KR20210082126A - Sealing agent for liquid crystal display elements, vertical conduction material, and liquid crystal display element - Google Patents
Sealing agent for liquid crystal display elements, vertical conduction material, and liquid crystal display element Download PDFInfo
- Publication number
- KR20210082126A KR20210082126A KR1020207019760A KR20207019760A KR20210082126A KR 20210082126 A KR20210082126 A KR 20210082126A KR 1020207019760 A KR1020207019760 A KR 1020207019760A KR 20207019760 A KR20207019760 A KR 20207019760A KR 20210082126 A KR20210082126 A KR 20210082126A
- Authority
- KR
- South Korea
- Prior art keywords
- liquid crystal
- crystal display
- meth
- acrylate
- compound
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 119
- 238000007789 sealing Methods 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 title description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 177
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 239000010419 fine particle Substances 0.000 claims description 17
- 125000003277 amino group Chemical group 0.000 claims description 6
- 238000011109 contamination Methods 0.000 abstract description 16
- 208000034189 Sclerosis Diseases 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 116
- 239000004593 Epoxy Substances 0.000 description 80
- -1 acrylic compound Chemical class 0.000 description 49
- 239000000126 substance Substances 0.000 description 22
- 239000000758 substrate Substances 0.000 description 19
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 17
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 13
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229920001187 thermosetting polymer Polymers 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011859 microparticle Substances 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 125000006850 spacer group Chemical group 0.000 description 7
- 238000012719 thermal polymerization Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 230000009257 reactivity Effects 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 2
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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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- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- 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
-
- 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
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- G—PHYSICS
- 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
- G02F1/13398—Spacer materials; Spacer properties
Abstract
본 발명은, 장파장의 광에 대한 경화성이 우수하고, 또한 저액정 오염성이 우수한 액정 표시 소자용 시일제를 제공하는 것을 목적으로 한다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공하는 것을 목적으로 한다.
본 발명은, 경화성 수지와 광중합 개시제를 함유하는 액정 표시 소자용 시일제로서, 상기 광중합 개시제는, 하기 식 (1) 로 나타내는 화합물을 함유하는 액정 표시 소자용 시일제이다.
식 (1) 중, R1 및 R8 은 각각 독립적으로 수소 원자, 또는, 티오크산톤 골격의 방향 고리와의 결합 위치에 질소 원자를 갖는 기이고, R1 및 R8 중 적어도 일방은 그 질소 원자를 갖는 기이다. R2 및 R7 은 각각 독립적으로 수소 원자 또는 수산기이고, R2 및 R7 중 적어도 일방은 수산기이다. R3 ∼ R6 은 각각 독립적으로 수소 원자 또는 임의의 치환기이다.An object of this invention is to provide the sealing compound for liquid crystal display elements excellent in sclerosis|hardenability with respect to long-wavelength light, and also excellent in low-liquid-crystal contamination property. Moreover, this invention aims at providing the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
This invention is a sealing compound for liquid crystal display elements containing curable resin and a photoinitiator, Comprising: The said photoinitiator is a sealing compound for liquid crystal display elements containing the compound represented by following formula (1).
In formula (1), R 1 and R 8 are each independently a hydrogen atom or a group having a nitrogen atom at the bonding position with the aromatic ring of the thioxanthone skeleton, and at least one of R 1 and R 8 is the nitrogen atom. It is a group with atoms. R 2 and R 7 are each independently a hydrogen atom or a hydroxyl group, and at least one of R 2 and R 7 is a hydroxyl group. R 3 to R 6 are each independently a hydrogen atom or an optional substituent.
Description
본 발명은, 장파장의 광에 대한 경화성이 우수하고, 또한 저액정 오염성이 우수한 액정 표시 소자용 시일제에 관한 것이다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자에 관한 것이다.This invention is excellent in sclerosis|hardenability with respect to long-wavelength light, and relates to the sealing compound for liquid crystal display elements excellent in low-liquid-crystal contamination property. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
최근, 액정 표시 셀 등의 액정 표시 소자의 제조 방법으로는, 택트 타임 단축, 사용 액정량의 최적화와 같은 관점에서, 특허문헌 1, 특허문헌 2 에 개시되어 있는 바와 같은 광열 병용 경화형의 시일제를 사용한 적하 공법으로 불리는 액정 적하 방식이 이용되고 있다.In recent years, as a manufacturing method of liquid crystal display elements, such as a liquid crystal display cell, the sealing compound of the light-and-heat combination hardening type which is disclosed by patent document 1, patent document 2 from viewpoints such as tact time shortening and optimization of the amount of liquid crystal used The liquid crystal dropping method called the used dripping method is used.
적하 공법에서는, 먼저, 2 장의 전극이 형성된 투명 기판 중 일방에, 디스펜스에 의해 프레임상의 시일 패턴을 형성한다. 이어서, 시일제가 미경화된 상태에서 액정의 미소적 (微小滴) 을 투명 기판의 프레임 내 전체면에 적하하고, 바로 타방의 투명 기판을 첩합하고, 시일부에 자외선 등의 광을 조사하여 임시 경화를 실시한다. 그 후, 액정 어닐시에 가열하여 본 경화를 실시하여, 액정 표시 소자를 제조한다. 기판의 첩합을 감압하에서 실시하도록 하면, 매우 높은 효율로 액정 표시 소자를 제조할 수 있어, 현재 이 적하 공법이 액정 표시 소자의 제조 방법의 주류가 되고 있다.In the dripping construction method, first, a frame-like seal pattern is formed by dispensing in one of the transparent substrates in which the electrode of 2 sheets was formed. Next, in the state in which the sealing compound was not hardened, the microdroplet of a liquid crystal is dripped at the whole surface inside the frame of a transparent substrate, the other transparent substrate is immediately bonded, irradiating light, such as an ultraviolet-ray, to a sealing part, and hardening temporarily. carry out Then, it heats at the time of liquid crystal annealing, main hardening is performed and a liquid crystal display element is manufactured. When bonding of a board|substrate is made to perform under reduced pressure, a liquid crystal display element can be manufactured with very high efficiency, and this dripping construction method is becoming the mainstream of the manufacturing method of a liquid crystal display element now.
휴대 전화, 휴대 게임기 등, 각종 액정 패널이 형성된 모바일 기기가 보급되어 있는 현대에 있어서, 장치의 소형화는 가장 요구되고 있는 과제이다. 장치의 소형화의 수법으로는, 액정 표시부의 프레임 협소화를 들 수 있으며, 예를 들어, 시일부의 위치를 블랙 매트릭스 아래에 배치하는 것이 실시되고 있다 (이하, 프레임 협소 설계라고도 한다).In the present age in which mobile devices with various liquid crystal panels, such as mobile phones and portable game machines, are widespread, miniaturization of devices is the most demanded subject. As a method of reducing the size of the device, a frame narrowing of the liquid crystal display part is mentioned, for example, arranging the position of the seal part under the black matrix (hereinafter also referred to as frame narrow design).
그러나, 프레임 협소 설계에서는 시일제가 블랙 매트릭스의 바로 아래에 배치되기 때문에, 적하 공법을 실시하면, 시일제를 광경화시킬 때에 조사한 광이 차단되어, 시일제의 내부까지 광이 도달하지 않아 경화가 불충분해진다는 문제가 있었다. 이와 같이 시일제의 경화가 불충분해지면, 미경화의 시일제 성분이 액정 중에 용출되어, 액정 오염이 발생한다는 문제가 있었다.However, in a frame narrow design, since the sealing compound is arrange|positioned just below the black matrix, when the dripping method is implemented, the light irradiated when making a sealing compound photocuring is blocked, light does not reach the inside of a sealing compound, hardening is insufficient. There was a problem with it being done. Thus, when hardening of a sealing compound became inadequate, the non-hardened sealing compound component eluted in a liquid crystal, and there existed a problem that a liquid-crystal contamination generate|occur|produced.
또, 통상적으로 시일제를 광경화시키는 방법으로서 자외선의 조사가 실시되고 있는데, 특히 액정 적하 공법에 있어서는, 액정을 적하한 후에 시일제를 경화시키기 때문에, 자외선을 조사함으로써 액정이 열화된다는 문제가 있었다. 그래서, 자외선에 의한 액정의 열화를 방지하기 위해, 가시광 영역의 장파장의 광에 대한 반응성이 우수한 광중합 개시제를 배합하고, 컷 필터 등을 통한 장파장의 광에 의해 광경화시키는 것이 실시되고 있다.Moreover, although irradiation of an ultraviolet-ray is normally performed as a method of photocuring a sealing compound, especially in the liquid crystal dropping method, in order to harden a sealing compound after dripping a liquid crystal, there existed a problem that a liquid crystal deteriorated by irradiating an ultraviolet-ray. Therefore, in order to prevent deterioration of the liquid crystal by ultraviolet rays, a photopolymerization initiator excellent in reactivity to long-wavelength light in the visible region is blended and photocured by long-wavelength light through a cut filter or the like.
본 발명은, 장파장의 광에 대한 경화성이 우수하고, 또한 저액정 오염성이 우수한 액정 표시 소자용 시일제를 제공하는 것을 목적으로 한다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공하는 것을 목적으로 한다.An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in sclerosis|hardenability with respect to long-wavelength light, and is excellent in low-liquid-crystal contamination property. Moreover, this invention aims at providing the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
본 발명은, 경화성 수지와 광중합 개시제를 함유하는 액정 표시 소자용 시일제로서, 상기 광중합 개시제는, 하기 식 (1) 로 나타내는 화합물을 함유하는 액정 표시 소자용 시일제이다.This invention is a sealing compound for liquid crystal display elements containing curable resin and a photoinitiator, Comprising: The said photoinitiator is a sealing compound for liquid crystal display elements containing the compound represented by following formula (1).
[화학식 1][Formula 1]
식 (1) 중, R1 및 R8 은 각각 독립적으로 수소 원자, 또는, 티오크산톤 골격의 방향 고리와의 결합 위치에 질소 원자를 갖는 기이고, R1 및 R8 중 적어도 일방은 그 질소 원자를 갖는 기이다. R2 및 R7 은 각각 독립적으로 수소 원자 또는 수산기이고, R2 및 R7 중 적어도 일방은 수산기이다. R3 ∼ R6 은 각각 독립적으로 수소 원자 또는 임의의 치환기이다.In formula (1), R 1 and R 8 are each independently a hydrogen atom or a group having a nitrogen atom at the bonding position with the aromatic ring of the thioxanthone skeleton, and at least one of R 1 and R 8 is the nitrogen atom. It is a group with atoms. R 2 and R 7 are each independently a hydrogen atom or a hydroxyl group, and at least one of R 2 and R 7 is a hydroxyl group. R 3 to R 6 are each independently a hydrogen atom or an optional substituent.
이하에 본 발명을 상세히 서술한다.Hereinafter, the present invention will be described in detail.
액정 표시 소자용 시일제에 장파장의 광에 대한 반응성이 우수한 광중합 개시제를 배합하고, 장파장의 광에 의해 광경화시킨 경우, 시일제에 의해 액정이 오염되는 경우가 있다는 문제가 있었다. 그래서 본 발명자는, 시일제에 사용하는 광중합 개시제로서 특정한 구조를 갖는 화합물을 사용하는 것을 검토하였다. 그 결과, 장파장의 광에 대한 경화성이 우수하고, 또한 저액정 오염성이 우수한 액정 표시 소자용 시일제를 얻을 수 있는 것을 알아내어, 본 발명을 완성시키기에 이르렀다.When the photoinitiator excellent in the reactivity with respect to long-wavelength light was mix|blended with the sealing compound for liquid crystal display elements, and it was photocured by long-wavelength light, there existed a problem that a liquid crystal may be contaminated with a sealing compound. Then, this inventor examined using the compound which has a specific structure as a photoinitiator used for a sealing compound. As a result, it was excellent in sclerosis|hardenability with respect to long-wavelength light, and it discovered that the sealing compound for liquid crystal display elements excellent in low-liquid-crystal contamination property could be obtained, and came to complete this invention.
