CN116790214B - Sealant composition and application thereof in liquid crystal display element - Google Patents
Sealant composition and application thereof in liquid crystal display element Download PDFInfo
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- CN116790214B CN116790214B CN202310562052.7A CN202310562052A CN116790214B CN 116790214 B CN116790214 B CN 116790214B CN 202310562052 A CN202310562052 A CN 202310562052A CN 116790214 B CN116790214 B CN 116790214B
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- epoxy resin
- sealant composition
- liquid crystal
- acrylic
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- 239000000565 sealant Substances 0.000 title claims abstract description 126
- 239000000203 mixture Substances 0.000 title claims abstract description 122
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 56
- 239000003822 epoxy resin Substances 0.000 claims abstract description 103
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 103
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 28
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 photoinitiator Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 17
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 20
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 150000008062 acetophenones Chemical class 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims 1
- 150000008366 benzophenones Chemical class 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 238000009472 formulation Methods 0.000 abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001723 curing Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 11
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical group NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 11
- 244000028419 Styrax benzoin Species 0.000 description 10
- 235000000126 Styrax benzoin Nutrition 0.000 description 10
- 235000008411 Sumatra benzointree Nutrition 0.000 description 10
- 229960002130 benzoin Drugs 0.000 description 10
- 235000019382 gum benzoic Nutrition 0.000 description 10
- 230000035699 permeability Effects 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- LKVFCSWBKOVHAH-UHFFFAOYSA-N 4-Ethoxyphenol Chemical compound CCOC1=CC=C(O)C=C1 LKVFCSWBKOVHAH-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 101100112111 Caenorhabditis elegans cand-1 gene Proteins 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the technical field of sealants used in the field of liquid crystal display elements, in particular to a sealant composition and application thereof, wherein the sealant composition comprises the following components: polyfunctional epoxy resin, monofunctional acrylic resin, acrylic modified epoxy resin, photoinitiator, coupling agent, curing agent and filler. The sealant composition of the present application can prevent moisture from entering the display region of the liquid crystal element by increasing Tg of the sealant composition by adding a multifunctional epoxy resin to the formulation of the sealant composition, and can realize high Tg and high adhesion of the sealant composition by adjusting problems of low adhesion and high viscosity due to excessively high Tg by adding a monofunctional acrylic resin, thereby realizing good high-temperature high-humidity reliability.
Description
Technical Field
The invention relates to the technical field of sealants used in the field of liquid crystal display elements, in particular to a sealant composition and application thereof in the liquid crystal display elements.
Background
In the field of liquid crystal elements, a liquid crystal dropping process is conventionally performed by using a photo-thermal curing type sealant containing a curable resin, an initiator, and a curing agent. The prior art reports that problems in the application of sealants to liquid crystal elements, particularly small liquid crystal elements, such as the contamination, viscosity and coatability of the sealants, are investigated.
The applicant has found that increasing the Tg (Glass transition temperature) of the sealant prevents moisture from entering the liquid crystal cell, whereas increasing Tg results in a decrease in the adhesion of the sealant and an increase in the viscosity of the sealant, without utilizing the service life of the liquid crystal cell. The present application aims to develop a sealant which has both high adhesion and high temperature and high humidity resistance.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, an object of the present invention is to provide a sealant composition and its application in a liquid crystal display device, in which Tg of the sealant is increased by adding a multifunctional epoxy resin to a sealant formulation, and moisture is prevented from entering a display region of the liquid crystal device, and problems of low adhesion and high viscosity due to excessively high Tg are solved by adding a monofunctional acrylic resin. I.e., by a formulation containing a monofunctional epoxy resin, a multifunctional epoxy resin, and other components.
To achieve the above and other related objects, one aspect of the present invention provides a sealant composition including a multifunctional epoxy resin, a monofunctional acrylic resin, an acrylic modified epoxy resin, a photoinitiator, a coupling agent, a curing agent, and a filler.
In some embodiments, the multifunctional epoxy resin is selected from at least one of the structures shown in formula I or formula II:
wherein n and m are independently selected from 1 to 5.
In some embodiments, the monofunctional acrylic resin is selected from the group consisting of monomer structures or oligomers represented by formula III:
wherein the oligomer has a degree of polymerization of 1 to 3.
