KR102240965B1 - Liquid-crystal-display-element sealant, vertical conductive material, and liquid-crystal display element - Google Patents
Liquid-crystal-display-element sealant, vertical conductive material, and liquid-crystal display element Download PDFInfo
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- KR102240965B1 KR102240965B1 KR1020157031377A KR20157031377A KR102240965B1 KR 102240965 B1 KR102240965 B1 KR 102240965B1 KR 1020157031377 A KR1020157031377 A KR 1020157031377A KR 20157031377 A KR20157031377 A KR 20157031377A KR 102240965 B1 KR102240965 B1 KR 102240965B1
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- South Korea
- Prior art keywords
- liquid crystal
- crystal display
- sealing agent
- formula
- meth
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 131
- 239000004020 conductor Substances 0.000 title 1
- 239000000565 sealant Substances 0.000 title 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- H01L51/5246—
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/842—Containers
- H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- G—PHYSICS
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- 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
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Abstract
본 발명은, 광 경화성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제를 제공하는 것을 목적으로 한다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 이용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공하는 것을 목적으로 한다.
본 발명은, 경화성 수지와, 하기 식 (1) 로 나타내는 티오크산톤계 중합 개시제와, 아민계 증감제를 함유하는 액정 표시 소자용 시일제이다.
식 (1) 중, n 은, 1 ∼ 6 이고, R3 은, 수소 원자, 메틸기, 또는 에틸기이고, n 이 1 보다 큰 경우, R3 으로 나타내는 기 또는 원자는, 동일해도 되고, 상이해도 된다. A 는, 식 -O-, -[O(CHR2CHR1)a]y-, -[O(CH2)bCO]y-, 또는 -[O(CH2)bCO](y-1)-[O(CHR2CHR1)a]- 의 기를 나타내고, R1 과 R2 의 일방은, 수소 원자를 나타내고, 타방은, 수소 원자, 메틸기, 또는 에틸기를 나타내고, a 는, 1 ∼ 2 이고, b 는, 4 ∼ 5 이고, Q 는, (폴리)에틸렌글리콜, (폴리)프로필렌글리콜, (폴리)부틸렌글리콜, 글리세린, 트리메틸올프로판, 디트리메틸올프로판, 펜타에리트리톨, 디펜타에리트리톨, 또는 카프로락톤 폴리올의 잔기이고, Q 내의 유리 하이드록실기가 에스테르화되어 있어도 되고, x 는, 1 보다 크고, Q 의 수산기의 수를 초과하지 않는 수이고, x 가 1 보다 크고, 2 를 초과하지 않는 경우, y 는 1 ∼ 10 이고, x 가 2 를 초과하는 경우, y 는 3 ∼ 10 이다.
[화학식 1]
An object of the present invention is to provide a sealing agent for a liquid crystal display device that is excellent in photocurability and can suppress liquid crystal contamination. Moreover, it is an object of the present invention to provide a vertical conduction material and a liquid crystal display element formed by using the sealing agent for a liquid crystal display element.
The present invention is a sealing agent for a liquid crystal display element containing a curable resin, a thioxanthone-based polymerization initiator represented by the following formula (1), and an amine-based sensitizer.
In formula (1), n is 1 to 6, R 3 is a hydrogen atom, a methyl group, or an ethyl group, and when n is greater than 1, the group or atom represented by R 3 may be the same or different. . A is the formula -O-, -[O(CHR 2 CHR 1 ) a ] y -, -[O(CH 2 ) b CO] y -, or -[O(CH 2 ) b CO] (y-1 ) Represents a group of -[O(CHR 2 CHR 1 ) a ]-, one of R 1 and R 2 represents a hydrogen atom, the other represents a hydrogen atom, a methyl group, or an ethyl group, and a represents 1 to 2 , B is 4 to 5, Q is (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaeryth It is a residue of lithol or caprolactone polyol, and the free hydroxyl group in Q may be esterified, x is a number greater than 1 and not exceeding the number of hydroxyl groups in Q, x is greater than 1, and 2 When it does not exceed, y is 1-10, and when x exceeds 2, y is 3-10.