본 발명의 액정 표시 소자용 시일제는, 광중합 개시제를 함유한다.The sealing compound for liquid crystal display elements of this invention contains a photoinitiator.
상기 광중합 개시제는, 상기 식 (1) 로 나타내는 화합물을 함유한다. 상기 광중합 개시제로서 상기 식 (1) 로 나타내는 화합물을 사용함으로써, 본 발명의 액정 표시 소자용 시일제는, 장파장의 광에 대한 경화성이 우수하고, 또한 저액정 오염성이 우수한 것이 된다.The said photoinitiator contains the compound represented by said Formula (1). By using the compound represented by the said Formula (1) as said photoinitiator, the sealing compound for liquid crystal display elements of this invention is excellent in sclerosis|hardenability with respect to long-wavelength light, and it becomes the thing excellent in low-liquid-crystal contamination property.
상기 식 (1) 중, R1 및 R8 은 각각 독립적으로 수소 원자, 또는, 티오크산톤 골격의 방향 고리와의 결합 위치에 질소 원자를 갖는 기이고, R1 및 R8 중 적어도 일방은 그 질소 원자를 갖는 기이다. R1 및 R8 중 적어도 일방이 상기 질소 원자를 갖는 기임으로써, 상기 식 (1) 로 나타내는 화합물은, 장파장의 광에 대한 반응성이 우수한 것이 된다.In the formula (1), R 1 and R 8 are each independently a hydrogen atom or a group having a nitrogen atom at the bonding position with the aromatic ring of the thioxanthone skeleton, and at least one of R 1 and R 8 is It is a group having a nitrogen atom. When at least one of R 1 and R 8 is a group having the nitrogen atom, the compound represented by the formula (1) is excellent in reactivity to long-wavelength light.
상기 질소 원자를 갖는 기로는, 예를 들어, 아미노기, 니트로기 등을 들 수 있다. 그 중에서도, 아미노기가 바람직하다.Examples of the group having a nitrogen atom include an amino group and a nitro group. Especially, an amino group is preferable.
상기 아미노기로는, 예를 들어, -NH2 기, -NH(CH3) 기, -NH(C2H5) 기, -N(CH3)2 기, -N(C2H5)2 기 등을 들 수 있다.Examples of the amino group include -NH 2 group, -NH(CH 3 ) group, -NH(C 2 H 5 ) group, -N(CH 3 ) 2 group, -N(C 2 H 5 ) 2 group and the like.
상기 식 (1) 중, R2 및 R7 은 각각 독립적으로 수소 원자 또는 수산기이고, R2 및 R7 중 적어도 일방은 수산기이다. R2 및 R7 중 적어도 일방이 수산기임으로써, 상기 식 (1) 로 나타내는 화합물은, 저액정 오염성이 우수한 것이 된다.In said formula (1), R<2> and R<7> are each independently a hydrogen atom or a hydroxyl group, and at least one of R<2> and R<7> is a hydroxyl group. When at least one of R 2 and R 7 is a hydroxyl group, the compound represented by the formula (1) is excellent in low-liquid-crystal fouling properties.
상기 식 (1) 중, R3 ∼ R6 은 각각 독립적으로 수소 원자 또는 임의의 치환기이다.In the formula (1), R 3 to R 6 are each independently a hydrogen atom or an optional substituent.
상기 식 (1) 중, R3 ∼ R6 이 임의의 치환기인 경우의 당해 치환기로는, 예를 들어, 아미노기, 니트로기 등을 들 수 있다.In said Formula (1), as said substituent in case R<3> -R<6> is an arbitrary substituent, an amino group, a nitro group, etc. are mentioned, for example.
상기 식 (1) 로 나타내는 화합물은, 장파장의 광에 대한 반응성 및 저액정 오염성이 보다 우수한 점에서, R1 이 상기 질소 원자를 갖는 기이고, 또한 R2 가 수산기인 화합물인 것이 바람직하고, 하기 식 (2) ∼ (7) 로 나타내는 화합물이 보다 바람직하다. The compound represented by the formula (1) is preferably a compound in which R 1 is a group having the nitrogen atom, and R 2 is a hydroxyl group, from the viewpoint of more excellent reactivity to long-wavelength light and low liquid crystal contamination, Compounds represented by formulas (2) to (7) are more preferable.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
상기 식 (1) 로 나타내는 화합물은, 장파장의 광에 대한 반응성이 우수하기 때문에, 광경화성을 유지할 수 있는 범위에서 함유량을 줄임으로써, 얻어지는 액정 표시 소자용 시일제가 저액정 오염성이 보다 우수한 것이 된다.Since the compound represented by said Formula (1) is excellent in the reactivity with respect to long-wavelength light, the sealing compound for liquid crystal display elements obtained by reducing content in the range which can maintain photocurability becomes the thing excellent in low-liquid-crystal contamination property.
상기 식 (1) 로 나타내는 화합물의 함유량은, 경화성 수지 100 중량부에 대하여, 바람직한 하한이 0.05 중량부, 바람직한 상한이 2.0 중량부이다. 상기 식 (1) 로 나타내는 화합물의 함유량이 0.05 중량부 이상임으로써, 얻어지는 액정 표시 소자용 시일제가 장파장의 광에 대한 경화성이 보다 우수한 것이 된다. 상기 식 (1) 로 나타내는 화합물의 함유량이 2.0 중량부 이하임으로써, 얻어지는 액정 표시 소자용 시일제가 저액정 오염성이 보다 우수한 것이 된다. 상기 식 (1) 로 나타내는 화합물의 함유량의 보다 바람직한 하한은 0.1 중량부, 보다 바람직한 상한은 1.0 중량부이다.As for content of the compound represented by said Formula (1), with respect to 100 weight part of curable resin, a preferable minimum is 0.05 weight part, and a preferable upper limit is 2.0 weight part. When content of the compound represented by said Formula (1) is 0.05 weight part or more, the sealing compound for liquid crystal display elements obtained becomes the thing more excellent in sclerosis|hardenability with respect to long-wavelength light. When content of the compound represented by said Formula (1) is 2.0 weight part or less, the sealing compound for liquid crystal display elements obtained becomes the thing more excellent in low-liquid-crystal contamination property. A more preferable minimum of content of the compound represented by said Formula (1) is 0.1 weight part, and a more preferable upper limit is 1.0 weight part.
본 발명의 액정 표시 소자용 시일제는, 경화성 수지를 함유한다.The sealing compound for liquid crystal display elements of this invention contains curable resin.
상기 경화성 수지는, (메트)아크릴 화합물을 함유하는 것이 바람직하다.It is preferable that the said curable resin contains a (meth)acrylic compound.
상기 (메트)아크릴 화합물로는, 예를 들어, (메트)아크릴산에스테르 화합물, 에폭시(메트)아크릴레이트, 우레탄(메트)아크릴레이트 등을 들 수 있다. 그 중에서도, 에폭시(메트)아크릴레이트가 바람직하다. 또, 상기 (메트)아크릴 화합물은, 반응성의 관점에서 1 분자 중에 (메트)아크릴로일기를 2 개 이상 갖는 것이 바람직하다.As said (meth)acrylic compound, a (meth)acrylic acid ester compound, epoxy (meth)acrylate, urethane (meth)acrylate, etc. are mentioned, for example. Especially, epoxy (meth)acrylate is preferable. Moreover, it is preferable that the said (meth)acryl compound has two or more (meth)acryloyl groups in 1 molecule from a reactive viewpoint.
또한, 본 명세서에 있어서, 상기「(메트)아크릴」이란, 아크릴 또는 메타크릴을 의미하고, 상기「(메트)아크릴 화합물」이란, (메트)아크릴로일기를 갖는 화합물을 의미하고, 상기「(메트)아크릴로일」이란, 아크릴로일 또는 메타크릴로일을 의미한다. 또, 상기「(메트)아크릴레이트」란, 아크릴레이트 또는 메타크릴레이트를 의미한다. 또한, 상기「에폭시(메트)아크릴레이트」란, 에폭시 화합물 중의 모든 에폭시기를 (메트)아크릴산과 반응시킨 화합물인 것을 나타낸다.In addition, in this specification, the said "(meth)acryl" means acryl or methacryl, and the said "(meth)acryl compound" means a compound having a (meth)acryloyl group, and the "( Meth)acryloyl" means acryloyl or methacryloyl. In addition, the said "(meth)acrylate" means an acrylate or a methacrylate. In addition, the said "epoxy (meth)acrylate" shows that it is the compound which made all the epoxy groups in an epoxy compound react with (meth)acrylic acid.
상기 (메트)아크릴산에스테르 화합물 중 단관능의 것으로는, 예를 들어, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, t-부틸(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, n-옥틸(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 이소노닐(메트)아크릴레이트, 이소데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 이소미리스틸(메트)아크릴레이트, 스테아릴(메트)아크릴레이트, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 비시클로펜테닐(메트)아크릴레이트, 벤질(메트)아크릴레이트, 2-메톡시에틸(메트)아크릴레이트, 2-에톡시에틸(메트)아크릴레이트, 2-부톡시에틸(메트)아크릴레이트, 2-페녹시에틸(메트)아크릴레이트, 메톡시에틸렌글리콜(메트)아크릴레이트, 메톡시폴리에틸렌글리콜(메트)아크릴레이트, 페녹시디에틸렌글리콜(메트)아크릴레이트, 페녹시폴리에틸렌글리콜(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, 에틸카르비톨(메트)아크릴레이트, 2,2,2-트리플루오로에틸(메트)아크릴레이트, 2,2,3,3-테트라플루오로프로필(메트)아크릴레이트, 1H,1H,5H-옥타플루오로펜틸(메트)아크릴레이트, 이미드(메트)아크릴레이트, 디메틸아미노에틸(메트)아크릴레이트, 디에틸아미노에틸(메트)아크릴레이트, 2-(메트)아크릴로일옥시에틸숙신산, 2-(메트)아크릴로일옥시에틸헥사하이드로프탈산, 2-(메트)아크릴로일옥시에틸 2-하이드록시프로필프탈레이트, 2-(메트)아크릴로일옥시에틸포스페이트, 글리시딜(메트)아크릴레이트 등을 들 수 있다.Among the (meth)acrylic acid ester compounds, the monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 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, isomyristyl (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, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl ( Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl ( Meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H,5H-octafluoropentyl (meth)acrylate, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2- (meth)acryloyloxy Ethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-hydroxypropylphthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl ( meth)acrylate and the like.
또, 상기 (메트)아크릴산에스테르 화합물 중 2 관능의 것으로는, 예를 들어, 1,3-부탄디올디(메트)아크릴레이트, 1,4-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 1,9-노난디올디(메트)아크릴레이트, 1,10-데칸디올디(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 테트라에틸렌글리콜디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 2-n-부틸-2-에틸-1,3-프로판디올디(메트)아크릴레이트, 디프로필렌글리콜디(메트)아크릴레이트, 트리프로필렌글리콜디(메트)아크릴레이트, 폴리프로필렌글리콜디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 에틸렌옥사이드 부가 비스페놀 A 디(메트)아크릴레이트, 프로필렌옥사이드 부가 비스페놀 A 디(메트)아크릴레이트, 에틸렌옥사이드 부가 비스페놀 F 디(메트)아크릴레이트, 디메틸올디시클로펜타디에닐디(메트)아크릴레이트, 에틸렌옥사이드 변성 이소시아누르산디(메트)아크릴레이트, 2-하이드록시-3-(메트)아크릴로일옥시프로필(메트)아크릴레이트, 카보네이트디올디(메트)아크릴레이트, 폴리에테르디올디(메트)아크릴레이트, 폴리에스테르디올디(메트)아크릴레이트, 폴리카프로락톤디올디(메트)아크릴레이트, 폴리부타디엔디올디(메트)아크릴레이트 등을 들 수 있다.Moreover, as a bifunctional thing of the said (meth)acrylic acid ester compound, 1, 3- butanediol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, and 1, 6- hexanediol are, for example. Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylic rate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate ) acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethyloldicyclopentadienyldi(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth)acrylate, 2-hydroxy- 3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth)acrylate, polybutadienediol di(meth)acrylate, etc. are mentioned.