In some embodiments, the sealant composition comprises the following components in parts by weight;
in some embodiments, the sealant composition comprises the following components in parts by weight;
in some embodiments of the invention, the sealant composition comprises the following components in parts by weight;
in some embodiments of the invention, the sealant composition comprises the following components in parts by weight;
in a second aspect of the present invention, there is provided a method for preparing a sealant composition comprising mixing a multifunctional epoxy resin, a monofunctional acrylic resin, an acrylic modified epoxy resin, a photoinitiator, a coupling agent, a curing agent, and a filler.
In a third aspect of the invention, there is provided a method of using a sealant composition: 1) Applying the sealant composition to a substrate with a seal;
2) Temporary fixation is performed by light irradiation; preferably, the light irradiation energy is 2000-5000 mJ/cm < 2 >, and the irradiation time is 0.1-5 min;
3) Final fixing by heating; preferably, the heating temperature is 40-100 ℃ and the heating time is 0.5-3 h.
In a fourth aspect, the present invention provides the use of the sealant composition of the present invention in a liquid crystal dropping process, or for the preparation of a vertically conducting material, or for the preparation of a liquid crystal display element.
A fifth aspect of the present invention provides an up-down conductive material comprising the sealant composition and conductive particles as described above.
A sixth aspect of the present invention provides a liquid crystal display element comprising the sealant composition as described above or the vertically conductive material as described above.
Compared with the prior art, the invention has the beneficial effects that: the high Tg and adhesion are tailored to achieve good high temperature high humidity reliability by adding a multifunctional epoxy resin and a monofunctional acrylic resin to the sealant composition formulation.
Detailed Description
Summary of The Invention
The following detailed description specifically discloses embodiments of a sealant composition and its application in liquid crystal display elements.
The "range" disclosed herein is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 5-30 and 20-40 are listed for a particular parameter, it is understood that ranges of 5-20 and 30-40 are also contemplated. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers.
The inventor provides a sealant composition and application thereof in a liquid crystal display element through a large amount of exploratory experiments, and the sealant composition is endowed with high Tg performance, high adhesive force and good high-temperature high-humidity dependence through adjusting a formula and combining monofunctional epoxy resin, polyfunctional epoxy resin and other components, so that a liquid crystal product using the sealant composition has good waterproof function. On this basis, the present invention has been completed.
Interpretation of the terms
"liquid crystal contamination", the sealant composition contacts the liquid crystal in an uncured state, and the components of the sealant composition dissolve out, resulting in liquid crystal contamination. The "adhesion" refers to the force with which the upper and lower substrates are bonded after the sealant composition has completely cured. "Tg" is the glass transition temperature. The sealant composition has high-quality high-temperature and high-humidity resistance under the high-temperature and high-humidity conditions, so that the liquid crystal element has high-temperature and high-humidity resistance when the sealant composition is applied to the liquid crystal element, and water is prevented from entering the liquid crystal element from a sealing position.
The "epoxy resin" appearing throughout the present invention is a monomer or oligomer thereof having an epoxy group functional group such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, and the like. Oligomer refers to a polymer having a relatively low molecular weight, generally referred to as being capable of being present in liquid form.
Detailed Description
In a first aspect, the present invention provides a sealant composition comprising a multifunctional epoxy resin, a monofunctional acrylic resin, an acrylic modified epoxy resin, a photoinitiator, a coupling agent, a curing agent, and a filler.
(1) "multifunctional epoxy resins" contain a plurality of epoxy reactive groups, typically at least 3 epoxy reactive groups in one molecule. In the application, the sealant composition comprises 5-40 parts by weight of the multifunctional epoxy resin. In some embodiments, the parts of the multifunctional epoxy may also be 5 to 10 parts, 10 to 15 parts, 15 to 20 parts, 20 to 25 parts, 25 to 30 parts, 30 to 35 parts, or 35 to 40 parts.
(2) "monofunctional epoxy resin", in this application, the sealant composition has 3 to 25 parts by weight of monofunctional epoxy resin. In some embodiments, the fraction of monofunctional acrylic resin may also be 3 to 5 parts, 5 to 10 parts, 10 to 15 parts, 15 to 20 parts, or 20 to 25 parts.
As above, by reasonable collocation of the multifunctional epoxy resin and the monofunctional epoxy resin and the combination of other formulas, the high Tg, the optimal adhesive force and the optimal high temperature and high humidity dependence are realized.
