KR101863011B1 - Method for producing liquid crystal display panel, liquid crystal display panel and liquid crystal sealing agent composition - Google Patents
Method for producing liquid crystal display panel, liquid crystal display panel and liquid crystal sealing agent composition Download PDFInfo
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- KR101863011B1 KR101863011B1 KR1020177001657A KR20177001657A KR101863011B1 KR 101863011 B1 KR101863011 B1 KR 101863011B1 KR 1020177001657 A KR1020177001657 A KR 1020177001657A KR 20177001657 A KR20177001657 A KR 20177001657A KR 101863011 B1 KR101863011 B1 KR 101863011B1
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- KR
- South Korea
- Prior art keywords
- liquid crystal
- organic acid
- group
- acid
- display panel
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 342
- 239000000203 mixture Substances 0.000 title claims abstract description 137
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- 239000003795 chemical substances by application Substances 0.000 title claims description 62
- 238000007789 sealing Methods 0.000 title description 35
- 239000000565 sealant Substances 0.000 claims abstract description 125
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 239000004927 clay Substances 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- GRGBENNNGZARRZ-UHFFFAOYSA-N dodecanedihydrazide Chemical compound NNC(=O)CCCCCCCCCCC(=O)NN GRGBENNNGZARRZ-UHFFFAOYSA-N 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-L ethyl phosphate(2-) Chemical compound CCOP([O-])([O-])=O ZJXZSIYSNXKHEA-UHFFFAOYSA-L 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical class OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
-
- 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
- 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
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Medicinal Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention provides a liquid crystal sealant composition which can be cured efficiently and is hardly dissolved in liquid crystals even when the uncured components are in contact with liquid crystal, and further, a liquid crystal sealant composition having high display reliability of the obtained liquid crystal display panel or a method of manufacturing a liquid crystal display panel using the composition . (A) an organic acid, (B) a photocurable resin having at least one ethylenically unsaturated double bond in one molecule (excluding the above organic acid), and (C) (1) of the organic acid (A) is 23 g / eq or more and 75 g / eq or less to form a liquid crystal seal pattern; and And a step of photo-curing the liquid crystal sealant composition.
(G / eq) = (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
Description
The present invention relates to a method of manufacturing a liquid crystal display panel, a liquid crystal display panel obtained by the method, and a liquid crystal sealant composition.
2. Description of the Related Art In recent years, liquid crystal display panels have been widely used as image display panels for various electronic apparatuses including mobile phones and personal computers. The liquid crystal display panel is an image display panel having a structure in which a liquid crystal material (hereinafter simply referred to as " liquid crystal ") is sandwiched between two transparent substrates provided with electrodes on its surface and the periphery thereof is sealed with a liquid crystal sealant .
The amount of the liquid crystal sealing agent used is a little, but it is in direct contact with the liquid crystal, which has a great influence on the reliability of the liquid crystal display panel. Therefore, in order to realize the high image quality of the liquid crystal display panel, liquid crystal sealing agents are required to be various and highly diverse.
Conventionally, a liquid crystal display panel is mainly manufactured by a liquid crystal injection technique. In the liquid crystal injection method, generally, (1) a liquid crystal sealant is applied on one transparent substrate to form a frame, (2) the liquid crystal sealant is dried by precuring the substrate, (3) heating and pressing the two substrates to adhere the substrates to each other to form a frame (cell) of the liquid crystal sealant between the substrates, and (4) And an injection port of the liquid crystal is sealed to manufacture a liquid crystal display panel.
On the other hand, in recent years, a liquid crystal dropping method has been studied as a manufacturing method of a liquid crystal display panel in which productivity is expected to be improved. The liquid crystal dripping method includes the steps of (1) applying a liquid crystal sealant on a transparent substrate to form a rim for filling the liquid crystal, (2) dropping a small amount of liquid crystal in the rim, (3) , And (4) the liquid crystal sealing agent is cured to manufacture a panel. Usually, in the liquid crystal dropping method, a light and heat curable liquid crystal sealant may be used. In the step (3), after the liquid crystal sealant is cured by irradiating light such as ultraviolet rays, .
In this liquid crystal dropping method, since the liquid crystal sealant comes into contact with the liquid crystal for a long time in an uncured state, components of the liquid crystal sealant are more likely to be dissolved in the liquid crystal than the liquid crystal injection method. Therefore, there has been a problem that the display characteristics of the liquid crystal display panel are easily deteriorated. Thus, for example, there has been proposed a sealant for a liquid crystal dropping process comprising a titanocene radical initiator, a photocurable resin, and a latent epoxy curing agent (Patent Document 1).
On the other hand, as a photopolymerizable composition used for dental materials and the like, there has been proposed a photopolymerizable composition comprising a titanocene derivative, a compound having a protonic hole-excitable group, and a compound having an ethylenically unsaturated double bond (Patent Document 2 And 3).
The resin composition of the above-mentioned Patent Document 1 is intended to suppress the dissolution of the liquid crystal sealant component in the liquid crystal by accelerating the photo-curing of the photo-curable resin with a titanocene radical initiator. However, the dissolution of the components of the liquid crystal sealant in the liquid crystal, which occurs at the time of charging the liquid crystal, is difficult to sufficiently suppress.
Therefore, there is a demand for a liquid crystal seal which is difficult to melt in liquid crystals and can be efficiently cured (before being dissolved in liquid crystals). The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid crystal sealant composition which can be cured efficiently, is hardly dissolved in liquid crystals even when the uncured components are in contact with liquid crystal, And a manufacturing method of a liquid crystal display panel.
In the present invention, by including a specific organic acid in the liquid crystal sealant composition, the photo-curing of the liquid crystal sealant composition tends to be facilitated. Further, in the case of a specific organic acid, even if the liquid crystal sealant before curing comes into contact with the liquid crystal, It becomes difficult.
A first aspect of the present invention relates to a method of manufacturing a liquid crystal display panel and a liquid crystal display panel obtained by the method.
(1) A method for producing a liquid crystal display panel by a liquid dropping method, comprising the steps of: (A) an organic acid, (B) a photocurable resin having at least one ethylenic unsaturated double bond in one molecule (A) an organic acid having an oxygen atom equivalent of 23 g / eq or more and 75 g / eq or less, represented by the following formula (1), is applied to the liquid crystal sealing composition A step of forming a liquid crystal seal pattern, and a step of photo-curing the liquid crystal sealant composition.
(G / eq) = (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
[2] The process for producing a liquid crystal display panel according to [1], wherein the organic acid (A) is an acid anhydride.
[3] The process for producing a liquid crystal display panel according to [1] or [2], wherein the organic acid (A) has at least one ethylenic unsaturated double bond.
(4) A process for producing an organic compound, which comprises reacting (A) an organic acid with one or more compounds selected from the group consisting of -OH group, -NH 2 group, -NHR group (R represents an aromatic, aliphatic hydrocarbon or a derivative thereof), -COOH group, (OH) 2 group, a -P (= O) (OH) 2 group, a -SO 3 H group, a -CONH 2 group, [1] a functional group selected from the group consisting of -NHOH having at least one - [3 Wherein the liquid crystal display panel is a liquid crystal display panel.
[5] The liquid crystal display panel according to any one of [1] to [4], wherein the photocurable resin (B) is a resin having at least one ethylenically unsaturated double bond and at least one epoxy group in one molecule of the (B2) Gt;
[6] A process for producing a liquid crystal display panel according to any one of [1] to [5], further comprising (D) a thermosetting resin.
[7] The method for producing a liquid crystal display panel according to [6], further comprising a thermosetting agent (E), wherein the thermosetting resin (D) is a resin having at least one epoxy group in one molecule .