또, 상기 (메트)아크릴산에스테르 화합물 중 3 관능 이상의 것으로는, 예를 들어, 트리메틸올프로판트리(메트)아크릴레이트, 에틸렌옥사이드 부가 트리메틸올프로판트리(메트)아크릴레이트, 프로필렌옥사이드 부가 트리메틸올프로판트리(메트)아크릴레이트, 카프로락톤 변성 트리메틸올프로판트리(메트)아크릴레이트, 에틸렌옥사이드 부가 이소시아누르산트리(메트)아크릴레이트, 글리세린트리(메트)아크릴레이트, 프로필렌옥사이드 부가 글리세린트리(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 트리스(메트)아크릴로일옥시에틸포스페이트, 디트리메틸올프로판테트라(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트 등을 들 수 있다.Moreover, as trifunctional or more than trifunctional thing among the said (meth)acrylic acid ester compound, trimethylol propane tri(meth)acrylate, ethylene oxide addition trimethylol propane tri(meth)acrylate, propylene oxide addition trimethylol propane 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)acrylic Rate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.
상기 에폭시(메트)아크릴레이트로는, 예를 들어, 에폭시 화합물과 (메트)아크릴산을 통상적인 방법에 따라 염기성 촉매의 존재하에서 반응시킴으로써 얻어지는 것 등을 들 수 있다.As said epoxy (meth)acrylate, the thing obtained by making an epoxy compound and (meth)acrylic acid react in presence of a basic catalyst according to a conventional method, etc. are mentioned, for example.
상기 에폭시(메트)아크릴레이트를 합성하기 위한 원료가 되는 에폭시 화합물로는, 예를 들어, 비스페놀 A 형 에폭시 화합물, 비스페놀 F 형 에폭시 화합물, 비스페놀 S 형 에폭시 화합물, 2,2'-디알릴비스페놀 A 형 에폭시 화합물, 수소 첨가 비스페놀형 에폭시 화합물, 프로필렌옥사이드 부가 비스페놀 A 형 에폭시 화합물, 레조르시놀형 에폭시 화합물, 비페닐형 에폭시 화합물, 술파이드형 에폭시 화합물, 디페닐에테르형 에폭시 화합물, 디시클로펜타디엔형 에폭시 화합물, 나프탈렌형 에폭시 화합물, 페놀 노볼락형 에폭시 화합물, 오르토크레졸 노볼락형 에폭시 화합물, 디시클로펜타디엔 노볼락형 에폭시 화합물, 비페닐 노볼락형 에폭시 화합물, 나프탈렌페놀 노볼락형 에폭시 화합물, 글리시딜아민형 에폭시 화합물, 알킬폴리올형 에폭시 화합물, 고무 변성형 에폭시 화합물, 글리시딜에스테르 화합물 등을 들 수 있다.As an epoxy compound used as a raw material for synthesizing the said epoxy (meth)acrylate, For example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, and 2,2'- diallyl bisphenol A Type epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide addition 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 novolak type epoxy compound, orthocresol novolak type epoxy compound, dicyclopentadiene novolak type epoxy compound, biphenyl novolak type epoxy compound, naphthalenephenol novolak type epoxy compound, gly A cydylamine type epoxy compound, an alkyl polyol type epoxy compound, a rubber-modified type epoxy compound, a glycidyl ester compound, etc. are mentioned.
상기 비스페놀 A 형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, jER828EL, jER1004 (모두 미츠비시 케미컬사 제조), EPICLON EXA-850CRP (DIC 사 제조) 등을 들 수 있다.As what is marketed among the said bisphenol A epoxy compounds, jER828EL, jER1004 (all are made by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (made by DIC Corporation), etc. are mentioned, for example.
상기 비스페놀 F 형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, jER806, jER4004 (모두 미츠비시 케미컬사 제조) 등을 들 수 있다.As what is marketed among the said bisphenol F-type epoxy compounds, jER806, jER4004 (all are the Mitsubishi Chemicals make), etc. are mentioned, for example.
상기 비스페놀 S 형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, EPICLON EXA1514 (DIC 사 제조) 등을 들 수 있다.As what is marketed among the said bisphenol S-type epoxy compounds, EPICLON EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
상기 2,2'-디알릴비스페놀 A 형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, RE-810NM (닛폰 화약사 제조) 등을 들 수 있다.As what is marketed among the said 2,2'- diallylbisphenol A epoxy compound, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
상기 수소 첨가 비스페놀형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, EPICLON EXA7015 (DIC 사 제조) 등을 들 수 있다.As what is marketed among the said hydrogenated bisphenol-type epoxy compounds, EPICLON EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
상기 프로필렌옥사이드 부가 비스페놀 A 형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, EP-4000S (ADEKA 사 제조) 등을 들 수 있다.As what is marketed among the said propylene oxide addition bisphenol A epoxy compound, EP-4000S (made by ADEKA) etc. are mentioned, for example.
상기 레조르시놀형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, EX-201 (나가세켐텍스사 제조) 등을 들 수 있다.As what is marketed among the said resorcinol type epoxy compound, EX-201 (made by Nagase Chemtex) etc. is mentioned, for example.
상기 비페닐형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, jER YX-4000H (미츠비시 케미컬사 제조) 등을 들 수 있다.As what is marketed among the said biphenyl type epoxy compound, jER YX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.
상기 술파이드형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, YSLV-50TE (신닛테츠 주금 화학사 제조) 등을 들 수 있다.As what is marketed among the said sulfide-type epoxy compounds, YSLV-50TE (made by a Nippon Steel Chemical Co., Ltd.) etc. are mentioned, for example.
상기 디페닐에테르형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, YSLV-80DE (신닛테츠 주금 화학사 제조) 등을 들 수 있다.As what is marketed among the said diphenyl ether type|mold epoxy compounds, YSLV-80DE (made by a Nippon Steel Chemical Co., Ltd. make) etc. are mentioned, for example.
상기 디시클로펜타디엔형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, EP-4088S (ADEKA 사 제조) 등을 들 수 있다.As what is marketed among the said dicyclopentadiene type epoxy compound, EP-4088S (made by ADEKA) etc. are mentioned, for example.
상기 나프탈렌형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, EPICLON HP4032, EPICLON EXA-4700 (모두 DIC 사 제조) 등을 들 수 있다.As what is marketed among the said naphthalene type epoxy compound, EPICLON HP4032, EPICLON EXA-4700 (all are the DIC company make), etc. are mentioned, for example.
상기 페놀 노볼락형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, EPICLON N-770 (DIC 사 제조) 등을 들 수 있다.As what is marketed among the said phenol novolak-type epoxy compounds, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example.
상기 오르토크레졸 노볼락형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, EPICLON N-670-EXP-S (DIC 사 제조) 등을 들 수 있다.As what is marketed among the said orthocresol novolak-type epoxy compounds, EPICLON N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.
상기 디시클로펜타디엔 노볼락형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, EPICLON HP7200 (DIC 사 제조) 등을 들 수 있다.As what is marketed among the said dicyclopentadiene novolak-type epoxy compounds, EPICLON HP7200 (made by DIC Corporation) etc. are mentioned, for example.
상기 비페닐 노볼락형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, NC-3000P (닛폰 화약사 제조) 등을 들 수 있다.As what is marketed among the said biphenyl novolak-type epoxy compounds, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
상기 나프탈렌페놀 노볼락형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, ESN-165S (신닛테츠 주금 화학사 제조) 등을 들 수 있다.As what is marketed among the said naphthalenephenol novolak-type epoxy compounds, ESN-165S (made by the Nippon Steel Chemicals) etc. are mentioned, for example.
상기 글리시딜아민형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, jER630 (미츠비시 케미컬사 제조), EPICLON 430 (DIC 사 제조), TETRAD-X (미츠비시 가스 화학사 제조) 등을 들 수 있다.As what is marketed among the said glycidylamine type epoxy compounds, jER630 (made by Mitsubishi Chemical Corporation), EPICLON 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemicals), etc. are mentioned, for example.
상기 알킬폴리올형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, ZX-1542 (신닛테츠 주금 화학사 제조), EPICLON 726 (DIC 사 제조), 에포라이트 80MFA (쿄에이샤 화학사 제조), 데나콜 EX-611 (나가세켐텍스사 제조) 등을 들 수 있다.As what is marketed among the said alkyl polyol type epoxy compounds, For example, ZX-1542 (made by Nippon Steel Chemicals), EPICLON 726 (made by DIC), Eporite 80MFA (made by Kyoeisha Chemicals), Denacol EX -611 (manufactured by Nagase Chemtex Co., Ltd.); and the like.
상기 고무 변성형 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어, YR-450, YR-207 (모두 신닛테츠 주금 화학사 제조), 에포리드 PB (다이셀사 제조) 등을 들 수 있다.As what is marketed among the said rubber-modified epoxy compounds, YR-450, YR-207 (all are made by a Shin-Nitetsu Shuzo Chemical Co., Ltd.), Epolide PB (made by a Daicel company), etc. are mentioned, for example.
상기 글리시딜에스테르 화합물 중 시판되고 있는 것으로는, 예를 들어, 데나콜 EX-147 (나가세켐텍스사 제조) 등을 들 수 있다.As what is marketed among the said glycidyl ester compound, Denacol EX-147 (made by Nagase Chemtex) etc. is mentioned, for example.
상기 에폭시 화합물 중 그 밖에 시판되고 있는 것으로는, 예를 들어, YDC-1312, YSLV-80XY, YSLV-90CR (모두 신닛테츠 주금 화학사 제조), XAC4151 (아사히 화성사 제조), jER1031, jER1032 (모두 미츠비시 케미컬사 제조), EXA-7120 (DIC 사 제조), TEPIC (닛산 화학사 제조) 등을 들 수 있다.Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemicals), XAC4151 (all manufactured by Asahi Chemical Company), jER1031, jER1032 (all manufactured by Mitsubishi). Chemical Corporation), EXA-7120 (made by DIC Corporation), TEPIC (made by Nissan Chemical Corporation), etc. are mentioned.
상기 에폭시(메트)아크릴레이트 중 시판되고 있는 것으로는, 예를 들어, 다이셀·올넥스사 제조의 에폭시(메트)아크릴레이트, 신나카무라 화학 공업사 제조의 에폭시(메트)아크릴레이트, 쿄에이샤 화학사 제조의 에폭시(메트)아크릴레이트, 나가세켐텍스사 제조의 에폭시(메트)아크릴레이트 등을 들 수 있다.As what is marketed among the said epoxy (meth)acrylates, For example, the epoxy (meth)acrylate by the Daicel Allnex company, the epoxy (meth)acrylate by the Shin-Nakamura Chemical Co., Ltd., Kyoeisha Chemical Co., Ltd. The epoxy (meth)acrylate of manufacture, the epoxy (meth)acrylate by the Nagase Chemtex company, etc. are mentioned.