(3) The "acrylic-modified epoxy resin" is specifically a substituted or unsubstituted acrylic-grafted modified epoxy resin, and functions to crosslink the multifunctional epoxy resin and the monofunctional epoxy resin in the present invention. The sealant composition may be free of acrylic modified epoxy in some embodiments. In some preferred embodiments, the sealant composition contains an acrylic modified epoxy resin. To sum up, the sealant composition may have 0 to 40 parts by weight of the acrylic-modified epoxy resin, and in some embodiments, 0 (excluding 0), 5 to 10 parts, 10 to 15 parts, 15 to 20 parts, 20 to 25 parts, 25 to 30 parts, 30 to 35 parts, or 35 to 40 parts of the acrylic-modified epoxy resin.
(4) Photoinitiators are compounds which generate free radicals by means of light irradiation, suitable photoinitiators for use in the present application being selected from benzoin compounds, for example benzoin and diethyl ether; copper diphenyl compounds such as benzophenone; acetophenones such as diethoxyacetophenone. Preferably, an initiator having a strong absorption in the violet range of wavelengths from 350 to 450 is used, such as Irgacure651 manufactured by BASF. In addition, photosensitizers reported in the prior art can be selected as required. In this application, the sealant composition comprises 3 to 10 parts by weight of the photoinitiator, and in some embodiments 3 to 5 parts by weight, or 5 to 10 parts by weight of the photoinitiator.
(5) The coupling agent is not particularly limited, and preferred coupling agents herein are selected from the group consisting of-glycidoxypropyl trimethoxysilane. In this application, the sealant composition comprises 3 to 10 parts by weight of the coupling agent, and in some embodiments 3 to 5 parts by weight, or 5 to 10 parts by weight of the coupling agent.
(6) The curing agent is not particularly limited, and preferred curing agents of the present application are at least one of organic acid hydrazides, amine compounds or imidazole compounds; preferably, the organic acid hydrazide is selected from sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide or malonic acid dihydrazide. In this application, the sealant composition comprises 5 to 15 parts by weight of the curing agent, and in some embodiments 5 to 10 parts by weight, or 10 to 15 parts by weight of the curing agent.
(7) The filler may be an inorganic filler or an organic filler as required, and the preferred filler herein is preferably an inorganic filler, specifically at least one selected from silica, alumina, zinc oxide, talc or silicon nitride. In this application, the sealant composition comprises, by weight, 20 to 40 parts of filler, and in some embodiments 20 to 25 parts, 25 to 30 parts, 30 to 35 parts, or 35 to 40 parts of filler.
In a preferred embodiment, the multifunctional epoxy resin is selected from at least one of the structures shown by formula I (dicyclopentadiene phenol type epoxy resin) or formula II (naphthalene type epoxy resin):
wherein n and m are independently selected from 1 to 5, optionally 1, 2, 3, 4 or 5.
The addition of the multifunctional epoxy resin increases the Tg of the sealant composition to prevent water from entering into the display area, but too high Tg affects the adhesion to become lower and the viscosity of the sealant composition also becomes higher. Specifically, the sealant is formed by polymerizing dicyclopentadiene and phenol monomers in the formula I, and the matching of the dicyclopentadiene skeleton and the benzene ring skeleton ensures that the resin I has certain rigidity, so that the Tg performance and the heat resistance and humidity resistance of the sealant composition can be improved. For example, the naphthalene type epoxy resin shown in the formula II is characterized in that a naphthalene ring with high rigidity and high hydrophobicity is introduced into a main chain, so that the resin has good rigidity, and a-CH 2-chain is introduced into the main chain, so that the resin has slight flexibility, and the matching of a naphthalene ring skeleton and a C chain enables the resin II to have proper rigidity. And it has been found that the Tg performance and the heat and moisture resistance of the sealant composition can be improved.
In a preferred embodiment, the monofunctional acrylic resin is selected from the group consisting of monomer structures or oligomers represented by formula III:
wherein the oligomer has a polymer of 1 to 3, alternatively 1, 2 or 3. The monofunctional resin with the structure shown in the formula III plays a role in regulating the hardness. In particular, the flexible hydrophobic backbone imparts flexibility and reduces moisture permeability to the sealant composition after application to a product.
In a preferred embodiment, the acrylic-modified epoxy resin is a partially acrylic-modified epoxy resin. Specifically, part of epoxy groups in the partially acrylic modified epoxy resin are modified by acrylic acid, that is, the resin has at least one acrylic ester group and at least one epoxy group. The epoxy resin is at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin or biphenyl type epoxy resin. The acrylic acid is at least one selected from unsubstituted acrylic acid, (meth) acrylic acid or (ethyl) acrylic acid.