[Formula 1]
Description
본 발명은, 광 경화성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제에 관한 것이다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 이용하여 이루어지는 상하 도통 재료 및 액정 표시 소자에 관한 것이다.The present invention relates to a sealing agent for a liquid crystal display device that is excellent in photocurability and can suppress liquid crystal contamination. In addition, the present invention relates to a vertical conduction material and a liquid crystal display element formed by using the sealing agent for a liquid crystal display element.
최근, 액정 표시 셀 등의 액정 표시 소자의 제조 방법으로는, 택트 타임 단축, 사용 액정량의 최적화라는 관점에서, 특허문헌 1, 특허문헌 2 에 개시되어 있는, 경화성 수지와 광 중합 개시제와 열 경화제를 함유하는 광열 병용 경화형의 시일제를 사용한 적하 공법이라 불리는 액정 적하 방식이 이용되고 있다.Recently, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin, a photopolymerization initiator, and a thermal curing agent disclosed in Patent Documents 1 and 2 from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a curing type sealing agent for light-heat combination containing containing is used.
적하 공법에서는, 먼저, 2 장의 전극이 형성된 기판의 일방에, 디스펜스에 의해 장방형상의 시일 패턴을 형성한다. 이어서, 시일제가 미경화 상태에서 액정의 미소 방울을 기판의 시일 프레임 내에 적하하고, 진공하에서 타방의 기판을 중첩하고, 시일부에 자외선 등의 광을 조사해 가경화를 실시한다. 그 후, 가열해 본경화를 실시해, 액정 표시 소자를 제작한다. 현재 이 적하 공법이 액정 표시 소자의 제조 방법의 주류가 되어 있다.In the dropping method, first, a rectangular seal pattern is formed by dispensing on one of the substrates on which the two electrodes are formed. Next, in a state where the sealing agent is not cured, microdroplets of liquid crystal are dripped into the sealing frame of the substrate, the other substrate is superimposed under vacuum, and the sealing portion is subjected to temporary curing by irradiating light such as ultraviolet rays. Then, it heats and performs main hardening, and the liquid crystal display element is produced. Currently, this dropping method has become a mainstream method for manufacturing a liquid crystal display element.
그런데, 휴대전화, 휴대게임기 등, 각종 액정 패널이 부착된 모바일 기기가 보급되어 있는 현대에 있어서, 기기의 소형화는 가장 요구되고 있는 과제이다. 기기의 소형화 수법으로는, 액정 표시부의 슬림 프레임화를 들 수 있고, 예를 들어 시일부의 위치를 블랙 매트릭스 아래에 배치하는 것이 실시되고 있다 (이하, 슬림 프레임 설계라고도 한다).By the way, in the modern era in which mobile devices equipped with various liquid crystal panels, such as mobile phones and portable game consoles, are widely used, miniaturization of devices is the most demanded subject. As a method of miniaturizing the device, a slim frame of the liquid crystal display is exemplified, and for example, the position of the seal is placed under a black matrix (hereinafter, also referred to as a slim frame design).
그러나, 슬림 프레임 설계에서는 시일제가 블랙 매트릭스의 바로 아래에 배치되기 때문에, 적하 공법을 실시하면, 시일제를 광 경화시킬 때에 조사한 광이 차단되어, 시일제의 내부에 광이 도달하기 어려워 경화가 불충분해진다는 문제가 있었다. 이와 같이 시일제의 경화가 불충분해지면, 미경화의 시일제 성분이 액정 중으로 용출되어 액정 오염을 발생시키기 쉬워진다는 문제가 있었다.However, in the slim frame design, since the sealing agent is disposed directly under the black matrix, when the dropping method is performed, the irradiated light is blocked when the sealing agent is photo-cured, and it is difficult to reach the inside of the sealing agent, so that the curing is insufficient. There was a problem of getting worse. In this way, when curing of the sealing agent becomes insufficient, there is a problem that the uncured sealing agent component elutes into the liquid crystal, and liquid crystal contamination is liable to occur.
