WO2022255291A1 - 液晶表示素子用シール剤及び液晶表示素子 - Google Patents
液晶表示素子用シール剤及び液晶表示素子 Download PDFInfo
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- WO2022255291A1 WO2022255291A1 PCT/JP2022/021897 JP2022021897W WO2022255291A1 WO 2022255291 A1 WO2022255291 A1 WO 2022255291A1 JP 2022021897 W JP2022021897 W JP 2022021897W WO 2022255291 A1 WO2022255291 A1 WO 2022255291A1
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- liquid crystal
- meth
- crystal display
- acrylate
- sealant
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- AMJYHMCHKZQLAY-UHFFFAOYSA-N tris(2-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound O=C=NC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)N=C=O)OC1=CC=CC=C1N=C=O AMJYHMCHKZQLAY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention relates to a sealant for liquid crystal display elements, which is excellent in visible light curability and low in liquid crystal contamination.
- the present invention also relates to a liquid crystal display element using the sealant for a liquid crystal display element.
- a photo-heat curing type seal disclosed in Patent Document 1 and Patent Document 2
- a liquid crystal dropping method called a dropping method using an agent is used.
- the dripping method first, a frame-shaped seal pattern is formed on one of two electrode-attached transparent substrates by dispensing.
- the sealant is not yet cured, liquid crystal microdroplets are dropped on the entire surface of the frame of the transparent substrate, the other transparent substrate is immediately attached, and the sealant is irradiated with light such as ultraviolet rays for temporary curing. .
- the liquid crystal is annealed for final curing by heating, and a liquid crystal display element is produced. If the bonding of the substrates is performed under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency.
- the uncured sealant component dissolves into the liquid crystal, causing a problem of liquid crystal contamination.
- UV irradiation is usually used as a method for photo-curing the sealant.
- the sealant is cured after the liquid crystal is dropped, so the UV irradiation causes the liquid crystal to deteriorate.
- a photopolymerization initiator with excellent reactivity to long wavelength light such as an oxime ester photopolymerization initiator is blended, and the sealant is removed by light irradiation through a cut filter or the like. Hardening is done.
- a photopolymerization initiator such as an oxime ester photopolymerization initiator is used, there is a problem that liquid crystal contamination tends to occur.
- the present disclosure 1 is a sealing agent for a liquid crystal display element containing a curable resin, a photopolymerization initiator, and a sensitizer, wherein the photopolymerization initiator includes camphorquinone, and the sensitizer has a concentration of When the absorbance spectrum is measured for a solution dissolved in acetonitrile so that is 20 mg / L, the maximum absorbance in the wavelength range of 300 nm or more and 550 nm or less is 1, and the absorbance at a wavelength of 400 nm is 0.1 or more. It is a sealant for liquid crystal display elements.
- Present Disclosure 2 is the sealant for a liquid crystal display element according to Present Disclosure 1, wherein the sensitizer has at least one structure selected from the group consisting of a coumarin skeleton, an acridine skeleton, and a thioxanthone skeleton.
- the present disclosure 3 is that the sensitizer is 3-benzoyl-7-diethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), acridine-3,6-diamine, and 2,4-diethylthioxanthene.
- -9-one, 9,10-phenanthrenequinone is at least one selected from the group consisting of the liquid crystal display element sealing agent of the present disclosure 2.
- Present Disclosure 4 is the sealant for a liquid crystal display element according to Present Disclosure 1, 2, or 3, wherein the content of the sensitizer with respect to 100 parts by weight of camphorquinone is 0.1 parts by weight or more and 200 parts by weight or less.
- 5 of the present disclosure is a liquid crystal display device having a cured product of the sealant for a liquid crystal display device of 1, 2, 3 or 4 of the present disclosure. The present invention will be described in detail below.
- the present inventors believe that the cause of liquid crystal contamination when using a photopolymerization initiator such as an oxime ester-based photopolymerization initiator is that these photopolymerization initiators are cleavage-type photopolymerization initiators. I thought that it was because the residue was generated later. Therefore, as a result of extensive studies, the present inventors have found that, among hydrogen abstraction type photopolymerization initiators, camphorquinone is used in combination with a specific sensitizer to achieve excellent visible light curability and low liquid crystal contamination. The present inventors have found that a sealing compound for liquid crystal display elements having excellent properties can be obtained, and have completed the present invention.
- the sealant for liquid crystal display elements of the present invention contains a photopolymerization initiator.
- the photopolymerization initiator contains the camphorquinone.
- the sealing agent for a liquid crystal display element of the present invention has excellent visible light curability and excellent low liquid crystal contamination resistance. Become.
- the preferable lower limit of the camphorquinone content is 0.3 parts by weight, and the preferable upper limit thereof is 3.0 parts by weight with respect to 100 parts by weight of the curable resin.
- the obtained sealing agent for liquid crystal display elements has excellent visible light curability.
- the obtained sealing compound for liquid crystal display elements is excellent in low liquid crystal contamination.
- a more preferable lower limit of the camphorquinone content is 0.7 parts by weight, a more preferable upper limit is 2.3 parts by weight, a still more preferable lower limit is 1.1 parts by weight, and a still more preferable upper limit is 1.8 parts by weight.
- the sealing compound for liquid crystal display elements of the present invention contains a sensitizer.
- the maximum absorbance at a wavelength of 300 nm or more and 550 nm or less is 1, and the maximum absorbance is 1 at a wavelength of 400 nm.
- Absorbance is 0.1 or more.
