained by modifying these aromatic diols with ethylene glycol, propylene glycol, alkylene glycol, and the like, and epichlorohydrin; a Novolac-type polyglycidyl ether compound obtained by the reaction of a polyphenol represented by a Novolac resin derived from phenol or cresol and formaldehyde, a polyalkenylphenol, a copolymer thereof, or the like, with epichlorohydrin; glycidyl ether compounds of xylylene phenol resins, and the like. Among them, preferred are cresol Novolac type epoxy compounds, phenol Novolac type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, triphenolylmethane type epoxy compounds, triphenolethane type epoxy compounds, triphenolic type epoxy compounds, dicyclopentadiene type epoxy compounds, diphenyl ether type epoxy compounds or biphenyl type epoxy compounds. The photothermal curable resin composition may contain only one epoxy compound, or may contain two or more epoxy compounds.
The epoxy compound may be in a liquid state or a solid state. From the viewpoint of easily improving the moisture resistance of the cured product, a solid epoxy compound is preferable. The softening point of the solid epoxy compound is preferably 40 ℃ to 150 ℃. The softening point can be measured by the ring and ball method defined in JIS K7234.
The content of the thermosetting compound is preferably 3 to 20% by mass relative to the photothermal curable resin composition. When the amount of the thermosetting compound is 3% by mass or more, the moisture resistance of a cured product (sealing member) of the photothermal curable resin composition can be easily improved. When the content of the thermosetting compound is 20% by mass or less, excessive viscosity increase is less likely to occur in the photothermal curable resin composition. The amount of the thermosetting compound is more preferably 3 to 15% by mass, and still more preferably 4 to 15% by mass, relative to the photothermal curable resin composition.
The content of the thermosetting compound is preferably 3.8 to 50% by mass, more preferably 5 to 30% by mass, based on the curable compound (a). When the content of the thermosetting compound is 3.8% by mass or more relative to the curable compound (a), the moisture resistance of the cured product and the adhesive strength to the glass substrate are further increased. On the other hand, if the content is 50% by mass or less, the compatibility with the curable compound (a) tends to be good during production.
1-7. other compounds
The photothermal curable resin composition of the present invention may further contain additives such as a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion scavenger, an ion exchanger, a leveling agent, a pigment, a dye, a sensitizer, a plasticizer, and a defoaming agent, as necessary.
Examples of the silane coupling agent include vinyltrimethoxysilane, gamma- (meth) acryloyloxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, and the like. The content of the silane coupling agent is preferably 0.01 to 5% by mass relative to the curable compound (a). When the content of the silane coupling agent is 0.01% by mass or more, a cured product of the photothermal curable resin composition tends to have sufficient adhesiveness.
The photothermal curable resin composition of the present invention may further include a spacer (spacer) for adjusting a gap of the liquid crystal display panel, and the like.
The total amount of the other components is preferably 1 to 50% by mass based on the total amount of the photothermal curable resin composition. When the total amount of the other components is 50% by mass or less, the viscosity of the photothermal curable resin composition is less likely to increase excessively, and the coating stability of the photothermal curable resin composition is less likely to be impaired.
1-8 Properties of photothermally curable resin composition
The photothermal curable resin composition of the present invention preferably has a viscosity at 25 ℃ and 2.5rpm of 200 to 450 pas, more preferably 300 to 400 pas, with an E-type viscometer. When the viscosity is within the above range, the application property of the photo-thermal curable resin composition by a dispenser becomes good.
The photothermal curable resin composition of the present invention can be used, for example, as a sealant. The photothermal curable resin composition is particularly suitable for a display element sealing agent used for sealing a display element such as a liquid crystal display element, an organic EL element, or an LED element. Further, the photothermal curable resin composition of the present invention is not liable to stain liquid crystal, and therefore, is very suitable for a liquid crystal sealing agent for a liquid crystal dropping process.
2. Liquid crystal display panel and method for manufacturing the same
The liquid crystal display panel of the present invention comprises: a pair of substrates (a display substrate and a counter substrate) each having an alignment film; a frame-shaped sealing member disposed between the alignment films of the pair of substrates; and a liquid crystal layer filled in a space surrounded by the aforementioned sealing member between the pair of substrates. The sealing member is a cured product of the photothermal curable resin composition (liquid crystal sealing agent).
The display substrate and the counter substrate are transparent substrates. The transparent substrate may be made of an inorganic material such as glass, or may be made of a plastic such as polycarbonate, polyethylene terephthalate, polyether sulfone, or PMMA.