특허문헌 3 에는, 시일제에 고감도의 광 중합 개시제를 배합하는 것이 개시되어 있다. 그러나, 단순히 고감도의 광 중합 개시제를 배합한 것만으로는, 충분히 시일제를 광 경화시킬 수 없었다. 또, 특허문헌 4 에는, 시일제에 고감도의 광 중합 개시제와 증감제를 조합하여 배합하는 것이 개시되어 있다. 그러나, 증감제를 사용함으로써, 액정 오염이 발생하기 쉬워진다는 문제가 있었다.In Patent Document 3, it is disclosed to mix a highly sensitive photopolymerization initiator with a sealing agent. However, simply by blending a highly sensitive photopolymerization initiator, the sealing agent could not be sufficiently photocured. In addition, Patent Literature 4 discloses a combination of a highly sensitive photopolymerization initiator and a sensitizer to be blended with a sealing agent. However, by using a sensitizer, there is a problem that liquid crystal contamination is liable to occur.
본 발명은, 광 경화성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제를 제공하는 것을 목적으로 한다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 이용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a sealing agent for a liquid crystal display device that is excellent in photocurability and can suppress liquid crystal contamination. Moreover, it is an object of the present invention to provide a vertical conduction material and a liquid crystal display element formed by using the sealing agent for a liquid crystal display element.
본 발명은, 경화성 수지와, 하기 식 (1) 로 나타내는 티오크산톤계 중합 개시제와, 아민계 증감제를 함유하는 액정 표시 소자용 시일제이다.The present invention is a sealing agent for a liquid crystal display element containing a curable resin, a thioxanthone-based polymerization initiator represented by the following formula (1), and an amine-based sensitizer.
[화학식 1][Formula 1]
식 (1) 중, n 은, 1 ∼ 6 이고, R3 은, 수소 원자, 메틸기, 또는 에틸기이고, n 이 1 보다 큰 경우, R3 으로 나타내는 기 또는 원자는, 동일해도 되고, 상이해도 된다. A 는, 식 -O-, -[O(CHR2CHR1)a]y-, -[O(CH2)bCO]y-, 또는 -[O(CH2)bCO](y-1)-[O(CHR2CHR1)a]- 의 기를 나타내고, R1 과 R2 의 일방은, 수소 원자를 나타내고, 타방은, 수소 원자, 메틸기, 또는 에틸기를 나타내고, a 는, 1 ∼ 2 이고, b 는, 4 ∼ 5 이고, Q 는, (폴리)에틸렌글리콜, (폴리)프로필렌글리콜, (폴리)부틸렌글리콜, 글리세린, 트리메틸올프로판, 디트리메틸올프로판, 펜타에리트리톨, 디펜타에리트리톨, 또는 카프로락톤 폴리올의 잔기이고, Q 내의 유리 하이드록실기가 에스테르화되어 있어도 되고, x 는, 1 보다 크고, Q 의 수산기의 수를 초과하지 않는 수이고, x 가 1 보다 크고, 2 를 초과하지 않는 경우, y 는 1 ∼ 10 이고, x 가 2 를 초과하는 경우, y 는 3 ∼ 10 이다.In formula (1), n is 1 to 6, R 3 is a hydrogen atom, a methyl group, or an ethyl group, and when n is greater than 1, the group or atom represented by R 3 may be the same or different. . A is the formula -O-, -[O(CHR 2 CHR 1 ) a ] y -, -[O(CH 2 ) b CO] y -, or -[O(CH 2 ) b CO] (y-1 ) Represents a group of -[O(CHR 2 CHR 1 ) a ]-, one of R 1 and R 2 represents a hydrogen atom, the other represents a hydrogen atom, a methyl group, or an ethyl group, and a represents 1 to 2 , B is 4 to 5, Q is (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaeryth It is a residue of lithol or caprolactone polyol, and the free hydroxyl group in Q may be esterified, x is a number greater than 1 and not exceeding the number of hydroxyl groups in Q, x is greater than 1, and 2 When it does not exceed, y is 1-10, and when x exceeds 2, y is 3-10.