- the absorbance spectrum of a solution dissolved in acetonitrile at a concentration of 20 mg/L is measured and the maximum absorbance in the wavelength range of 300 nm or more and 550 nm or less is 1, the absorbance at a wavelength of 400 nm is 0.5.
- a sensitizer having a number of 1 or more is also referred to as "a sensitizer according to the present invention".
- the sealant for liquid crystal display elements of the present invention has excellent visible light curability and excellent low liquid crystal contamination resistance.
- the sensitizer according to the present invention is dissolved in acetonitrile at a concentration of 20 mg/L, and the absorbance spectrum is measured.
- Absorbance at a wavelength of 400 nm is 0.1 or more. Since the absorbance of the sensitizer according to the present invention at a wavelength of 400 nm is 0.1 or more, the sealant for a liquid crystal display element of the present invention has excellent visible light curability. It is also excellent in the effect of suppressing the liquid crystal contamination caused by the residual of the adhesive resin.
- the absorbance at a wavelength of 400 nm of the sensitizer according to the present invention is preferably 0.3 or more, more preferably 0.5 or more.
- the absorbance can be measured using a spectrophotometer under the condition of an optical path length of 1 cm. Examples of the spectrophotometer include U-3900 (manufactured by Hitachi High-Tech Science).
- the sensitizer according to the present invention is dissolved in acetonitrile at a concentration of 20 mg/L, and the absorbance spectrum is measured.
- the absorbance at a wavelength of 450 nm is preferably 0.07 or more.
- the sealing agent for a liquid crystal display element of the present invention becomes more excellent in visible light curability, and as a result, uncured cured
- the effect of suppressing the liquid crystal contamination caused by the remaining of the curable resin is also excellent.
- the absorbance at the wavelength of 450 nm of the sensitizer according to the present invention is more preferably 0.2 or more, even more preferably 0.3 or more.
- Sensitizers according to the present invention include, for example, 3-benzoyl-7-diethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), acridine-3,6-diamine, 2,4-diethylthioxanthene- 9-one, 9,10-phenanthrenequinone and the like.
- the sensitizer according to the present invention may be used alone, or two or more of them may be used in combination.
- the sensitizer according to the present invention preferably has at least one structure selected from the group consisting of a coumarin skeleton, an acridine skeleton, and a thioxanthone skeleton, 3-benzoyl-7-diethylaminocoumarin, 3 ,3-carbonylbis(7-diethylaminocoumarin), acridine-3,6-diamine, and at least one selected from the group consisting of 2,4-diethylthioxanthene-9-one and 9,10-phenanthrenequinone is more preferable.
- a preferable lower limit of the content ratio of the sensitizer according to the present invention to 100 parts by weight of camphorquinone is 0.1 part by weight, and a preferable upper limit is 200 parts by weight.
- the content of the sensitizer according to the present invention is within this range, the obtained sealing agent for liquid crystal display elements is excellent in visible light curability and low liquid crystal contamination resistance.
- a more preferable lower limit of the content of the sensitizer according to the present invention is 1 part by weight, a more preferable upper limit is 50 parts by weight, and a further preferable upper limit is 10 parts by weight.
- the sealant for liquid crystal display elements of the present invention contains a curable resin.
- the curable resin preferably contains a (meth)acrylic compound.
- the (meth)acrylic compound include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, and urethane (meth)acrylates. Among them, epoxy (meth)acrylate is preferred.
- the (meth)acrylic compound preferably has two or more (meth)acryloyl groups in one molecule from the viewpoint of reactivity.
- the above “(meth)acryl” means acrylic or methacryl
- the above “(meth)acrylic compound” means a compound having a (meth)acryloyl group
- the above “( meth)acryloyl” means acryloyl or methacryloyl.
- the above-mentioned “(meth)acrylate” means acrylate or methacrylate.
- the above-mentioned “epoxy (meth)acrylate” represents a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid.
- monofunctional ones include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.
- t-butyl (meth)acrylate 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, iso myristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl ( meth)acrylate, isobornyl (meth)acrylate, bicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate,
- bifunctional ones include, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexane Diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate (Meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) acrylate, polypropylene glycol di(meth)acrylate, neopen
- trifunctional or higher ones include, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri( meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acryl
- Examples of the epoxy (meth)acrylate include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.
- epoxy compounds that are raw materials for synthesizing the epoxy (meth)acrylate include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, and 2,2′-diallylbisphenol A type epoxy compounds. , hydrogenated bisphenol type epoxy compound, propylene oxide added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol Novolac-type epoxy compounds, ortho-cresol novolac-type epoxy compounds, dicyclopentadiene novolak-type epoxy compounds, biphenyl novolak-type epoxy compounds, naphthalenephenol novolak-type epoxy compounds, glycidylamine-type epoxy compounds, alkylpolyol-type epoxy compounds, rubber-modified epoxy compounds , glycidyl ester compounds, and the like.
- bisphenol A type epoxy compounds include, for example, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (manufactured by DIC Corporation), and the like.
- Examples of commercially available bisphenol F-type epoxy compounds include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
- Examples of commercially available bisphenol S-type epoxy compounds include EPICLON EXA1514 (manufactured by DIC Corporation).
- Examples of commercially available 2,2'-diallylbisphenol A type epoxy compounds include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of commercially available hydrogenated bisphenol type epoxy compounds include EPICLON EXA7015 (manufactured by DIC Corporation).
- Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
- Commercially available resorcinol-type epoxy compounds include, for example, EX-201 (manufactured by Nagase ChemteX Corporation).
- commercially available biphenyl-type epoxy compounds include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
- Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
- Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.). Examples of commercially available dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA). Examples of commercially available naphthalene-type epoxy compounds include EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation). Examples of commercially available phenolic novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation). Examples of commercially available ortho-cresol novolac type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Corporation).
- Examples of commercially available dicyclopentadiene novolac type epoxy compounds include EPICLON HP7200 (manufactured by DIC Corporation).
- Commercially available biphenyl novolac type epoxy compounds include, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of commercially available naphthalenephenol novolac type epoxy compounds include ESN-165S (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
- Examples of commercially available glycidylamine type epoxy compounds include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.
- Examples of commercially available alkyl polyol type epoxy compounds include ZX-1542 (manufactured by Nippon Steel Chemical & Materials), EPICLON 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX. -611 (manufactured by Nagase ChemteX Corporation) and the like.
- Examples of commercially available rubber-modified epoxy compounds include YR-450 and YR-207 (both manufactured by Nippon Steel Chemical & Materials) and Epolead PB (manufactured by Daicel).
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
- Other commercially available epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical & Materials), XAC4151 (manufactured by Asahi Kasei), jER1031, and jER1032. (all manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.
- epoxy (meth)acrylates include, for example, epoxy (meth)acrylate manufactured by Daicel Allnex, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry, epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. ( meth) acrylate, epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation, and the like.
- Epoxy Ester M-600A Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA and the like.
- Examples of epoxy (meth)acrylates manufactured by Nagase ChemteX Co., Ltd. include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911, and the like.
- the urethane (meth)acrylate can be obtained, for example, by reacting a polyfunctional isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin compound.
- polyfunctional isocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), Hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) thiophosphate, tetramethyl xylylene diisocyanate, 1,6,11-undecane triisocyanate, and the like.
- MDI diphenylmethane-4,4′-diisocyanate
- polyfunctional isocyanate compound a chain-extended polyfunctional isocyanate compound obtained by reacting a polyol with an excess polyfunctional isocyanate compound can also be used.
- the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and the like.
- Examples of the (meth)acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono(meth)acrylates, dihydric alcohol mono(meth)acrylates, trihydric alcohol mono(meth)acrylates and di(meth)acrylates. , epoxy (meth)acrylate, and the like.
- Examples of the hydroxyalkyl mono(meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like. mentioned.
- Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
- Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, glycerin and the like.
- Examples of the epoxy (meth)acrylate include bisphenol A type epoxy acrylate.
- urethane (meth) acrylates examples include urethane (meth) acrylate manufactured by Toagosei Co., Ltd., urethane (meth) acrylate manufactured by Daicel Allnex, and urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. acrylate, urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.
- Examples of the urethane (meth)acrylates manufactured by Toagosei Co., Ltd. examples include M-1100, M-1200, M-1210 and M-1600.
- urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T. be done.
- the curable resin may contain an epoxy compound for the purpose of improving the adhesiveness of the obtained sealing agent for liquid crystal display elements.
- the epoxy compound include an epoxy compound that serves as a raw material for synthesizing the epoxy (meth)acrylate described above, a partially (meth)acryl-modified epoxy compound, and the like.
- the partially (meth)acrylic-modified epoxy compound means, for example, reacting a part of the epoxy group of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid. means a compound having one or more epoxy groups and one or more (meth)acryloyl groups in one molecule, which can be obtained by
- the curable resin contains the (meth)acrylic compound and the epoxy compound, or when the partially (meth)acryl-modified epoxy compound is contained, the (meth)acryloyl group in the curable resin and the epoxy It is preferable that the ratio of the (meth)acryloyl group in the total of the groups is 30 mol % or more and 95 mol % or less. When the ratio of the (meth)acryloyl group is within this range, the resulting sealant for liquid crystal display elements has excellent adhesion while suppressing the occurrence of liquid crystal contamination.
- the curable resin has a hydrogen-bonding unit such as —OH group, —NH— group, or —NH 2 group, from the viewpoint of making the obtained sealing agent for liquid crystal display element more excellent in low liquid crystal contamination resistance. is preferred.
- the curable resins may be used alone, or two or more of them may be used in combination.
- the sealant for liquid crystal display elements of the present invention may contain a thermal polymerization initiator as long as the object of the present invention is not impaired.
- the thermal polymerization initiator include those composed of azo compounds, organic peroxides, and the like. Among them, a polymeric azo initiator composed of a polymeric azo compound is preferable.
- the above thermal polymerization initiators may be used alone, or two or more of them may be used in combination.
- the term "polymeric azo compound” refers to a compound having an azo group and a number average molecular weight of 300 or more, which generates a radical capable of curing a (meth)acryloyloxy group by heat. means.
- a preferable lower limit of the number average molecular weight of the above high-molecular azo compound is 1,000, and a preferable upper limit thereof is 300,000.
- the lower limit of the number average molecular weight of the high-molecular azo compound is more preferably 5,000, the upper limit is 100,000, the lower limit is still more preferably 10,000, and the upper limit is still more preferably 90,000.
- Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
- the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group one having a polyethylene oxide structure is preferable.
- Specific examples of the high-molecular azo compound include polycondensates of 4,4′-azobis(4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis(4-cyanopentanoic acid). and a polycondensate of polydimethylsiloxane having a terminal amino group.
- Examples of commercially available polymeric azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). be done.
