TWI848961B - Sealant for liquid crystal display element, upper and lower conductive material, and liquid crystal display element - Google Patents
Sealant for liquid crystal display element, upper and lower conductive material, and liquid crystal display element Download PDFInfo
- Publication number
- TWI848961B TWI848961B TW108124623A TW108124623A TWI848961B TW I848961 B TWI848961 B TW I848961B TW 108124623 A TW108124623 A TW 108124623A TW 108124623 A TW108124623 A TW 108124623A TW I848961 B TWI848961 B TW I848961B
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- TW
- Taiwan
- Prior art keywords
- liquid crystal
- crystal display
- sealant
- display elements
- display element
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 112
- 239000000565 sealant Substances 0.000 title claims abstract description 85
- 239000004020 conductor Substances 0.000 title claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000004642 Polyimide Substances 0.000 claims abstract description 29
- 229920001721 polyimide Polymers 0.000 claims abstract description 29
- 238000003860 storage Methods 0.000 claims abstract description 28
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 16
- 238000012360 testing method Methods 0.000 claims abstract description 13
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 12
- -1 cyclic lactone Chemical class 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 49
- 150000001412 amines Chemical class 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 8
- 239000011859 microparticle Substances 0.000 claims description 7
- 229920001971 elastomer Chemical group 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 239000005060 rubber Chemical group 0.000 claims description 6
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 11
- 239000003822 epoxy resin Substances 0.000 description 31
- 229920000647 polyepoxide Polymers 0.000 description 31
- 239000000758 substrate Substances 0.000 description 29
- 239000004593 Epoxy Substances 0.000 description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 21
- 239000010936 titanium Substances 0.000 description 21
- 229910052719 titanium Inorganic materials 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 10
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- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 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 9
- 238000001723 curing Methods 0.000 description 8
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 8
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- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
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- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical group C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
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- 125000001424 substituent group Chemical group 0.000 description 4
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 3
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- 238000013461 design Methods 0.000 description 3
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- 150000003254 radicals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical class C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
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- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- OALYTRUKMRCXNH-QMMMGPOBSA-N gamma-Nonalactone Natural products CCCCC[C@H]1CCC(=O)O1 OALYTRUKMRCXNH-QMMMGPOBSA-N 0.000 description 2
- IFYYFLINQYPWGJ-UHFFFAOYSA-N gamma-decalactone Chemical compound CCCCCCC1CCC(=O)O1 IFYYFLINQYPWGJ-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
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- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
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- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
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- HGCMSCWGVAYWHR-UHFFFAOYSA-N 1,3,5-trimethyl-2-[[phenyl-[(2,4,6-trimethylphenyl)methyl]phosphoryl]methyl]benzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)CC1=C(C)C=C(C)C=C1C HGCMSCWGVAYWHR-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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- LESMLVDJJCWZAJ-UHFFFAOYSA-N 2-(diphenylphosphorylmethyl)-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 LESMLVDJJCWZAJ-UHFFFAOYSA-N 0.000 description 1
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- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
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- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- BOOMCRRUAZSMAM-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC(C(=O)C=1SC=C(C1)C)(C)N1CCOCC1.CC(C(=O)C=1SC=C(C1)C)(C)N1CCOCC1 BOOMCRRUAZSMAM-UHFFFAOYSA-N 0.000 description 1
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
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- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 239000001095 magnesium carbonate Substances 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
Abstract
本發明之目的在於提供一種即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 本發明為一種液晶顯示元件用密封劑，其含有硬化性樹脂與聚合起始劑及/或熱硬化劑，該液晶顯示元件用密封劑其藉由依據JIS K 6852之常態試驗測得之硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度為30 kgf/cm2 以上，且硬化物於25℃之儲存彈性模數為2.5 GPa以下。The purpose of the present invention is to provide a sealant for liquid crystal display elements that can maintain excellent adhesion even during special-shaped processing. In addition, the purpose of the present invention is to provide an upper and lower conductive material and a liquid crystal display element formed by using the sealant for liquid crystal display elements. The present invention is a sealant for liquid crystal display elements, which contains a curable resin and a polymerization initiator and/or a thermosetting agent. The sealant for liquid crystal display elements has a compressive shear bonding strength of 30 kgf/cm2 or more for polyimide at 25°C measured by a normal test according to JIS K 6852 , and the storage elastic modulus of the cured product at 25°C is less than 2.5 GPa.
Description
本發明係關於一種即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑。又，本發明係關於一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。The present invention relates to a sealant for a liquid crystal display element which can maintain excellent adhesion even when processed into a special shape, and also to an upper and lower conductive material and a liquid crystal display element formed by using the sealant for a liquid crystal display element.
近年來，作為液晶顯示元件之製造方法，就產距時間（tact time）之縮短、液晶使用量之最佳化等觀點而言，使用如專利文獻1、專利文獻2所揭示般之被稱為滴下法之液晶滴下方式，該滴下法使用含有硬化性樹脂、光聚合起始劑及熱硬化劑之光熱併用硬化型密封劑。In recent years, as a manufacturing method for liquid crystal display elements, from the viewpoints of shortening the tact time and optimizing the amount of liquid crystal used, a liquid crystal dropping method called a dropping method as disclosed in Patent Document 1 and Patent Document 2 is used. The dropping method uses a photothermal curing sealant containing a curable resin, a photopolymerization initiator, and a thermosetting agent.
滴下法中，首先，於2片附電極之透明基板之一透明基板上，藉由滴塗（dispense）形成長方形之密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微滴滴滿透明基板之框內整個面，其後立即使另一透明基板重合，對密封部照射紫外線等光進行暫時硬化。其後，進行加熱使其正式硬化，而製作液晶顯示元件。藉由於減壓下進行基板之貼合，能夠以極高之效率製造液晶顯示元件，該滴下法成為當前液晶顯示元件之製造方法之主流。In the drip method, first, a rectangular sealing pattern is formed by dispensing on one of the two transparent substrates with electrodes. Then, before the sealant is cured, droplets of liquid crystal are filled on the entire surface of the frame of the transparent substrate, and then the other transparent substrate is immediately overlapped, and the sealing part is irradiated with ultraviolet light or other light for temporary curing. After that, it is heated to formally cure, and a liquid crystal display element is produced. By laminating the substrates under reduced pressure, liquid crystal display elements can be manufactured with extremely high efficiency, and this drip method has become the mainstream method for manufacturing liquid crystal display elements.
且說，於行動電話、攜帶型遊戲機等各種附有液晶面板之移動式機器普及之當代，要求最多的課題即為機器之小型化。作為機器之小型化之手法，可列舉液晶顯示部之窄邊緣化，例如將密封部之位置配置於黑矩陣下方（以下，亦稱為窄邊緣設計）。伴隨此種窄邊緣設計，密封劑之塗佈位置位於聚醯亞胺等配向膜上之情況變多。 先前技術文獻 專利文獻In the current era when various mobile devices with liquid crystal panels such as mobile phones and portable game consoles are becoming popular, the most demanding issue is the miniaturization of the devices. As a method for miniaturizing the devices, the narrow edge of the liquid crystal display part can be cited, for example, the position of the sealing part is arranged below the black matrix (hereinafter also referred to as the narrow edge design). With this narrow edge design, the coating position of the sealant is more often located on the alignment film such as polyimide. Prior art literature Patent literature
專利文獻1：日本特開2001-133794號公報 專利文獻2：日本特開平5-295087號公報Patent document 1: Japanese Patent Publication No. 2001-133794 Patent document 2: Japanese Patent Publication No. 5-295087
[發明所欲解決之課題][The problem that the invention wants to solve]
本發明之目的在於提供一種即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用上述液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 [解決課題之技術手段]The purpose of the present invention is to provide a sealant for liquid crystal display elements that can maintain excellent adhesion even during special-shaped processing. In addition, the purpose of the present invention is to provide an upper and lower conductive material and a liquid crystal display element formed by using the sealant for liquid crystal display elements. [Technical means to solve the problem]
本發明之液晶顯示元件用密封劑含有硬化性樹脂與聚合起始劑及/或熱硬化劑，該液晶顯示元件用密封劑其藉由依據JIS K 6852之常態試驗測得之硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度為30 kgf/cm2 以上，且硬化物於25℃之儲存彈性模數（storage elastic modulus）為2.5 GPa以下。 以下，對本發明進行詳細說明。The sealant for liquid crystal display element of the present invention contains a curable resin and a polymerization initiator and/or a thermosetting agent, and the sealant for liquid crystal display element has a compressive shear strength of 30 kgf/cm2 or more for polyimide at 25°C measured by a normal test according to JIS K 6852 , and a storage elastic modulus of 2.5 GPa or less at 25°C. The present invention is described in detail below.