The part of acrylic acid modified epoxy resin is acrylic acid grafted modified epoxy resin, and the grafting rate of acrylic ester groups of the part of acrylic acid modified epoxy resin is 30-80%. In some embodiments, the grafting ratio is 30-40%, 40-50%, 50-60%, 60-70%, or 70-80%. Meets a certain grafting rate and plays a good role in crosslinking the multifunctional epoxy resin and the monofunctional acrylic resin. Part of the acrylic-modified epoxy resin is preferably a (meth) acrylic-modified epoxy resin, "(meth) acrylic-modified epoxy resin" i.e., a resin having at least one (meth) acrylate group and at least one epoxy group therein.
In a specific embodiment, the sealant composition comprises the following components in parts by weight;
5-40 parts of multifunctional epoxy resin; 3-30 parts of monofunctional acrylic resin; 0-40 parts of acrylic modified epoxy resin; 3-10 parts of photoinitiator; 3-10 parts of a coupling agent; 5-15 parts of curing agent; 20-40 parts of filler.
In a specific embodiment, the sealant composition comprises the following components in parts by weight; 20-40 parts of multifunctional epoxy resin; 10-30 parts of monofunctional acrylic resin; 3-10 parts of photoinitiator; 3-10 parts of a coupling agent; 5-15 parts of curing agent; 20-40 parts of filler.
In a specific embodiment, the sealant composition comprises the following components in parts by weight; 5-20 parts of multifunctional epoxy resin; 5-20 parts of monofunctional acrylic resin; 10-40 parts of acrylic modified epoxy resin; 3-10 parts of photoinitiator; 3-10 parts of a coupling agent; 5-15 parts of curing agent; 20-40 parts of filler.
The second aspect of the present application also provides a preparation method using the sealant composition described above, including the steps of: the epoxy resin is prepared by mixing multifunctional epoxy resin, monofunctional acrylic resin, acrylic modified epoxy resin, photoinitiator, coupling agent, curing agent and filler.
Specifically, the photoinitiator was added to the multifunctional epoxy resin and the monofunctional acrylic resin and dissolved at 120 to 180℃for 30 to 60 minutes, after confirming that the photoinitiator was completely dissolved, the acrylic-modified epoxy resin was added, and the coupling agent was stirred under vacuum for 30 to 60 minutes, confirming that the total amount was mixed. Adding filler and stirring for 30-60 min under vacuum. After stirring, the stirring pot is stopped, and after the temperature of the stirring pot is reduced to 25 ℃, the curing agent is added, and stirring is carried out for 30-60 minutes under vacuum under the condition that the temperature of the stirring pot is controlled to be not more than 28 ℃. Finally, three-roller grinding (the clearance of the roller is controlled below 5 um) and filtering (the filtering precision is above 5 um).
The sealant composition fills the finished product. The filling process is a conventional process, in which 2 transparent substrates with electrodes are placed opposite each other at predetermined intervals, the peripheries thereof are sealed with the above-mentioned sealant composition, a cell is formed, liquid crystal is injected into the cell through a liquid crystal injection port provided in a part of the cell, and the liquid crystal injection port is sealed with the sealant composition, thereby producing a finished product.
A third aspect of the present application provides a method of using the above sealant composition or a sealant composition prepared by a method of preparation, comprising the steps of:
1) Assembling the sealant assemblyThe compound is applied to the upper and lower substrates; 2) Temporary fixation is performed by light irradiation; preferably, the light irradiation energy is 2000-5000 mJ/cm 2 The irradiation time is 0.1-5 min; 3) Final fixing by heating; preferably, the heating temperature is 40-100 ℃ and the heating time is 0.5-3 h.
A fourth aspect of the present application is the use of the sealant composition described above or a sealant composition prepared by a preparation method in a liquid crystal dropping process, or for preparing a vertically conducting material, or for preparing a liquid crystal display element.
The liquid crystal dropping process is a process in which a liquid crystal composition is placed between a pair of substrates of a liquid crystal display element, and then sealed with a sealant composition by using light and heat containing a curable resin, an initiator, and a curing agent.
A fifth aspect of the present application provides a vertically conducting material comprising the above-described sealant composition or a sealant composition prepared by a preparation method and conductive particles. The conductive fine particles are not particularly limited, and the purpose is to form a conductive metal layer on the resin surface.
A sixth aspect of the present application provides a liquid crystal display element, including the above-described sealant composition or the sealant composition prepared by the preparation method or the above-described upper and lower conductive material.
The advantageous effects of the present invention are further illustrated below with reference to examples.