[8] The thermosetting resin composition according to any one of [1] to [8], wherein the heat curing agent (E) is selected from the group consisting of a dihydrazide type thermal latent curing agent, an imidazole type thermal latent curing agent, an amine adduct type thermal latent curing agent, and a polyamine type thermal latent curing agent Is at least one kind of thermal latent curing agent.
[9] The method for producing a liquid crystal display panel according to any one of [6] to [8], further comprising a step of further thermally curing the liquid crystal sealant composition.
[10] The production method of a liquid crystal display panel according to any one of [1] to [9], wherein light to be irradiated in the photo-curing step includes a visible light region.
[11] A liquid crystal display panel manufactured by the method for manufacturing a liquid crystal display panel according to any one of [1] to [10].
A second aspect of the present invention relates to the following liquid crystal sealant composition.
(12) A photocurable resin composition comprising (A) an organic acid, (B) a photocurable resin having at least one ethylenic unsaturated double bond in one molecule (excluding the above organic acid), and (C) , And the oxygen atom equivalent of the organic acid (A) represented by the following formula (1) is 23 g / eq or more and 75 g / eq or less.
(G / eq) = (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
According to the method for producing a liquid crystal display panel of the present invention, even if the liquid crystal sealant composition comes into contact with the liquid crystal in an uncured state, the liquid crystal is less contaminated. Further, by using the above liquid crystal sealing composition, the liquid crystal display panel can be efficiently cured in a short period of time, and a liquid crystal display panel having excellent display reliability can be obtained.
1. Liquid crystal sealant composition
The liquid crystal sealing composition of the present invention contains at least the (A) the organic acid, (B) the photocurable resin, and (C) the tantanocene-based photopolymerization initiator. The liquid crystal sealant composition of the present invention may contain other components as required, such as (D) a thermosetting resin, (E) a thermosetting agent, (F) an inorganic filler, and (G) an organic filler.
In the conventional liquid crystal sealant composition, when the liquid crystal sealant composition is brought into contact with the liquid crystal in an uncured state, the resin component and the like are liable to be dissolved in the liquid crystal, and the display characteristics of the liquid crystal display panel are deteriorated. Furthermore, when the liquid crystal sealant composition is photo-cured, the liquid crystal sealant composition is not sufficiently cured in a region not irradiated with the irradiation light. For this reason, in the region where only scattered light is irradiated, for example, at the end of the liquid crystal panel, uncured components of the liquid crystal sealing composition easily remain, and display characteristics of the liquid crystal display panel are likely to be deteriorated. It is known that the addition of an organic acid tends to increase the curability of the photopolymerizable composition. However, if a common organic acid is added to the liquid crystal sealing agent, the organic acid is dissolved in the liquid crystal, so that the display characteristics of the liquid crystal display panel are likely to be deteriorated.
On the other hand, the liquid crystal sealant composition of the present invention includes (A) an organic acid having a specific oxygen atom equivalent. In the liquid crystal sealing agent containing the organic acid (A), the photo-curing reaction of the photo-curing resin (B) is promoted. Therefore, even in a region where light is not sufficiently irradiated, the liquid crystal sealing composition sufficiently cures. On the other hand, an organic acid (A) having a specific oxygen atom equivalent is difficult to dissolve in liquid crystals because of its low affinity for liquid crystals. Therefore, even if the uncured liquid crystal sealant composition and the liquid crystal are in contact with each other, the components in the liquid crystal sealant composition are hardly dissolved in the liquid crystal. That is, in the display panel to be obtained, the display characteristics are hardly lowered, and the voltage holding ratio is less likely to be lowered.
(A) Organic acid
As described above, when (A) an organic acid is contained in the liquid crystal sealant composition, the liquid crystal sealant composition tends to have high curability. In the present invention, the organic acid (A) also includes a compound having an acid anhydride structure. The organic acid (A) has an oxygen atom equivalent of 23 g / eq or more and 75 g / eq or less, preferably 25 to 60 g / eq, more preferably 27 to 55 g / eq, to be.
(G / eq) = (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
If the above-mentioned oxygen atom equivalent is excessively high, (A) even when a slight amount of the organic acid is eluted into the liquid crystal, the liquid crystal has a large influence. That is, it is easy to contaminate the liquid crystal. On the other hand, when the oxygen atom equivalent is 75 g / eq or less, (A) the influence of the organic acid on the liquid crystal is small and the contamination of the liquid crystal is suppressed. When the oxygen atom equivalent is more than 23 g / eq, (A) the organic acid becomes less compatible with the liquid crystal, and the contamination of the liquid crystal is suppressed.
Here, (A) is an organic acid, -OH group, -NH 2 group, -NHR group (R represents an aromatic, an aliphatic hydrocarbon or a derivative thereof), -COOH group, -OP (= O) (OH ) 2 Group, a -P (= O) (OH) 2 group, -SO 3 H group, -CONH 2 group or -NHOH group. (A) When these groups are contained in the organic acid, (A) the organic acid and the liquid crystal become difficult to be used, and the contamination of the liquid crystal is liable to be suppressed. The organic acid (A) may contain only one of these groups, or two or more of these groups.
In the organic acid (A), an ethylenically unsaturated double bond may be contained in the molecule. When (A) at least one unsaturated double bond is contained in one molecule of the organic acid, (A) the organic acid is polymerized with the (B) photo-curable resin, and the (A) organic acid is hardly exuded from the cured product of the liquid crystal sealant composition. The number of unsaturated double bonds contained in one molecule of the organic acid (A) may be two or more.
Examples of the organic acid (A) having an unsaturated double bond in one molecule include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- Acid anhydride modified compounds of bisphenol A type epoxy acrylate, phosphoric acid modified compounds of bisphenol A type epoxy (meth) acrylate, acid anhydride modified compounds of bisphenol F type epoxy (meth) acrylate, bisphenol F type epoxy Phosphoric acid-modified compounds of acrylate, and phosphoric acid (meth) acrylates. Here, the phosphoric acid (meth) acrylates include, for example, [CH 2 ═CRCOOCH 2 CH 2 OCO (CH 2 ) 6 ] a O] b PO (OH) 3-b , a represents 0~2, b represents 1 or 2), [CH 2 = CRCOOCH 2 CH 2 [OCH 2 CH (CH 3)] c O] d PO (OH) 3-e (R is hydrogen An atom or a methyl group, d represents 0 to 2, and c and e represent 1 or 2).
On the other hand, examples of the organic acid (A) having no ethylenically unsaturated double bond in one molecule include acetic acid, butyric acid, oxalic acid, citric acid, lauric acid, stearic acid, malonic acid, adipic acid, tartaric acid, benzoic acid, salicylic acid, , Monoethyl phosphate, monophenyl phosphate, diethyl phosphate, mono 2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, benzenesulfonic acid, toluenesulfonic acid, sulfobenzoic acid, formic acid, propionic acid, valeric acid, But are not limited to, adipic acid, caproic acid, caproic acid, myristic acid, palmitic acid, magaric acid, succinic acid, glutaric acid, dodecanedioic acid, sebacic acid, isophthalic acid, terephthalic acid, benzenetricarboxylic acid 4-hydroxyphenyl) benzoic acid, 6-hydroxy-1-naphthoic acid, phenylphosphonic acid, glycolic acid, trimellitic acid, trimellitic acid anhydride, 4'- -Hydroxy-4-biphenylcarboxylic acid and the like . On the other hand, the organic acid (A) may be a high molecular weight compound of the above compound.