近年來，正在進行使用藉由凹槽（notch）加工等異型加工而加工為矩形以外之異型形狀之面板的液晶顯示元件之開發，然而尤其是於製造窄邊緣設計之液晶顯示元件時進行異型加工之情形時，有時會在加工過程中發生基板剝落之問題。 本發明人為了防止此種異型加工時之基板之剝落，研究了藉由使用柔軟之材料作為用於液晶顯示元件用密封劑之硬化性樹脂，而使硬化物之儲存彈性模數成為特定值以下。然而，僅藉由降低儲存彈性模數無法充分地防止異型加工時之基板之剝落。因此，本發明人研究了不僅將硬化物之儲存彈性模數設為特定值以下，且將利用密封劑使聚醯亞胺基板彼此接著時之壓縮剪切接著強度設為特定值以上。其結果為，發現獲得即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑，從而完成本發明。In recent years, the development of liquid crystal display elements using panels processed into irregular shapes other than rectangular shapes by irregular processing such as notch processing has been underway. However, when performing irregular processing when manufacturing liquid crystal display elements with narrow edge designs, the problem of substrate peeling sometimes occurs during the processing. In order to prevent the peeling of the substrate during such irregular processing, the inventors have studied the use of a soft material as a curable resin used as a sealant for liquid crystal display elements, so that the storage elastic modulus of the cured product becomes less than a specific value. However, it is not possible to fully prevent the peeling of the substrate during irregular processing by simply reducing the storage elastic modulus. Therefore, the inventors studied how to set the storage elastic modulus of the cured product below a specific value and how to set the compressive shear bonding strength of the polyimide substrates bonded together by the sealant to a specific value or above. As a result, they found a sealant for liquid crystal display elements that can maintain excellent adhesion even when processed into special shapes, and thus completed the present invention.
關於本發明之液晶顯示元件用密封劑，藉由依據JIS K 6852之常態試驗測得之硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度之下限為30 kgf/cm2 。藉由上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度為30 kgf/cm2 以上，且後述之硬化物於25℃之儲存彈性模數為2.5 GPa以下，從而使得本發明之液晶顯示元件用密封劑即便於異型加工時亦可維持優異之接著性。上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度之較佳之下限為35 kgf/cm2 。 上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度之較佳之上限無特別限制，實質性之上限為100 kgf/cm2 。 再者，上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度可利用以下之方法測定。 即，首先，於長度45 mm、寬度25 mm、厚度0.7 mm之ITO基板以100 nm左右之膜厚塗佈聚醯亞胺溶液，經處理而獲得基板（聚醯亞胺基板），準備2片該基板，於其中一基板上以接著時之直徑為3 mm之方式點塗密封劑。使另一聚醯亞胺基板以於長邊方向上錯開10 mm之方式經由密封劑重合於點塗有密封劑之聚醯亞胺基板。其後，使用金屬鹵化物燈等照射100 mW/cm2 之光30秒鐘後，於120℃加熱1小時，而使密封劑硬化，獲得試片。對於所獲得之試片，可藉由進行依據JIS K 6852之常態試驗測定壓縮剪切接著強度。Regarding the sealant for liquid crystal display elements of the present invention, the lower limit of the compressive shear bonding strength of the cured product to polyimide at 25°C measured by the normal test according to JIS K 6852 is 30 kgf/cm 2. Since the compressive shear bonding strength of the cured product to polyimide at 25°C is 30 kgf/cm 2 or more, and the storage elastic modulus of the cured product at 25°C described later is 2.5 GPa or less, the sealant for liquid crystal display elements of the present invention can maintain excellent adhesion even when processed into special shapes. The preferred lower limit of the compressive shear bonding strength of the cured product to polyimide at 25°C is 35 kgf/cm 2 . The preferred upper limit of the compression shear bonding strength of the above-mentioned cured product to polyimide at 25°C is not particularly limited, and the substantial upper limit is 100 kgf/ cm2 . Furthermore, the compression shear bonding strength of the above-mentioned cured product to polyimide at 25°C can be measured by the following method. That is, first, a polyimide solution is applied to an ITO substrate having a length of 45 mm, a width of 25 mm, and a thickness of 0.7 mm with a film thickness of about 100 nm, and a substrate (polyimide substrate) is obtained after treatment. Two substrates are prepared, and a sealant is applied to one of the substrates in such a manner that the diameter at the time of bonding is 3 mm. Another polyimide substrate is overlapped with the polyimide substrate dotted with the sealant through the sealant in a manner that the substrate is staggered by 10 mm in the long-side direction. After that, the sealant is cured by irradiating the substrate with 100 mW/ cm2 light using a metal halide lamp for 30 seconds and then heating at 120°C for 1 hour to obtain a test piece. The obtained test piece can be measured for compressive shear bond strength by a normal test according to JIS K 6852.
關於本發明之液晶顯示元件用密封劑，其硬化物於25℃之儲存彈性模數之上限為2.5 GPa。藉由上述硬化物於25℃之儲存彈性模數為2.5 GPa以下，且上述之硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度為30 kgf/cm2 以上，從而使得本發明之液晶顯示元件用密封劑即便於異型加工時亦可維持優異之接著性。上述硬化物於25℃之儲存彈性模數之較佳之上限為2.0 GPa，更佳之上限為1.5 GPa。 又，就使被接著體貼合時之接著性之觀點而言，上述硬化物於25℃之儲存彈性模數之較佳之下限為0.1 GPa，更佳之下限為1.0 GPa。 再者，作為測定上述儲存彈性模數之硬化物，使用如下述般硬化而成者：於使用金屬鹵化物燈等對密封劑照射100 mW/cm2 之光30秒鐘後，於120℃加熱1小時使其硬化。又，該硬化物係指液晶顯示元件中用於基板等之貼合或密封之密封劑硬化物。 又，上述儲存彈性模數可使用動態黏彈性測定裝置（例如，IT計測制御公司製造，「DVA-200」等），以拉伸模式、試片寬度5 mm、厚度0.35 mm、抓持寬度25 mm、升溫速度10℃/分鐘、頻率10 Hz之條件進行測定。Regarding the sealant for liquid crystal display elements of the present invention, the upper limit of the storage elastic modulus of the cured product at 25°C is 2.5 GPa. Since the storage elastic modulus of the cured product at 25°C is less than 2.5 GPa, and the compressive shear bonding strength of the cured product at 25°C to polyimide is more than 30 kgf/ cm2 , the sealant for liquid crystal display elements of the present invention can maintain excellent adhesion even during special-shaped processing. The upper limit of the storage elastic modulus of the cured product at 25°C is preferably 2.0 GPa, and the more preferably upper limit is 1.5 GPa. In terms of adhesion when bonding the adherend, the lower limit of the storage elastic modulus of the above-mentioned cured product at 25°C is preferably 0.1 GPa, and the lower limit is more preferably 1.0 GPa. Furthermore, as the cured product for measuring the above-mentioned storage elastic modulus, the one cured by irradiating the sealant with light of 100 mW/ cm2 for 30 seconds using a metal halide lamp or the like, and then curing it by heating at 120°C for 1 hour. In addition, the cured product refers to a cured sealant used for bonding or sealing substrates, etc. in liquid crystal display devices. The storage elastic modulus can be measured using a dynamic viscoelasticity measuring device (e.g., "DVA-200" manufactured by IT Measurement & Control Co., Ltd.) in a tensile mode, with a specimen width of 5 mm, a thickness of 0.35 mm, a gripping width of 25 mm, a heating rate of 10°C/min, and a frequency of 10 Hz.
關於本發明之液晶顯示元件用密封劑，其硬化物之玻璃轉移溫度之較佳之上限為75℃。藉由上述硬化物之玻璃轉移溫度為75℃以下，從而使得本發明之液晶顯示元件用密封劑成為於異型加工時接著性更加優異者。上述硬化物之玻璃轉移溫度之更佳之上限為70℃。 又，就防透濕性等觀點而言，上述硬化物之玻璃轉移溫度之較佳之下限為30℃，更佳之下限為35℃。 再者，於本說明書中，上述「玻璃轉移溫度」係指藉由動態黏彈性測定而獲得之損耗正切（tanδ）之極大之中，出現起因於微布朗運動之極大時之溫度。上述玻璃轉移溫度可利用使用黏彈性測定裝置等之習知公知之方法測定。 又，作為測定上述玻璃轉移溫度之硬化物，與測定上述儲存彈性模數之硬化物同樣地使用使密封劑硬化而成者。Regarding the sealant for liquid crystal display elements of the present invention, the upper limit of the glass transition temperature of the cured product is preferably 75°C. By setting the glass transition temperature of the cured product to be below 75°C, the sealant for liquid crystal display elements of the present invention has better adhesion during special-shaped processing. The upper limit of the glass transition temperature of the cured product is more preferably 70°C. In addition, from the perspective of moisture permeability, the lower limit of the glass transition temperature of the cured product is preferably 30°C, and the lower limit is more preferably 35°C. Furthermore, in this specification, the "glass transition temperature" refers to the temperature at which the maximum due to micro-Brownian motion appears among the maximum loss tangent (tanδ) obtained by dynamic viscoelasticity measurement. The glass transition temperature can be measured by a known method such as a viscoelasticity measuring device. In addition, as a hardened material for measuring the glass transition temperature, a sealant hardened material is used in the same manner as the hardened material for measuring the storage elastic modulus.
對於後述之硬化性樹脂、聚合起始劑及/或熱硬化劑、以及填充劑等其他成分，藉由選擇其等之種類及調整含有比率，可將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。By selecting the types of the curable resin, polymerization initiator and/or thermosetting agent, and other components such as fillers described below and adjusting their content ratios, the compressive shear strength of the cured product at 25°C to polyimide and the storage elastic modulus of the cured product at 25°C can be set within the above ranges.
本發明之液晶顯示元件用密封劑含有硬化性樹脂。 上述硬化性樹脂較佳為含有：具有聚合性官能基與柔軟骨架之化合物（以下，亦稱為「具有柔軟骨架之硬化性樹脂」）。藉由含有上述具有柔軟骨架之硬化性樹脂，從而容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。The sealant for liquid crystal display elements of the present invention contains a curable resin. The curable resin preferably contains: a compound having a polymerizable functional group and a flexible skeleton (hereinafter, also referred to as a "curable resin having a flexible skeleton"). By containing the curable resin having a flexible skeleton, it is easy to set the compressive shear bonding strength of the cured product to polyimide at 25°C and the storage elastic modulus of the cured product at 25°C to the above range.