- Examples of non-polymeric azo compounds include V-65 and V-501 (both manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).
- organic peroxides examples include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides and peroxydicarbonates.
- the content of the thermal polymerization initiator has a preferable lower limit of 0.05 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin.
- the sealing agent for liquid crystal display elements of the present invention becomes excellent in thermosetting property.
- the sealant for liquid crystal display elements of the present invention is excellent in low liquid crystal contamination and storage stability.
- a more preferred lower limit to the content of the thermal polymerization initiator is 0.1 parts by weight, and a more preferred upper limit is 5 parts by weight.
- the sealing compound for liquid crystal display elements of the present invention may contain a thermosetting agent.
- the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among them, organic acid hydrazides are preferably used.
- the thermosetting agents may be used alone, or two or more of them may be used in combination.
- Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide.
- Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.
- Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
- Examples of the organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Inc. include Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J.
- the content of the thermosetting agent has a preferable lower limit of 1 part by weight and a preferable upper limit of 50 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the thermosetting agent is within this range, the obtained sealing compound for liquid crystal display elements can be made more excellent in thermosetting properties without deteriorating the applicability and the like.
- a more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
- the sealant for liquid crystal display elements of the present invention preferably contains a filler for the purpose of improving viscosity, improving adhesiveness due to a stress dispersion effect, improving coefficient of linear expansion, and the like.
- An inorganic filler or an organic filler can be used as the filler.
- inorganic fillers include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide. , calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
- the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like. The above fillers may be used alone, or two or more of them may be used in combination.
- the preferred lower limit of the content of the filler is 30 parts by weight, and the preferred upper limit thereof is 80 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the filler is within this range, the effect of improving adhesiveness and the like is excellent without deteriorating coatability and the like.
- a more preferable lower limit of the filler content is 45 parts by weight, and a more preferable upper limit thereof is 65 parts by weight.
- the sealing compound for liquid crystal display elements of the present invention preferably contains a silane coupling agent.
- the silane coupling agent mainly serves as an adhesion assistant for good adhesion between the sealing agent and the substrate.
- silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These are excellent in the effect of improving the adhesiveness to a substrate or the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin.
- the silane coupling agents may be used alone, or two or more of them may be used in combination.
- a preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the liquid crystal display element sealing compound of the present invention is 0.1 parts by weight, and a preferable upper limit thereof is 10 parts by weight.
- the content of the silane coupling agent is within this range, the effect of improving adhesion while suppressing the occurrence of liquid crystal contamination is more excellent.
- a more preferable lower limit to the content of the silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.
- the sealing agent for liquid crystal display elements of the present invention further contains additives such as reactive diluents, thixotropic agents, spacers, curing accelerators, antifoaming agents, leveling agents and polymerization inhibitors, if necessary. may
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mixer is used to mix a curable resin with light.
- the conductive fine particles a metal ball, a resin fine particle having a conductive metal layer formed on its surface, or the like can be used.
- the one in which a conductive metal layer is formed on the surface of the resin fine particles is preferable because the excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.
- a liquid crystal display element having a cured product of the sealant for a liquid crystal display element of the present invention is also one aspect of the present invention.
- a liquid crystal display element having a narrow frame design is preferable.
- the width of the frame portion around the liquid crystal display section is 2 mm or less.
- the coating width of the sealant for a liquid crystal display element of the present invention when manufacturing the liquid crystal display element of the present invention is 1 mm or less.
- a liquid crystal dropping method is preferably used, and specific examples thereof include a method including the following steps.
- a step is performed in which the liquid crystal liquid crystal sealing agent of the present invention is in an uncured state, and liquid crystal microdroplets are applied dropwise within the frame of the seal pattern of the substrate, and the other transparent substrate is superimposed under vacuum.
- a liquid crystal display element can be obtained by a method of performing a step of photocuring the sealing agent by irradiating the sealing pattern portion of the sealing agent for a liquid crystal display element of the present invention with light through a cut filter or the like.
- a step of heating the sealant to thermally cure it may be performed.
- the sealing compound for liquid crystal display elements which is excellent in visible light curability, and is excellent in low liquid-crystal contamination property can be provided. Further, according to the present invention, it is possible to provide a liquid crystal display element using the sealant for a liquid crystal display element.
- Examples 1 to 19 and Comparative Examples 1 to 7 According to the compounding ratio described in Tables 1 to 3, after mixing each material using a planetary stirrer, the liquid crystals of Examples 1 to 19 and Comparative Examples 1 to 7 were further mixed using three rolls. A sealant for display elements was prepared. Awatori Mixer (manufactured by Thinky Corporation) was used as the planetary stirrer.
- the "absorbance at a wavelength of 400 nm" and “absorbance at a wavelength of 450 nm” of the sensitizer are the values obtained when the absorption spectrum was measured for a solution dissolved in acetonitrile so that the concentration was 20 mg / L. It is the value of absorbance at each wavelength when the maximum absorbance in the wavelength range of 300 nm or more and 550 nm or less is set to 1.
- a glass substrate of the same size was bonded to the substrate coated with the sealant under a reduced pressure of 5 Pa using a vacuum bonding apparatus to obtain a test piece.
- the sealant portion of the obtained test piece was irradiated with light of 100 mW/cm 2 for 30 seconds from a metal halide lamp through a cut filter.
- a cut filter As a cut filter, a 340 nm cut filter that cuts light with a wavelength of 340 nm or less, a 400 nm cut filter that cuts light with a wavelength of 400 nm or less, a 420 nm cut filter that cuts light with a wavelength of 420 nm or less, or cuts light with a wavelength of 440 nm or less.