상기 다이셀·올넥스사 제조의 에폭시(메트)아크릴레이트로는, 예를 들어, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182 등을 들 수 있다.As the epoxy (meth)acrylate manufactured by Daicel Allnex, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, DX can be heard
상기 신나카무라 화학 공업사 제조의 에폭시(메트)아크릴레이트로는, 예를 들어, EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 등을 들 수 있다.As said Shin-Nakamura Chemical Co., Ltd. epoxy (meth)acrylate, EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 etc. are mentioned, for example.
상기 쿄에이샤 화학사 제조의 에폭시(메트)아크릴레이트로는, 예를 들어, 에폭시에스테르 M-600A, 에폭시에스테르 40EM, 에폭시에스테르 70PA, 에폭시에스테르 200PA, 에폭시에스테르 80MFA, 에폭시에스테르 3002M, 에폭시에스테르 3002A, 에폭시에스테르 1600A, 에폭시에스테르 3000M, 에폭시에스테르 3000A, 에폭시에스테르 200EA, 에폭시에스테르 400EA 등을 들 수 있다.As the epoxy (meth)acrylate manufactured by Kyoeisha Chemical, for example, 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, etc. are mentioned.
상기 나가세켐텍스사 제조의 에폭시(메트)아크릴레이트로는, 예를 들어, 데나콜아크릴레이트 DA-141, 데나콜아크릴레이트 DA-314, 데나콜아크릴레이트 DA-911 등을 들 수 있다.As said Nagase Chemtex company make epoxy (meth)acrylate, denacol acrylate DA-141, denacol acrylate DA-314, denacol acrylate DA-911 etc. are mentioned, for example.
상기 우레탄(메트)아크릴레이트는, 예를 들어, 다관능 이소시아네이트 화합물에 대하여 수산기를 갖는 (메트)아크릴산 유도체를, 촉매량의 주석계 화합물 존재하에서 반응시킴으로써 얻을 수 있다.The urethane (meth)acrylate can be obtained by, for example, reacting a (meth)acrylic acid derivative having a hydroxyl group with a polyfunctional isocyanate compound in the presence of a tin-based compound in a catalytic amount.
상기 다관능 이소시아네이트 화합물로는, 예를 들어, 이소포론디이소시아네이트, 2,4-톨릴렌디이소시아네이트, 2,6-톨릴렌디이소시아네이트, 헥사메틸렌디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트, 디페닐메탄-4,4'-디이소시아네이트 (MDI), 수소 첨가 MDI, 폴리메릭 MDI, 1,5-나프탈렌디이소시아네이트, 노르보르난디이소시아네이트, 톨리딘디이소시아네이트, 자일릴렌디이소시아네이트 (XDI), 수소 첨가 XDI, 리신디이소시아네이트, 트리페닐메탄트리이소시아네이트, 트리스(이소시아네이트페닐)티오포스페이트, 테트라메틸자일릴렌디이소시아네이트, 1,6,11-운데칸트리이소시아네이트 등을 들 수 있다.Examples of the polyfunctional isocyanate compound 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(isocyanatephenyl)thiophosphate, tetramethylxylylene diisocyanate, 1,6,11- undecane triisocyanate, etc. are mentioned.
또, 상기 다관능 이소시아네이트 화합물로는, 폴리올과 과잉의 다관능 이소시아네이트 화합물의 반응에 의해 얻어지는 사슬 연장된 다관능 이소시아네이트 화합물도 사용할 수 있다.Moreover, as said polyfunctional isocyanate compound, the chain extension polyfunctional isocyanate compound obtained by reaction of a polyol and an excess polyfunctional isocyanate compound can also be used.
상기 폴리올로는, 예를 들어, 에틸렌글리콜, 프로필렌글리콜, 글리세린, 소르비톨, 트리메틸올프로판, 카보네이트디올, 폴리에테르디올, 폴리에스테르디올, 폴리카프로락톤디올 등을 들 수 있다.Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyetherdiol, polyesterdiol, and polycaprolactonediol.
상기 수산기를 갖는 (메트)아크릴산 유도체로는, 예를 들어, 하이드록시알킬모노(메트)아크릴레이트, 2 가의 알코올의 모노(메트)아크릴레이트, 3 가의 알코올의 모노(메트)아크릴레이트 또는 디(메트)아크릴레이트, 에폭시(메트)아크릴레이트 등을 들 수 있다.As the (meth)acrylic acid derivative having a hydroxyl group, for example, hydroxyalkyl mono(meth)acrylate, dihydric alcohol mono(meth)acrylate, trihydric alcohol mono(meth)acrylate or di( Meth)acrylate, epoxy (meth)acrylate, etc. are mentioned.
상기 하이드록시알킬모노(메트)아크릴레이트로는, 예를 들어, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트 등을 들 수 있다.Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate etc. are mentioned.
상기 2 가의 알코올로는, 예를 들어, 에틸렌글리콜, 프로필렌글리콜, 1,3-프로판디올, 1,3-부탄디올, 1,4-부탄디올, 폴리에틸렌글리콜 등을 들 수 있다.As said dihydric alcohol, ethylene glycol, propylene glycol, 1, 3- propanediol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol etc. are mentioned, for example.
상기 3 가의 알코올로는, 예를 들어, 트리메틸올에탄, 트리메틸올프로판, 글리세린 등을 들 수 있다.As said trihydric alcohol, trimethylolethane, a trimethylol propane, glycerol etc. are mentioned, for example.
상기 에폭시(메트)아크릴레이트로는, 예를 들어, 비스페놀 A 형 에폭시아크릴레이트 등을 들 수 있다.As said epoxy (meth)acrylate, bisphenol A epoxy acrylate etc. are mentioned, for example.
상기 우레탄(메트)아크릴레이트 중 시판되고 있는 것으로는, 예를 들어, 토아 합성사 제조의 우레탄(메트)아크릴레이트, 다이셀·올넥스사 제조의 우레탄(메트)아크릴레이트, 네가미 공업사 제조의 우레탄(메트)아크릴레이트, 신나카무라 화학 공업사 제조의 우레탄(메트)아크릴레이트, 쿄에이샤 화학사 제조의 우레탄(메트)아크릴레이트 등을 들 수 있다.As what is marketed among the said urethane (meth)acrylates, For example, the urethane (meth)acrylate by the Toa Synthesis company, the urethane (meth)acrylate by the Daicel Allnex company, the urethane by the Negami Kogyo company (meth)acrylate, the urethane (meth)acrylate by the Shin-Nakamura Chemical Industry company, the urethane (meth)acrylate by the Kyoeisha Chemical company, etc. are mentioned.
상기 토아 합성사 제조의 우레탄(메트)아크릴레이트로는, 예를 들어, M-1100, M-1200, M-1210, M-1600 등을 들 수 있다.Examples of the urethane (meth)acrylate manufactured by Toa Synthesis Co., Ltd. include M-1100, M-1200, M-1210, and M-1600.
상기 다이셀·올넥스사 제조의 우레탄(메트)아크릴레이트로는, 예를 들어, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 등을 들 수 있다.As said Daicel Allnex urethane (meth)acrylate, For example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL4858, EBECRYL8, EBECRYL8807, EBECRYL9260, etc. are mentioned.
상기 네가미 공업사 제조의 우레탄(메트)아크릴레이트로는, 예를 들어, 아트 레진 UN-330, 아트 레진 SH-500B, 아트 레진 UN-1200TPK, 아트 레진 UN-1255, 아트 레진 UN-3320HB, 아트 레진 UN-7100, 아트 레진 UN-9000A, 아트 레진 UN-9000H 등을 들 수 있다.As said Negami Kogyo urethane (meth)acrylate, For example, Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN-3320HB. Resin UN-7100, Art resin UN-9000A, Art resin UN-9000H, etc. are mentioned.
상기 신나카무라 화학 공업사 제조의 우레탄(메트)아크릴레이트로는, 예를 들어, 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 등을 들 수 있다.As the urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., for example, 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, etc. are mentioned.
상기 쿄에이샤 화학사 제조의 우레탄(메트)아크릴레이트로는, 예를 들어, AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T 등을 들 수 있다.As the urethane (meth)acrylate manufactured by Kyoeisha Chemical, for example, AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA- 306T etc. are mentioned.
상기 경화성 수지는, 얻어지는 액정 표시 소자용 시일제의 접착성을 향상시키는 것 등을 목적으로 하여, 에폭시 화합물을 함유해도 된다. 상기 에폭시 화합물로는, 예를 들어, 상기 서술한 에폭시(메트)아크릴레이트를 합성하기 위한 원료가 되는 에폭시 화합물이나, 부분 (메트)아크릴 변성 에폭시 화합물 등을 들 수 있다.The said curable resin may contain an epoxy compound for the purpose of improving the adhesiveness of the sealing compound for liquid crystal display elements obtained, etc. As said epoxy compound, the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, a partial (meth)acryl modified|denatured epoxy compound, etc. are mentioned, for example.
또한, 본 명세서에 있어서 상기 부분 (메트)아크릴 변성 에폭시 화합물이란, 예를 들어, 1 분자 중에 2 개 이상의 에폭시기를 갖는 에폭시 화합물의 일부의 에폭시기를 (메트)아크릴산과 반응시킴으로써 얻을 수 있는, 1 분자 중에 에폭시기와 (메트)아크릴로일기를 각각 1 개 이상 갖는 화합물을 의미한다.In addition, in this specification, the said partially (meth)acrylic-modified epoxy compound is, for example, one molecule obtained by reacting a part of the epoxy group of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid. In it, it means the compound which has an epoxy group and 1 or more (meth)acryloyl groups, respectively.
상기 경화성 수지로서 상기 (메트)아크릴 화합물과 상기 에폭시 화합물을 함유하는 경우, 또는, 상기 부분 (메트)아크릴 변성 에폭시 화합물을 함유하는 경우, 상기 경화성 수지 중의 (메트)아크릴로일기와 에폭시기의 합계 중에 있어서의 (메트)아크릴로일기의 비율을 30 몰％ 이상 95 몰％ 이하가 되도록 하는 것이 바람직하다. 상기 (메트)아크릴로일기의 비율이 이 범위임으로써, 액정 오염의 발생을 억제하면서, 얻어지는 액정 표시 소자용 시일제가 접착성이 보다 우수한 것이 된다.When the (meth)acrylic compound and the epoxy compound are contained as the curable resin, or when the partially (meth)acryl modified epoxy compound is contained, in the sum of the (meth)acryloyl group and the epoxy group in the curable resin It is preferable to make the ratio of the (meth)acryloyl group in 30 mol% or more and 95 mol% or less. When the ratio of the said (meth)acryloyl group is this range, the sealing compound for liquid crystal display elements obtained becomes more excellent in adhesiveness, suppressing generation|occurrence|production of a liquid-crystal contamination.
상기 경화성 수지는, 얻어지는 액정 표시 소자용 시일제를 저액정 오염성이 보다 우수한 것으로 하는 관점에서, -OH 기, -NH- 기, -NH2 기 등의 수소 결합성의 유닛을 갖는 것이 바람직하다.The curable resin is a liquid crystal display element for the seal is obtained in view of the liquid crystal to be better than the low-staining, it is preferable to have a hydrogen bond Castle unit such as -OH group, -NH- group, -NH 2 group.
상기 경화성 수지는, 단독으로 사용되어도 되고, 2 종 이상이 조합하여 사용되어도 된다.The said curable resin may be used independently and may be used in combination of 2 or more type.