作為上述聚合性官能基，例如可列舉：(甲基)丙烯醯基、環氧基等。又，上述具有柔軟骨架之硬化性樹脂較佳為於1分子中具有2個以上之上述聚合性官能基。 再者，於本說明書中，上述「(甲基)丙烯醯基」係指丙烯醯基或甲基丙烯醯基。Examples of the polymerizable functional group include (meth)acryl and epoxy groups. In addition, the hardening resin having a flexible skeleton preferably has two or more polymerizable functional groups in one molecule. In addition, in this specification, the "(meth)acryl" refers to an acryl or a methacryl group.
上述柔軟骨架較佳為選自由環狀內酯之開環結構、環氧烷（alkylene oxide）結構、及橡膠結構所組成之群之至少1種，更佳為環狀內酯之開環結構及/或橡膠結構，進而較佳為環狀內酯之開環結構。藉由使用具有此種柔軟骨架之硬化性樹脂，從而更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。The soft skeleton is preferably at least one selected from the group consisting of a ring-opening structure of a cyclic lactone, an alkylene oxide structure, and a rubber structure, more preferably a ring-opening structure of a cyclic lactone and/or a rubber structure, and more preferably a ring-opening structure of a cyclic lactone. By using a curable resin having such a soft skeleton, it is easier to set the compressive shear bonding strength of the cured product to polyimide at 25°C and the storage elastic modulus of the cured product at 25°C to the above ranges.
作為上述環狀內酯，例如可列舉：γ-十一內酯、ε-己內酯、γ-癸內酯、σ-十二內酯、γ-壬內酯（γ-nonalactone）、γ-壬內酯（γ-nonanolactone）、γ-戊內酯、σ-戊內酯、β-丁內酯、γ-丁內酯、β-丙內酯、σ-己內酯、7-丁基-2-氧雜環庚烷酮（7-butyl-2-oxepanone）等。其中，較佳為開環時主骨架之直鏈部分之碳數為5〜7者。Examples of the cyclic lactones include γ-undecalactone, ε-caprolactone, γ-decanolactone, σ-dodecalactone, γ-nonalactone, γ-nonanolactone, γ-valerolactone, σ-valerolactone, β-butyrolactone, γ-butyrolactone, β-propiolactone, σ-caprolactone, and 7-butyl-2-oxepanone. Among them, preferably, the number of carbon atoms in the straight chain portion of the main skeleton when the ring is opened is 5 to 7.
作為上述環氧烷結構，例如可列舉：環氧乙烷結構、環氧丙烷結構、環氧丁烷結構等。其中，較佳為環氧丁烷結構。Examples of the alkylene oxide structure include ethylene oxide structure, propylene oxide structure, butylene oxide structure, etc. Among them, the butylene oxide structure is preferred.
上述橡膠結構較佳為於主鏈具有不飽和鍵之結構、或於主鏈具有聚矽氧烷骨架之結構。 作為上述於主鏈具有不飽和鍵之結構，例如可列舉：於主鏈具有因共軛二烯之聚合而產生之骨架之結構等。 作為上述因共軛二烯之聚合而產生之骨架，例如可列舉：丙烯腈-丁二烯骨架、聚丁二烯骨架、聚異戊二烯骨架、苯乙烯-丁二烯骨架、聚異丁烯骨架、聚氯丁二烯骨架等。 其中，上述橡膠結構較佳為具有丙烯腈-丁二烯骨架之結構。The rubber structure is preferably a structure having an unsaturated bond in the main chain or a structure having a polysiloxane skeleton in the main chain. As the structure having an unsaturated bond in the main chain, for example, there can be listed: a structure having a skeleton generated by polymerization of a conjugated diene in the main chain, etc. As the skeleton generated by polymerization of a conjugated diene, for example, there can be listed: an acrylonitrile-butadiene skeleton, a polybutadiene skeleton, a polyisoprene skeleton, a styrene-butadiene skeleton, a polyisobutylene skeleton, a polychloroprene skeleton, etc. Among them, the rubber structure is preferably a structure having an acrylonitrile-butadiene skeleton.
上述具有柔軟骨架之硬化性樹脂之分子量之較佳之下限為100，較佳之上限為10萬。藉由上述具有柔軟骨架之硬化性樹脂之分子量為該範圍，從而更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。上述具有柔軟骨架之硬化性樹脂之分子量之更佳之下限為200，更佳之上限為5萬。 再者，於本說明書中，關於上述「分子量」，對於分子結構被特定出之化合物而言，係根據結構式而求出者，但對於聚合度之分佈較廣之化合物及改質部位不特定之化合物而言，有時使用重量平均分子量表示。又，上述「重量平均分子量」係利用凝膠滲透層析法（GPC）使用四氫呋喃作為溶劑進行測定，根據聚苯乙烯換算求出之值。作為利用GPC測定根據聚苯乙烯換算之重量平均分子量時所使用之管柱，例如可列舉：Shodex LF-804（昭和電工公司製造）等。The molecular weight of the hardening resin with a flexible skeleton preferably has a lower limit of 100 and an upper limit of 100,000. By setting the molecular weight of the hardening resin with a flexible skeleton to this range, it is easier to set the compressive shear bonding strength of the hardened material to polyimide at 25°C and the storage elastic modulus of the hardened material at 25°C to the above range. The molecular weight of the hardening resin with a flexible skeleton preferably has a lower limit of 200 and an upper limit of 50,000. In addition, in this specification, the "molecular weight" is obtained based on the structural formula for compounds with a specific molecular structure, but for compounds with a wide distribution of polymerization degrees and compounds with unspecified modified sites, the weight average molecular weight is sometimes used. The above-mentioned "weight average molecular weight" is a value obtained by measuring the weight average molecular weight in terms of polystyrene by using tetrahydrofuran as a solvent using gel permeation chromatography (GPC). Examples of columns used when measuring the weight average molecular weight in terms of polystyrene by using GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).
作為上述具有柔軟骨架之硬化性樹脂，具體而言，例如可列舉：己內酯改質雙酚A型環氧(甲基)丙烯酸酯、己內酯改質雙酚F型環氧(甲基)丙烯酸酯、己內酯改質雙酚E型環氧(甲基)丙烯酸酯、環氧乙烷改質雙酚A型環氧(甲基)丙烯酸酯、環氧乙烷改質雙酚F型環氧(甲基)丙烯酸酯、環氧乙烷改質雙酚E型環氧(甲基)丙烯酸酯、環氧丙烷改質雙酚A型環氧(甲基)丙烯酸酯、環氧丙烷改質雙酚F型環氧(甲基)丙烯酸酯、環氧丙烷改質雙酚E型環氧(甲基)丙烯酸酯、含封端胺基之丁二烯-丙烯腈（ATBN）改質環氧(甲基)丙烯酸酯、含封端羧基之丁二烯-丙烯腈（CTBN）改質環氧(甲基)丙烯酸酯、(甲基)丙烯酸改質異戊二烯橡膠、(甲基)丙烯酸改質丁二烯橡膠、(甲基)丙烯酸改質聚矽氧橡膠、己內酯改質雙酚A型環氧樹脂、己內酯改質雙酚F型環氧樹脂、己內酯改質雙酚E型環氧樹脂、環氧乙烷改質雙酚A型環氧樹脂、環氧乙烷改質雙酚F型環氧樹脂、環氧乙烷改質雙酚E型環氧樹脂、環氧丙烷改質雙酚A型環氧樹脂、環氧丙烷改質雙酚F型環氧樹脂、環氧丙烷改質雙酚E型環氧樹脂、NBR改質雙酚A型環氧樹脂、ATBN改質環氧樹脂、CTBN改質環氧樹脂、環氧改質異戊二烯橡膠、環氧改質丁二烯橡膠、環氧改質聚矽氧橡膠等。 上述具有柔軟骨架之硬化性樹脂可單獨地使用，亦可組合2種以上使用。 再者，於本說明書中，上述所謂「(甲基)丙烯酸酯」係指丙烯酸酯或甲基丙烯酸酯，上述所謂「環氧(甲基)丙烯酸酯」係指使環氧化合物中之全部環氧基與(甲基)丙烯酸反應而成之化合物。As the above-mentioned hardening resin having a soft skeleton, specifically, for example, caprolactone-modified bisphenol A type epoxy (meth) acrylate, caprolactone-modified bisphenol F type epoxy (meth) acrylate, caprolactone-modified bisphenol E type epoxy (meth) acrylate, ethylene oxide-modified bisphenol A type epoxy (meth) acrylate, ethylene oxide-modified bisphenol F type epoxy (meth) acrylate, ethylene oxide-modified Ethylene oxide modified bisphenol E type epoxy (meth) acrylate, propylene oxide modified bisphenol A type epoxy (meth) acrylate, propylene oxide modified bisphenol F type epoxy (meth) acrylate, propylene oxide modified bisphenol E type epoxy (meth) acrylate, butadiene-acrylonitrile (ATBN) modified epoxy (meth) acrylate containing terminal amino group, butadiene-acrylonitrile (CTBN) modified epoxy (meth) acrylate containing terminal carboxyl group BN) modified epoxy (meth) acrylate, (meth) acrylic modified isoprene rubber, (meth) acrylic modified butadiene rubber, (meth) acrylic modified silicone rubber, caprolactone modified bisphenol A type epoxy resin, caprolactone modified bisphenol F type epoxy resin, caprolactone modified bisphenol E type epoxy resin, ethylene oxide modified bisphenol A type epoxy resin, ethylene oxide modified bisphenol F type epoxy resin Resin, ethylene oxide modified bisphenol E type epoxy resin, propylene oxide modified bisphenol A type epoxy resin, propylene oxide modified bisphenol F type epoxy resin, propylene oxide modified bisphenol E type epoxy resin, NBR modified bisphenol A type epoxy resin, ATBN modified epoxy resin, CTBN modified epoxy resin, epoxy modified isoprene rubber, epoxy modified butadiene rubber, epoxy modified polysilicone rubber, etc. The above-mentioned hardening resins with a soft skeleton can be used alone or in combination of two or more. In this specification, the above-mentioned "(meth)acrylate" refers to acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" refers to a compound formed by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid.