본 발명자들은, 놀랍게도, 특정 구조를 갖는 화합물이, 액정에 대한 오염성이 낮고, 또한 광 반응성이 우수한 것을 알아냈다. 그래서 본 발명자들은, 그 화합물을 광 중합 개시제로서 배합함으로써, 광 경화성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제를 얻을 수 있는 것을 찾아내, 본 발명을 완성시키기에 이르렀다.The inventors of the present invention have surprisingly found that a compound having a specific structure has low contamination to liquid crystal and excellent photoreactivity. Therefore, the inventors of the present invention found that by blending the compound as a photopolymerization initiator, a sealing agent for a liquid crystal display device that is excellent in photocurability and that can suppress liquid crystal contamination can be obtained, and came to complete the present invention. .
본 발명의 액정 표시 소자용 시일제는, 상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제를 함유한다. 상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제를 아민계 증감제와 조합하여 함유함으로써, 본 발명의 액정 표시 소자용 시일제는, 고감도이고 광 경화성이 우수하고, 또한 액정 오염을 억제할 수 있는 것이 된다.The sealing agent for liquid crystal display elements of this invention contains the thioxanthone type polymerization initiator represented by said formula (1). By containing the thioxanthone-based polymerization initiator represented by the above formula (1) in combination with an amine-based sensitizer, the sealing agent for a liquid crystal display device of the present invention is highly sensitive, has excellent photocurability, and can suppress liquid crystal contamination. It becomes what there is.
상기 식 (1) 중, x 는, 1 보다 크고, Q 의 수산기의 수를 초과하지 않는 수이고, 바람직한 하한은 2, 바람직한 상한은 6 이다. 상기 x 가 2 미만이면, 액정 오염을 일으키는 경우가 있다. 상기 x 가 6 을 초과하면, 점도가 높아져, 취급이 곤란해지는 경우가 있다.In the above formula (1), x is a number greater than 1 and not exceeding the number of hydroxyl groups of Q, a preferred lower limit of 2 and a preferred upper limit of 6. When x is less than 2, liquid crystal contamination may occur. When the said x exceeds 6, the viscosity becomes high and handling may become difficult.
상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제는, 상기 식 (1) 중의 n 이 1 이고, R3 이 수소 원자이고, A 가 식 -O- 의 기인 것이 바람직하다.In the thioxanthone polymerization initiator represented by the above formula (1), it is preferable that n in the above formula (1) is 1, R 3 is a hydrogen atom, and A is a group of the formula -O-.
상기 식 (1) 중의 Q 는, 폴리부틸렌글리콜의 잔기인 것이 바람직하다.It is preferable that Q in said formula (1) is a residue of polybutylene glycol.
또, Q 내의 유리 하이드록실기가 에스테르화되어 있는 경우, 상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제는, 저급 지방산 에스테르인 것이 바람직하다. Moreover, when the free hydroxyl group in Q is esterified, it is preferable that the thioxanthone type polymerization initiator represented by said formula (1) is a lower fatty acid ester.
상기 식 (1) 중, A-Q 의 분자량의 바람직한 하한은 100, 바람직한 상한은 2000 이다. A-Q 의 분자량이 100 미만이면, 액정 오염을 일으키는 경우가 있다. A-Q 의 분자량이 2000 을 초과하면, 점도가 지나치게 높아져 취급이 곤란해지는 경우가 있다.In the formula (1), the preferred lower limit of the molecular weight of A-Q is 100, and the preferred upper limit is 2000. When the molecular weight of A-Q is less than 100, liquid crystal contamination may occur. When the molecular weight of A-Q exceeds 2000, the viscosity becomes too high and handling may become difficult.
상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제를 제조하는 방법으로는, 구체적으로는 예를 들어, 카르복시메톡시티오크산톤과 폴리에틸렌글리콜을 반응시키는 방법 등을 들 수 있다.Specific examples of the method for producing the thioxanthone-based polymerization initiator represented by the above formula (1) include, for example, a method of reacting carboxymethoxy thioxanthone and polyethylene glycol.