본 발명의 액정 표시 소자용 시일제는, 증감제를 함유해도 된다. 상기 증감제는, 상기 광중합 개시제의 중합 개시 효율을 보다 향상시켜, 본 발명의 액정 표시 소자용 시일제의 경화 반응을 보다 촉진시키는 역할을 갖는다.The sealing compound for liquid crystal display elements of this invention may contain a sensitizer. The said sensitizer improves the polymerization initiation efficiency of the said photoinitiator more, and has a role which accelerates|stimulates the hardening reaction of the sealing compound for liquid crystal display elements of this invention more.
상기 증감제로는, 예를 들어, 4-(디메틸아미노)벤조산에틸, 9,10-디부톡시안트라센, 2,4-디에틸티오크산톤, 2,2-디메톡시-1,2-디페닐에탄-1-온, 벤조페논, 2,4-디클로로벤조페논, o-벤조일벤조산메틸, 4,4'-비스(디메틸아미노)벤조페논, 4-벤조일-4'-메틸디페닐술파이드 등을 들 수 있다.As the sensitizer, for example, 4-(dimethylamino)ethyl benzoate, 9,10-dibutoxyanthracene, 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane -1-one, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, etc. can
상기 증감제의 함유량은, 상기 경화성 수지 100 중량부에 대하여, 바람직한 하한이 0.01 중량부, 바람직한 상한이 3 중량부이다. 상기 증감제의 함유량이 0.01 중량부 이상임으로써, 증감 효과가 보다 발휘된다. 상기 증감제의 함유량이 3 중량부 이하임으로써, 흡수가 지나치게 커지지 않고 심부까지 광을 전달할 수 있다. 상기 증감제의 함유량의 보다 바람직한 하한은 0.1 중량부, 보다 바람직한 상한은 1 중량부이다.As for content of the said sensitizer, with respect to 100 weight part of said curable resin, a preferable minimum is 0.01 weight part, and a preferable upper limit is 3 weight part. When content of the said sensitizer is 0.01 weight part or more, a sensitizing effect is exhibited more. When content of the said sensitizer is 3 weight part or less, light can be transmitted to a deep part without absorption becoming large too much. A more preferable minimum of content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
본 발명의 액정 표시 소자용 시일제는, 본 발명의 목적을 저해하지 않는 범위에서, 열중합 개시제를 함유해도 된다.The sealing compound for liquid crystal display elements of this invention may contain a thermal-polymerization initiator in the range which does not impair the objective of this invention.
상기 열중합 개시제로는, 예를 들어, 아조 화합물, 유기 과산화물 등으로 이루어지는 것을 들 수 있다. 그 중에서도, 고분자 아조 화합물로 이루어지는 고분자 아조 개시제가 바람직하다.As said thermal polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Especially, the polymeric azo initiator which consists of a polymeric azo compound is preferable.
상기 열중합 개시제는, 단독으로 사용되어도 되고, 2 종 이상이 조합하여 사용되어도 된다.The said thermal-polymerization initiator may be used independently and may be used in combination of 2 or more type.
또한, 본 명세서에 있어서 상기「고분자 아조 화합물」이란, 아조기를 갖고, 열에 의해 (메트)아크릴로일옥시기를 경화시킬 수 있는 라디칼을 생성하는, 수평균 분자량이 300 이상인 화합물을 의미한다.In addition, in this specification, the said "polymer azo compound" means a compound having an azo group and generating a radical capable of curing a (meth)acryloyloxy group by heat and having a number average molecular weight of 300 or more.
상기 고분자 아조 화합물의 수평균 분자량의 바람직한 하한은 1000, 바람직한 상한은 30 만이다. 상기 고분자 아조 화합물의 수평균 분자량이 이 범위임으로써, 액정 오염을 억제하면서, 경화성 수지와 용이하게 혼합할 수 있다. 상기 고분자 아조 화합물의 수평균 분자량의 보다 바람직한 하한은 5000, 보다 바람직한 상한은 10 만이고, 더욱 바람직한 하한은 1 만, 더욱 바람직한 상한은 9 만이다.The preferable lower limit of the number average molecular weight of the said high molecular weight azo compound is 1000, and a preferable upper limit is 300,000. When the number average molecular weight of the high molecular weight azo compound is within this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination. A more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, a more preferable upper limit is 100,000, a still more preferable lower limit is 10,000, and a more preferable upper limit is 90,000.
상기 고분자 아조 화합물로는, 예를 들어, 아조기를 개재하여 폴리알킬렌옥사이드나 폴리디메틸실록산 등의 유닛이 복수 결합된 구조를 갖는 것을 들 수 있다.Examples of the high molecular weight 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.
상기 아조기를 개재하여 폴리알킬렌옥사이드 등의 유닛이 복수 결합된 구조를 갖는 고분자 아조 화합물로는, 폴리에틸렌옥사이드 구조를 갖는 것이 바람직하다.As the high molecular weight azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, it is preferable to have a polyethylene oxide structure.
상기 고분자 아조 화합물로는, 구체적으로는 예를 들어, 4,4'-아조비스(4-시아노펜탄산) 과 폴리알킬렌글리콜의 중축합물이나, 4,4'-아조비스(4-시아노펜탄산) 과 말단 아미노기를 갖는 폴리디메틸실록산의 중축합물 등을 들 수 있다.Specific examples of the polymer azo compound include a polycondensate of 4,4'-azobis(4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis(4-cyanophene). carbonic acid) and polydimethylsiloxane having a terminal amino group; and the like.
상기 고분자 아조 화합물 중 시판되고 있는 것으로는, 예를 들어, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (모두 후지 필름 와코 순약사 제조) 등을 들 수 있다.As what is marketed among the said polymeric azo compounds, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all are made by Fujifilm Wako Pure Pharmaceutical Co., Ltd.) etc. are mentioned, for example.
또, 고분자가 아닌 아조 화합물로는, 예를 들어, V-65, V-501 (모두 후지 필름 와코 순약사 제조) 등을 들 수 있다.Moreover, as an azo compound which is not polymer|macromolecule, V-65, V-501 (all are the Fujifilm Wako Pure Pharmaceutical Co., Ltd. make) etc. are mentioned, for example.
상기 유기 과산화물로는, 예를 들어, 케톤퍼옥사이드, 퍼옥시케탈, 하이드로퍼옥사이드, 디알킬퍼옥사이드, 퍼옥시에스테르, 디아실퍼옥사이드, 퍼옥시디카보네이트 등을 들 수 있다.Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkylperoxide, peroxyester, diacylperoxide, and peroxydicarbonate.
상기 열중합 개시제의 함유량은, 상기 경화성 수지 100 중량부에 대하여, 바람직한 하한이 0.05 중량부, 바람직한 상한이 10 중량부이다. 상기 열중합 개시제의 함유량이 0.05 중량부 이상임으로써, 본 발명의 액정 표시 소자용 시일제가 열경화성이 보다 우수한 것이 된다. 상기 열중합 개시제의 함유량이 10 중량부 이하임으로써, 본 발명의 액정 표시 소자용 시일제가 저액정 오염성이나 보존 안정성이 보다 우수한 것이 된다. 상기 열중합 개시제의 함유량의 보다 바람직한 하한은 0.1 중량부, 보다 바람직한 상한은 5 중량부이다.As for content of the said thermal-polymerization initiator, with respect to 100 weight part of said curable resin, a preferable lower limit is 0.05 weight part, and a preferable upper limit is 10 weight part. When content of the said thermal-polymerization initiator is 0.05 weight part or more, the sealing compound for liquid crystal display elements of this invention becomes the thing more excellent in thermosetting. When content of the said thermal-polymerization initiator is 10 weight part or less, the sealing compound for liquid crystal display elements of this invention becomes the thing more excellent in low-liquid-crystal contamination property and storage stability. A more preferable lower limit of the content of the thermal polymerization initiator is 0.1 parts by weight, and a more preferable upper limit thereof is 5 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 열경화제를 함유해도 된다.The sealing compound for liquid crystal display elements of this invention may contain a thermosetting agent.
상기 열경화제로는, 예를 들어, 유기산 히드라지드, 이미다졸 유도체, 아민 화합물, 다가 페놀계 화합물, 산 무수물 등을 들 수 있다. 그 중에서도, 유기산 히드라지드가 바람직하게 사용된다.As said thermosetting agent, organic acid hydrazide, an imidazole derivative, an amine compound, polyhydric phenol type compound, acid anhydride etc. are mentioned, for example. Among them, organic acid hydrazide is preferably used.
상기 열경화제는, 단독으로 사용되어도 되고, 2 종 이상이 조합하여 사용되어도 된다.The said thermosetting agent may be used independently and may be used in combination of 2 or more type.
상기 유기산 히드라지드로는, 예를 들어, 세바크산디히드라지드, 이소프탈산디히드라지드, 아디프산디히드라지드, 말론산디히드라지드 등을 들 수 있다.As said organic acid hydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, etc. are mentioned, for example.
상기 유기산 히드라지드 중 시판되고 있는 것으로는, 예를 들어, 오오츠카 화학사 제조의 유기산 히드라지드, 아지노모토 파인 테크노사 제조의 유기산 히드라지드 등을 들 수 있다.As what is marketed among the said organic acid hydrazide, the organic acid hydrazide by the Otsuka Chemical company, the organic acid hydrazide by the Ajinomoto Fine Techno company, etc. are mentioned, for example.
상기 오오츠카 화학사 제조의 유기산 히드라지드로는, 예를 들어, SDH, ADH 등을 들 수 있다.As said organic acid hydrazide by the Otsuka Chemical Company, SDH, ADH, etc. are mentioned, for example.
상기 아지노모토 파인 테크노사 제조의 유기산 히드라지드로는, 예를 들어, 아미큐어 VDH, 아미큐어 VDH-J, 아미큐어 UDH, 아미큐어 UDH-J 등을 들 수 있다.As said organic acid hydrazide by the said Ajinomoto Fine Techno company, Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J etc. are mentioned, for example.
상기 열경화제의 함유량은, 상기 경화성 수지 100 중량부에 대하여, 바람직한 하한이 1 중량부, 바람직한 상한이 50 중량부이다. 상기 열경화제의 함유량이 이 범위임으로써, 얻어지는 액정 표시 소자용 시일제의 도포성 등을 악화시키지 않고, 열경화성이 보다 우수한 것으로 할 수 있다. 상기 열경화제의 함유량의 보다 바람직한 상한은 30 중량부이다.As for content of the said thermosetting agent, with respect to 100 weight part of said curable resins, a preferable lower limit is 1 weight part, and a preferable upper limit is 50 weight part. When content of the said thermosetting agent is this range, thermosetting property can be made more excellent, without worsening the applicability|paintability of the sealing compound for liquid crystal display elements obtained, etc. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 점도의 향상, 응력 분산 효과에 의한 접착성의 개선, 선 팽창률의 개선 등을 목적으로 하여 충전제를 함유하는 것이 바람직하다.It is preferable that the sealing compound for liquid crystal display elements of this invention contains a filler for the purpose of the improvement of a viscosity, the adhesive improvement by a stress dispersion effect, the improvement of a coefficient of linear expansion, etc.
상기 충전제로는, 무기 충전제나 유기 충전제를 사용할 수 있다.As the filler, an inorganic filler or an organic filler can be used.
상기 무기 충전제로는, 예를 들어, 실리카, 탤크, 유리 비즈, 석면, 석고, 규조토, 스멕타이트, 벤토나이트, 몬모릴로나이트, 세리사이트, 활성 백토, 알루미나, 산화아연, 산화철, 산화마그네슘, 산화주석, 산화티탄, 탄산칼슘, 탄산마그네슘, 수산화마그네슘, 수산화알루미늄, 질화알루미늄, 질화규소, 황산바륨, 규산칼슘 등을 들 수 있다.Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, 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, and the like.