上述硬化性樹脂較佳為以調整上述硬化物之於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數，或進一步提高貼合被接著體時之接著性或低液晶污染性等為目的，含有上述具有柔軟骨架之硬化性樹脂以外之其他硬化性樹脂。 於含有上述其他硬化性樹脂之情形時，上述具有柔軟骨架之硬化性樹脂於上述硬化性樹脂100重量份中之含量之較佳之下限為30重量份，較佳之上限為90重量份。藉由上述具有柔軟骨架之硬化性樹脂之含量為該範圍，從而更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。上述具有柔軟骨架之硬化性樹脂之含量之更佳之下限為50重量份，更佳之上限為70重量份。 又，較佳為於上述硬化性樹脂100重量份中含有20重量份以上且80重量份以下之上述具有柔軟骨架之硬化性樹脂中之具有上述環狀內酯之開環結構之硬化性樹脂。The curable resin preferably contains other curable resins other than the curable resin with a flexible skeleton for the purpose of adjusting the compressive shear bonding strength of the cured product to polyimide at 25°C and the storage elastic modulus of the cured product at 25°C, or further improving the adhesion or low liquid crystal contamination when attached to the adherend. When the other curable resin is contained, the content of the curable resin with a flexible skeleton in 100 parts by weight of the curable resin is preferably 30 parts by weight at the lower limit and 90 parts by weight at the upper limit. By setting the content of the above-mentioned hardening resin with a flexible skeleton to the above-mentioned range, it is easier to set the compressive shear bonding strength of the above-mentioned hardened material to polyimide at 25°C and the storage elastic modulus of the above-mentioned hardened material at 25°C to the above-mentioned range. The better lower limit of the content of the above-mentioned hardening resin with a flexible skeleton is 50 parts by weight, and the better upper limit is 70 parts by weight. In addition, it is preferred that the hardening resin having the ring-opening structure of the above-mentioned cyclic lactone in the above-mentioned hardening resin with a flexible skeleton is contained in 100 parts by weight of the above-mentioned hardening resin.
作為上述其他硬化性樹脂，例如可列舉：不具有柔軟骨架之其他環氧化合物或不具有柔軟骨架之其他(甲基)丙烯酸化合物等。再者，於本說明書中，上述所謂「(甲基)丙烯酸」係指丙烯酸或甲基丙烯酸，上述所謂「(甲基)丙烯酸化合物」係指具有(甲基)丙烯醯基之化合物。Examples of the other curable resins include other epoxy compounds without a flexible skeleton or other (meth) acrylic compounds without a flexible skeleton. In this specification, the so-called "(meth) acrylic" refers to acrylic acid or methacrylic acid, and the so-called "(meth) acrylic compound" refers to a compound having a (meth)acrylic group.
作為上述其他環氧化合物，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚E型環氧樹脂、雙酚S型環氧樹脂、2,2'-二烯丙基雙酚A型環氧樹脂、氫化雙酚型環氧樹脂、間苯二酚型環氧樹脂、聯苯型環氧樹脂、硫醚（sulfide）型環氧樹脂、二苯醚型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、二環戊二烯酚醛清漆型環氧樹脂、聯苯酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、環氧丙基胺型環氧樹脂、環氧丙基酯化合物等。Examples of the other epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallylbisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, Resins, diphenyl ether type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, phenol novolac type epoxy resins, o-cresol novolac type epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, naphthol novolac type epoxy resins, glycidylamine type epoxy resins, glycidyl ester compounds, etc.
又，上述硬化性樹脂亦可含有於1分子中具有環氧基與(甲基)丙烯醯基之化合物作為上述其他環氧化合物。作為此種化合物，例如可列舉部分(甲基)丙烯酸改質環氧樹脂等，其藉由使於1分子中具有2個以上環氧基之環氧化合物之一部分之環氧基與(甲基)丙烯酸反應而獲得。Furthermore, the curable resin may contain a compound having an epoxy group and a (meth)acryl group in one molecule as the other epoxy compound. Examples of such a compound include a partially (meth)acrylic acid-modified epoxy resin obtained by reacting a portion of the epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid.
作為上述其他(甲基)丙烯酸化合物，較佳為環氧(甲基)丙烯酸酯。又，就更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍之觀點而言，上述其他(甲基)丙烯酸化合物較佳為於1分子中具有2個以上之(甲基)丙烯醯基之多官能(甲基)丙烯酸化合物。又，就上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度之觀點而言，較佳為不含有於1分子中具有1個(甲基)丙烯醯基之單官能(甲基)丙烯酸化合物。As the other (meth)acrylic compound, epoxy (meth)acrylate is preferred. Furthermore, from the viewpoint of making it easier to set the compression shear adhesion strength of the cured product to polyimide at 25°C and the storage elastic modulus of the cured product at 25°C within the above range, the other (meth)acrylic compound is preferably a multifunctional (meth)acrylic compound having two or more (meth)acrylic groups in one molecule. Furthermore, from the viewpoint of the compression shear adhesion strength of the cured product to polyimide at 25°C, it is preferred that the other (meth)acrylic compound does not contain one (meth)acrylic group in one molecule.
作為上述環氧(甲基)丙烯酸酯，例如可列舉藉由依據常規方法於鹼性觸媒之存在下使環氧化合物與(甲基)丙烯酸反應而獲得者等。Examples of the epoxy (meth)acrylate include those obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of an alkaline catalyst according to a conventional method.
作為用於合成上述環氧(甲基)丙烯酸酯之原料之環氧化合物，可列舉與上述之其他環氧化合物相同者。As the raw material of the epoxy (meth)acrylate, the same epoxy compounds as those mentioned above can be cited.
上述硬化性樹脂可單獨地使用，亦可組合2種以上使用。The above-mentioned curable resins may be used alone or in combination of two or more.
本發明之液晶顯示元件用密封劑較佳為將硬化性樹脂中之(甲基)丙烯醯基與環氧基之合計中之(甲基)丙烯醯基之含有比率設為50莫耳%以上95莫耳%以下。The sealant for liquid crystal display elements of the present invention preferably has a (meth)acryl group content ratio in the total of (meth)acryl groups and epoxy groups in the curable resin of not less than 50 mol % and not more than 95 mol %.
本發明之液晶顯示元件用密封劑含有聚合起始劑及/或熱硬化劑。 作為上述聚合起始劑，例如可列舉：藉由光照射產生自由基之光自由基聚合起始劑、或藉由加熱產生自由基之熱自由基聚合起始劑等。The sealant for liquid crystal display elements of the present invention contains a polymerization initiator and/or a thermosetting agent. As the above-mentioned polymerization initiator, for example, there can be listed: a photo-radical polymerization initiator that generates free radicals by light irradiation, or a thermal-radical polymerization initiator that generates free radicals by heating, etc.
作為上述光自由基聚合起始劑，就反應性之觀點而言，較佳為含有肟酯（oxime ester）化合物及9-氧硫 （thioxanthone）化合物之至少任一者。 再者，於本說明書中，上述「9-氧硫 化合物」係指具有9-氧硫 基（thioxanthonyl group）之化合物，上述「9-氧硫 基」係指9-側氧-9H-硫 -基。As the above-mentioned photo-radical polymerization initiator, from the viewpoint of reactivity, it is preferred to contain an oxime ester compound and 9-oxysulfur In the present specification, the above-mentioned "9-thioxanthone" Compounds are compounds having 9-oxosulfur The above-mentioned "9-oxysulfur "Hydrogen" refers to 9-hydroxy-9H-sulfur -base.
作為上述肟酯化合物，例如可列舉：1-(4-(苯硫基)苯基)-1,2-辛二酮2-(O-苯甲醯肟）、O-乙醯基-1-(6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基)乙酮肟、下述式（1）所表示之化合物、下述式（2）所表示之化合物等。Examples of the oxime ester compound include 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime), O-acetyl-1-(6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3-yl)ethanone oxime, a compound represented by the following formula (1), and a compound represented by the following formula (2).
上述式（1）、上述式（2）中之芳香環中之氫原子亦可經取代基取代。作為該取代基，例如可列舉：甲基、乙基、丙基等。The hydrogen atom in the aromatic ring in the above formula (1) and the above formula (2) may be substituted by a substituent. Examples of the substituent include methyl, ethyl, propyl, and the like.
上述9-氧硫 化合物較佳為於主鏈之末端具有9-氧硫 基。 又，上述9-氧硫 化合物較佳為於1分子中具有3個以上之9-氧硫 基。藉由上述9-氧硫 化合物於1分子中具有3個以上之9-氧硫 基，從而使得所獲得之液晶顯示元件用密封劑成為對於長波長之光之深部硬化性更加優異者。The above 9-oxysulfur The compound preferably has a 9-oxosulfur group at the end of the main chain. Furthermore, the above 9-oxysulfur The compound preferably has three or more 9-oxosulfur groups in one molecule. By the above 9-oxysulfur The compound has three or more 9-oxosulfur groups in one molecule. The obtained sealant for liquid crystal display elements has a more excellent deep curing property against long-wavelength light.