본 발명의 액정 표시 소자용 시일제 100 중량부 중에 있어서의 상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제의 함유량의 바람직한 하한은 0.1 중량부, 바람직한 상한은 10 중량부이다. 상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제의 함유량이 0.1 중량부 미만이면, 얻어지는 액정 표시 소자용 시일제의 광 중합이 충분히 진행되지 않는 경우가 있다. 상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제의 함유량이 10 중량부를 초과하면, 미반응의 식 (1) 로 나타내는 티오크산톤계 중합 개시제가 많이 남아, 얻어지는 액정 표시 소자용 시일제가, 내후성이나 보존 안정성이 열등한 것이 되거나, 액정 오염이 발생하거나 하는 경우가 있다. 상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제의 함유량의 보다 바람직한 하한은 0.3 중량부, 보다 바람직한 상한은 7 중량부이다.A preferable lower limit of the content of the thioxanthone polymerization initiator represented by the formula (1) in 100 parts by weight of the sealing agent for a liquid crystal display device of the present invention is 0.1 parts by weight, and a preferable upper limit is 10 parts by weight. When the content of the thioxanthone polymerization initiator represented by the above formula (1) is less than 0.1 parts by weight, photopolymerization of the obtained sealing agent for a liquid crystal display device may not sufficiently proceed. When the content of the thioxanthone polymerization initiator represented by the above formula (1) exceeds 10 parts by weight, a large amount of the thioxanthone polymerization initiator represented by the unreacted formula (1) remains, and the resulting liquid crystal display sealing agent is weather resistant. However, storage stability may become inferior, or liquid crystal contamination may occur. A more preferable lower limit of the content of the thioxanthone polymerization initiator represented by the above formula (1) is 0.3 parts by weight, and a more preferable upper limit is 7 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 아민계 증감제를 함유한다. 상기 아민계 증감제로는, 예를 들어 하기 식 (2) 로 나타내는 화합물, 4,4'-비스(디에틸아미노)벤조페논, 2-디메틸아미노-에틸벤조에이트, 에틸4-(디메틸아미노)벤조에이트, 2-에틸헥실-4-디메틸아미노벤조에이트, 이소아밀-4-(디메틸아미노)벤조에이트, 부톡시에틸-4-(디메틸아미노)벤조에이트 등을 들 수 있다. 그 중에서도, 얻어지는 액정 표시 소자용 시일제가 경화성이 우수한 것이 되는 점에서, 하기 식 (2) 로 나타내는 화합물 (이하, 「식 (2) 로 나타내는 아민계 증감제」라고도 한다) 이 바람직하다.The sealing agent for liquid crystal display elements of this invention contains an amine-type sensitizer. As the amine-based sensitizer, for example, a compound represented by the following formula (2), 4,4'-bis(diethylamino)benzophenone, 2-dimethylamino-ethylbenzoate, ethyl 4-(dimethylamino)benzo Acid, 2-ethylhexyl-4-dimethylaminobenzoate, isoamyl-4-(dimethylamino)benzoate, butoxyethyl-4-(dimethylamino)benzoate, and the like. Among them, the compound represented by the following formula (2) (hereinafter, also referred to as "the amine-based sensitizer represented by the formula (2)") is preferred from the viewpoint of the obtained sealing agent for a liquid crystal display device having excellent curability.
[화학식 2][Formula 2]
식 (2) 중, z 는, 1 이상의 정수를 나타내고, P 는, (폴리)에틸렌글리콜, (폴리)프로필렌글리콜, (폴리)부틸렌글리콜, 글리세린, 트리메틸올프로판, 디트리메틸올프로판, 펜타에리트리톨, 디펜타에리트리톨, 또는 카프로락톤 폴리올의 잔기이다.In formula (2), z represents an integer of 1 or more, and P is (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaeryth It is a residue of lithol, dipentaerythritol, or caprolactone polyol.
상기 식 (2) 중, z 는, 1 이상의 정수를 나타내고, 바람직한 하한은 2, 바람직한 상한은 6 이다. 상기 z 가 2 미만이면, 액정 오염을 일으키는 경우가 있다. 상기 z 가 6 을 초과하면, 점도가 높아져, 취급이 곤란해지는 경우가 있다.In the above formula (2), z represents an integer of 1 or more, and a preferable lower limit is 2 and a preferable upper limit is 6. When z is less than 2, liquid crystal contamination may occur. When the said z exceeds 6, the viscosity becomes high and handling may become difficult.