Examples of preferred organic acids (A) include oxalic acid, tartaric acid, trimellitic acid, trimellitic acid anhydride, isophthalic acid, phenylphosphonic acid, 4'-hydroxy- .
Examples of the organic acid (A) having the bond include a carboxylic acid or a phosphoric acid including the bond and include, for example, a compound represented by the following formula.
The preferred molecular weight of the organic acid (A) is 60 to 3,000, more preferably 60 to 1,000, and still more preferably 60 to 500. When the molecular weight of the organic acid (A) is in the above range, the organic acid (A) easily flows in the liquid crystal sealant composition, and the photo-curing of the liquid crystal sealant composition tends to be accelerated.
The content of the organic acid (A) relative to 100 parts by mass of the liquid crystal sealant composition is 0.01 to 10 parts by mass, preferably 0.05 to 2 parts by mass. When the organic acid (A) is contained in the above range, the liquid crystal sealant composition tends to have a high photo-curability, and (A) the liquid crystal is less likely to be contaminated by the organic acid.
(B) a photocurable resin
The photo-curable resin (B) is not particularly limited as long as it is a resin having at least one ethylenic unsaturated double bond in one molecule. However, the photocurable resin (B) does not include the compound corresponding to the organic acid (A) described above. (Meth) acryl-modified epoxy resins each having at least one epoxy group and at least one (meth) acrylic group in one molecule of the (B1) (meth) acrylic resin or (B2) If the photo-curing resin is a (B1) (meth) acrylic resin or a (B2) (meth) acryl-modified epoxy resin, the photo-curability of the liquid crystal sealant composition tends to be sufficiently high. In particular, when the photocurable resin is the (B2) (meth) acryl-modified epoxy resin, the moisture resistance of the cured product of the liquid crystal sealant composition tends to be high. On the other hand, the liquid crystal sealing composition of the present invention may contain (B1) (meth) acrylic resin and (B2) (meth) acrylic modified epoxy resin.
(B1) The (meth) acrylic resin is a compound containing at least one (meth) acryl group in one molecule, and is a compound not containing an epoxy group. On the other hand, (meth) acryl refers to acrylic or methacrylic.
Examples of (B1) (meth) acrylic resins include diacrylates and / or dimethacrylates such as polyethylene glycol, propylene glycol and polypropylene glycol; Diacrylates and / or dimethacrylates of tris (2-hydroxyethyl) isocyanurate; Diacrylates and / or dimethacrylates of diols obtained by addition of at least 4 moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol; Diacrylates and / or dimethacrylates of diols obtained by addition of 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A; Diol or triacrylate and / or di or trimethacrylate obtained by addition of at least 3 moles of ethylene oxide or propylene oxide to 1 mole of trimethylol propane; Diacrylates and / or dimethacrylates of diols obtained by addition of at least 4 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A; Tris (2-hydroxyethyl) isocyanurate triacrylate and / or trimethacrylate; Trimethylol propane triacrylate and / or trimethacrylate, or oligomers thereof; Pentaerythritol triacrylate and / or trimethacrylate, or oligomers thereof; Polyacrylates and / or polymethacrylates of dipentaerythritol; Tris (acryloxyethyl) isocyanurate; Caprolactone modified tris (acryloxyethyl) isocyanurate; Caprolactone modified tris (methacryloxyethyl) isocyanurate; Polyacrylates and / or polymethacrylates of alkyl-modified dipentaerythritol; Polyacrylates and / or polymethacrylates of caprolactone-modified dipentaerythritol; Hydroxypivalic neopentyl glycol diacrylate and / or dimethacrylate; Caprolactone-modified hydroxypivalic neopentyl glycol diacrylate and / or dimethacrylate; Ethylene oxide modified phosphoric acid acrylate and / or dimethacrylate; Ethylene oxide modified alkylated phosphoric acid acrylate and / or dimethacrylate; Neopentyl glycol, trimethylol propane, pentaerythritol oligoglycollate and / or oligomethacrylate, and the like.
The weight average molecular weight of the (B1) (meth) acrylic resin may be, for example, about 310 to 1000. The weight average molecular weight Mw of the (B1) (meth) acrylic resin can be measured, for example, by gel permeation chromatography (GPC).
The amount of the (B1) (meth) acrylic resin in the liquid crystal sealant composition also depends on the degree of curability required, but is preferably 10 to 99 parts by mass, more preferably 20 to 100 parts by mass based on 100 parts by mass of the liquid crystal sealant composition, More preferably 99 parts by mass.
On the other hand, the (B2) (meth) acryl-modified epoxy resin is a compound containing at least one (meth) acryl group and at least one epoxy group, preferably an epoxy resin and (meth) acrylic acid, In the presence of a basic catalyst.
The (B2) (meth) acryl-modified epoxy resin has an epoxy group and a (meth) acryl group in the molecule, and therefore can combine both light curing property and heat curability. In addition, even when the (meth) acryl-modified epoxy resin is an amorphous epoxy resin, since the ratio of the number of hydroxyl groups to the number of epoxy groups is large, the affinity to the liquid crystal is low and dissolution of the liquid crystal is sufficiently suppressed.
The epoxy resin to be a raw material of the (B2) (meth) acryl-modified epoxy resin may be a bifunctional or more epoxy resin having two or more epoxy groups in the molecule. Examples thereof include bisphenol A, bisphenol F, 2,2'-diallyl bisphenol Bisphenol type epoxy resins such as A type, bisphenol AD type, and hydrogenated bisphenol type; Novolak type epoxy resins such as phenol novolac type, cresol novolak type, biphenyl novolac type, and trisphenol novolak type; Biphenyl-type epoxy resins; Naphthalene type epoxy resin, and the like. (Meth) acrylic modified epoxy resin obtained by (meth) acrylic modification of a polyfunctional epoxy resin such as trifunctional or tetrafunctional is likely to have a low crosslinking density and a low adhesion strength. Therefore, the (meth) acrylic modified epoxy resin The epoxy resin to be a raw material of the resin is preferably a bifunctional epoxy resin.
Particularly, the bifunctional epoxy resin is preferably a biphenyl type epoxy resin, a naphthalene type epoxy resin, and a bisphenol type epoxy resin. Among them, a bisphenol type epoxy resin such as a bisphenol A type and a bisphenol F type, From the viewpoints of application properties of the composition and the like.
The epoxy resin to be used as the raw material may be one kind alone, or two or more kinds may be combined. The epoxy resin as a raw material is preferably highly purified by a molecular distillation method, a washing method or the like.
The (B2) (meth) acrylic modified epoxy resin is preferably one in which 10 to 99.5% of the epoxy group of the raw epoxy resin is modified with a (meth) acrylic group, more preferably 30 to 70% . When the epoxy group is modified with the (meth) acrylic group within the above range, the liquid crystal sealant composition has good photo-curability and thermal curability, and further, the moisture resistance of the cured product of the liquid crystal sealant composition tends to be low.
The weight average molecular weight of the (B2) (meth) acryl-modified epoxy resin may be, for example, about 310 to 1,000. The weight average molecular weight Mw of the (B2) (meth) acryl-modified epoxy resin can be measured by, for example, gel permeation chromatography (GPC).
The amount of the (B2) (meth) acrylic-modified epoxy resin in the liquid crystal sealant composition depends on the degree of the required curability, but is preferably from 10 to 99 parts by mass, More preferably 99 parts by mass.