- a 440 nm cut filter was used.
- FT-IR measurement of the sealant was performed using an infrared spectrometer, and the amount of change in the peak derived from the (meth)acryloyl group was measured. It was measured.
- FTS3000 manufactured by BIORAD
- the photocurability was evaluated as "X" when the decrease in the peak derived from the (meth)acryloyl group after light irradiation was less than 70%.
- microdroplets of the liquid crystal taken out from the sample bottle were dropped and applied to the entire surface of the frame on the substrate, and another glass substrate was superimposed in a vacuum.
- the vacuum was released, and light of 100 mW/cm 2 was applied from a metal halide lamp through a cut filter for 30 seconds.
- a cut filter a 340 nm cut filter, a 400 nm cut filter, a 420 nm cut filter, or a 440 nm cut filter was used.
- the sealant was thermally cured by heating at 120° C. for 1 hour to obtain a liquid crystal display element.
- the sealing compound for liquid crystal display elements which is excellent in visible light curability, and is excellent in low liquid-crystal contamination property can be provided. Further, according to the present invention, it is possible to provide a liquid crystal display element using the sealant for a liquid crystal display element.
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Abstract
Description
滴下工法では、まず、2枚の電極付き透明基板の一方に、ディスペンスにより枠状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下し、すぐに他方の透明基板を貼り合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、液晶アニール時に加熱して本硬化を行い、液晶表示素子を作製する。基板の貼り合わせを減圧下で行うようにすれば、極めて高い効率で液晶表示素子を製造することができ、現在この滴下工法が液晶表示素子の製造方法の主流となっている。
しかしながら、狭額縁設計ではシール剤がブラックマトリックスの直下に配置されるため、滴下工法を行うと、シール剤を光硬化させる際に照射した光が遮られ、シール剤の内部まで光が到達せず硬化が不充分となるという問題があった。このようにシール剤の硬化が不充分となると、未硬化のシール剤成分が液晶中に溶出し、液晶汚染が発生するという問題があった。
また、通常、シール剤を光硬化させる方法として紫外線の照射が行われているが、特に液晶滴下工法においては、液晶を滴下した後にシール剤を硬化させるため、紫外線を照射することによって液晶が劣化するという問題があった。そこで、紫外線による液晶の劣化を防止するため、オキシムエステル系光重合開始剤等の長波長の光に対する反応性に優れる光重合開始剤を配合し、カットフィルター等を介した光照射によりシール剤を硬化させることが行われている。しかしながら、オキシムエステル系光重合開始剤等の光重合開始剤を用いた場合、液晶汚染が生じやすいという問題があった。
本開示2は、上記増感剤は、クマリン骨格、アクリジン骨格、及び、チオキサントン骨格からなる群より選択される少なくとも1種の構造を有する本開示1の液晶表示素子用シール剤である。
本開示3は、上記増感剤は、3-ベンゾイル-7-ジエチルアミノクマリン、3,3-カルボニルビス(7-ジエチルアミノクマリン)、アクリジン-3,6-ジアミン、及び、2,4-ジエチルチオキサンテン-9-オン、9,10-フェナントレンキノンからなる群より選択される少なくとも1種である本開示2の液晶表示素子用シール剤である。
本開示4は、上記カンファーキノン100重量部に対する上記増感剤の含有割合が0.1重量部以上200重量部以下である本開示1、2又は3の液晶表示素子用シール剤である。
本開示5は、本開示1、2、3又は4の液晶表示素子用シール剤の硬化物を有する液晶表示素子である。
以下に本発明を詳述する。
上記光重合開始剤は、上記カンファーキノンを含む。上記光重合開始剤として上記カンファーキノンを後述する増感剤と組み合わせて用いることにより、本発明の液晶表示素子用シール剤は、可視光硬化性に優れ、かつ、低液晶汚染性に優れるものとなる。
上記増感剤は、濃度が20mg/Lとなるようにアセトニトリルに溶解させた溶液について吸光スペクトルを測定した際の波長300nm以上550nm以下の範囲における吸光度の最大値を1としたとき、波長400nmにおける吸光度が0.1以上である。以下、濃度が20mg/Lとなるようにアセトニトリルに溶解させた溶液について吸光スペクトルを測定した際の波長300nm以上550nm以下の範囲における吸光度の最大値を1としたとき、波長400nmにおける吸光度が0.1以上である増感剤を「本発明にかかる増感剤」ともいう。本発明にかかる増感剤を上記カンファーキノンと組み合わせて用いることにより、本発明の液晶表示素子用シール剤は、可視光硬化性に優れ、かつ、低液晶汚染性に優れるものとなる。