作為上述9-氧硫 化合物，具體而言，較佳為下述式（3-1）所表示之化合物及下述式（3-2）所表示之化合物之至少任一者。As the above 9-oxosulfur Specifically, the compound is preferably at least one of a compound represented by the following formula (3-1) and a compound represented by the following formula (3-2).
式（3-2）中，n為1〜10（平均值）。In formula (3-2), n is 1 to 10 (average value).
上述式（3-1）、上述式（3-2）中之芳香環中之氫原子亦可經取代基取代。作為該取代基，例如可列舉：甲基、乙基、丙基等。The hydrogen atom in the aromatic ring in the above formula (3-1) and the above formula (3-2) may be substituted by a substituent. Examples of the substituent include methyl, ethyl, and propyl.
作為上述肟酯化合物及上述9-氧硫 化合物以外之其他光自由基聚合起始劑，例如可列舉：二苯甲酮化合物、苯乙酮化合物、醯基氧化膦化合物、二茂鈦化合物、安息香醚化合物等。As the above-mentioned oxime ester compound and the above-mentioned 9-oxysulfur Other photo-radical polymerization initiators other than the compounds include, for example, benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titaniumocene compounds, benzoin ether compounds, and the like.
作為上述其他光自由基聚合起始劑，具體而言，例如可列舉：1-羥基環己基苯基酮、2-苄基-2-二甲基胺基-1-(4-啉基苯基)-1-丁酮、2-(二甲基胺基)-2-((4-甲基苯基)甲基)-1-(4-(4-啉基)苯基)-1-丁酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2-甲基-1-(4-甲基噻吩基)-2-啉基丙烷-1-酮（2-methyl-1-(4-methylthiophenyl)-2-morpholino propan-1-one）、1-(4-(2-羥基乙氧基)-苯基)-2-羥基-2-甲基-1-丙烷-1-酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、安息香甲醚、安息香乙醚、安息香異丙醚等。Specific examples of the other photo-radical polymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4- 1-(4-(4-(4-(4-phenyl)-1-(4 ... 1-Butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-methyl-1-(4-methylthienyl)-2- Morpholinopropan-1-one (2-methyl-1-(4-methylthiophenyl)-2-morpholino propan-1-one), 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2,4,6-trimethylbenzyldiphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc.
上述光自由基聚合起始劑可單獨地使用，亦可組合2種以上使用。The above-mentioned photoradical polymerization initiators may be used alone or in combination of two or more.
作為上述熱自由基聚合起始劑，例如可列舉由偶氮化合物或有機過氧化物等構成者。其中，就抑制液晶污染之觀點而言，較佳為由偶氮化合物構成之起始劑（以下，亦稱為「偶氮起始劑」），更佳為由高分子偶氮化合物構成之起始劑（以下，亦稱為「高分子偶氮起始劑」）。 再者，於本說明書中，上述所謂「高分子偶氮化合物」係指具有偶氮基，且藉由熱生成可使(甲基)丙烯醯基硬化之自由基之數量平均分子量為300以上之化合物。As the above-mentioned thermal free radical polymerization initiator, for example, those composed of azo compounds or organic peroxides can be listed. Among them, from the viewpoint of suppressing liquid crystal contamination, the initiator composed of azo compounds (hereinafter, also referred to as "azo initiator") is preferred, and the initiator composed of high molecular azo compounds (hereinafter, also referred to as "high molecular azo initiator") is more preferred. Furthermore, in this specification, the above-mentioned "high molecular azo compound" refers to a compound having an azo group and a number average molecular weight of 300 or more of free radicals that can harden (meth)acrylic groups by heat generation.
上述高分子偶氮化合物之數量平均分子量之較佳之下限為1000，較佳之上限為30萬。藉由上述高分子偶氮化合物之數量平均分子量為該範圍，從而可防止對液晶造成不良影響，且容易與硬化性樹脂混合。上述高分子偶氮化合物之數量平均分子量之更佳之下限為5000，更佳之上限為10萬，進而較佳之下限為1萬，進而較佳之上限為9萬。 再者，於本說明書中，上述數量平均分子量係利用凝膠滲透層析法（GPC）使用四氫呋喃作為溶劑進行測定，根據聚苯乙烯換算求出之值。作為利用GPC測定根據聚苯乙烯換算之數量平均分子量時所使用之管柱，例如可列舉：Shodex LF-804（昭和電工公司製造）等。The preferred lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 1000, and the preferred upper limit is 300,000. By having the number average molecular weight of the above-mentioned high molecular weight azo compound within this range, it is possible to prevent adverse effects on liquid crystals and to easily mix with curable resins. The preferred lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 5000, and the preferred upper limit is 100,000, further preferred lower limit is 10,000, and further preferred upper limit is 90,000. Furthermore, in this specification, the above-mentioned number average molecular weight is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and is calculated based on polystyrene conversion. Examples of columns used when measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).
作為上述高分子偶氮化合物，例如可列舉具有「聚環氧烷或聚二甲基矽氧烷等單元經由偶氮基而複數個鍵結之結構」者。 作為具有聚環氧烷等單元經由上述偶氮基而複數個鍵結之結構之高分子偶氮化合物，較佳為具有聚環氧乙烷結構者。 作為上述高分子偶氮化合物，具體而言，例如可列舉：4,4'-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之縮聚物、或4,4'-偶氮雙(4-氰基戊酸)與具有封端胺基之聚二甲基矽氧烷之縮聚物等。 作為上述高分子偶氮起始劑之市售品，例如可列舉：VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001（均為FUJIFILM WAKO PURE CHEMICAL公司製造）等。 又，作為非高分子之偶氮起始劑，例如可列舉：V-65、V-501（均為FUJIFILM WAKO PURE CHEMICAL公司製造）等。As the above-mentioned high molecular weight azo compound, for example, there can be cited those having a "structure in which units such as polyoxyalkylene or polydimethylsiloxane are multiple bonded via an azo group". As the high molecular weight azo compound having a structure in which units such as polyoxyalkylene are multiple bonded via the above-mentioned azo group, it is preferably a structure of polyethylene oxide. As the above-mentioned high molecular weight azo compound, specifically, for example, there can be cited: a condensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or a condensate of 4,4'-azobis(4-cyanovaleric acid) and polydimethylsiloxane having a terminal amino group, etc. Examples of commercially available polymer azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by FUJIFILM WAKO PURE CHEMICAL). In addition, examples of non-polymer azo initiators include V-65 and V-501 (all manufactured by FUJIFILM WAKO PURE CHEMICAL).
作為上述有機過氧化物，例如可列舉：酮過氧化物、過氧縮酮、氫過氧化物、二烷基過氧化物、過氧酯、二醯基過氧化物、過氧化二碳酸酯等。Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
上述熱自由基聚合起始劑可單獨地使用，亦可組合2種以上使用。The above-mentioned thermal radical polymerization initiators may be used alone or in combination of two or more.
上述聚合起始劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為0.01重量份，較佳之上限為10重量份。藉由上述聚合起始劑之含量為該範圍，從而使得所獲得之液晶顯示元件用密封劑成為抑制液晶污染，且保存穩定性或硬化性更加優異者。上述聚合起始劑之含量之更佳之下限為0.1重量份，更佳之上限為5重量份。The content of the polymerization initiator is preferably 0.01 parts by weight and 10 parts by weight relative to 100 parts by weight of the curable resin. When the content of the polymerization initiator is within this range, the obtained sealant for liquid crystal display elements can suppress liquid crystal contamination and have better storage stability or curability. The lower limit of the content of the polymerization initiator is more preferably 0.1 parts by weight and the upper limit is more preferably 5 parts by weight.
上述熱硬化劑較佳為含有胺加成化合物。藉由使用上述胺加成化合物作為上述熱硬化劑，從而使得所獲得之液晶顯示元件用密封劑成為可兼具於低溫之熱硬化性與保存穩定性，且低液晶污染性更加優異者。The thermosetting agent preferably contains an amine addition compound. By using the amine addition compound as the thermosetting agent, the obtained sealant for liquid crystal display elements can have both low-temperature thermosetting properties and storage stability, and has excellent low liquid crystal contamination properties.
作為上述胺加成化合物，例如可列舉藉由使咪唑化合物或一至三級胺等胺系化合物與環氧化合物等反應而獲得之加成體等。Examples of the amine addition compound include an adduct obtained by reacting an amine compound such as an imidazole compound or a mono- to tertiary amine with an epoxy compound or the like.