상기 유기 충전제로는, 예를 들어, 폴리에스테르 미립자, 폴리우레탄 미립자, 비닐 중합체 미립자, 아크릴 중합체 미립자 등을 들 수 있다.As said organic filler, polyester microparticles|fine-particles, polyurethane microparticles|fine-particles, vinyl polymer microparticles|fine-particles, acrylic polymer microparticles|fine-particles, etc. are mentioned, for example.
상기 충전제는, 단독으로 사용되어도 되고, 2 종 이상이 조합하여 사용되어도 된다.The said filler may be used independently and may be used in combination of 2 or more type.
상기 충전제의 함유량은, 상기 경화성 수지 100 중량부에 대하여, 바람직한 하한이 30 중량부, 바람직한 상한이 80 중량부이다. 상기 충전제의 함유량이 이 범위임으로써, 도포성 등을 악화시키지 않고, 접착성의 개선 등의 효과가 보다 우수한 것이 된다. 상기 충전제의 함유량의 보다 바람직한 하한은 45 중량부, 보다 바람직한 상한은 65 중량부이다.As for content of the said filler, with respect to 100 weight part of said curable resin, a preferable minimum is 30 weight part, and a preferable upper limit is 80 weight part. When content of the said filler is this range, it becomes a thing excellent in the effect, such as an adhesive improvement, without worsening applicability|paintability etc. A more preferable lower limit of the content of the filler is 45 parts by weight, and a more preferable upper limit thereof is 65 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 실란 커플링제를 함유하는 것이 바람직하다. 상기 실란 커플링제는, 주로 시일제와 기판 등을 양호하게 접착하기 위한 접착 보조제로서의 역할을 갖는다.It is preferable that the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent. The said silane coupling agent mainly has a role as an adhesion auxiliary agent for adhering a sealing compound, a board|substrate, etc. favorably.
상기 실란 커플링제로는, 예를 들어, 3-아미노프로필트리메톡시실란, 3-메르캅토프로필트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-이소시아네이트프로필트리메톡시실란 등이 바람직하게 사용된다. 이것들은, 기판 등과의 접착성을 향상시키는 효과가 우수하고, 경화성 수지와 화학 결합됨으로써 액정 중으로의 경화성 수지의 유출을 억제할 수 있다.Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and the like. This is preferably used. These are excellent in the effect of improving adhesiveness with a board|substrate etc., and can suppress the outflow of curable resin to the inside of a liquid crystal by chemically bonding with curable resin.
상기 실란 커플링제는, 단독으로 사용되어도 되고, 2 종 이상이 조합하여 사용되어도 된다.The said silane coupling agent may be used independently and may be used in combination of 2 or more type.
본 발명의 액정 표시 소자용 시일제 100 중량부 중에 있어서의 상기 실란 커플링제의 함유량의 바람직한 하한은 0.1 중량부, 바람직한 상한은 10 중량부이다. 상기 실란 커플링제의 함유량이 이 범위임으로써, 액정 오염의 발생을 억제하면서, 접착성을 향상시키는 효과가 보다 우수한 것이 된다. 상기 실란 커플링제의 함유량의 보다 바람직한 하한은 0.3 중량부, 보다 바람직한 상한은 5 중량부이다.The minimum with preferable content of the said silane coupling agent in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part. When content of the said silane coupling agent is this range, the effect of improving adhesiveness becomes more excellent, suppressing generation|occurrence|production of a liquid-crystal contamination. A more preferable lower limit of content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.
본 발명의 액정 표시 소자용 시일제는, 추가로, 필요에 따라, 반응성 희석제, 요변제, 스페이서, 경화 촉진제, 소포제, 레벨링제, 중합 금지제 등의 첨가제를 함유해도 된다.The sealing compound for liquid crystal display elements of this invention may contain additives, such as a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, an antifoamer, a leveling agent, and a polymerization inhibitor, further as needed.
본 발명의 액정 표시 소자용 시일제를 제조하는 방법으로는, 예를 들어, 호모 디스퍼, 호모 믹서, 만능 믹서, 플래니터리 믹서, 니더, 3 개 롤 등의 혼합기를 사용하여, 경화성 수지와, 광중합 개시제와, 필요에 따라 첨가하는 실란 커플링제 등을 혼합하는 방법 등을 들 수 있다.As a method of manufacturing the sealing compound for liquid crystal display elements of this invention, for example, using mixers, such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, three rolls, curable resin and and the method of mixing a photoinitiator, the silane coupling agent etc. which are added as needed, etc. are mentioned.
본 발명의 액정 표시 소자용 시일제에 도전성 미립자를 배합함으로써, 상하 도통 재료를 제조할 수 있다. 본 발명의 액정 표시 소자용 시일제와 도전성 미립자를 함유하는 상하 도통 재료도 또한, 본 발명의 하나이다.A vertical conduction material can be manufactured by mix|blending electroconductive microparticles|fine-particles with the sealing compound for liquid crystal display elements of this invention. The vertical conduction material containing the sealing compound for liquid crystal display elements of this invention, and electroconductive fine particles is also one of this invention.
상기 도전성 미립자로는, 금속 볼, 수지 미립자의 표면에 도전 금속층을 형성한 것 등을 사용할 수 있다. 그 중에서도, 수지 미립자의 표면에 도전 금속층을 형성한 것은, 수지 미립자의 우수한 탄성에 의해, 투명 기판 등을 손상시키지 않고 도전 접속이 가능한 점에서 바람직하다.As the conductive fine particles, metal balls, those in which a conductive metal layer is formed on the surface of the resin fine particles, etc. can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable at the point that conductive connection is possible without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.
본 발명의 액정 표시 소자용 시일제의 경화물, 또는, 본 발명의 상하 도통 재료의 경화물을 갖는 액정 표시 소자도 또한, 본 발명의 하나이다.The liquid crystal display element which has the hardened|cured material of the sealing compound for liquid crystal display elements of this invention, or the hardened|cured material of the vertical conduction material of this invention is also one of this invention.
본 발명의 액정 표시 소자로는, 프레임 협소 설계의 액정 표시 소자가 바람직하다. 구체적으로는, 액정 표시부의 주위의 프레임 부분의 폭이 2 ㎜ 이하인 것이 바람직하다.As a liquid crystal display element of this invention, the liquid crystal display element of a frame narrow design is preferable. Specifically, it is preferable that the width of the frame portion around the liquid crystal display portion is 2 mm or less.
또, 본 발명의 액정 표시 소자를 제조할 때의 본 발명의 액정 표시 소자용 시일제의 도포 폭은 1 ㎜ 이하인 것이 바람직하다.Moreover, it is preferable that the application width|variety of the sealing compound for liquid crystal display elements of this invention at the time of manufacturing the liquid crystal display element of this invention is 1 mm or less.
본 발명의 액정 표시 소자를 제조하는 방법으로는, 액정 적하 공법이 바람직하게 이용되며, 구체적으로는 예를 들어, 이하의 각 공정을 갖는 방법 등을 들 수 있다.As a method of manufacturing the liquid crystal display element of this invention, the liquid-crystal dropping method is used suitably, Specifically, the method etc. which have the following each process are mentioned, for example.
먼저, ITO 박막 등의 전극 및 배향막을 갖는 2 장의 투명 기판 중 일방에, 본 발명의 액정 표시 소자용 시일제를 스크린 인쇄, 디스펜서 도포 등에 의해 도포하여 프레임상의 시일 패턴을 형성하는 공정을 실시한다. 이어서, 본 발명의 액정 표시 소자용 시일제가 미경화된 상태에서 액정의 미소적을 기판의 시일 패턴의 프레임 내에 적하 도포하고, 진공하에서 타방의 투명 기판을 중첩시키는 공정을 실시한다. 그 후, 본 발명의 액정 표시 소자용 시일제의 시일 패턴 부분에 자외선, 또는, 컷 필터 등을 통하여 장파장의 광을 조사함으로써, 시일제를 광경화시키는 공정을 실시하는 방법에 의해, 액정 표시 소자를 얻을 수 있다. 또, 상기 시일제를 광경화시키는 공정에 추가하여, 시일제를 가열하여 열경화시키는 공정을 실시해도 된다.First, the sealing compound for liquid crystal display elements of this invention is apply|coated by screen printing, dispenser application|coating, etc. to one of two transparent substrates which have electrodes, such as an ITO thin film, and an orientation film, The process of forming a frame-shaped sealing pattern is performed. Next, in the non-hardened state of the sealing compound for liquid crystal display elements of this invention, the microdroplet of a liquid crystal is drip-coated in the frame of the sealing pattern of a board|substrate, and the process of overlapping the other transparent substrate under vacuum is performed. Then, by irradiating the long-wavelength light to the sealing pattern part of the sealing compound for liquid crystal display elements of this invention through an ultraviolet-ray or a cut filter etc., by the method of performing the process of photocuring a sealing compound, a liquid crystal display element can be obtained Moreover, in addition to the process of photocuring the said sealing compound, you may implement the process of heating and thermosetting a sealing compound.
본 발명에 의하면, 장파장의 광에 대한 경화성이 우수하고, 또한 저액정 오염성이 우수한 액정 표시 소자용 시일제를 제공할 수 있다. 또, 본 발명에 의하면, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공할 수 있다.ADVANTAGE OF THE INVENTION According to this invention, it is excellent in sclerosis|hardenability with respect to long-wavelength light, and the sealing compound for liquid crystal display elements excellent in low-liquid-crystal contamination property can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
이하에 실시예를 들어 본 발명을 더욱 상세하게 설명하는데, 본 발명은 이들 실시예에만 한정되지 않는다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited only to these Examples.
(식 (2) 로 나타내는 화합물의 제조)(Preparation of the compound represented by Formula (2))
2-하이드록시티오크산톤 20 g 과 질산세륨암모늄 12 g 을 아세트산 58 ㎖ 에 첨가하고, 실온에서 1 시간 교반하였다. 2-하이드록시티오크산톤은, 일본 공개특허공보 소58-79991호에 개시된 방법에 의해 합성하였다.20 g of 2-hydroxythioxanthone and 12 g of cerium ammonium nitrate were added to 58 ml of acetic acid, and the mixture was stirred at room temperature for 1 hour. 2-hydroxythioxanthone was synthesized by the method disclosed in Japanese Patent Application Laid-Open No. 58-79991.
그 후, 얻어진 혼합액에 1 ㏖/ℓ 의 수산화나트륨 수용액 300 ㎖ 를 첨가하여 침전을 석출시킨 후, 여과하여 고액 분리를 실시하였다. 얻어진 고체와 아연 분체 58 g 과 염화암모늄 95 g 을 메탄올 700 ㎖ 에 첨가하고, 실온에서 1 시간 교반하였다. 얻어진 반응액을 여과하고, 여과액을 감압 건조시킨 후, 실리카 칼럼 크로마토그래피로 정제하여, 상기 식 (2) 로 나타내는 화합물을 얻었다.Then, after adding 300 ml of 1 mol/L sodium hydroxide aqueous solution to the obtained liquid mixture to precipitate a precipitate, it filtered and performed solid-liquid separation. The obtained solid, 58 g of zinc powder, and 95 g of ammonium chloride were added to 700 ml of methanol, and it stirred at room temperature for 1 hour. After filtering the obtained reaction liquid and drying the filtrate under reduced pressure, it refine|purified by silica column chromatography, and obtained the compound represented by said Formula (2).