上記吸光度は、分光光度計を用いて光路長1cmの条件で測定することができる。上記分光光度計としては、例えば、U-3900(日立ハイテクサイエンス社製)等が挙げられる。
なかでも、本発明にかかる増感剤は、クマリン骨格、アクリジン骨格、及び、チオキサントン骨格からなる群より選択される少なくとも1種の構造を有することが好ましく、3-ベンゾイル-7-ジエチルアミノクマリン、3,3-カルボニルビス(7-ジエチルアミノクマリン)、アクリジン-3,6-ジアミン、及び、2,4-ジエチルチオキサンテン-9-オン、9,10-フェナントレンキノンからなる群より選択される少なくとも1種であることがより好ましい。
上記硬化性樹脂は、(メタ)アクリル化合物を含有することが好ましい。
上記(メタ)アクリル化合物としては、例えば、(メタ)アクリル酸エステル化合物、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート等が挙げられる。なかでも、エポキシ(メタ)アクリレートが好ましい。また、上記(メタ)アクリル化合物は、反応性の観点から1分子中に(メタ)アクリロイル基を2つ以上有するものが好ましい。
なお、本明細書において、上記「(メタ)アクリル」とは、アクリル又はメタクリルを意味し、上記「(メタ)アクリル化合物」とは、(メタ)アクリロイル基を有する化合物を意味し、上記「(メタ)アクリロイル」とは、アクリロイル又はメタクリロイルを意味する。また、上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味する。更に、上記「エポキシ(メタ)アクリレート」とは、エポキシ化合物中の全てのエポキシ基を(メタ)アクリル酸と反応させた化合物のことを表す。
上記ビスフェノールF型エポキシ化合物のうち市販されているものとしては、例えば、jER806、jER4004(いずれも三菱ケミカル社製)等が挙げられる。
上記ビスフェノールS型エポキシ化合物のうち市販されているものとしては、例えば、EPICLON EXA1514(DIC社製)等が挙げられる。
上記2,2’-ジアリルビスフェノールA型エポキシ化合物のうち市販されているものとしては、例えば、RE-810NM(日本化薬社製)等が挙げられる。
上記水添ビスフェノール型エポキシ化合物のうち市販されているものとしては、例えば、EPICLON EXA7015(DIC社製)等が挙げられる。
上記プロピレンオキシド付加ビスフェノールA型エポキシ化合物のうち市販されているものとしては、例えば、EP-4000S(ADEKA社製)等が挙げられる。
上記レゾルシノール型エポキシ化合物のうち市販されているものとしては、例えば、EX-201(ナガセケムテックス社製)等が挙げられる。
上記ビフェニル型エポキシ化合物のうち市販されているものとしては、例えば、jER YX-4000H(三菱ケミカル社製)等が挙げられる。
上記スルフィド型エポキシ化合物のうち市販されているものとしては、例えば、YSLV-50TE(日鉄ケミカル&マテリアル社製)等が挙げられる。
上記ジフェニルエーテル型エポキシ化合物のうち市販されているものとしては、例えば、YSLV-80DE(日鉄ケミカル&マテリアル社製)等が挙げられる。
上記ジシクロペンタジエン型エポキシ化合物のうち市販されているものとしては、例えば、EP-4088S(ADEKA社製)等が挙げられる。
上記ナフタレン型エポキシ化合物のうち市販されているものとしては、例えば、EPICLON HP4032、EPICLON EXA-4700(いずれもDIC社製)等が挙げられる。
上記フェノールノボラック型エポキシ化合物のうち市販されているものとしては、例えば、EPICLON N-770(DIC社製)等が挙げられる。
上記オルトクレゾールノボラック型エポキシ化合物のうち市販されているものとしては、例えば、EPICLON N-670-EXP-S(DIC社製)等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ化合物のうち市販されているものとしては、例えば、EPICLON HP7200(DIC社製)等が挙げられる。
上記ビフェニルノボラック型エポキシ化合物のうち市販されているものとしては、例えば、NC-3000P(日本化薬社製)等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ化合物のうち市販されているものとしては、例えば、ESN-165S(日鉄ケミカル&マテリアル社製)等が挙げられる。
上記グリシジルアミン型エポキシ化合物のうち市販されているものとしては、例えば、jER630(三菱ケミカル社製)、EPICLON 430(DIC社製)、TETRAD-X(三菱ガス化学社製)等が挙げられる。
上記アルキルポリオール型エポキシ化合物のうち市販されているものとしては、例えば、ZX-1542(日鉄ケミカル&マテリアル社製)、EPICLON 726(DIC社製)、エポライト80MFA(共栄社化学社製)、デナコールEX-611(ナガセケムテックス社製)等が挙げられる。
上記ゴム変性型エポキシ化合物のうち市販されているものとしては、例えば、YR-450、YR-207(いずれも日鉄ケミカル&マテリアル社製)、エポリードPB(ダイセル社製)等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールEX-147(ナガセケムテックス社製)等が挙げられる。
上記エポキシ化合物のうちその他に市販されているものとしては、例えば、YDC-1312、YSLV-80XY、YSLV-90CR(いずれも日鉄ケミカル&マテリアル社製)、XAC4151(旭化成社製)、jER1031、jER1032(いずれも三菱ケミカル社製)、EXA-7120(DIC社製)、TEPIC(日産化学社製)等が挙げられる。
上記ダイセル・オルネクス社製のエポキシ(メタ)アクリレートとしては、例えば、EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3708、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182等が挙げられる。
上記新中村化学工業社製のエポキシ(メタ)アクリレートとしては、例えば、EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020等が挙げられる。