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is described in further detail below with reference to examples. However, it should be understood that the examples of the present invention are merely for the purpose of explaining the present invention and are not intended to limit the present invention, and the examples of the present invention are not limited to the examples given in the specification. The specific experimental or operating conditions were not noted in the examples and were made under conventional conditions or under conditions recommended by the material suppliers.
In the examples described below, reagents, materials and apparatus used are commercially available unless otherwise specified.
1) The multifunctional epoxy resin of formula I is prepared by polymerizing dicyclopentadiene phenol resin with phenol and dicyclopentadiene monomer, and then reacting with epichlorohydrin, or is prepared by the method of commercial sale: the epoxy equivalent weight/g/eg is 245-280, and the ICI viscosity/Pa.s is 0.15-0.5.
The specific synthetic route can be selected as follows: in the first step, dicyclopentadiene and phenol are subjected to Friedel-Crafts alkylation reaction to generate dicyclopentadienyl-phenol type phenolic resin, and then the dicyclopentadienyl-phenol type phenolic resin and epichlorohydrin are subjected to epoxidation reaction under the condition of strong alkali to generate the multifunctional epoxy resin shown in the formula I.
2) The multifunctional epoxy resin formula II is prepared by polymerizing naphthol and hydroxytoluene (containing aldehyde group) monomers to form naphthalene resin, then reacting the naphthalene resin with epoxy chloropropane, and the preparation method refers to Pu Qilong and is a preparation method for synthesizing linear naphthol phenolic resin by polymerizing alpha-naphthol and formaldehyde aqueous solution, and then reacting the naphthalene resin with epoxy chloropropane to obtain the multifunctional epoxy resin shown in the formula II. Or the epoxy equivalent weight/g/eg is 221-223 and ICI viscosity/Pa.s is 0.5-1.
3) The monofunctional acrylic resin III is commercially available, for example, DCP-A of Kyowa chemical Co., ltd.
4) A method for producing a partially (meth) acrylic acid-modified bisphenol A-type epoxy resin, wherein 1000 parts by weight of bisphenol A-type epoxy resin (manufactured by Mitsubishi chemical corporation, "jER828 EL"), 2 parts by weight of p-ethoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 253 parts by weight of methacrylic acid were refluxed and stirred at 90℃for 5 hours while air was blown in, and reacted. 100 parts by weight of the resultant reaction product was filtered to obtain 50% part of methacrylic acid-modified bisphenol A-type epoxy resin.
5) The photoinitiator benzoin diethyl ether (IR-651) was purchased from BASF. Coupling agent 3-epoxypropoxy propyl trimethoxy silane, curing agent sebacic dihydrazide and filler silica are purchased from market.
Example 1
This example relates to a sealant composition, the parts by weight of the components are shown in table 1:
TABLE 1
| Sealant composition formulation | Parts by weight of |
| Multifunctional epoxy resin formula I | 10 |
| Partial (meth) acrylic acid modified bisphenol A type epoxy resin | 35 |
| Monofunctional acrylic resin III | 5 |
| Benzoin diethyl ether (IR-651) | 5 |
| 3-epoxypropoxypropyl trimethoxysilane | 5 |
| Sebacic dihydrazide | 10 |
| Silica dioxide | 30 |
The sealant composition formula is adopted to prepare a product A-1, a multifunctional epoxy resin formula I and a monofunctional acrylic resin III are mixed in a planetary stirring instrument, IR-651 is added, the mixture is dissolved for 30 minutes at 160 ℃, part of (methyl) acrylic acid modified bisphenol A type epoxy resin is added, and a coupling agent 3-glycidoxypropyl trimethoxysilane is stirred for 30 to 60 minutes under vacuum. Adding filler silicon dioxide, and stirring for 30-60 minutes under vacuum. And (3) standing the stirring pot after stirring, after the temperature of the stirring pot is reduced to 25 ℃, adding the thermosetting agent sebacic dihydrazide, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring pot is controlled to be not more than 28 ℃. Finally, the mixture was subjected to three-roll polishing (the gap between rolls was 5 μm or less), and filtration (the filtration accuracy was 5 μm or more) to obtain a sealant composition a-1. Filling the liquid crystal substrate with the sealant composition a-1 to obtain a product A-1.
Examples 2 to 4
Examples 2-4 sealant compositions a-2, a-3 and a-4 were prepared using the sealant composition formulations shown in table 2, respectively. The sealant compositions a-2, a-3 and a-4 were filled into the liquid crystal substrates, respectively, to prepare products A-2 and A-3 and A-4. The preparation of product A-2, product A-3 and product A-4 is described in example 1.