또한, 얻어진 상기 식 (2) 로 나타내는 화합물의 구조는, 1H-NMR, 13C-NMR, 및 FT-IR 에 의해 확인하였다.In addition, the structure of the obtained compound represented by said Formula (2) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
(식 (3), (4), (5), (6) 으로 나타내는 화합물의 제조)(Preparation of compounds represented by formulas (3), (4), (5), (6))
1.5 ㏖/ℓ 의 질산 수용액 50 ㎖ 에 파라포름알데히드 25 g 을 첨가하고, 80 ℃ 로 가열하여 파라포름알데히드를 완전히 용해시킨 후, 방랭시켜 실온으로 되돌렸다. 얻어진 수용액에 대하여, 식 (2) 로 나타내는 화합물 5 g 과 수산화붕소나트륨 5 g 을 테트라하이드로푸란 100 ㎖ 에 용해시킨 수용액을 천천히 적하하였다. 그 후, 얻어진 용액을 1 ㏖/ℓ 의 수산화나트륨 수용액으로 중화시키고, 아세트산에틸로 추출하였다. 계속해서, 실리카 칼럼 크로마토그래피로 정제하여, 상기 식 (3), (4), (5), (6) 으로 나타내는 화합물을 각각 얻었다.25 g of paraformaldehyde was added to 50 ml of a 1.5 mol/L aqueous nitric acid solution, and paraformaldehyde was completely dissolved by heating at 80°C, followed by cooling to return to room temperature. With respect to the obtained aqueous solution, the aqueous solution which melt|dissolved 5 g of the compound represented by Formula (2) and 5 g of sodium boron hydroxide in 100 ml of tetrahydrofuran was dripped slowly. Then, the obtained solution was neutralized with 1 mol/L sodium hydroxide aqueous solution, and it extracted with ethyl acetate. Then, it refine|purified by silica column chromatography, and obtained the compound represented by said Formula (3), (4), (5), (6), respectively.
또한, 얻어진 상기 식 (3), (4), (5), (6) 으로 나타내는 화합물의 구조는, 1H-NMR, 13C-NMR, 및 FT-IR 에 의해 확인하였다.In addition, the structure of the obtained compound represented by said Formula (3), (4), (5), (6) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
(식 (7) 로 나타내는 화합물의 제조)(Preparation of compound represented by formula (7))
파라포름알데히드 25 g 을 아세트알데히드 25 g 으로 변경한 것 이외에는, 상기「(식 (3), (4), (5), (6) 으로 나타내는 화합물의 제조)」와 동일하게 하여 상기 식 (7) 로 나타내는 화합물을 얻었다.Except for changing 25 g of paraformaldehyde to 25 g of acetaldehyde, in the same manner as in the above "(Preparation of compounds represented by formulas (3), (4), (5), (6))", the formula (7) ) was obtained.
또한, 얻어진 상기 식 (7) 로 나타내는 화합물의 구조는, 1H-NMR, 13C-NMR, 및 FT-IR 에 의해 확인하였다.In addition, the structure of the obtained compound represented by said Formula (7) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
(식 (8) 로 나타내는 화합물의 제조)(Preparation of compound represented by formula (8))
디클로로메탄 100 중량부에 4-(디메틸아미노)벤조일클로라이드 10 중량부와 촉매인 피리딘 0.5 중량부를 첨가하고, 0 ℃ 의 환경하에서 글리시돌 1 중량부를 적하하고, 방랭 후, 실온에서 밤새 교반하였다. 얻어진 반응액으로부터 디클로로메탄을 제거함으로써 반응 생성물을 얻었다.10 parts by weight of 4-(dimethylamino)benzoylchloride and 0.5 parts by weight of pyridine as a catalyst were added to 100 parts by weight of dichloromethane, 1 part by weight of glycidol was added dropwise in an environment of 0°C, and after standing to cool, the mixture was stirred at room temperature overnight. A reaction product was obtained by removing dichloromethane from the obtained reaction solution.
N,N-디메틸포름아미드 100 중량부에 얻어진 반응 생성물 10 중량부와 2-하이드록시-9H-티오크산텐-9-온 5 중량부를 첨가하고, 염기성 촉매로서 탄산칼륨 존재하에서, 120 ℃ 에서 48 시간 교반하면서 반응시켰다. 얻어진 반응액으로부터 N,N-디메틸포름아미드를 제거하고, 칼럼 크로마토그래피로 정제함으로써, 하기 식 (8) 로 나타내는 화합물을 얻었다.10 parts by weight of the obtained reaction product and 5 parts by weight of 2-hydroxy-9H-thioxanthene-9-one were added to 100 parts by weight of N,N-dimethylformamide, in the presence of potassium carbonate as a basic catalyst, at 120° C. The reaction was carried out while stirring for a period of time. N,N-dimethylformamide was removed from the obtained reaction liquid, and the compound represented by following formula (8) was obtained by refine|purifying by column chromatography.
또한, 얻어진 하기 식 (8) 로 나타내는 화합물의 구조는, 1H-NMR, 13C-NMR, 및 FT-IR 에 의해 확인하였다.In addition, the structure of the obtained compound represented by following formula (8) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
[화학식 8][Formula 8]
(식 (9) 로 나타내는 화합물의 제조)(Preparation of compound represented by formula (9))
일본 공개특허공보 소58-79991호에 개시된 방법에 의해, 하기 식 (9) 로 나타내는 화합물 (2-하이드록시티오크산톤) 을 합성하였다.A compound (2-hydroxythioxanthone) represented by the following formula (9) was synthesized by the method disclosed in Japanese Patent Laid-Open No. 58-79991.
[화학식 9][Formula 9]
(식 (10) 으로 나타내는 화합물의 제조)(Preparation of compound represented by formula (10))
2-하이드록시티오크산톤 20 g 을 티오크산톤 20 g 으로 변경한 것 이외에는, 상기「(식 (3), (4), (5), (6) 으로 나타내는 화합물의 제조)」와 동일하게 하여, 하기 식 (10) 으로 나타내는 화합물을 얻었다.Except that 20 g of 2-hydroxythioxanthone was changed to 20 g of thioxanthone, in the same manner as in the above "(Preparation of compound represented by formula (3), (4), (5), (6))" Thus, a compound represented by the following formula (10) was obtained.
또한, 얻어진 하기 식 (10) 으로 나타내는 화합물의 구조는, 1H-NMR, 13C-NMR, 및 FT-IR 에 의해 확인하였다.In addition, the structure of the obtained compound represented by following formula (10) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
[화학식 10][Formula 10]
(실시예 1 ∼ 9 및 비교예 1 ∼ 7)(Examples 1 to 9 and Comparative Examples 1 to 7)
표 1, 2 에 기재된 배합비에 따라, 각 재료를 유성식 교반기를 사용하여 혼합한 후, 추가로 3 개 롤을 사용하여 혼합함으로써 실시예 1 ∼ 9 및 비교예 1 ∼ 7 의 액정 표시 소자용 시일제를 조제하였다. 유성식 교반기로는, 아와토리 렌타로 (싱키사 제조) 를 사용하였다.According to the compounding ratio of Tables 1 and 2, after mixing each material using the planetary stirrer, by mixing using 3 rolls further, the sealing compound for liquid crystal display elements of Examples 1-9 and Comparative Examples 1-7 was prepared. As the planetary stirrer, Awatori Rentaro (manufactured by Thinkki Corporation) was used.
＜평가＞<Evaluation>
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제에 대해 이하의 평가를 실시하였다. 결과를 표 1, 2 에 나타냈다.The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
(광경화성)(photocurable)
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제 100 중량부에 스페이서 미립자 1 중량부를 분산시켰다. 스페이서 미립자로는, 마이크로 펄 SI-H050 (세키스이 화학 공업사 제조) 을 사용하였다. 이어서, 시일제를 디스펜스용의 시린지에 충전하고, 탈포 처리를 실시하고 나서, 디스펜서로 유리 기판 상에 도포하였다. 디스펜스용의 시린지로는, PSY-10E (무사시 엔지니어링사 제조) 를 사용하고, 디스펜서로는, SHOTMASTER300 (무사시 엔지니어링사 제조) 을 사용하였다. 시일제를 도포한 기판에 진공 첩합 장치로 5 ㎩ 의 감압하에서 동 사이즈의 유리 기판을 첩합하였다. 첩합된 유리 기판의 시일제 부분에 메탈 할라이드 램프를 사용하여 100 ㎽/㎠ 의 광을 10 초 조사하였다. 광 조사는, 파장 420 ㎚ 이하의 광을 컷하는 컷 필터 (420 ㎚ 컷 필터) 를 통하여 실시하였다.1 weight part of spacer microparticles|fine-particles were disperse|distributed to 100 weight part of sealing compounds for liquid crystal display elements obtained by the Example and the comparative example. As the spacer fine particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used. Next, after filling the syringe for dispensing with a sealing compound and performing a defoaming process, it apply|coated on the glass substrate with the dispenser. As a syringe for dispensing, PSY-10E (manufactured by Musashi Engineering) was used, and as a dispenser, SHOTMASTER300 (manufactured by Musashi Engineering) was used. The glass substrate of the same size was bonded together under the pressure_reduction|reduced_pressure of 5 Pa with the vacuum bonding apparatus to the board|substrate which apply|coated the sealing compound. The light of 100 mW/cm<2> was irradiated to the sealing compound part of the bonded glass substrate for 10 second using a metal halide lamp. Light irradiation was performed through a cut filter (420 nm cut filter) that cuts light having a wavelength of 420 nm or less.
적외 분광 장치를 사용하여 시일제의 FT-IR 측정을 실시하고, (메트)아크릴로일기 유래 피크의 광 조사 전후에서의 변화량을 측정하였다. 적외 분광 장치로는, FTS3000 (BIORAD 사 제조) 을 사용하였다. 광 조사 후에 (메트)아크릴로일기 유래의 피크가 80 ％ 이상 감소한 경우를「◎」, 70 ％ 이상 80 ％ 미만 감소한 경우를「○」, 60 ％ 이상 70 ％ 미만 감소한 경우를「△」, 광 조사 후의 (메트)아크릴로일기 유래의 피크의 감소가 60 ％ 미만이었던 경우를「×」로 하여 광경화성을 평가하였다.FT-IR measurement of the sealing compound was performed using the infrared spectroscopy apparatus, and the change amount before and behind light irradiation of the peak derived from a (meth)acryloyl group was measured. As the infrared spectrometer, FTS3000 (manufactured by BIORAD) was used. After light irradiation, the case where the peak derived from the (meth)acryloyl group decreased by 80% or more was “◎”, the case where it decreased by 70% or more and less than 80% was “○”, and the case where it decreased by 60% or more and less than 70% was “Δ”, the light The case where the reduction|decrease of the peak derived from the (meth)acryloyl group after irradiation was less than 60 % was made into "x", and photocurability was evaluated.
(접착성)(Adhesive)
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제 100 중량부에 스페이서 미립자 1 중량부를 분산시키고, 2 장의 ITO 박막이 형성된 유리 기판 (30 × 40 ㎜) 중 일방에 미소 적하하였다. 스페이서 미립자로는, 마이크로 펄 SI-H050 (세키스이 화학 공업사 제조) 을 사용하였다. 이것에 다른 일방의 ITO 박막이 형성된 유리 기판을 십자상으로 첩합하고, 메탈 할라이드 램프로 100 ㎽/㎠ 의 광을 30 초 조사한 후, 120 ℃ 에서 60 분 가열함으로써 접착성 시험편을 얻었다. 광 조사는, 파장 420 ㎚ 이하의 광을 컷하는 컷 필터 (420 ㎚ 컷 필터) 를 통하여 실시하였다.1 weight part of spacer microparticles|fine-particles were disperse|distributed to 100 weight part of each sealing compound for liquid crystal display elements obtained by the Example and the comparative example, and it was microdropped at one of the glass substrates (30 x 40 mm) in which the ITO thin film of 2 sheets was formed. As the spacer fine particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used. The other glass substrate on which the ITO thin film was formed was bonded to this crosswise, and after irradiating 100 mW/cm<2> light for 30 second with a metal halide lamp, the adhesive test piece was obtained by heating at 120 degreeC for 60 minutes. Light irradiation was performed through a cut filter (420 nm cut filter) that cuts light having a wavelength of 420 nm or less.