上記共栄社化学社製のエポキシ(メタ)アクリレートとしては、例えば、エポキシエステルM-600A、エポキシエステル40EM、エポキシエステル70PA、エポキシエステル200PA、エポキシエステル80MFA、エポキシエステル3002M、エポキシエステル3002A、エポキシエステル1600A、エポキシエステル3000M、エポキシエステル3000A、エポキシエステル200EA、エポキシエステル400EA等が挙げられる。
上記ナガセケムテックス社製のエポキシ(メタ)アクリレートとしては、例えば、デナコールアクリレートDA-141、デナコールアクリレートDA-314、デナコールアクリレートDA-911等が挙げられる。
上記ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、グリセリン、ソルビトール、トリメチロールプロパン、カーボネートジオール、ポリエーテルジオール、ポリエステルジオール、ポリカプロラクトンジオール等が挙げられる。
上記ヒドロキシアルキルモノ(メタ)アクリレートとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等が挙げられる。
上記二価のアルコールとしては、例えば、エチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ポリエチレングリコール等が挙げられる。
上記三価のアルコールとしては、例えば、トリメチロールエタン、トリメチロールプロパン、グリセリン等が挙げられる。
上記エポキシ(メタ)アクリレートとしては、例えば、ビスフェノールA型エポキシアクリレート等が挙げられる。
上記東亞合成社製のウレタン(メタ)アクリレートとしては、例えば、M-1100、M-1200、M-1210、M-1600等が挙げられる。
上記ダイセル・オルネクス社製のウレタン(メタ)アクリレートとしては、例えば、EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、EBECRYL8803、EBECRYL8804、EBECRYL8807、EBECRYL9260等が挙げられる。
上記根上工業社製のウレタン(メタ)アクリレートとしては、例えば、アートレジンUN-330、アートレジンSH-500B、アートレジンUN-1200TPK、アートレジンUN-1255、アートレジンUN-3320HB、アートレジンUN-7100、アートレジンUN-9000A、アートレジンUN-9000H等が挙げられる。
上記新中村化学工業社製のウレタン(メタ)アクリレートとしては、例えば、U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6HA、U-6LPA、U-10H、U-15HA、U-108、U-108A、U-122A、U-122P、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4000、UA-4100、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A等が挙げられる。
上記共栄社化学社製のウレタン(メタ)アクリレートとしては、例えば、AH-600、AI-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T等が挙げられる。
なお、本明細書において上記部分(メタ)アクリル変性エポキシ化合物とは、例えば、1分子中に2つ以上のエポキシ基を有するエポキシ化合物の一部のエポキシ基を(メタ)アクリル酸と反応させることによって得ることができる、1分子中にエポキシ基と(メタ)アクリロイル基とをそれぞれ1つ以上有する化合物を意味する。
上記熱重合開始剤としては、例えば、アゾ化合物、有機過酸化物等で構成されるものが挙げられる。なかでも、高分子アゾ化合物で構成される高分子アゾ開始剤が好ましい。
上記熱重合開始剤は、単独で用いられてもよいし、2種以上が組み合わせて用いられてもよい。
なお、本明細書において上記「高分子アゾ化合物」とは、アゾ基を有し、熱によって(メタ)アクリロイルオキシ基を硬化させることができるラジカルを生成する、数平均分子量が300以上の化合物を意味する。
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ化合物としては、ポリエチレンオキサイド構造を有するものが好ましい。
上記高分子アゾ化合物としては、具体的には例えば、4,4’-アゾビス(4-シアノペンタン酸)とポリアルキレングリコールの重縮合物や、4,4’-アゾビス(4-シアノペンタン酸)と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられる。
上記高分子アゾ化合物のうち市販されているものとしては、例えば、VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001(いずれも富士フイルム和光純薬社製)等が挙げられる。
また、高分子ではないアゾ化合物としては、例えば、V-65、V-501(いずれも富士フイルム和光純薬社製)等が挙げられる。
上記熱硬化剤としては、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。
上記熱硬化剤は、単独で用いられてもよいし、2種以上が組み合わせて用いられてもよい。
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、大塚化学社製の有機酸ヒドラジド、味の素ファインテクノ社製の有機酸ヒドラジド等が挙げられる。
上記大塚化学社製の有機酸ヒドラジドとしては、例えば、SDH、ADH等が挙げられる。
上記味の素ファインテクノ社製の有機酸ヒドラジドとしては、例えば、アミキュアVDH、アミキュアVDH-J、アミキュアUDH、アミキュアUDH-J等が挙げられる。
上記無機充填剤としては、例えば、シリカ、タルク、ガラスビーズ、石綿、石膏、珪藻土、スメクタイト、ベントナイト、モンモリロナイト、セリサイト、活性白土、アルミナ、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、水酸化アルミニウム、窒化アルミニウム、窒化珪素、硫酸バリウム、珪酸カルシウム等が挙げられる。
上記有機充填剤としては、例えば、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等が挙げられる。