The (B1) (meth) acrylic resin and (B2) (meth) acrylic modified epoxy resin preferably have a hydrogen bonding functional group such as a hydroxyl group, a urethane bond, an amide group or a carboxyl group. Examples of the hydrogen bonding functional groups include hydroxyl groups formed by reacting an epoxy group of an epoxy resin with (meth) acrylic acid, hydroxyl groups formed by reacting a (meth) acrylic resin and (B2) a (meth) acrylic modified epoxy resin ), Hydroxyl group, urethane bond, carboxyl group, and amide group contained in acrylic acid or epoxy resin. (B) When the photocurable resin has a hydrogen-bonding functional group, the compatibility with the hydrophobic liquid crystal material is lowered, and dissolution of the liquid crystal is suppressed. As a result, a liquid crystal sealant suitable for a liquid crystal dropping method is obtained.
(B1) (meth) acrylic resin and (B2) (meth) hydrogen-bonding functional group equivalent weight of the acrylic-modified epoxy resin is, 1.0 × 10 -4 ~5 × 10 -3 mol / g and the preferable, 3.5 × 10 - More preferably 3 to 4.5 x 10 < -3 > mol / g. When the hydrogen-bonding functional group equivalent is 1.0 x 10 -4 mol / g or more, a sufficient number of hydrogen bonding functional groups are contained in one molecule of the (B1) (meth) acrylic resin or the (B2) (meth) acrylic modified epoxy resin. Therefore, dissolution of the photo-curable resin (B) in the liquid crystal is liable to be suppressed. On the other hand, when the hydrogen-bonding functional group equivalent is 5 × 10 -3 mol / g or less, the cured product of the (B1) (meth) acrylic resin and the (B2) The humidity resistance of the cured product of the sealant composition is hardly lowered.
(Mol) / (g) of the hydrogen-bonding functional groups (B1) of the (meth) acrylic resin and the (B2) Number of hydrogen-bonding functional groups contained in one molecule of the epoxy resin " / (weight average molecular weight (Mw) of the (B1) (meth) acrylic resin or (B2) (meth) acrylic modified epoxy resin. For example, in the case of having only a hydroxyl group obtained by reacting (meth) acrylic acid with an epoxy resin as a hydrogen bonding functional group, the hydrogen bonding functional group equivalent can be determined by changing the molar number of the (meth) acrylic acid reacted to (meth) And the weight average molecular weight (Mw) of the resin.
The hydrogen-bonding functional group equivalent of the (B1) (meth) acrylic resin is controlled by adjusting the amount of the hydrogen-bonding functional group of the (B1) (meth) acrylic resin itself. On the other hand, the hydrogen-bonding functional group equivalent of the (B2) (meth) acrylic-modified epoxy resin can be adjusted, for example, by adjusting the number of moles of (meth) acrylic acid reacted with the epoxy resin as a raw material; And controlling the amount of the hydrogen-bonding functional group of the (meth) acrylic acid or the epoxy resin as the raw material.
The total amount of the photocurable resin (B) (for example, the total amount of the (B1) (meth) acrylic resin and the (B2) (meth) acrylic modified epoxy resin) to 100 parts by mass of the liquid crystal sealant composition is preferably 10 to 99 mass More preferably 20 to 99 parts by mass.
(C) Titanosene-based photopolymerization initiator
The (C) titanocene photopolymerization initiator contained in the liquid crystal sealing composition of the present invention is a compound for curing the above-mentioned (B) photocurable resin; If the photopolymerization initiator is a compound of the titanocene type, the curability of the liquid crystal sealant composition tends to be high. Further, the liquid crystal sealant composition can be cured by the irradiation light including the visible light region.
Examples of the photopolymerization initiator (C) titanocene-based photopolymerization initiator include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro- (Cyclopentadienyl) -bis (cyclopentadienyl) -dichloro titanium, bis (cyclopentadienyl) -diphenyl titanium, bis (cyclopentadienyl) -bis Bis (cyclopentadienyl) -bis (2,6-difluorophenyl) titanium, bis (methylcyclopentadienyl) -bis (2,3,4- Bis (2,6-difluorophenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluorophenyl) titanium, bis Bis (cyclopentadienyl) -bis [2,6-difluoro-3 - ((1-phenyl) Methyl) phenyl] titanium, bis (methylcyclopentadienyl) -bis [2,6-difluoro-3 - ((1 Yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3 - ((2,5- Methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3 - ((3-trimethylsilyl-2,5- (Methylphenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3 - ((2,5- Methyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-4 - ((2,5- Bis (cyclopentadienyl) -bis [2,6-difluoro-3-methyl-4- (2- ) - bis [2,6-difluoro-3- (1-methyl-2- (1-pyr- 1- yl) ethyl) phenyl] titanium, bis (cyclopentadienyl) -Difluoro-3- (6- (9-carbazol-9-yl) hexyl) phenyl] titanium, bis (cyclopentadienyl Yl) propyl] phenyl] titanium, bis (2,6-dihydroxy-3- (Cyclopentadienyl) -bis [2,6-difluoro-3 - ((acetylamino) methyl) phenyl] titanium, bis Phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (4- (pivaloylamino) , Bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (2,2-dimethylpentanylamino) ethyl) phenyl] Bis [2,6-difluoro-3- (2- (4-fluorophenyl) phenyl] titanium, bis (cyclopentadienyl) (N-allylmethylsulfonylamino) ethyl) phenyl] titanium and the like. The liquid crystal sealant composition may contain only one kind of the above-mentioned compounds, or two or more kinds thereof.
The content of the (C) titanocene photopolymerization initiator relative to 100 parts by mass of the liquid crystal sealant composition is 0.01 to 10 parts by mass, preferably 0.1 to 2 parts by mass. When the liquid crystal sealant composition contains the (C) titanocene-based photo polymerization initiator within the above-mentioned range, the photo-curability of the liquid crystal sealant composition tends to be high.
(D) Thermosetting resin
The liquid crystal sealing composition of the present invention may contain (D) a thermosetting resin. When the thermosetting resin (D) is included, moisture resistance of the cured product of the liquid crystal sealant composition tends to increase. (D) An example of the thermosetting resin (D) is an epoxy resin having at least one epoxy group in one molecule. The number of epoxy groups is preferably 2 or more, particularly preferably 2.
(D1) Examples of the epoxy resin include, for example, bisphenol-type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol S type, 2,2'-diallyl bisphenol A type, bisphenol AD type and hydrogenated bisphenol type; Diphenylether epoxy resins; Novolak type epoxy resins such as phenol novolak type, cresol novolak type, biphenyl novolak type, bisphenol novolac type, naphthol novolak type, trisphenol novolak type and dicyclopentadien novolac type; Biphenyl-type epoxy resins; Naphthyl type epoxy resin; Triphenolalkene-type epoxy resins such as triphenol methane type, triphenol ethane type, and triphenol propane type; Alicyclic epoxy resins and the like. Among them, bisphenol type epoxy resins such as bisphenol A type and bisphenol F type are more preferable. These bisphenol-type epoxy resins have an advantage of being excellent in coating stability because they are low in crystallinity as compared with diphenylether-type epoxy resins and the like.
Further, the (D1) epoxy resin has low solubility and diffusibility in the liquid crystal, and not only the display characteristics of the obtained liquid crystal panel are improved, but also the moisture resistance of the cured product of the liquid crystal sealant composition is enhanced.
The weight average molecular weight (Mw) of the epoxy resin (D1) is preferably 300 to 3000, more preferably 300 to 2000. (D1) The weight average molecular weight of the epoxy resin can be measured by gel permeation chromatography (GPC) using polystyrene as a standard. (D1) The epoxy resin may be either liquid or solid. In the case of a solid epoxy resin, it is preferable that the softening point is 40 占 폚 or more and 150 占 폚 or less.