作為上述胺加成化合物之市售品，例如可列舉：Ajinomoto Fine-Techno公司製造之胺加成化合物、四國化成工業公司製造之胺加成化合物、三菱化學公司製造之胺加成化合物、ADEKA公司製造之胺加成化合物、T&K TOKA公司製造之胺加成化合物等。 作為上述Ajinomoto Fine-Techno公司製造之胺加成化合物，例如可列舉：Amicure PN-23、Amicure PN-23J、Amicure PN-H、Amicure PN-31、Amicure PN-31J、Amicure PN-40、Amicure PN-40J、Amicure PN-50、Amicure PN-F、Amicure MY-24、Amicure MY-H等。 作為上述四國化成工業公司製造之胺加成化合物，例如可列舉P-0505等。 作為上述三菱化學公司製造之胺加成化合物，例如可列舉P-200等。 作為上述ADEKA公司製造之胺加成化合物，例如可列舉：ADEKA HARDENER EH-5001P、ADEKA HARDENER EH-5057PK、ADEKA HARDENER EH-5030S、ADEKA HARDENER EH-5011S等。 作為上述T&K TOKA公司製造之胺加成化合物，例如可列舉：Fujicure-FXR-1036、Fujicure-FXR-1020、Fujicure-FXR-1081等。Examples of commercially available products of the above-mentioned amine addition compounds include: amine addition compounds manufactured by Ajinomoto Fine-Techno, amine addition compounds manufactured by Shikoku Chemical Industries, amine addition compounds manufactured by Mitsubishi Chemical, amine addition compounds manufactured by ADEKA, amine addition compounds manufactured by T&K TOKA, etc. Examples of the amine addition compounds manufactured by Ajinomoto Fine-Techno include: Amicure PN-23, Amicure PN-23J, Amicure PN-H, Amicure PN-31, Amicure PN-31J, Amicure PN-40, Amicure PN-40J, Amicure PN-50, Amicure PN-F, Amicure MY-24, Amicure MY-H, etc. Examples of amine addition compounds manufactured by the above-mentioned Shikoku Chemical Industries include P-0505, etc. Examples of amine addition compounds manufactured by the above-mentioned Mitsubishi Chemical Corporation include P-200, etc. Examples of amine addition compounds manufactured by the above-mentioned ADEKA Corporation include ADEKA HARDENER EH-5001P, ADEKA HARDENER EH-5057PK, ADEKA HARDENER EH-5030S, ADEKA HARDENER EH-5011S, etc. Examples of amine addition compounds manufactured by the above-mentioned T&K TOKA Corporation include Fujicure-FXR-1036, Fujicure-FXR-1020, Fujicure-FXR-1081, etc.
作為上述胺加成化合物以外之其他熱硬化劑，例如可列舉：有機酸醯肼、多酚系化合物、酸酐等。其中，較好地使用有機酸醯肼。Examples of other heat curing agents other than the above-mentioned amine addition compounds include organic acid hydrazides, polyphenol compounds, acid anhydrides, etc. Among them, organic acid hydrazides are preferably used.
作為上述有機酸醯肼，例如可列舉：1,3-雙(肼基羰乙基)-5-異丙基乙內醯脲、癸二酸二醯肼、間苯二甲酸二醯肼、己二酸二醯肼、丙二酸二醯肼等。 作為上述有機酸醯肼之市售品，例如可列舉：Otsuka Chemical公司製造之有機酸醯肼、Japan Finechem公司製造之有機酸醯肼、Ajinomoto Fine-Techno公司製造之有機酸醯肼等。 作為上述Otsuka Chemical公司製造之有機酸醯肼，例如可列舉：SDH、ADH等。 作為上述Japan Finechem公司製造之有機酸醯肼，例如可列舉：MDH等。 作為上述Ajinomoto Fine-Techno公司製造之有機酸醯肼，例如可列舉：Amicure VDH、Amicure VDH-J、Amicure UDH等。Examples of the organic acid hydrazide include 1,3-bis(hydrazinocarbonylethyl)-5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, etc. Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical, organic acid hydrazides manufactured by Japan Finechem, and organic acid hydrazides manufactured by Ajinomoto Fine-Techno. Examples of organic acid hydrazides manufactured by Otsuka Chemical include SDH, ADH, etc. Examples of organic acid hydrazides manufactured by Japan Finechem include MDH, etc. Examples of the organic acid hydrazide manufactured by the aforementioned Ajinomoto Fine-Techno Company include Amicure VDH, Amicure VDH-J, and Amicure UDH.
上述熱硬化劑可單獨地使用，亦可組合2種以上使用。The above-mentioned thermosetting agents may be used alone or in combination of two or more.
上述熱硬化劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為1重量份，較佳之上限為50重量份。藉由上述熱硬化劑之含量為該範圍，從而可於不使所獲得之液晶顯示元件用密封劑之塗佈性等變差之情況下使熱硬化性更加優異。上述熱硬化劑之含量之更佳之上限為30重量份。The content of the thermosetting agent is preferably 1 part by weight and 50 parts by weight relative to 100 parts by weight of the curable resin. When the content of the thermosetting agent is within this range, the thermosetting property of the obtained sealant for liquid crystal display elements can be improved without deteriorating the coating property. The more preferred upper limit of the content of the thermosetting agent is 30 parts by weight.
本發明之液晶顯示元件用密封劑較佳為以提高黏度、藉由應力分散效應而進一步提高接著性、改善線膨脹率、提高硬化物之耐濕性等為目的，含有填充劑。又，藉由含有上述填充劑，從而更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。The sealant for liquid crystal display elements of the present invention preferably contains a filler for the purpose of increasing viscosity, further improving adhesion by stress dispersion effect, improving linear expansion rate, and improving moisture resistance of the cured product. In addition, by containing the filler, it is easier to set the compression shear adhesion strength of the cured product to polyimide at 25°C and the storage elastic modulus of the cured product at 25°C to the above ranges.
作為上述填充劑，可使用無機填充劑或有機填充劑。 作為上述無機填充劑，例如可列舉：矽石、滑石、玻璃珠、石棉、石膏、矽藻土、膨潤石、膨潤土、蒙脫石、絹雲母、活性白土、氧化鋁、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、氮化鋁、氮化矽、硫酸鋇、矽酸鈣等。 作為上述有機填充劑，例如可列舉：聚酯微粒子、聚胺酯（polyurethane）微粒子、乙烯系聚合物微粒子、丙烯酸聚合物微粒子等。 上述填充劑可單獨地使用，亦可組合2種以上使用。As the above-mentioned filler, an inorganic filler or an organic filler can be used. As the above-mentioned inorganic filler, for example, silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, aluminum oxide, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc. As the above-mentioned organic filler, for example, polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, etc. The above-mentioned fillers can be used alone or in combination of two or more.
上述填充劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為10重量份，較佳之上限為80重量份。藉由上述填充劑之含量為該範圍，從而使得於不使塗佈性等變差之情況下改善接著性等效果更加優異，且更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。上述填充劑之含量之更佳之下限為30重量份，更佳之上限為60重量份。The content of the filler is preferably 10 parts by weight and 80 parts by weight relative to 100 parts by weight of the curable resin. When the content of the filler is within this range, the effect of improving adhesion is more excellent without deteriorating the coating properties, and it is easier to set the compression shear strength of the cured product to polyimide at 25°C and the storage elastic modulus of the cured product at 25°C within the above range. The lower limit of the content of the filler is more preferably 30 parts by weight and the upper limit is more preferably 60 parts by weight.
本發明之液晶顯示元件用密封劑較佳為含有矽烷偶合劑。上述矽烷偶合劑主要具有作為用於使密封劑與基板等良好地接著之接著助劑之作用。The sealant for liquid crystal display element of the present invention preferably contains a silane coupling agent. The silane coupling agent mainly serves as a bonding aid for making the sealant and the substrate etc. bond well.
作為上述矽烷偶合劑，例如可較好地使用3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷等。該等矽烷偶合劑之提高與基板等之接著性之效果優異，藉由與硬化性樹脂化學鍵結而可抑制硬化性樹脂流出至液晶中。 上述矽烷偶合劑可單獨地使用，亦可組合2種以上使用。As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-butylpropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. can be preferably used. These silane coupling agents are excellent in improving the adhesion with the substrate, etc., and can inhibit the curable resin from flowing out into the liquid crystal by chemically bonding with the curable resin. The above-mentioned silane coupling agents can be used alone or in combination of two or more.
本發明之液晶顯示元件用密封劑100重量份中之上述矽烷偶合劑之含量之較佳之下限為0.1重量份，較佳之上限為10重量份。藉由上述矽烷偶合劑之含量為該範圍，從而抑制液晶污染之發生，且提高接著性之效果更加優異。上述矽烷偶合劑之含量之更佳之下限為0.3重量份，更佳之上限為5重量份。The preferred lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the occurrence of liquid crystal contamination is suppressed, and the effect of improving adhesion is more excellent. The preferred lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the preferred upper limit is 5 parts by weight.
本發明之液晶顯示元件用密封劑亦可含有遮光劑。藉由含有上述遮光劑，從而使得本發明之液晶顯示元件用密封劑可較好地用作遮光密封劑。The sealant for liquid crystal display element of the present invention may also contain a light-shielding agent. By containing the light-shielding agent, the sealant for liquid crystal display element of the present invention can be preferably used as a light-shielding sealant.
作為上述遮光劑，例如可列舉：氧化鐵、鈦黑、苯胺黑、花青黑、富勒烯、碳黑、樹脂被覆型碳黑等。其中，較佳為鈦黑。Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, etc. Among them, titanium black is preferred.