A matrix TFT, a color filter, a black matrix, or the like may be disposed on the surface of the display substrate or the counter substrate. An alignment film is further disposed on the surface of the display substrate or the counter substrate. The alignment film contains known organic and inorganic alignment agents.
As described above, a sealing member obtained from a general liquid crystal sealing agent may have low adhesion to these alignment films. In contrast, the photothermal curable resin composition (liquid crystal sealing agent) described above can relax residual stress generated in the sealing member at the time of curing or absorb stress applied to the liquid crystal display panel from the outside. Therefore, even if the sealing member is disposed in the region where the alignment film is formed, peeling is less likely to occur at the interface between the sealing member and the region. Therefore, the liquid crystal display panel of the present invention can realize a narrow bezel.
A liquid crystal display panel can be manufactured using the liquid crystal sealant of the present invention. The liquid crystal display panel is preferably manufactured by a liquid crystal dropping process.
The manufacturing method of the liquid crystal display panel based on the liquid crystal dropping process comprises the following steps:
step 1) of applying the liquid crystal sealing agent to an alignment film of one of a pair of substrates each having an alignment film to form a seal pattern;
a step 2) of dropping a liquid crystal onto one substrate or the other substrate in a region surrounded by the seal pattern in a state where the seal pattern is not cured;
step 3) of laminating one substrate and the other substrate with a seal pattern interposed therebetween; and
step 4), the seal pattern is cured.
In step 2), the uncured state of the seal pattern means a state in which the curing reaction of the liquid crystal sealing agent does not proceed to the gelation point. Therefore, in the step 2), the seal pattern may be semi-cured by light irradiation or heating in order to suppress dissolution of the liquid crystal sealing agent into the liquid crystal. One substrate and the other substrate are a display substrate or a counter substrate, respectively.
In step 4), curing may be performed only by light irradiation, or curing may be performed by heating after curing by light irradiation. By performing curing by light irradiation, the liquid crystal sealing agent can be cured in a short time, and thus dissolution into the liquid crystal can be suppressed. By combining curing by light irradiation and curing by heating, damage to the liquid crystal layer by light can be reduced as compared with the case of curing by light irradiation alone.
The light to be irradiated may be appropriately selected depending on the kind of the photopolymerization initiator (B) in the liquid crystal sealing agent (photothermal curable resin composition), but light in the visible light region is preferable, and light having a wavelength of 370 to 450nm, for example, is preferable. This is because the light having the wavelength described above causes less damage to the liquid crystal material and the driving electrode. The light irradiation may use a known light source that emits ultraviolet light or visible light. In the case of irradiating 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 irradiation energy may be energy that can cure the curable compound (a). The photocuring time depends on the composition of the liquid crystal sealing agent, but is, for example, about 10 minutes.
The heat curing temperature depends on the composition of the liquid crystal sealing agent, but is, for example, 120 ℃ and the heat curing time is about 2 hours.
Examples
The present invention will be described in detail based on examples, but the present invention is not limited to these examples.
1. Preparation of curable Compound (A)
< Synthesis example 1: curable Compound (A-1) >
160g of liquid bisphenol F type epoxy resin (Epotohto YDF-8170C, manufactured by Tokyo Kasei Co., Ltd., epoxy equivalent of 160g/eq), 0.1g of a polymerization inhibitor (p-methoxyphenol), 0.2g of a catalyst (triethanolamine), and 43.0g of methacrylic acid were charged into a flask. Then, dry air was introduced, and the reaction was carried out at 90 ℃ for 5 hours with stirring under reflux. The obtained compound was washed with ultrapure water 20 times to obtain a methacrylic acid partially-modified bisphenol F type epoxy resin (curable compound (A-1)).
< Synthesis example 2: curable Compound (A-2) >
116g of 2-hydroxyethyl acrylate, 0.1g of a polymerization inhibitor (p-methoxyphenol), and 100g of succinic anhydride were charged into a flask. Then, dry air was introduced, and the reaction was carried out for 5 hours while stirring the mixture at 90 ℃ under reflux. Subsequently, 170g of bisphenol A diglycidyl ether was added, and the reaction was similarly carried out at 90 ℃ for 5 hours with stirring under reflux. The obtained compound was washed 20 times with ultrapure water to obtain a curable compound (A-2).