上記充填剤は、単独で用いられてもよいし、2種以上が組み合わせて用いられてもよい。
上記シランカップリング剤は、単独で用いられてもよいし、2種以上が組み合わせて用いられてもよい。
本発明の液晶表示素子としては、狭額縁設計の液晶表示素子が好ましい。具体的には、液晶表示部の周囲の枠部分の幅が2mm以下であることが好ましい。
また、本発明の液晶表示素子を製造する際の本発明の液晶表示素子用シール剤の塗布幅は1mm以下であることが好ましい。
まず、ITO薄膜等の電極及び配向膜を有する2枚の透明基板の一方に、本発明の液晶表示素子用シール剤をスクリーン印刷、ディスペンサー塗布等により塗布して枠状のシールパターンを形成する工程を行う。次いで、本発明の液晶表示素子用シール剤が未硬化の状態で液晶の微小滴を基板のシールパターンの枠内に滴下塗布し、真空下で他方の透明基板を重ね合わせる工程を行う。その後、本発明の液晶表示素子用シール剤のシールパターン部分にカットフィルター等を介して光を照射することにより、シール剤を光硬化させる工程を行う方法により、液晶表示素子を得ることができる。また、上記シール剤を光硬化させる工程に加えて、シール剤を加熱して熱硬化させる工程を行ってもよい。
表1~3に記載された配合比に従い、各材料を遊星式撹拌機を用いて混合した後、更に3本ロールを用いて混合することにより実施例1~19及び比較例1~7の液晶表示素子用シール剤を調製した。遊星式撹拌機としては、あわとり練太郎(シンキー社製)を用いた。
なお、表1~3中、増感剤の「波長400nmにおける吸光度」及び「波長450nmにおける吸光度」は、濃度が20mg/Lとなるようにアセトニトリルに溶解させた溶液について吸光スペクトルを測定した際の波長300nm以上550nm以下の範囲における吸光度の最大値を1としたときの、それぞれの波長における吸光度の値である。
実施例及び比較例で得られた各液晶表示素子用シール剤について以下の評価を行った。結果を表1~3に示した。
実施例及び比較例で得られた各液晶表示素子用シール剤100重量部にスペーサー微粒子1重量部を分散させた。スペーサー微粒子としては、ミクロパールSI-H050(積水化学工業社製)を用いた。次いで、シール剤をディスペンス用のシリンジに充填し、脱泡処理を行ってから、ディスペンサーにてガラス基板上に塗布した。ディスペンス用のシリンジとしては、PSY-10E(武蔵エンジニアリング社製)を用い、ディスペンサーとしては、SHOTMASTER300(武蔵エンジニアリング社製)を用いた。シール剤を塗布した基板に、真空貼り合わせ装置にて5Paの減圧下にて同サイズのガラス基板を貼り合わせて試験片を得た。得られた試験片のシール剤部分にメタルハライドランプを用いて100mW/cm2の光をカットフィルターを介して30秒照射した。カットフィルターとしては、波長340nm以下の光をカットする340nmカットフィルター、波長400nm以下の光をカットする400nmカットフィルター、波長420nm以下の光をカットする420nmカットフィルター、又は、波長440nm以下の光をカットする440nmカットフィルターを用いた。
光照射前の試験片と各カットフィルターを介した光照射後の試験片とについて、赤外分光装置を用いてシール剤のFT-IR測定を行い、(メタ)アクリロイル基由来ピークの変化量を測定した。赤外分光装置としては、FTS3000(BIORAD社製)を用いた。光照射後に(メタ)アクリロイル基由来のピークが85%以上減少した場合を「◎」、75%以上85%未満減少した場合を「○」、70%以上75%未満減少した場合を「△」、光照射後の(メタ)アクリロイル基由来のピークの減少が70%未満であった場合を「×」として光硬化性を評価した。
サンプル瓶に液晶(チッソ社製、「JC-5001LA」)0.5gを入れ、実施例及び比較例で得られた各液晶表示素子用シール剤0.1gを加えて振とうした後、120℃で1時間加熱し、室温(25℃)に戻した。透明電極と配向膜(日産化学社製、「SE7492」)とを有するガラス基板の配向膜上に、実施例及び比較例で得られた各液晶表示素子用シール剤を正方形の枠を描くようにディスペンサーで塗布した。続いて、上記サンプル瓶から取り出した液晶の微小滴を基板上の枠内全面に滴下塗布し、真空中にて別のガラス基板を重ね合わせた。真空を解除し、メタルハライドランプを用いて100mW/cm2の光をカットフィルターを介して30秒照射した。カットフィルターとしては、340nmカットフィルター、400nmカットフィルター、420nmカットフィルター、又は、440nmカットフィルターを用いた。その後、120℃で1時間加熱することによりシール剤を熱硬化させて液晶表示素子を得た。
得られた液晶表示素子について、液晶物性評価システム6254型(東陽テクニカ社製)を用いて、25℃において、1.0V、1.0Hzの交流電圧を印加し、100ミリ秒後の保持電圧を測定することによって、液晶の電圧保持率を算出した。電圧保持率が90%以上であった場合を「◎」、85%以上90%未満であった場合を「○」、80%以上85%未満であった場合を「△」、80%未満であった場合を「×」として、低液晶汚染性を評価した。
Claims (5)
- 硬化性樹脂と光重合開始剤と増感剤とを含有する液晶表示素子用シール剤であって、
前記光重合開始剤は、カンファーキノンを含み、
前記増感剤は、濃度が20mg/Lとなるようにアセトニトリルに溶解させた溶液について吸光スペクトルを測定した際の波長300nm以上550nm以下の範囲における吸光度の最大値を1としたとき、波長400nmにおける吸光度が0.1以上である
ことを特徴とする液晶表示素子用シール剤。 - 前記増感剤は、クマリン骨格、アクリジン骨格、及び、チオキサントン骨格からなる群より選択される少なくとも1種の構造を有する請求項1記載の液晶表示素子用シール剤。
- 前記増感剤は、3-ベンゾイル-7-ジエチルアミノクマリン、3,3-カルボニルビス(7-ジエチルアミノクマリン)、アクリジン-3,6-ジアミン、及び、2,4-ジエチルチオキサンテン-9-オン、9,10-フェナントレンキノンからなる群より選択される少なくとも1種である請求項2記載の液晶表示素子用シール剤。
- 前記カンファーキノン100重量部に対する前記増感剤の含有割合が0.1重量部以上200重量部以下である請求項1、2又は3記載の液晶表示素子用シール剤。
- 請求項1、2、3又は4記載の液晶表示素子用シール剤の硬化物を有する液晶表示素子。
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