상기 식 (2) 중, P 는, (폴리)에틸렌글리콜, (폴리)프로필렌글리콜, (폴리)부틸렌글리콜, 글리세린, 트리메틸올프로판, 디트리메틸올프로판, 펜타에리트리톨, 디펜타에리트리톨, 또는 카프로락톤 폴리올의 잔기이다.In the formula (2), P is (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, or It is the residue of caprolactone polyol.
상기 식 (2) 중의 P 의 분자량의 바람직한 하한은 100, 바람직한 상한은 2000 이다. P 의 분자량이 100 미만이면, 액정 오염을 일으키는 경우가 있다. P 의 분자량이 2000 을 초과하면, 점도가 지나치게 높아져, 취급이 곤란해지는 경우가 있다.The preferable lower limit of the molecular weight of P in the above formula (2) is 100, and the preferable upper limit is 2000. When the molecular weight of P is less than 100, liquid crystal contamination may occur. When the molecular weight of P exceeds 2000, the viscosity becomes too high and handling may become difficult.
상기 식 (2) 로 나타내는 아민계 증감제는, 식 (2) 중의 z 가 2 이고, P 가 폴리에틸렌글리콜의 잔기인 것이 바람직하다.As for the amine-based sensitizer represented by the above formula (2), z in formula (2) is 2, and it is preferable that P is a residue of polyethylene glycol.
상기 식 (2) 로 나타내는 아민계 증감제를 제조하는 방법으로는, 구체적으로는 예를 들어, 4-(디메틸아미노)벤조일클로라이드와 폴리에틸렌옥사이드를 반응시키는 방법 등을 들 수 있다.Specific examples of the method for producing the amine-based sensitizer represented by the above formula (2) include, for example, a method of reacting 4-(dimethylamino)benzoyl chloride and polyethylene oxide.
본 발명의 액정 표시 소자용 시일제 100 중량부 중에 있어서의 상기 아민계 증감제의 함유량의 바람직한 하한은 0.1 중량부, 바람직한 상한은 10 중량부이다. 상기 아민계 증감제의 함유량이 0.1 중량부 미만이면, 얻어지는 액정 표시 소자용 시일제가 광 경화성이 열등한 것이 되고, 액정 오염이 발생하는 경우가 있다. 상기 아민계 증감제의 함유량이 10 중량부를 초과하면, 아민계 증감제에 의한 액정 오염이 발생하는 경우가 있다. 상기 아민계 증감제의 함유량의 보다 바람직한 하한은 0.3 중량부, 보다 바람직한 상한은 7 중량부이다.A preferable lower limit of the content of the amine-based sensitizer in 100 parts by weight of the sealing agent for a liquid crystal display device of the present invention is 0.1 parts by weight, and a preferable upper limit is 10 parts by weight. When the content of the amine-based sensitizer is less than 0.1 part by weight, the obtained sealing agent for a liquid crystal display device is inferior in photocurability, and liquid crystal contamination may occur. When the content of the amine-based sensitizer exceeds 10 parts by weight, liquid crystal contamination by the amine-based sensitizer may occur. A more preferable lower limit of the content of the amine-based sensitizer is 0.3 parts by weight, and a more preferable upper limit is 7 parts by weight.