上述鈦黑係相較於對於波長300 nm以上800 nm以下之光之平均透過率，對於紫外線區域附近、尤其是波長370 nm以上450 nm以下之光之透過率更高之物質。即，上述鈦黑係具有如下性質之遮光劑：藉由充分地遮斷可見光區域之波長之光而對本發明之液晶顯示元件用密封劑賦予遮光性，另一方面使紫外線區域附近之波長之光透過。因此，使用能夠藉由上述鈦黑之透過率更高之波長（370 nm以上450 nm以下）之光使得反應開始者作為上述光自由基聚合起始劑，藉此可進一步增強本發明之液晶顯示元件用密封劑之光硬化性。又，作為本發明之液晶顯示元件用密封劑所含有之遮光劑，較佳為高絕緣性之物質，鈦黑亦可較好地作為高絕緣性之遮光劑。 上述鈦黑之每1 μm之光學濃度（OD值）較佳為3以上，更佳為4以上。上述鈦黑之遮光性越高越好，上述鈦黑之OD值之較佳之上限無特別限制，通常為5以下。The titanium black is a substance having a higher transmittance to light near the ultraviolet region, especially to light of wavelengths of 370 nm to 450 nm, than the average transmittance to light of wavelengths of 300 nm to 800 nm. That is, the titanium black is a light-shielding agent having the following properties: it imparts light-shielding properties to the sealant for liquid crystal display elements of the present invention by fully blocking light of wavelengths in the visible light region, while allowing light of wavelengths near the ultraviolet region to pass through. Therefore, by using a substance that can initiate a reaction with light of a wavelength (370 nm to 450 nm) with a higher transmittance of the titanium black as the photo-radical polymerization initiator, the light curing property of the sealant for liquid crystal display elements of the present invention can be further enhanced. Furthermore, the light-shielding agent contained in the sealant for the liquid crystal display element of the present invention is preferably a highly insulating substance, and titanium black can also be preferably used as a highly insulating light-shielding agent. The optical density (OD value) of the titanium black per 1 μm is preferably 3 or more, and more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The upper limit of the OD value of the titanium black is not particularly limited, and is usually 5 or less.
上述鈦黑雖即便未經表面處理亦發揮充分之效果，但亦可使用經表面處理之鈦黑，如表面經偶合劑等有機成分處理者、或經氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等。其中，就可更進一步提高絕緣性之觀點而言，較佳為經有機成分處理者。 又，使用含有上述鈦黑作為遮光劑之本發明之液晶顯示元件用密封劑所製造之液晶顯示元件由於具有充分之遮光性，故而可實現不會發生漏光而具有高對比度、具有優異之影像顯示品質之液晶顯示元件。Although the titanium black mentioned above can fully exert its effect even without surface treatment, titanium black that has been surface treated can also be used, such as titanium black that has been surface treated with an organic component such as a coupling agent, or titanium black that has been coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Among them, from the perspective of further improving the insulation, it is preferably treated with an organic component. In addition, the liquid crystal display element manufactured using the sealant for liquid crystal display elements of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, so it is possible to realize a liquid crystal display element that does not leak light and has a high contrast and excellent image display quality.
作為上述鈦黑之市售品，例如可列舉：三菱綜合材料公司製造之鈦黑、AKO KASEI公司製造之鈦黑等。 作為上述三菱綜合材料公司製造之鈦黑，例如可列舉：12S、13M、13M-C、13R-N、14M-C等。 作為上述AKO KASEI公司製造之鈦黑，例如可列舉：Tilack D等。Examples of commercially available titanium black include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by AKO KASEI Corporation. Examples of titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, and 14M-C. Examples of titanium black manufactured by AKO KASEI Corporation include Tilack D.
上述鈦黑之比表面積之較佳之下限為13 m2 /g，較佳之上限為30 m2 /g，更佳之下限為15 m2 /g，更佳之上限為25 m2 /g。 又，上述鈦黑之體積電阻之較佳之下限為0.5 Ω・cm，較佳之上限為3 Ω・cm，更佳之下限為1 Ω・cm，更佳之上限為2.5 Ω・cm。The preferred lower limit of the specific surface area of the titanium black is 13 m 2 /g, the preferred upper limit is 30 m 2 /g, the more preferred lower limit is 15 m 2 /g, and the more preferred upper limit is 25 m 2 /g. In addition, the preferred lower limit of the volume resistivity of the titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 2.5 Ω·cm.
關於上述遮光劑之一次粒徑，只要為液晶顯示元件之基板間之距離以下，則無特別限定，較佳之下限為1 nm，較佳之上限為5000 nm。藉由上述遮光劑之一次粒徑為該範圍，從而可於不使所獲得之液晶顯示元件用密封劑之塗佈性等變差之情況下使遮光性更加優異。上述遮光劑之一次粒徑之更佳之下限為5 nm，更佳之上限為200 nm，進而較佳之下限為10 nm，進而較佳之上限為100 nm。 再者，上述遮光劑之一次粒徑可使用NICOMP 380ZLS（PARTICLE SIZING SYSTEMS公司製造），使上述遮光劑分散於溶劑（水、有機溶劑等）中而測定。The primary particle size of the light-shielding agent is not particularly limited as long as it is less than the distance between the substrates of the liquid crystal display element. The preferred lower limit is 1 nm and the preferred upper limit is 5000 nm. By having the primary particle size of the light-shielding agent within this range, the light-shielding property of the obtained liquid crystal display element sealant can be made more excellent without deteriorating the coating property of the obtained liquid crystal display element sealant. The preferred lower limit of the primary particle size of the light-shielding agent is 5 nm, the preferred upper limit is 200 nm, the further preferred lower limit is 10 nm, and the further preferred upper limit is 100 nm. The primary particle size of the sunscreen can be measured by dispersing the sunscreen in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
本發明之液晶顯示元件用密封劑100重量份中之上述遮光劑之含量之較佳之下限為5重量份，較佳之上限為80重量份。藉由上述遮光劑之含量為該範圍，從而可於不使所獲得之液晶顯示元件用密封劑之接著性、硬化後之強度、及繪圖性降低之情況下，進一步發揮提高遮光性之效果。上述遮光劑之含量之更佳之下限為10重量份，更佳之上限為70重量份，進而較佳之下限為30重量份，進而較佳之上限為60重量份。The lower limit of the content of the above-mentioned light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is preferably 5 parts by weight, and the upper limit is preferably 80 parts by weight. By having the content of the above-mentioned light-shielding agent within this range, the effect of improving the light-shielding property can be further exerted without reducing the adhesion, strength after curing, and drawing properties of the sealant for liquid crystal display elements obtained. The lower limit of the content of the above-mentioned light-shielding agent is more preferably 10 parts by weight, the upper limit is more preferably 70 parts by weight, the lower limit is more preferably 30 parts by weight, and the upper limit is more preferably 60 parts by weight.
本發明之液晶顯示元件用密封劑亦可視需要進而含有應力緩和劑、反應性稀釋劑、觸變劑、間隔物、硬化促進劑、消泡劑、調平劑、聚合抑制劑等添加劑。The sealant for liquid crystal display elements of the present invention may further contain additives such as stress relaxants, reactive diluents, thixotropic agents, spacers, curing accelerators, defoaming agents, leveling agents, polymerization inhibitors, etc. as needed.
作為製造本發明之液晶顯示元件用密封劑之方法，例如可列舉以下方法等：使用勻相分散機、均質攪拌機、萬能攪拌機、行星式混合機、捏合機、三輥研磨機等混合機，將硬化性樹脂、聚合起始劑及/或熱硬化劑、及視需要所添加之矽烷偶合劑等添加劑進行混合。As a method for producing the sealant for liquid crystal display elements of the present invention, for example, the following method can be cited: using a mixer such as a homogenizer, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll grinder, etc., a curable resin, a polymerization initiator and/or a thermosetting agent, and additives such as a silane coupling agent added as needed are mixed.
藉由向本發明之液晶顯示元件用密封劑中摻合導電性微粒子，從而可製造上下導通材料。此種含有本發明之液晶顯示元件用密封劑與導電性微粒子之上下導通材料亦為本發明之一。By mixing conductive microparticles into the sealant for liquid crystal display elements of the present invention, a vertical conductive material can be produced. Such a vertical conductive material containing the sealant for liquid crystal display elements of the present invention and conductive microparticles is also one of the present invention.
作為上述導電性微粒子，可使用金屬球、於樹脂微粒子之表面形成有導電金屬層者等。其中，於樹脂微粒子之表面形成有導電金屬層者藉由樹脂微粒子之優異之彈性而能夠於不損傷透明基板等之情況下實現導電連接，因此較佳。As the conductive particles, metal spheres, resin particles with a conductive metal layer formed on the surface, etc. can be used. Among them, resin particles with a conductive metal layer formed on the surface are preferred because they can achieve conductive connection without damaging a transparent substrate due to the excellent elasticity of the resin particles.
使用本發明之液晶顯示元件用密封劑或本發明之上下導通材料而成之液晶顯示元件亦為本發明之一。A liquid crystal display element made by using the sealant for liquid crystal display element of the present invention or the top-bottom conductive material of the present invention is also one of the present invention.
本發明之液晶顯示元件用密封劑可較好地用於利用液晶滴下法之液晶顯示元件之製造。作為利用液晶滴下法製造本發明之液晶顯示元件之方法，例如可列舉以下方法等。 首先，進行以下步驟：藉由網版印刷、滴塗塗佈等於基板上塗佈本發明之液晶顯示元件用密封劑，形成框狀之密封圖案。繼而，進行以下步驟：於本發明之液晶顯示元件用密封劑等未硬化之狀態下，將液晶之微滴滴下塗佈於密封圖案之框內整個面，其後立即使另一基板重合。其後，進行對密封圖案部分照射紫外線等光使密封劑暫時硬化之步驟、及對暫時硬化之密封劑進行加熱使其正式硬化之步驟，藉由以上方法可獲得液晶顯示元件。 發明之效果The sealant for liquid crystal display elements of the present invention can be preferably used for manufacturing liquid crystal display elements using the liquid crystal dripping method. As a method for manufacturing the liquid crystal display element of the present invention using the liquid crystal dripping method, for example, the following method can be listed. First, the following steps are performed: the sealant for liquid crystal display elements of the present invention is applied on the substrate by screen printing, dripping, etc. to form a frame-shaped sealing pattern. Then, the following steps are performed: in the uncured state of the sealant for liquid crystal display elements of the present invention, droplets of liquid crystal are applied to the entire surface of the frame of the sealing pattern, and then another substrate is immediately overlapped. Thereafter, a step of temporarily curing the sealant by irradiating the sealing pattern portion with ultraviolet light or the like, and a step of heating the temporarily cured sealant to formally cure it is performed. By the above method, a liquid crystal display element can be obtained. Effect of the invention
根據本發明，可提供一種即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。According to the present invention, a sealant for a liquid crystal display element can be provided which can maintain excellent adhesion even when processed into a special shape. In addition, according to the present invention, a top-bottom conductive material and a liquid crystal display element formed by using the sealant for a liquid crystal display element can be provided.