TABLE 2
Example 5
Example 5 sealant compositions a-5 were prepared using the sealant composition formulations shown in table 3. The sealant composition a-5 was filled in the liquid crystal substrate to prepare a product A-5, and the preparation method of the product A-5 was as described in reference to example 1, except that a part of the (meth) acrylic-modified bisphenol A type epoxy resin was not contained.
TABLE 3 Table 3
| Sealant composition | Parts by weight of |
| Multifunctional epoxy resin formula I | 30 |
| Monofunctional acrylic resin III | 20 |
| Benzoin diethyl ether (IR-651) | 5 |
| 3-epoxypropoxypropyl trimethoxysilane | 5 |
| Sebacic dihydrazide | 10 |
| Silica dioxide | 30 |
Comparative example 1
Comparative example 1A product C-1 was prepared using the sealant composition formulation shown in Table 4, and the preparation of product C-1 was conducted in accordance with example 1, except that the monofunctional acrylic resin III was not contained.
TABLE 4 Table 4
| Sealant composition | Parts by weight of |
| Multifunctional epoxy resin formula I | 20 |
| Partial (meth) acrylic acid modified bisphenol A type epoxy resin | 30 |
| Benzoin diethyl ether (IR-651) | 5 |
| 3-epoxypropoxypropyl trimethoxysilane | 5 |
| Sebacic dihydrazide | 10 |
| Silica dioxide | 30 |
Comparative example 2
Comparative example 2A product C-2 was prepared using the sealant composition formulation shown in Table 5, and the preparation method of the product C-2 was as described in reference to example 1, except that the part of the (meth) acrylic-modified bisphenol A type epoxy resin was not contained.
TABLE 5
| Sealant composition | Parts by weight of |
| Multifunctional epoxy resin formula I | 20 |
| Monofunctional acrylic resin III | 30 |
| Benzoin diethyl ether (IR-651) | 5 |
| 3-epoxypropoxypropyl trimethoxysilane | 5 |
| Sebacic dihydrazide | 10 |
| Silica dioxide | 30 |
Example 6
Example 6 sealant composition b-1 was prepared using the sealant composition formulation shown in table 6. The sealant composition B-1 was filled into a liquid crystal substrate to prepare a product B-1, and the preparation method of the product B-1 was referred to in example 1, mainly with the difference that the multifunctional epoxy resin formula I in example 1 was replaced with the multifunctional epoxy resin formula II.
TABLE 6
| Sealant composition | Parts by weight of |
| Multifunctional epoxy resin type II | 10 |
| Partial (meth) acrylic acid modified bisphenol A type epoxy treeFat | 35 |
| Monofunctional acrylic resin III | 5 |
| Benzoin diethyl ether (IR-651) | 5 |
| 3-epoxypropoxypropyl trimethoxysilane | 5 |
| Sebacic dihydrazide | 10 |
| Silica dioxide | 30 |
Examples 7 to 9
Examples 7-9 sealant compositions b-2, b-3, b-4 were obtained using the sealant composition formulations shown in Table 7. The sealant compositions B-2, B-3, B-4 were filled into the liquid crystal substrates to prepare products B-2 and B-3 and B-4, respectively. The preparation of products B-2 and B-3 and B-4 is described in example 6.
TABLE 7
Example 10
Example 10 sealant composition b-5 was prepared using the sealant composition formulation shown in table 8. The sealant composition B-5 was filled in the liquid crystal substrate to prepare a product B-5, and the preparation method of the product B-5 was as described in reference to example 6, except that a part of the (meth) acrylic-modified bisphenol A type epoxy resin was not contained.
TABLE 8
| Sealant composition | Parts by weight of |
| Multifunctional epoxy resin type II | 30 |
| Monofunctional acrylic resin III | 20 |
| Benzoin diethyl ether (IR-651) | 5 |
| 3-epoxypropoxypropyl trimethoxysilane | 5 |
| Sebacic dihydrazide | 10 |
| Silica dioxide | 30 |
Comparative example 3
Comparative example 3 product D-1 was prepared using the sealant composition formulation shown in table 9, and the preparation of product D-1 was performed with reference to example 1, with the main difference being monofunctional acrylic resin III.