< Synthesis example 3: curable Compound (A-3) >
160g of a liquid bisphenol F-type epoxy resin (Epotohto YDF-8170C, manufactured by Tokyo Chemicals Co., Ltd., epoxy equivalent of 160g/eq), 0.1g of a polymerization inhibitor (p-methoxyphenol), 0.2g of a catalyst (triethanolamine), and 81.7g of methacrylic acid were charged into a flask, and the reaction was carried out for 5 hours while feeding dry air and carrying out reflux stirring at 90 ℃. The obtained compound was washed 20 times with ultrapure water to obtain a 95% methacrylic acid partially modified bisphenol F type epoxy resin (curable compound (A-3)).
< preparation of curable Compound (A-4) >
As the curable compound (A-4), an acrylic resin (polyethylene glycol diacrylate, Light Acrylate 14EG-A, manufactured by Kyoeisha chemical Co., Ltd.) was used.
2. Preparation of organic Fine particles (D)
< Synthesis example 4: organic Fine particles (D-1) >
Preparation of an emulsion D' comprising a core
500 parts by mass of deionized water, 3 parts by mass of sodium lauryl sulfate, 0.6 part by mass of potassium persulfate, 187.5 parts by mass of butadiene, and 62.5 parts by mass of styrene were charged into an autoclave equipped with a stirrer and replaced with nitrogen, and a reaction was carried out at 70 ℃ for 10 hours. After the obtained emulsion was cooled to normal temperature, ion-exchanged water was added thereto to adjust the solid content to 30% by mass.
Formation of the housing part
Into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, 500 parts by mass of the emulsion D' containing the core portion, 169 parts by mass of ion-exchanged water, and 0.4 part by mass of sodium lauryl sulfate were charged, and the temperature was raised to 70 ℃ while nitrogen substitution was performed under stirring. While maintaining the internal temperature at 70 ℃, 0.5 part by mass of potassium persulfate was added as a polymerization initiator. Further, a monomer mixed solution in which 23 parts by mass of styrene, 19 parts by mass of methyl methacrylate, 12 parts by mass of acrylonitrile, and 15 parts by mass of glycidyl methacrylate were previously mixed was continuously dropped into the reaction solution over 3 hours. After completion of the dropwise addition, the mixture was aged for 3 hours. After completion of the aging, the obtained aqueous emulsion was cooled to normal temperature, and then, using a spray dryer, organic fine particles (D-1) having an average particle diameter of 0.2 μm were obtained.
< Synthesis example 5: synthesis of organic Fine particle (D-2)
Into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, 500 parts by mass of the emulsion D' containing a core part obtained in synthesis example 4, 169 parts by mass of ion-exchanged water, and 0.4 part by mass of sodium lauryl sulfate were charged, and the temperature was raised to 70 ℃ while nitrogen substitution was performed under stirring. While maintaining the internal temperature at 70 ℃, 0.5 part by mass of potassium persulfate was added as a polymerization initiator. Further, a monomer mixture obtained by previously mixing 23 parts by mass of styrene, 23.3 parts by mass of methyl methacrylate, 12 parts by mass of acrylonitrile, and 10.8 parts by mass of n-butyl methacrylate was continuously added dropwise to the reaction solution over 3 hours. After completion of the dropwise addition, the mixture was aged for 3 hours. After completion of the aging, the obtained aqueous emulsion was cooled to normal temperature, and then, using a spray dryer, organic fine particles (D-2) having an average particle diameter of 0.2 μm were obtained.
3. Preparation of other materials
As the other material, the following material was used.
An epoxy compound: epikote 1004, manufactured by JER Inc., softening point 97 deg.C
Photopolymerization initiator (B): IRGACURE OXE01 manufactured by BASF corporation
Latent heat-curing agent (C): adipic acid dihydrazide (ADH, manufactured by Japan chemical Co., Ltd., melting point 177-184 ℃ C.)
Inorganic filler (E): silica particles (S-100, manufactured by Nippon catalytic chemical Co., Ltd.)
Other particles:
fine particle Polymer (F351, Aica Kogyo Co., manufactured by Ltd. (core is a polymer of n-butyl acrylate and shell is a core-shell particle of polymethyl methacrylate))
Polymethylsilsesquioxane particle (MSP-N080 manufactured by Nikkorica)
Polymethylsilsesquioxane particles (MSP-N050, Nikkorica Co., Ltd.)
Polymethylsilsesquioxane particle (X-52-854, manufactured by shin-Etsu chemical Co., Ltd.)
Melamine/formaldehyde condensate (Epostar S, manufactured by Nippon catalyst Co., Ltd.)