The liquid crystal sealant composition may contain only one kind of thermosetting resin (D), or two or more kinds of thermosetting resins different in kind and molecular weight. The amount of the thermosetting resin (D) relative to 100 parts by mass of the liquid crystal sealant composition is 20 parts by mass or less, preferably 10 parts by mass or less. When the thermosetting resin (D) is included, moisture resistance of the liquid crystal sealant composition tends to increase.
(E) Thermosetting agent
The liquid crystal sealing composition of the present invention may contain (E) a thermosetting agent. The (E) thermosetting agent is a compound for curing the thermosetting resin, and the type thereof is not particularly limited, but it is preferable that the thermosetting agent is a thermal latent curing agent. The thermal latent curing agent is a curing agent that cures the thermosetting resin by heating without curing the thermosetting resin in a state of preserving the liquid crystal sealant composition (at room temperature).
The thermal latent curing agent may be a known one, but it is preferably a thermal latent curing agent having a melting point of 50 ° C or more and 250 ° C or less in order to improve the viscosity stability of the liquid crystal sealant composition. From the viewpoint of curing the resin even at a low thermal curing temperature (about 80 to 100 占 폚), it is more preferable that the melting point is not less than 50 占 폚 and not more than 150 占 폚.
Preferable examples of the thermal latent curing agent include a dihydrazide-based thermal latent curing agent, an imidazole-based thermal latent curing agent, an amine adduct-based thermal latent curing agent, and a polyamine-based thermal latent curing agent.
Examples of the dihydrazide type thermal latent curing agent include adipic acid dihydrazide (melting point 181 캜), 1,3-bis (hydrazinocarboethyl) -5-isopropyl hydantoin (melting point 120 캜 ), 7,11-octadecadien-1,18-dicabohydrazide (melting point 160 캜), dodecanedioic acid dihydrazide (melting point 190 캜), and sebacic acid dihydrazide (melting point 189 ° C) and the like.
The imidazole-based thermal latent curing agent may be, for example, a compound having a structure represented by the following formula (X).
In the formula (X), R 1 and R 2 are each independently a hydrogen atom, a lower alkyl group, a lower hydroxyalkyl group, a phenyl group or a benzyl group. R 3 and R 4 are each independently a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group. And at least one of R 1 to R 4 is a lower hydroxyalkyl group. As described above, the imidazole-based thermal latent curing agent having a lower hydroxyalkyl group is difficult to dissolve in liquid crystals because it contains a hydroxyl group.
The lower alkyl group which may be represented by R 1 to R 4 in the formula (X) is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a propyl group, preferably a methyl group or an ethyl group. On the other hand, the lower hydroxyalkyl group is a hydroxyalkyl group having 1 to 4 carbon atoms such as a hydroxymethyl group and a hydroxyethyl group, and is preferably a hydroxymethyl group. The lower hydroxyalkyl group may contain a plurality of hydroxyl groups.
The number of hydroxyl groups contained in the imidazole-based curing catalyst is not particularly limited, but if the number of hydroxyl groups is 2 or more, the water resistance may be lowered. Therefore, from the viewpoint of not lowering the water resistance, Do.
The melting point of the imidazole-based thermal latent curing agent represented by the formula (X) depends on the thermal curing temperature of the liquid crystal sealant composition, but when it is thermally cured at a relatively low temperature (for example, about 80 to 100 캜) Deg.] C or lower, more preferably 120 deg. C or lower, still more preferably 60 to 120 deg. C, and particularly preferably 80 to 100 deg. When the melting point of the imidazole-based thermal latent curing agent is too low, the imidazole-based thermal latent curing agent is melted at room temperature. Then, the curing reaction of the thermosetting resin (D) proceeds and the storage stability of the liquid crystal sealant composition at room temperature deteriorates. On the other hand, if the melting point is too high, the catalytic function of the imidazole-based thermal latent curing agent becomes difficult to sufficiently exert at the thermal curing temperature of the liquid crystal sealant composition. The melting point of the imidazole-based thermal latent curing agent can be lowered, for example, by making it not contain an aromatic ring.
R 2 is preferably a group other than a phenyl group or a benzyl group, that is, a hydrogen atom, a lower alkyl group or a lower hydroxyalkyl group in view of lowering the melting point of the imidazole-based thermal latent curing agent, more preferably a lower hydroxyalkyl group Do.
Examples of the imidazole-based thermal latent curing agent represented by the formula (X) include 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole , 2-hydroxymethylimidazole, 1-benzyl-5-hydroxymethylimidazole, 1,2-dihydroxyethylimidazole, and the like. Among them, 2-hydroxymethylimidazole can be cited as an imidazole-based thermal latent curing agent having a melting point of 150 캜 or lower.
The amine adduct-based thermal latent curing agent may be an addition compound obtained by reacting an amine compound having a catalytic activity with an arbitrary compound. Such an amine adduct thermal latent curing agent is activated by dissociation of the amine by heat. Examples of the amine compound include amicure PN-40 (melting point 110 deg. C), Amicure PN-23 (melting point 100 deg. C), amide PN- Cure PN-31 (melting point 115 캜), Amicure PN-H (melting point 115 캜), Amicure MY-24 (melting point 120 캜), Amicure MY- ), And the like.
The polyamine-based thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine with an epoxy. Specific examples thereof include ADEKA HARDNER EH4339S (softening point 120 to 130 DEG C, manufactured by ADEKA) ADEKA ADADA HARDNER EH4357S (softening point 73 to 83 DEG C) and the like.
The content of the (E) thermosetting agent is preferably 30 parts by mass or less, more preferably 15 parts by mass or less based on 100 parts by mass of the total amount of the (B) the photocurable resin and (D) the thermosetting resin. When the (E) thermosetting agent is included, the thermosetting reaction of the liquid crystal sealant composition tends to proceed sufficiently.
(F) Inorganic filler
The liquid crystal sealant composition of the present invention may further contain (F) an inorganic filler. (F) Addition of an inorganic filler can control the viscosity of the liquid crystal sealant composition, the strength of the cured product, and the control of the linear expansion property.
The inorganic filler (F) is not particularly limited, and examples thereof include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina) , Inorganic fillers such as potassium titanate, kaolin, talc, glass beads, cericite, activated clay, bentonite, aluminum nitride, silicon nitride, and titanium nitride. Silicon dioxide and talc are preferable.
(F) The shape of the inorganic filler is not particularly limited, and may be either a regular shape such as a spherical shape, a plate shape, a needle shape, or an irregular shape. (F) an inorganic filler has an average primary particle diameter and it is preferably 1.5μm or less, and it is preferred that its specific surface area of 1m 2 / g~500m 2 / g. (F) The average primary particle diameter of the inorganic filler can be measured by laser diffraction described in JIS Z8825. The specific surface area can be measured by the BET method described in JIS Z8830.
The amount of the inorganic filler (F) is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the liquid crystal sealant composition.
(G) organic filler
The liquid crystal sealant composition of the present invention may optionally contain (G) an organic filler. When the organic sealant (G) is contained in the liquid crystal sealant composition, the impact resistance of the cured product of the liquid crystal sealant composition tends to be high. The kind of the organic filler (G) is not particularly limited, but when the organic filler (G) is melted in the vicinity of the thermosetting temperature when the liquid crystal sealant composition is thermally cured, the liquid crystal sealant composition is deflected. On the other hand, if the melting point or softening point of the (G) organic filler is too high, (G) the organic filler is less likely to be deformed. Therefore, it is preferable that the melting point or softening point of the (G) organic filler is 30 to 120 占 폚.