TABLE 9
| Sealant composition | Parts by weight of |
| Multifunctional epoxy resin type II | 20 |
| Partial (meth) acrylic acid modified bisphenol A type epoxy resin | 30 |
| Benzoin diethyl ether (IR-651) | 5 |
| 3-epoxypropoxypropyl trimethoxysilane | 5 |
| Sebacic dihydrazide | 10 |
| Silica dioxide | 30 |
Comparative example 4
Comparative example 4A product D-2 was prepared using the sealant composition formulation shown in Table 10, and the preparation method of the product D-2 was as described in reference to example 1, except that the epoxy resin did not contain a part of the (meth) acrylic-modified bisphenol A.
Table 10
| Sealant composition | Parts by weight of |
| Multifunctional epoxy resin type II | 20 |
| Monofunctional acrylic resin III | 30 |
| Benzoin diethyl ether (IR-651) | 5 |
| 3-epoxypropoxypropyl trimethoxysilane | 5 |
| Sebacic dihydrazide | 10 |
| Silica dioxide | 30 |
The testing method comprises the following steps:
1) Viscosity.
The viscosity of the sealant was measured using an E-type viscometer at 25℃and 1 rpm.
Wherein, the viscosity is marked as O when 250-350 Pa.s, delta when 150-250 Pa.s or 350-450 Pa.s, and X when 50-150 Pa.s or 450-550 Pa.s.
2) Adhesion to
A very small amount of the sealant for a liquid crystal display element obtained in each of examples and comparative examples was placed on a 20mm X50 mm polyethylene terephthalate (PET) film (LINTEC CO., LTD., "PET 50")11 ") and a sealing agent for a liquid crystal display element is pressed and spread by overlapping the same size PET5011 on the central portion. In this state, a metal halide lamp was used, and irradiated with 100mW/cm for 30 seconds 2 After ultraviolet rays (wavelength: 365 nm), the mixture was heated at 120℃for 1 hour to prepare an adhesion test piece. The adhesive strength of the obtained adhesive test piece was measured using an EZgraph (manufactured by shimadzu corporation). Further, an adhesion test piece was produced in the same manner using a glass substrate instead of PET5011, and the adhesion strength was measured.
The adhesion was evaluated as "O" when the adhesion was 3.5kg/cm or more, as "delta" when the adhesion was 3.0kg/cm or more and less than 3.5kg/cm, and as "X" when the adhesion was less than 3.0 kg/cm.
3) High temperature and high humidity reliability;
the sealants for liquid crystal display elements obtained in examples and comparative examples were applied in a smooth mold release film form with a thickness of 200 to 300. Mu.m, and irradiated with a metal halide lamp for 30 seconds at 100mW/cm 2 After ultraviolet rays (wavelength: 365 nm), the film was heated at 120℃for 1 hour to obtain a cured film for moisture permeability measurement. A cup for moisture permeability test was prepared by a moisture permeability test method (cup method) of moisture proof packaging material based on JIS Z0208, and the obtained cured film for moisture permeability measurement was mounted, and the resultant was put into a constant temperature and humidity oven at a temperature of 60℃and a humidity of 90% RH, and the moisture permeability was measured for 24 hours.
The obtained moisture permeability has a value of less than 20g/m 2 The time was marked as "O" and was 20g/m 2 Above and below 40g/m 2 The time is designated as ". DELTA.", 40g/m 2 The above was designated as "X", and the moisture permeability was evaluated.
4) Liquid crystal contamination.
1 part by weight of spacer particles (MICRO PEARL SI-H050, manufactured by Seisakusho chemical Co., ltd.) was dispersed in 100 parts by weight of each of the sealants for liquid crystal display elements obtained in examples and comparative examples, and one of two substrates (75 mm in length, 75mm in width, and 0.7mm in thickness) with the brushed alignment film and the transparent electrode was applied by dispensing with a sealant line width of 1mm so that the display portion became 45mm X55 mm.
Next, a fine droplet of liquid crystal (manufactured by CHISSOCORPORATION, "JC-5004 LA") was dropped onto the entire inner surface of the frame of the sealant coated with the transparent electrode substrate, and another color filter substrate with a transparent electrode was immediately bonded, and the sealant was irradiated with 100mW/cm for 30 seconds using a metal halide lamp 2 After ultraviolet rays (wavelength: 365 nm), the mixture was heated at 120℃for 1 hour to obtain a liquid crystal display element.
After an operation test was performed for 100 hours on the obtained liquid crystal display element, it was visually confirmed that the liquid crystal alignment was disturbed in the vicinity of the sealant in a state where a voltage was applied at 80 ℃ for 1000 hours.