Single layer polymethyl methacrylate (Art Pearl J-3PY, manufactured by Gentle industries Co., Ltd.)
Silane coupling agent: KBM-403
4. Preparation of photothermally curable resin composition
< example 1 >
Using three rolls, 40 parts by mass of an epoxy compound, 230 parts by mass of the curable compound (A-1) obtained in Synthesis example 1, 50 parts by mass of the curable compound (A-2) obtained in Synthesis example 2, 250 parts by mass of the curable compound (A-3) obtained in Synthesis example 3, 150 parts by mass of the curable compound (A-4), 50 parts by mass of the latent heat-curing agent (C), 60 parts by mass of the inorganic filler (E), 150 parts by mass of the curable resin (D-1) obtained in Synthesis example 4, 10 parts by mass of a silane coupling agent (KBM-403, manufactured by shin-Etsu chemical industries Co., Ltd.), and 10 parts by mass of the photopolymerization initiator (B) were sufficiently mixed to obtain a uniform liquid, and a photothermal curable resin composition was obtained.
< examples 2 to 6 and comparative examples 1 to 6 >
A photothermal curable resin composition was produced in the same manner as in example 1, except that the composition shown in table 1 was changed.
5. Evaluation of
The photo-thermal curable resin compositions obtained in examples 1 to 6 and comparative examples 1 to 6 were evaluated for adhesive strength by the following method.
< adhesion Strength test >
A40 mm X45 mm glass substrate (RT-DM88-PIN, EHC) having transparent electrodes and an alignment film formed on the entire surface thereof was coated with a dispenser (dispenser, Musashi Engineering Co., Ltd.)Prepared) was formed into a linear seal pattern of 38mm × 38mm square (2500 μm in cross-sectional area) 2 ). Next, the pair of glass substrates were bonded under reduced pressure so as to be perpendicular to the glass substrate on which the seal pattern was formed, and then the bonding was performed by opening the atmosphere. Then, the bonded 2 glass substrates were kept in a light-shielding box for 1 minute, and then irradiated at 3000mJ/cm 2 The test piece is obtained by heating the light (light having a wavelength of 370 to 450 nm) containing visible light at 120 ℃ for 1 hour.
The resulting test piece was perpendicularly pressed into a corner (outside the line) of the seal pattern at a distance of 4.5mm at a rate of 5 mm/min using an indentation tester (Model210, manufactured by INTESCO corporation), and the stress at which the cured product of the thermosetting resin composition was peeled was measured. The adhesion strength was determined by dividing the stress by the line width of the cured product. The results are shown in Table 1.
[ Table 1]
As shown in examples 1 to 6 in table 1, the results of the adhesion strength test were all good in the photothermal curable resin composition having the outer shell portion and the core portion, and the core portion including 1 or more rubbers selected from the group consisting of rubbers having a structural unit derived from a conjugated diene and silicone rubbers. It is considered that the residual stress generated when the photothermal curable resin composition is cured is relaxed by the organic fine particles (D), and when external stress is applied, the organic fine particles (D) disperse the stress. Therefore, it is assumed that peeling at the interface between the cured product and the substrate is not easily generated in examples 1 to 6.
On the other hand, even in the case of fine particles having a core-shell structure, when the rubber is not contained in the core portion, the residual stress and the stress from the outside are not sufficiently dispersed, and the result of the adhesion strength test is low (comparative example 1). Further, the effect of improving the adhesive strength was not obtained in the polymethylsilsesquioxane particles, the melamine/formaldehyde condensate, the particles made of polymethyl methacrylate, or the like, which did not have the core portion and the shell portion (comparative examples 2 to 6).
The present application claims priority based on Japanese patent application No. 2020 and 018755 filed on 6.2.2020. The contents described in the specification of this application are all incorporated in the specification of this application.
Industrial applicability
According to the photothermal curable resin composition of the present invention, a cured product having high adhesion to various substrates can be obtained. Therefore, the photothermal curable resin composition is very useful as a sealant for various liquid crystal display devices and the like.
Claims (11)
1. A photothermal curable resin composition comprising a curable compound (A) having an ethylenically unsaturated double bond in the molecule, a photopolymerization initiator (B), a latent heat-curing agent (C), and organic fine particles (D),
the organic fine particles (D) have an outer shell portion and a core portion,
the core portion includes at least one of a conjugated diene rubber and a silicone rubber containing a structural unit derived from a conjugated diene.