Examples of the organic filler (G) include fine particles selected from the group consisting of silicon fine particles, acrylic fine particles, styrene fine particles such as styrene / divinylbenzene copolymer, and polyolefin fine particles.
The shape of the organic filler (G) is not particularly limited and may be, for example, spherical. The average particle diameter of the organic filler (G) is preferably 0.05 to 5 mu m, and more preferably 0.07 to 3 mu m since the gap of the liquid crystal cell is usually 5 mu m or less. The average particle diameter of the organic filler (G) can be measured, for example, by laser diffraction described in JIS Z8825.
The amount of the organic filler (G) is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the liquid crystal sealant composition.
(H) Other additives
Additives such as a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trap agent, an ion exchanger, a leveling agent, a pigment, a dye, a plasticizer and a defoaming agent are added to the liquid crystal sealant composition of the present invention . Further, a spacer or the like may be blended to adjust the gap of the liquid crystal panel.
· Use of liquid crystal sealant composition
The liquid crystal sealing agent of the present invention can be used for both liquid crystal injection method and liquid crystal dropping method. Particularly, the liquid crystal sealant composition of the present invention is preferably used in a liquid dropping method in that it is hardly dissolved in liquid crystals and can be cured in a short time. The curing in the liquid crystal dropping method may be a combination of photo-curing and thermal curing, but it is preferable that the photo-curing and the thermal curing are carried out in view of the fact that deterioration of the liquid crystal by heating is small, It is preferable to use them in combination.
The liquid crystal sealing agent for liquid crystal dropping method using both photo-curing and thermosetting is a photo-curable resin, (C) a photocurable polymerization initiator, (A) an organic acid, (D) a thermosetting resin, (E) (F) an inorganic filler, (G) an organic filler, and the like.
The viscosity of the liquid crystal sealant composition of the present invention at 25 캜 and 2.5 rpm using an E-type viscometer is preferably 30 to 350 Pa · s. The liquid crystal sealing agent having a viscosity in the above range is excellent in coating stability.
2. Manufacturing Method of Liquid Crystal Display Panel
A liquid crystal display panel according to the present invention is a liquid crystal display panel comprising a display substrate, a counter substrate paired therewith, a seal member having a frame shape interposed between the display substrate and the counter substrate, and a seal member between the display substrate and the counter substrate And a filled liquid crystal layer. The cured product of the liquid crystal sealant of the present invention can be used as a seal member.
Both the display substrate and the counter substrate are transparent substrates. The material of the transparent substrate may be glass or plastic such as polycarbonate, polyethylene terephthalate, polyethersulfone and 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. On the surface of the display substrate or the counter substrate, an alignment film is further formed. The alignment film includes known organic alignment agents and inorganic alignment agents.
Such a liquid crystal display panel can be manufactured using the liquid crystal sealing composition of the present invention. The liquid crystal display panel manufacturing method includes a liquid crystal dropping method and a liquid crystal injection method.
A method of manufacturing a liquid crystal display panel by a liquid crystal dropping method,
a1) a first step of applying a liquid crystal sealing composition of the present invention to one of the substrates to form a liquid crystal sealing pattern,
a2) In a state in which a liquid crystal seal pattern made of a liquid crystal sealant composition is uncured, a liquid crystal material is applied to a region surrounded by the liquid crystal seal pattern or a region of the other substrate opposite to the region surrounded by the liquid crystal seal pattern, The process,
and a3) a third step of superposing one substrate and the other substrate via a liquid crystal seal pattern to photo-cure the liquid crystal sealant composition.
The state in which the seal pattern is uncured in the step a2) means that the curing reaction of the liquid crystal sealant does not proceed to the gelation point. For this reason, in the step a2), the seal pattern may be irradiated with light or heated to be semi-cured in order to suppress the dissolution of the liquid crystal sealant into the liquid crystal. One substrate and the other substrate are a display substrate or an opposing substrate, respectively.
In the step of a3), it is possible to perform only curing with light, but it is preferable to perform curing (hardening) by heating after curing (hardening) by irradiation of light. This is because the liquid crystal sealant is instantaneously cured by light curing by light irradiation, whereby the dissolution in the liquid crystal can be suppressed.
Irradiation energy, (B) it is enough to cure the photocurable resin, etc. and, 1000~3000mJ / cm 2 or so, preferably about 2000mJ / cm 2. Since the liquid crystal sealant composition of the present invention includes the (C) titanocene-based photopolymerization initiator, the irradiation light may be ultraviolet light or light including a visible region. On the other hand, the thermal curing temperature depends on the composition of the liquid crystal sealant, but is preferably as low as possible, for example, about 120 ° C, preferably 80 to 100 ° C in view of reducing deterioration of the liquid crystal, The time is about 1-2 hours.
In the liquid crystal dropping method, since the contact time between the uncured liquid crystal sealant composition and the liquid crystal is relatively long, liquid crystal contamination tends to occur. On the other hand, the liquid crystal sealing composition of the present invention has a low solubility in the liquid crystal, so that the liquid crystal display panel obtained by the liquid crystal dropping method using the liquid crystal sealing composition of the present invention has excellent display reliability.
On the other hand, in a method of manufacturing a liquid crystal display panel by a liquid crystal injection method,
b1) a first step of applying a liquid crystal sealing composition of the present invention to one of the substrates to form a liquid crystal sealing pattern,
b2) a second step of superimposing one of the substrates and the other of the substrates via a liquid crystal seal pattern,
b3) a third step of photo-curing the liquid crystal seal pattern to obtain a liquid crystal injection cell having an injection port for injecting liquid crystal,
b4) a fourth step of injecting the liquid crystal into the liquid crystal injection cell through the injection port,
and b5) sealing the injection port.
In the steps b1) to b3), a liquid crystal injection cell is prepared. First, two transparent substrates (for example, glass plates) are prepared. Then, a liquid crystal sealant pattern is formed on one of the substrates with a liquid crystal sealant composition. The liquid crystal seal pattern may be cured after the other substrate is superimposed on the surface of the substrate on which the seal pattern is formed. At this time, it is necessary to provide an injection port for injecting the liquid crystal into a part of the liquid crystal injection cell, but an opening may be provided in a part of the injection port when drawing the liquid crystal seal pattern. Further, after forming the liquid crystal seal pattern, a liquid crystal seal pattern at a desired position may be removed to provide an injection port.
b3) light curing conditions in the process, is also dependent on the composition of the liquid crystal sealant, however, for example, irradiation energy is 1000~3000mJ / cm 2 or so.
The step b4) may be carried out in accordance with a known method in which the inside of the liquid crystal injection cell obtained in the processes of b1) to b3) is in a vacuum state and the liquid crystal is sucked from the injection port of the liquid crystal injection cell. b5), the liquid crystal sealant may be sealed in the injection port of the cell for injecting the liquid crystal, and then cured.
In the liquid crystal injection method, the contact time of the uncured liquid crystal seal composition with the liquid crystal is relatively short. However, liquid crystal may be injected even if the liquid crystal sealant composition of the liquid crystal injecting cell is not sufficiently cured. Since the liquid crystal sealing composition of the present invention has low solubility in liquid crystals, it is difficult to contaminate the liquid crystal even in such a case. Therefore, a liquid crystal display panel having excellent display reliability can be obtained also by the liquid crystal injection method using the liquid crystal sealing composition of the present invention.
Example
EXAMPLES Hereinafter, examples according to the present invention will be specifically described, but the present invention is not limited to these examples. Therefore, materials, manufacturing methods, and the like can be appropriately changed unless they deviate from the present invention.