The alignment disorder was determined by the color unevenness of the display unit, and the low liquid crystal contamination was evaluated by marking "o" when the alignment disorder was completely absent, marking "Δ" when the length of the alignment disorder was 1% or less of the length of the sealant, and marking "x" when the length of the alignment disorder was 1% or more of the length of the sealant, depending on the degree of the color unevenness.
The liquid crystal display element evaluated as "Σ" is a level having no problem in practical use, "Δj" is a level at which a problem may occur depending on the display design of the liquid crystal display element, and "×" is a level not suitable for practical use.
5) Coating workability
The glue is filled into a rubber tube, after the rubber tube is defoamed by a vacuum defoamation machine, the coating machine is suitable for coating, the coating sectional area is controlled below 2000um, continuous drawing is carried out for 1h, the number of broken wires is counted, the number of broken wires is 0 to 3, marked as O, and 3 to 5 are marked as delta 5 or more, and marked as X.
The product evaluations of examples 1 to 5, comparative example 1 and comparative example 2 are shown in Table 11
TABLE 11
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The product evaluations of the above examples 6 to 10, comparative example 3, comparative example 4 are shown in Table 12
Table 12
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various modifications and additions may be made without departing from the scope of the invention. Equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, when considered in the light of the foregoing disclosure, and without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (8)
1. A sealant composition, which consists of the following components in parts by weight;
the multifunctional epoxy resin is selected from at least one of structures shown in a formula I or a formula II:
wherein n and m are independently selected from 1 to 5;
the monofunctional acrylic resin is selected from monomer structures or oligomers represented by formula III:
wherein the oligomer has a degree of polymerization of 1 to 3;
the acrylic acid modified epoxy resin is a part of acrylic acid modified epoxy resin.
2. The sealant composition of claim 1, wherein the sealant composition comprises any one or more of the following conditions:
a1 The photoinitiator is at least one selected from benzoin compounds, benzophenone compounds or acetophenone compounds;
a2 The coupling agent is selected from silane coupling agents;
a3 At least one curing agent selected from organic acid hydrazide, amine compounds or imidazole compounds;
a4 The filler is at least one selected from silicon dioxide, aluminum oxide, zinc oxide, talcum or silicon nitride.
3. The sealant composition of claim 1, wherein the partially acrylic modified epoxy resin is an acrylic graft modified epoxy resin and comprises at least one of the following technical characteristics:
a1, the grafting rate of the acrylic ester group of the partial acrylic acid modified epoxy resin is 30-80%;
a2, the epoxy resin is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin or biphenyl type epoxy resin;
a3, the acrylic acid is at least one of (methyl) acrylic acid or ethyl acrylic acid.
4. A method for producing the sealant composition as claimed in any one of claims 1 to 3, comprising mixing a multifunctional epoxy resin, a monofunctional acrylic resin, an acrylic-modified epoxy resin, a photoinitiator, a coupling agent, a curing agent and a filler.
5. A method of using the sealant composition of any of claims 1-3, comprising the steps of:
1) Applying the sealant composition to a substrate with a seal;
2) Temporary fixation is performed by light irradiation;
3) Final fixation is performed by heating.
6. Use of a sealant composition according to any of claims 1-3 in a liquid crystal dropping process, or for the preparation of a vertically conducting material, or for the preparation of a liquid crystal display element.
7. A vertically conducting material comprising the sealant composition according to any one of claims 1 to 3 and conductive particles.
8. A liquid crystal display element comprising the sealant composition according to any one of claims 1 to 3 or the vertically conductive material according to claim 7.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1711300A (en) * | 2002-11-06 | 2005-12-21 | 日本化药株式会社 | Sealing material for liquid crystal and liquid crystal display cell using same |
| CN107615151A (en) * | 2015-10-26 | 2018-01-19 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells |
| CN112080239A (en) * | 2020-09-10 | 2020-12-15 | 苏州润邦半导体材料科技有限公司 | Sealant composition and preparation method and application thereof |
| WO2023286700A1 (en) * | 2021-07-14 | 2023-01-19 | ナミックス株式会社 | Curable resin composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711300A (en) * | 2002-11-06 | 2005-12-21 | 日本化药株式会社 | Sealing material for liquid crystal and liquid crystal display cell using same |
| CN107615151A (en) * | 2015-10-26 | 2018-01-19 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells |
| CN112080239A (en) * | 2020-09-10 | 2020-12-15 | 苏州润邦半导体材料科技有限公司 | Sealant composition and preparation method and application thereof |
| WO2023286700A1 (en) * | 2021-07-14 | 2023-01-19 | ナミックス株式会社 | Curable resin composition |
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