以下，揭示實施例對本發明進而詳細地進行說明，但本發明並非僅限定於該等實施例。The present invention is described in further detail below with reference to the disclosed embodiments, but the present invention is not limited to the embodiments.
（實施例1〜8、比較例1〜4） 依據表1中所記載之摻合比，使用行星式攪拌機（Thinky公司製造，「去泡攪拌太郎」）將各材料混合，其後進而使用三輥研磨機進行混合，藉此製備實施例1〜8及比較例1〜4之液晶顯示元件用密封劑。 於長度45 mm、寬度25 mm、厚度0.7 mm之2片聚醯亞胺基板之一基板上以接著時之直徑為3 mm之方式點塗所獲得之液晶顯示元件用密封劑。使另一聚醯亞胺基板以於長邊方向上錯開10 mm之方式經由密封劑重合於點塗有密封劑之聚醯亞胺基板。其後，使用金屬鹵化物燈等照射100 mW/cm2 之紫外線（波長365 nm）30秒鐘後，於120℃加熱1小時，而使密封劑硬化，獲得試片。對所獲得之試片，使用自動立體測圖儀AGX（島津製作所製造），藉由依據JIS K 6852之常態試驗，測定於25℃之壓縮剪切接著強度。將結果示於表1。 又，對所獲得之各液晶顯示元件用密封劑，使用金屬鹵化物燈照射100 mW/cm2 之紫外線（波長365 nm）30秒鐘後，於120℃加熱1小時，而獲得硬化物。對所獲得之硬化物，使用動態黏彈性測定裝置，以試片寬度5 mm、厚度0.35 mm、抓持寬度25 mm、升溫速度10℃/分鐘、頻率10 Hz之條件測定儲存彈性模數。又，求出損耗正切（tanδ）之極大值之溫度作為玻璃轉移溫度。使用DVA-200（IT計測制御公司製造）作為上述動態黏彈性測定裝置。將儲存彈性模數及玻璃轉移溫度之測定結果示於表1。(Examples 1 to 8, Comparative Examples 1 to 4) The materials were mixed according to the blending ratio listed in Table 1 using a planetary mixer (manufactured by Thinky, "Defoaming Mixer Taro"), and then further mixed using a three-roll grinder to prepare the sealants for liquid crystal display elements of Examples 1 to 8 and Comparative Examples 1 to 4. The sealant for liquid crystal display elements obtained was dotted on one of two polyimide substrates having a length of 45 mm, a width of 25 mm, and a thickness of 0.7 mm in such a manner that the diameter when connected was 3 mm. The other polyimide substrate was overlapped with the polyimide substrate dotted with the sealant through the sealant in such a manner that the gap was 10 mm in the long side direction. After that, the sealant was cured by irradiating with ultraviolet light (wavelength 365 nm) of 100 mW/cm 2 for 30 seconds using a metal halide lamp, and then heated at 120°C for 1 hour to obtain a test piece. The compression shear strength of the obtained test piece at 25°C was measured by a normal test in accordance with JIS K 6852 using an automatic stereogrammer AGX (manufactured by Shimadzu Corporation). The results are shown in Table 1. In addition, the sealant for each obtained liquid crystal display element was irradiated with ultraviolet light (wavelength 365 nm) of 100 mW/cm 2 for 30 seconds using a metal halide lamp, and then heated at 120°C for 1 hour to obtain a cured product. The obtained hardened material was tested for storage elastic modulus using a dynamic viscoelasticity measuring device under the conditions of specimen width 5 mm, thickness 0.35 mm, grip width 25 mm, heating rate 10°C/min, and frequency 10 Hz. In addition, the temperature at which the maximum value of the loss tangent (tanδ) was obtained was taken as the glass transition temperature. DVA-200 (manufactured by IT Measurement Control Co., Ltd.) was used as the above-mentioned dynamic viscoelasticity measuring device. The test results of storage elastic modulus and glass transition temperature are shown in Table 1.
＜評價＞ 對實施例及比較例中所獲得之各液晶顯示元件用密封劑進行以下之評價。將結果示於表1。<Evaluation> Each of the sealants for liquid crystal display elements obtained in the examples and comparative examples was evaluated as follows. The results are shown in Table 1.
（異型加工時之接著性） 使間隔物微粒子（積水化學工業公司製造，「Micropearl SI-H050」）1重量份分散於實施例及比較例中所獲得之各液晶顯示元件用密封劑100重量份。繼而，將分散有間隔物微粒子之密封劑滴塗塗佈於2片附有經過摩擦處理之配向膜及透明電極之基板（長度75 mm、寬度75 mm、厚度0.7 mm）之一基板上。密封劑之塗佈形狀為與於長度45 mm、寬度55 mm之範圍之上部具有長度5 mm、寬度10 mm之邊緣部分之液晶顯示元件之顯示區域對應的線寬0.7 mm之框狀。繼而，將液晶（Chisso公司製造，「JC-5004LA」）之微滴滴下塗佈於密封劑之框內整個面，其後立即使另一基板貼合，使用金屬鹵化物燈對密封劑部分照射100 mW/cm2 之紫外線（波長365 nm）30秒鐘後，於120℃加熱1小時，藉此獲得液晶顯示元件。關於實施例及比較例中所獲得之各液晶顯示元件用密封劑，分別各製作10單元液晶顯示元件。 對所獲得之各液晶顯示元件，進行使用微型研磨機對密封周邊及邊緣部分進行加工直至距密封邊界1 mm為止之研磨試驗。研磨試驗後，將全部單元均未發生因剝落或破裂而造成之液晶漏液之情形設為「◎」、將1單元以上且未達4單元之液晶顯示元件發生液晶漏液之情形設為「○」、將4單元以上且未達7單元之液晶顯示元件發生液晶漏液之情形設為「Δ」、將7單元以上之液晶顯示元件發生液晶漏液之情形設為「×」，以此評價接著性。(Adhesion during irregular processing) 1 part by weight of spacer particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Industries, Ltd.) was dispersed in 100 parts by weight of the sealant for each liquid crystal display element obtained in the embodiment and the comparative example. Then, the sealant dispersed with the spacer particles was drop-coated on one of the two substrates (length 75 mm, width 75 mm, thickness 0.7 mm) with a friction-treated alignment film and a transparent electrode. The sealant was applied in a frame shape with a line width of 0.7 mm corresponding to the display area of the liquid crystal display element having an edge portion with a length of 5 mm and a width of 10 mm on the upper part of a range of a length of 45 mm and a width of 55 mm. Then, droplets of liquid crystal (manufactured by Chisso, "JC-5004LA") were applied to the entire surface of the sealant frame, and then another substrate was immediately attached. The sealant part was irradiated with ultraviolet light (wavelength 365 nm) of 100 mW/ cm2 for 30 seconds using a metal halide lamp, and then heated at 120°C for 1 hour to obtain a liquid crystal display element. For each of the sealants for liquid crystal display elements obtained in the embodiment and the comparative example, 10 units of liquid crystal display elements were produced. For each of the obtained liquid crystal display elements, a grinding test was performed using a micro-grinder to process the seal periphery and edge parts until 1 mm from the seal boundary. After the grinding test, the situation where all units had no liquid crystal leakage due to peeling or cracking was marked as "◎", the situation where more than 1 unit but less than 4 units of liquid crystal display elements had liquid crystal leakage was marked as "○", the situation where more than 4 units but less than 7 units of liquid crystal display elements had liquid crystal leakage was marked as "Δ", and the situation where more than 7 units of liquid crystal display elements had liquid crystal leakage was marked as "×", so as to evaluate the adhesion.
[表1]
根據本發明，可提供一種即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。According to the present invention, a sealant for a liquid crystal display element can be provided which can maintain excellent adhesion even when processed into a special shape. In addition, according to the present invention, a top-bottom conductive material and a liquid crystal display element formed by using the sealant for a liquid crystal display element can be provided.
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- 2019-07-11 JP JP2019545829A patent/JP6835980B2/en active Active
- 2019-07-11 WO PCT/JP2019/027484 patent/WO2020013272A1/en active Application Filing
- 2019-07-12 TW TW108124623A patent/TWI848961B/en active
-
2021
- 2021-01-28 JP JP2021012037A patent/JP2021073530A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005181986A (en) * | 2003-11-28 | 2005-07-07 | Shin Etsu Chem Co Ltd | Sealing agent composition for liquid crystal display element |
| TW201728668A (en) * | 2015-11-09 | 2017-08-16 | Sekisui Chemical Co Ltd | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020013272A1 (en) | 2020-08-06 |
| JP6835980B2 (en) | 2021-02-24 |
| WO2020013272A1 (en) | 2020-01-16 |
| TW202007703A (en) | 2020-02-16 |
| JP2021073530A (en) | 2021-05-13 |
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