상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제와 상기 아민계 증감제의 함유 비율은, 중량비로, 식 (1) 로 나타내는 티오크산톤계 중합 개시제 : 아민계 증감제 = 1 : 0.05 ∼ 1 : 5 인 것이 바람직하다. 상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제와 상기 아민계 증감제의 함유 비율이 이 범위 내임으로써, 본 발명의 액정 표시 소자용 시일제는, 액정 오염을 억제하는 효과, 및 광 경화성이 특히 우수해진다. 상기 식 (1) 로 나타내는 티오크산톤계 중합 개시제와 상기 아민계 증감제의 함유 비율은, 식 (1) 로 나타내는 티오크산톤계 중합 개시제 : 아민계 증감제 = 1 : 0.1 ∼ 1 : 2 인 것이 보다 바람직하다.The content ratio of the thioxanthone-based polymerization initiator represented by the formula (1) and the amine-based sensitizer is a weight ratio, and the thioxanthone-based polymerization initiator represented by the formula (1): amine-based sensitizer = 1: 0.05 to 1 : It is preferable that it is 5. When the content ratio of the thioxanthone-based polymerization initiator represented by the formula (1) and the amine-based sensitizer is within this range, the sealing agent for a liquid crystal display device of the present invention has an effect of suppressing liquid crystal contamination, and photocurability. It becomes especially excellent. The content ratio of the thioxanthone-based polymerization initiator represented by the formula (1) and the amine-based sensitizer is the thioxanthone-based polymerization initiator represented by the formula (1): amine-based sensitizer = 1: 0.1 to 1: 2 It is more preferable.
본 발명의 액정 표시 소자용 시일제는, 경화성 수지를 함유한다.The sealing agent for liquid crystal display elements of this invention contains a curable resin.
상기 경화성 수지는, (메트)아크릴 수지를 함유하는 것이 바람직하다.It is preferable that the said curable resin contains a (meth)acrylic resin.
상기 (메트)아크릴 수지로는, 예를 들어 (메트)아크릴산에 수산기를 갖는 화합물을 반응시킴으로써 얻어지는 에스테르 화합물, (메트)아크릴산과 에폭시 화합물을 반응시킴으로써 얻어지는 에폭시(메트)아크릴레이트, 이소시아네이트 화합물에 수산기를 갖는 (메트)아크릴산 유도체를 반응시킴으로써 얻어지는 우레탄(메트)아크릴레이트 등을 들 수 있다. 그 중에서도, 에폭시(메트)아크릴레이트가 바람직하다.As the (meth)acrylic resin, for example, an ester compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, an epoxy (meth)acrylate obtained by reacting a (meth)acrylic acid and an epoxy compound, and a hydroxyl group in an isocyanate compound Urethane (meth)acrylate obtained by reacting a (meth)acrylic acid derivative having. Among them, epoxy (meth)acrylate is preferred.
또한, 본 명세서에 있어서, 상기 「(메트)아크릴」이란, 아크릴 또는 메타크릴을 의미하고, 상기 「(메트)아크릴 수지」란, 아크릴로일기 또는 메타크릴로일기 (이하, 합쳐서 「(메트)아크릴로일기」라고도 한다) 를 갖는 수지를 의미한다. 또, 상기 「(메트)아크릴레이트」란, 아크릴레이트 또는 메타크릴레이트를 의미한다. 또한, 상기 「에폭시(메트)아크릴레이트」란, 에폭시 수지 중의 모든 에폭시기를 (메트)아크릴산과 반응시킨 화합물을 나타낸다.In addition, in this specification, the "(meth)acrylic" means acrylic or methacrylic, and the "(meth)acrylic resin" means an acryloyl group or a methacryloyl group (hereinafter, collectively, "(meth) It means a resin having an acryloyl group"). Moreover, the said "(meth)acrylate" means an acrylate or a methacrylate. In addition, the said "epoxy (meth)acrylate" refers to the compound which made all the epoxy groups in an epoxy resin react with (meth)acrylic acid.