2. The photothermally curable resin composition according to claim 1, wherein the organic fine particles (D) are composed of the outer shell portion and the core portion,
the core portion includes a conjugated diene rubber containing a structural unit derived from a conjugated diene and an aromatic vinyl compound,
the outer shell portion includes a polymer having 1 or more structures selected from the group consisting of a methyl methacrylate structure, a styrene structure, an acrylonitrile structure, and a glycidyl structure.
3. The photothermally curable resin composition according to claim 1 or 2, further comprising an inorganic filler (E).
4. The photothermally curable resin composition according to any one of claims 1 to 3, wherein the content of the organic fine particles (D) is 5 to 17% by mass.
5. The photothermally curable resin composition according to any one of claims 1 to 4, wherein the latent heat curing agent (C) is at least 1 curing agent selected from the group consisting of an organic acid dihydrazide-based heat latent curing agent, an amine adduct-based heat latent curing agent, and a polyamine-based heat latent curing agent.
6. A liquid crystal sealing agent comprising the photothermal curable resin composition according to any one of claims 1 to 5.
7. A method of manufacturing a liquid crystal display panel, comprising:
applying the liquid crystal sealing agent according to claim 6 to the alignment film of one of a pair of substrates each having an alignment film, thereby forming a seal pattern;
dropping a liquid crystal on the first substrate in a region of the seal pattern or on the second substrate in a state where the seal pattern is not cured;
a step of laminating the first substrate and the second substrate with the seal pattern interposed therebetween; and
and curing the seal pattern.
8. The method of manufacturing a liquid crystal display panel according to claim 7, wherein in the step of curing the seal pattern, the seal pattern is cured by irradiating light to the seal pattern.
9. The method of manufacturing a liquid crystal display panel according to claim 8, wherein the light irradiated to the seal pattern includes light in a visible light region.
10. The method of manufacturing a liquid crystal display panel according to claim 8 or 9, wherein in the step of curing the seal pattern, the seal pattern irradiated with the light is further heated.
11. A liquid crystal display panel, comprising:
a pair of substrates each having an alignment film;
a frame-shaped sealing member disposed between the alignment films of the pair of substrates; and
a liquid crystal layer filled in a space surrounded by the sealing member between the pair of substrates,
the sealing member is a cured product of the liquid crystal sealing agent according to claim 6.
Applications Claiming Priority (3)
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JP2020-018755 | 2020-02-06 | ||
JP2020018755 | 2020-02-06 | ||
PCT/JP2021/002135 WO2021157377A1 (en) | 2020-02-06 | 2021-01-22 | Light- and heat-curable resin composition, liquid crystal sealing agent containing same, liquid crystal display panel, and manufacturing method therefor |
Publications (1)
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CN115004093A true CN115004093A (en) | 2022-09-02 |
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CN202180011019.4A Pending CN115004093A (en) | 2020-02-06 | 2021-01-22 | Photothermally curable resin composition, liquid crystal sealing agent comprising same, liquid crystal display panel, and method for producing same |
Country Status (5)
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JP (1) | JP7411693B2 (en) |
KR (1) | KR20220123426A (en) |
CN (1) | CN115004093A (en) |
TW (1) | TW202132394A (en) |
WO (1) | WO2021157377A1 (en) |
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JP4014352B2 (en) * | 1999-04-01 | 2007-11-28 | 三井化学株式会社 | Liquid crystal sealant composition |
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WO2019198631A1 (en) * | 2018-04-11 | 2019-10-17 | 積水化学工業株式会社 | Photopolymerization initiator, sealant for display elements, vertical conduction material, display element, and compound |
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2021
- 2021-01-22 CN CN202180011019.4A patent/CN115004093A/en active Pending
- 2021-01-22 JP JP2021575714A patent/JP7411693B2/en active Active
- 2021-01-22 KR KR1020227026217A patent/KR20220123426A/en unknown
- 2021-01-22 WO PCT/JP2021/002135 patent/WO2021157377A1/en active Application Filing
- 2021-02-01 TW TW110103629A patent/TW202132394A/en unknown
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JPH09236809A (en) * | 1995-12-27 | 1997-09-09 | Mitsui Toatsu Chem Inc | Resin composition to seal liquid crystal |
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JP7411693B2 (en) | 2024-01-11 |
JPWO2021157377A1 (en) | 2021-08-12 |
WO2021157377A1 (en) | 2021-08-12 |
TW202132394A (en) | 2021-09-01 |
KR20220123426A (en) | 2022-09-06 |
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