[Synthesis Example 1] (Synthesis of methacrylic acid-modified bisphenol F type epoxy resin (95% partial methacrylate))
(Epoxy equivalent of 160 g / eq, manufactured by Epson YDF-8170C Shin-Etsu Chemical Co., Ltd.), 0.1 g of p-methoxyphenol (polymerization inhibitor), 0.2 g of triethanolamine (catalyst) And 81.7 g of methacrylic acid were charged into a flask. Dry air was fed into the flask and reacted for 5 hours while refluxing at 90 캜 with stirring. The obtained compound was washed with ultrapure water 20 times to obtain methacrylic acid-modified bisphenol F type epoxy resin (weight average molecular weight: 484).
[Example 1]
100 parts by mass of the methacrylic acid-modified bisphenol F type epoxy resin obtained in Synthesis Example 1, 100 parts by mass of bis (? 5-2,4-cyclopentadien-1-yl) -Pyrrol-1-yl) -phenyl) titanium (trade name: IGACURE 784, BASF), and 0.5 parts by mass of oxalic acid were mixed to prepare a liquid crystal sealant composition.
[Example 2]
A liquid crystal sealant composition was prepared in the same manner as in Example 1 except that oxalic acid was changed to tartaric acid.
[Example 3]
A liquid crystal sealant composition was prepared in the same manner as in Example 1 except that oxalic acid was changed to trimellitic acid.
[Example 4]
A liquid crystal sealant composition was prepared in the same manner as in Example 1 except that oxalic acid was changed to trimellitic anhydride.
[Example 5]
A liquid crystal sealant composition was prepared in the same manner as in Example 1 except that oxalic acid was changed to isophthalic acid.
[Example 6]
A liquid crystal sealant composition was prepared in the same manner as in Example 1 except that oxalic acid was changed to phenylphosphonic acid.
[Example 7]
A liquid crystal sealant composition was prepared in the same manner as in Example 1 except that oxalic acid was changed to 4'-hydroxy-4-biphenylcarboxylic acid.
[Comparative Example 1]
A liquid crystal sealant composition was prepared in the same manner as in Example 1 except that oxalic acid was not added.
[Comparative Example 2]
A liquid crystal sealant composition was prepared in the same manner as in Example 1 except that oxalic acid was changed to 2-ethylhexylphosphate.
[Comparative Example 3]
A liquid crystal sealant composition was prepared in the same manner as in Example 1 except that oxalic acid was changed to 3,5-bistrifluoromethylbenzoic acid.
[evaluation]
The liquid crystal sealing compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated by 1) voltage holding ratio of liquid crystal and 2) photocurable property by the following method. The results are shown in Table 1.
1) Voltage maintenance ratio of liquid crystal
0.1 g of the liquid crystal sealant composition obtained in Examples and Comparative Examples and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck) were placed in a vial bottle and heated at 120 占 폚 for 1 hour to obtain a liquid crystal mixture. Subsequently, this liquid crystal mixture was taken out and injected into a glass cell (KSSZ-10 / B111M1NSS05, manufactured by EHC) in which a transparent electrode had been formed in advance, and a voltage of 1 V was applied to it. The voltage holding ratio at 60 Hz was measured with a 6254- ). Evaluation was performed as follows.
&Amp; cir &: When the voltage holding ratio was 90% or more (less contamination to the liquid crystal)
X: When the voltage holding ratio was less than 90% (contamination to liquid crystal occurred)
2) Photocurable
VISCOANALYSER VAR100 (manufactured by REOLOGICA INSTRUMENT) was used to measure the viscosity rise behavior after light of 1 mW / cm 2 (wavelength cut to 400 nm or less and calibrated with a 405 nm sensor) was irradiated to the liquid crystal sealant composition obtained in Examples and Comparative Examples, . The curing time until the viscosity of the liquid crystal sealant composition after light irradiation became 50% with respect to the value of the saturated viscosity was measured. The saturated viscosity value is a viscosity when the liquid crystal sealant composition is fully cured. The shorter the curing time, the better the curability can be judged.
As shown in Table 1, when the liquid crystal sealant composition contained an organic acid (Examples 1 to 7 and Comparative Examples 2 and 3), the photo-curability was improved as compared with the case where no organic acid was contained (Comparative Example 1). Compared with the case where the oxygen atom equivalent of the organic acid is 23 g / eq or more and 75 g / eq or less (Examples 1 to 7) and the oxygen atom equivalent is more than 75 g / eq (Comparative Examples 2 and 3) This was extremely good. In Comparative Examples 2 and 3, although the photo-curability was good, the liquid crystal was contaminated, and the voltage holding ratio was lowered.
[Example 8]
43 parts by mass of the methacrylic acid-modified bisphenol F type epoxy resin obtained in Synthesis Example 1, 5 parts by mass of a solid epoxy resin (jER1004, softening point 97 占 폚, manufactured by Mitsubishi Chemical Corporation), 5 parts by mass of an acrylic resin (polyethylene glycol diacrylate, Acrylate 14EG-A, weight average molecular weight: 708), 9 parts by mass of adipic acid dihydrazide (ADH manufactured by Nippon Hoso Chemical Co., Ltd., melting point: 177 to 184 占 폚) as a thermosetting agent, 20 parts by mass of silica particles: , 7 parts by mass of an organic filler (fine particle polymer, F351 manufactured by Zeon Corporation) obtained by copolymerizing a (meth) acrylic acid ester monomer and a monomer copolymerizable therewith, 13 parts by mass of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) , 0.5 part by mass of titanium (IGACURE 784, manufactured by BASF), and 0.5 part by mass of oxalic acid, And the mixture was thoroughly mixed to obtain a homogeneous liquid by using a mill to obtain a liquid crystal sealant composition.
[Example 9]
A liquid crystal sealant composition was obtained in the same manner as in Example 8 except that oxalic acid was changed to tartaric acid.
[Example 10]
A liquid crystal sealant composition was obtained in the same manner as in Example 8 except that oxalic acid was changed to trimellitic acid.
[Example 11]
A liquid crystal sealant composition was obtained in the same manner as in Example 8 except that oxalic acid was changed to trimellitic anhydride.
[Example 12]
A liquid crystal sealant composition was obtained in the same manner as in Example 8 except that oxalic acid was changed to isophthalic acid.
[Example 13]
A liquid crystal sealant composition was obtained in the same manner as in Example 8 except that oxalic acid was changed to phenylphosphonic acid.
[Example 14]
A liquid crystal sealing composition was obtained in the same manner as in Example 8 except that oxalic acid was changed to 4'-hydroxy-4-biphenylcarboxylic acid.
[Comparative Example 4]
A liquid crystal sealant composition was obtained in the same manner as in Example 8 except that oxalic acid was not added.
[Comparative Example 5]
A liquid crystal sealant composition was obtained in the same manner as in Example 8 except that oxalic acid was changed to 2-ethylhexylphosphate.
[Comparative Example 6]
A liquid crystal sealant composition was obtained in the same manner as in Example 8 except that oxalic acid was changed to 3,5-bistrifluoromethylbenzoic acid.
[evaluation]
The liquid crystal sealing composition obtained in Examples 8 to 14 and Comparative Examples 4 to 6 was evaluated by the following methods: 3) liquid crystal display panel display characteristic test; and 4) display property test at the time of energization of the liquid crystal panel. The results are shown in Table 2.