얻어진 접착성 시험편에 대해, 상하에 배치한 척으로 인장 시험 (5 ㎜/sec) 을 실시하였다. 얻어진 측정값 (㎏f) 을 시일 도포 단면적 (㎠) 으로 나눈 값이 2.5 ㎏f/㎠ 이상이었던 경우를「○」, 1.5 ㎏f/㎠ 이상 2.5 ㎏f/㎠ 미만이었던 경우를「△」, 1.5 ㎏f/㎠ 미만이었던 경우를「×」로 하여 접착성을 평가하였다.About the obtained adhesive test piece, the tensile test (5 mm/sec) was implemented with the chuck arrange|positioned up and down. When the obtained measured value (kgf) divided by the seal application cross-sectional area (cm2) was 2.5 kgf/cm2 or more, "○", when 1.5 kgf/cm2 or more and less than 2.5 kgf/cm2 was "Δ", The case where it was less than 1.5 kgf/cm<2> was made into "x", and adhesiveness was evaluated.
(저액정 오염성)(Low liquid crystal contamination)
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제 100 중량부에 스페이서 미립자 1 중량부를 분산시켰다. 스페이서 미립자로는, 마이크로 펄 SP-250 (세키스이 화학 공업사 제조) 을 사용하였다. 이어서, 시일제를 디스펜스용의 시린지에 충전하고, 탈포 처리를 실시하였다. 디스펜스용의 시린지로는, PSY-10E (무사시 엔지니어링사 제조) 를 사용하였다. 탈포 처리 후의 시일제를, 2 장의 러빙이 완료된 배향막 및 투명 전극이 형성된 기판 중 일방에 선폭이 1 ㎜ 인 프레임상이 되도록 디스펜서로 도포하였다. 디스펜서로는, SHOTMASTER300 (무사시 엔지니어링사 제조) 을 사용하였다.1 weight part of spacer microparticles|fine-particles were disperse|distributed to 100 weight part of sealing compounds for liquid crystal display elements obtained by the Example and the comparative example. As the spacer fine particles, Micropearl SP-250 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used. Next, the sealing compound was filled in the syringe for dispensing, and the defoaming process was performed. As a syringe for dispensing, PSY-10E (manufactured by Musashi Engineering Co., Ltd.) was used. The sealing compound after a defoaming process was apply|coated with the dispenser so that it might become a frame shape with a line|wire width of 1 mm on one of the board|substrate with the orientation film and transparent electrode which the rubbing of 2 sheets was completed. As the dispenser, SHOTMASTER300 (manufactured by Musashi Engineering Co., Ltd.) was used.
계속해서 액정의 미소적을 투명 전극이 형성된 기판의 시일제의 프레임 내 전체면에 적하 도포하고, 바로 타방의 기판을 첩합하였다. 액정으로는, JC-5004LA (칫소사 제조) 를 사용하였다. 그 후, 시일제 부분에 메탈 할라이드 램프를 사용하여 100 ㎽/㎠ 의 광을 30 초 조사한 후, 120 ℃ 에서 60 분 가열함으로써 액정 표시 소자를 얻었다. 광 조사는, 파장 420 ㎚ 이하의 광을 컷하는 컷 필터 (420 ㎚ 컷 필터) 를 통하여 실시하였다.Then, the microdroplet of a liquid crystal was drip-coated to the whole surface in the flame|frame of the sealing compound of the board|substrate with a transparent electrode, and the other board|substrate was immediately bonded together. As the liquid crystal, JC-5004LA (manufactured by Chisso Corporation) was used. Then, the liquid crystal display element was obtained by heating at 120 degreeC for 60 minutes, after irradiating a 100 mW/cm<2> light for 30 second using a metal halide lamp to a sealing compound part. Light irradiation was performed through a cut filter (420 nm cut filter) that cuts light having a wavelength of 420 nm or less.
얻어진 액정 표시 소자에 대해, 80 ℃, 90 ％RH 의 환경하에서 1 시간 전압 인가 상태로 한 후의 액정 배향 흐트러짐 (표시 불균일) 를 육안으로 확인하였다.About the obtained liquid crystal display element, the liquid-crystal orientation disorder (display nonuniformity) after setting it as a voltage application state in 80 degreeC and 90 %RH environment was visually confirmed.
액정 표시 소자에 표시 불균일이 전혀 보이지 않았던 경우를「○」, 액정 표시 소자의 시일제 부근 (주변부) 에 표시 불균일이 보였던 경우를「△」, 표시 불균일이 주변부 뿐만 아니라, 중앙부까지 확산되어 있었던 경우를「×」로 하여 저액정 오염성을 평가하였다.The case where the display unevenness was not seen at all in the liquid crystal display element was "○", the case where the display unevenness was seen in the sealing compound vicinity (peripheral part) of the liquid crystal display element was "Δ", and the display unevenness had spread to the central part as well as the peripheral part. The low-liquid-crystal staining property was evaluated by making "x".
또한, 평가가「○」인 액정 표시 소자는 실용에 전혀 문제가 없는 레벨이고,「△」인 액정 표시 소자는 설계에 따라서는 문제가 될 가능성이 있는 레벨이고,「×」인 액정 표시 소자는 실용에 견딜 수 없는 레벨이다.In addition, a liquid crystal display element with an evaluation of "○" is a level with no problem at all in practical use, a liquid crystal display element with a "Δ" is a level that may cause problems depending on design, and a liquid crystal display element with "x" is a level This level is unbearable for practical use.
산업상 이용가능성Industrial Applicability
본 발명에 의하면, 장파장의 광에 대한 경화성이 우수하고, 또한 저액정 오염성이 우수한 액정 표시 소자용 시일제를 제공할 수 있다. 또, 본 발명에 의하면, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공할 수 있다.ADVANTAGE OF THE INVENTION According to this invention, it is excellent in sclerosis|hardenability with respect to long-wavelength light, and the sealing compound for liquid crystal display elements excellent in low-liquid-crystal contamination property can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
Claims (5)
상기 광중합 개시제는, 하기 식 (1) 로 나타내는 화합물을 함유하는 것을 특징으로 하는 액정 표시 소자용 시일제.
식 (1) 중, R1 및 R8 은 각각 독립적으로 수소 원자, 또는, 티오크산톤 골격의 방향 고리와의 결합 위치에 질소 원자를 갖는 기이고, R1 및 R8 중 적어도 일방은 그 질소 원자를 갖는 기이다. R2 및 R7 은 각각 독립적으로 수소 원자 또는 수산기이고, R2 및 R7 중 적어도 일방은 수산기이다. R3 ∼ R6 은 각각 독립적으로 수소 원자 또는 임의의 치환기이다.As a sealing compound for liquid crystal display elements containing curable resin and a photoinitiator,
The said photoinitiator contains the compound represented by following formula (1), The sealing compound for liquid crystal display elements characterized by the above-mentioned.
In formula (1), R 1 and R 8 are each independently a hydrogen atom or a group having a nitrogen atom at the bonding position with the aromatic ring of the thioxanthone skeleton, and at least one of R 1 and R 8 is the nitrogen atom. It is a group with atoms. R 2 and R 7 are each independently a hydrogen atom or a hydroxyl group, and at least one of R 2 and R 7 is a hydroxyl group. R 3 to R 6 are each independently a hydrogen atom or an optional substituent.
상기 질소 원자를 갖는 기는 아미노기인 액정 표시 소자용 시일제.The method of claim 1,
The sealing compound for liquid crystal display elements whose group which has the said nitrogen atom is an amino group.
상기 식 (1) 로 나타내는 화합물의 함유량이, 상기 경화성 수지 100 중량부에 대하여 0.05 중량부 이상 2.0 중량부 이하인 액정 표시 소자용 시일제.3. The method according to claim 1 or 2,
The sealing compound for liquid crystal display elements whose content of the compound represented by the said Formula (1) is 0.05 weight part or more and 2.0 weight part or less with respect to 100 weight part of said curable resins.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018201727 | 2018-10-26 | ||
| JPJP-P-2018-201727 | 2018-10-26 | ||
| PCT/JP2019/037512 WO2020084988A1 (en) | 2018-10-26 | 2019-09-25 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
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| Publication Number | Publication Date |
|---|---|
| KR20210082126A true KR20210082126A (en) | 2021-07-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020207019760A KR20210082126A (en) | 2018-10-26 | 2019-09-25 | Sealing agent for liquid crystal display elements, vertical conduction material, and liquid crystal display element |
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| Country | Link |
|---|---|
| JP (1) | JP6725771B1 (en) |
| KR (1) | KR20210082126A (en) |
| CN (1) | CN111742258A (en) |
| TW (1) | TWI809206B (en) |
| WO (1) | WO2020084988A1 (en) |
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| JP7144627B2 (en) * | 2020-09-30 | 2022-09-29 | 積水化学工業株式会社 | Thioxanthone compound, photopolymerization initiator, curable resin composition, composition for display element, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001133794A (en) | 1999-11-01 | 2001-05-18 | Kyoritsu Kagaku Sangyo Kk | Sealing agent for dropping process of lcd panel |
| WO2002092718A1 (en) | 2001-05-16 | 2002-11-21 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5152868B2 (en) * | 2009-06-11 | 2013-02-27 | 日本化薬株式会社 | Visible light curable liquid crystal sealant and liquid crystal display cell using the same |
| CN103026292B (en) * | 2011-04-05 | 2014-03-05 | 积水化学工业株式会社 | Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element |
| WO2015072416A1 (en) * | 2013-11-13 | 2015-05-21 | 積水化学工業株式会社 | Liquid-crystal-display-element sealant, vertical conductive material, and liquid-crystal display element |
| WO2015083663A1 (en) * | 2013-12-05 | 2015-06-11 | 積水化学工業株式会社 | Polymerizable monomer, polymer compound, photocurable resin composition, sealing element for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN107111194B (en) * | 2015-06-02 | 2020-12-11 | 积水化学工业株式会社 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| JP6127223B1 (en) * | 2015-06-30 | 2017-05-10 | 三井化学株式会社 | Photocurable resin composition, display element sealant, liquid crystal sealant, liquid crystal display panel, and method for producing liquid crystal display panel |
| JP6197020B2 (en) * | 2015-12-17 | 2017-09-13 | 三井化学株式会社 | Photocurable resin composition, display element sealant, liquid crystal sealant, liquid crystal display panel, and method for producing the same |
| JP2018104662A (en) * | 2016-12-22 | 2018-07-05 | 日本化薬株式会社 | Photocurable resin composition and electronic component sealant |
-
2019
- 2019-09-25 KR KR1020207019760A patent/KR20210082126A/en not_active Application Discontinuation
- 2019-09-25 CN CN201980013366.3A patent/CN111742258A/en active Pending
- 2019-09-25 WO PCT/JP2019/037512 patent/WO2020084988A1/en active Application Filing
- 2019-09-25 JP JP2019555501A patent/JP6725771B1/en active Active
- 2019-09-27 TW TW108135132A patent/TWI809206B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001133794A (en) | 1999-11-01 | 2001-05-18 | Kyoritsu Kagaku Sangyo Kk | Sealing agent for dropping process of lcd panel |
| WO2002092718A1 (en) | 2001-05-16 | 2002-11-21 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020084988A1 (en) | 2021-02-15 |
| JP6725771B1 (en) | 2020-07-22 |
| TW202028408A (en) | 2020-08-01 |
| WO2020084988A1 (en) | 2020-04-30 |
| TWI809206B (en) | 2023-07-21 |
| CN111742258A (en) | 2020-10-02 |
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