3) Liquid crystal display panel display characteristic test
The liquid crystal sealing composition obtained in Examples and Comparative Examples was placed on a 40 mm x 45 mm glass substrate (RT-DM88-PIN made by EHC) on which a transparent electrode and an alignment film were previously formed using a dispenser (SCHARTMASHER, manufactured by Musashi Engineering Co., Ltd.) dimensions 35mm × 40mm, the seal pattern of the edge shape of the rectangle is the line width after that cheophap 0.7mm (cross-sectional area 3500μm 2) (main seal), and the outer dimensions 38mm × 43mm, a square that is after the line width is 1.0mm in the outer periphery cheophap Thereby forming a rim-shaped seal pattern.
Subsequently, a liquid crystal material (MLC-7021-000, manufactured by Merck) corresponding to the panel content after substrate bonding was precisely dripped into the rim of the main seal using a dispenser. The glass substrates to be paired were laminated under reduced pressure, and then opened to the atmosphere to be bonded. Then, the two bonded glass substrates were held in the light shielding box for 3 minutes. Thereafter, the substrate was coated with a substrate coated with a square black matrix of 36 mm x 41 mm so that the main seal was not irradiated with the light directly. In this state, light of 3000 mJ / cm 2 (light whose wavelength is 400 nm or less was cut out and calibrated by a 405 nm sensor) was irradiated and further heated at 120 캜 for 1 hour. Thereafter, polarizing films were attached to both surfaces.
The liquid crystal display panel after curing treatment of the liquid crystal sealing composition was evaluated as follows.
&Amp; cir &: When the liquid crystal is aligned to the edge of the main seal of the liquid crystal panel and there is no color unevenness (display characteristics are good)
X: In the case where the vicinity of the edge of the main seal is not normally oriented and color unevenness occurs (display characteristics are inferior)
4) Test the display characteristics when the liquid crystal display panel is energized
The liquid crystal panel produced in the same manner as in Test 3) liquid crystal display panel display characteristic test described above was driven with an applied voltage of 5 V by using a direct current power source. The display characteristics at this time were evaluated as follows.
&Amp; cir &: When the liquid crystal display function in the vicinity of the main seal is exerted (display characteristics are good)
X: When the vicinity of the main seal is not normally driven and white spots are generated (display characteristics are poor)
As shown in Table 2, as compared with the case of containing an organic acid in the liquid crystal sealant composition (Examples 8 to 14 and Comparative Examples 5 and 6) and the case of not containing an organic acid (Comparative Example 4) Was good. It is considered that the inclusion of the organic acid sufficiently cures even when the liquid crystal sealant is not directly irradiated with light upon curing, and the dissolution of the uncured component of the liquid crystal sealant composition into the liquid crystal is remarkably suppressed.
Compared with the case where the oxygen atom equivalent of the organic acid is 23 g / eq or more and 75 g / eq or less (Examples 8 to 14) and the oxygen atom equivalent is more than 75 g / eq (Comparative Examples 5 and 6) The display characteristics of the hour were good. This is considered to be because when the oxygen atom equivalent is within the above range, the uncured component of the composition for a liquid crystal seal hardly affects the liquid crystal and is hardly dissolved, so that the voltage retention ratio of the liquid crystal is remarkably improved.
The present application claims priority based on Japanese Patent Application No. 2014-221018 filed on October 30, 2014. The contents of which are incorporated herein by reference.
Since the liquid crystal sealing composition of the present invention contains an organic acid, the liquid crystal sealing composition of the present invention has very good curability, and the dissolution of the uncured component in the liquid crystal is very small. Therefore, it is possible to provide a liquid crystal panel having excellent display reliability, and is suitable for manufacturing various liquid crystal display panels.
Claims (12)
On the substrate
(A) an organic acid,
(B) a photocurable resin having at least one ethylenically unsaturated double bond in one molecule (excluding the above organic acid), and
(C) Titanosene-based photopolymerization initiator
Lt; / RTI >
(1) of the organic acid (A) is 23 g / eq or more and 75 g / eq or less, to form a liquid crystal seal pattern;
And a photo-curing step of photo-curing the liquid crystal sealant composition.
(G / eq) = (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
Wherein the organic acid (A) is an acid anhydride.
Wherein the organic acid (A) has at least one ethylenic unsaturated double bond.
(O) (OH) 2 group, -NHR group (R represents an aromatic, aliphatic hydrocarbon or a derivative thereof), -COOH group, -OP (= O) And at least one functional group selected from the group consisting of -P (= O) (OH) 2 group, -SO 3 H group, -CONH 2 group and -NHOH group.
Wherein the photocurable resin (B) is a resin having at least one ethylenically unsaturated double bond and at least one epoxy group in one molecule (B2).
(D) a thermosetting resin.
(E) a thermosetting agent, and further comprises
Wherein the thermosetting resin (D) is a resin (D1) having at least one epoxy group in one molecule.
Wherein the thermosetting agent (E) is at least one selected from the group consisting of a dihydrazide type thermal latent curing agent, an imidazole type thermal latent curing agent, an amine adduct type thermal latent curing agent, and a polyamine type thermal latent curing agent Wherein the thermal latent curing agent is a thermal latent curing agent of a species.
Further comprising a step of further thermally curing the liquid crystal sealant composition.
Wherein the light irradiated in the photo-curing step includes a visible light region.
(B) a photocurable resin having at least one ethylenically unsaturated double bond in one molecule (excluding the above organic acid), and
(C) Titanosene-based photopolymerization initiator
Lt; / RTI >
Wherein the organic acid (A) has an oxygen atom equivalent of not less than 23 g / eq and not greater than 75 g / eq expressed by the following formula (1).
(G / eq) = (molecular weight of organic acid) / (number of oxygen atoms in one molecule of organic acid) (1)
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| JP2014221018 | 2014-10-30 | ||
| JPJP-P-2014-221018 | 2014-10-30 | ||
| PCT/JP2015/005354 WO2016067582A1 (en) | 2014-10-30 | 2015-10-26 | Method for producing liquid crystal display panel, liquid crystal display panel and liquid crystal sealing agent composition |
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| KR101863011B1 true KR101863011B1 (en) | 2018-05-31 |
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| KR102509153B1 (en) * | 2018-07-24 | 2023-03-10 | 미쓰이 가가쿠 가부시키가이샤 | Light-shielding sealing agent for liquid crystal dropping method, and manufacturing method of liquid crystal display panel using the same |
| JP2020177039A (en) * | 2019-04-15 | 2020-10-29 | 凸版印刷株式会社 | Dimming sheet and laminated glass |
| CN113661437A (en) * | 2019-05-17 | 2021-11-16 | 三井化学株式会社 | Sealant for liquid crystal dropping process, liquid crystal display panel using same, and method for manufacturing same |
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| JP2001316416A (en) | 2000-05-10 | 2001-11-13 | Nippon Paint Co Ltd | Photopolymerizing composition and photopolymerizing putty composition |
| US8410188B2 (en) * | 2009-07-13 | 2013-04-02 | Adeka Corporation | Sealant for one-drop fill process |
| JP2011023498A (en) * | 2009-07-15 | 2011-02-03 | Panasonic Corp | Semiconductor device, and method of manufacturing the same |
| CN102472929B (en) * | 2010-03-25 | 2014-07-30 | 三井化学株式会社 | Liquid crystal sealing agent, method for producing liquid crystal display panel using same, and liquid crystal display panel |
| JP2012173488A (en) * | 2011-02-21 | 2012-09-10 | Sekisui Chem Co Ltd | Sealing agent for liquid crystal dropping method, and manufacturing method of liquid crystal display |
| CN102702987B (en) * | 2012-03-21 | 2015-02-18 | 北京京东方光电科技有限公司 | Frame sealant composition, liquid crystal pollution prevention method, liquid crystal display panel and display device |
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| CN106489098A (en) | 2017-03-08 |
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