상기 에스테르 화합물 중 단관능인 것으로는, 예를 들어 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, t-부틸(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 스테아릴(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 2-메톡시에틸(메트)아크릴레이트, 메톡시에틸렌글리콜(메트)아크릴레이트, 2-에톡시에틸(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, 벤질(메트)아크릴레이트, 에틸카르비톨(메트)아크릴레이트, 페녹시에틸(메트)아크릴레이트, 페녹시디에틸렌글리콜(메트)아크릴레이트, 페녹시폴리에틸렌글리콜(메트)아크릴레이트, 메톡시폴리에틸렌글리콜(메트)아크릴레이트, 2,2,2-트리플루오로에틸(메트)아크릴레이트, 2,2,3,3-테트라플루오로프로필(메트)아크릴레이트, 1H,1H,5H-옥타플루오로펜틸(메트)아크릴레이트, 이미드(메트)아크릴레이트, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, n-부틸(메트)아크릴레이트, 프로필(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, n-옥틸(메트)아크릴레이트, 이소노닐(메트)아크릴레이트, 이소미리스틸(메트)아크릴레이트, 2-부톡시에틸(메트)아크릴레이트, 2-페녹시에틸(메트)아크릴레이트, 비시클로펜테닐(메트)아크릴레이트, 이소데실(메트)아크릴레이트, 디에틸아미노에틸(메트)아크릴레이트, 디메틸아미노에틸(메트)아크릴레이트, 2-(메트)아크릴로일옥시에틸숙신산, 2-(메트)아크릴로일옥시에틸헥사하이드로프탈산, 2-(메트)아크릴로일옥시에틸2-하이드록시프로필프탈레이트, 글리시딜(메트)아크릴레이트, 2-(메트)아크릴로일옥시에틸포스페이트 등을 들 수 있다.As a monofunctional one of the ester compounds, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxybutyl (Meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (Meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (Meth)acrylate, benzyl (meth)acrylate, ethylcarbitol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate , Methoxypolyethylene glycol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H -Octafluoropentyl (meth)acrylate, imide (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, propyl (meth)acrylate, 2 -Ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isononyl (meth)acrylate, isomyristyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxy Ethyl (meth)acrylate, bicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 2-(meth)acrylic Royloxyethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl2-hydroxypropylphthalate, glycidyl(meth)acrylate, 2-(meth) ) Acryloyloxyethyl phosphate, etc. are mentioned.
또, 상기 에스테르 화합물 중 2 관능인 것으로는, 예를 들어 1,4-부탄디올디(메트)아크릴레이트, 1,3-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 1,9-노난디올디(메트)아크릴레이트, 1,10-데칸디올디(메트)아크릴레이트, 2-n-부틸-2-에틸-1,3-프로판디올디(메트)아크릴레이트, 디프로필렌글리콜디(메트)아크릴레이트, 트리프로필렌글리콜디(메트)아크릴레이트, 폴리프로필렌글리콜(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 테트라에틸렌글리콜디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 프로필렌옥사이드 부가 비스페놀 A 디(메트)아크릴레이트, 에틸렌옥사이드 부가 비스페놀 A 디(메트)아크릴레이트, 에틸렌옥사이드 부가 비스페놀 F 디(메트)아크릴레이트, 디메틸올디시클로펜타디에닐디(메트)아크릴레이트, 1,3-부틸렌글리콜디(메트)아크릴레이트, 네오펜틸글리콜디(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 among the said ester compounds, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic Rate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanedioldi(meth)acrylate , Dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetra Ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol F di(meth) )Acrylate, dimethyloldicyclopentadienyldi(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, neopentylglycol di(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth) Acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, carbonate dioldi(meth)acrylate, polyetherdioldi(meth)acrylate, polyesterdioldi(meth) Acrylate, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate, and the like.
또, 상기 에스테르 화합물 중 3 관능 이상인 것으로는, 예를 들어 펜타에리트리톨트리(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 프로필렌옥사이드 부가 트리메틸올프로판트리(메트)아크릴레이트, 에틸렌옥사이드 부가 트리메틸올프로판트리(메트)아크릴레이트, 카프로락톤 변성 트리메틸올프로판트리(메트)아크릴레이트, 에틸렌옥사이드 부가 이소시아누르산트리(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트, 디트리메틸올프로판테트라(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트, 글리세린트리(메트)아크릴레이트, 프로필렌옥사이드 부가 글리세린트리(메트)아크릴레이트, 트리스(메트)아크릴로일옥시에틸포스페이트 등을 들 수 있다. In addition, examples of the ester compound having three or more functionalities include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, and ethylene oxide. Added trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide added isocyanuric acid tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, di Pentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide added glycerin tri(meth)acrylate, And tris(meth)acryloyloxyethyl phosphate.
상기 에폭시(메트)아크릴레이트로는, 예를 들어 에폭시 수지와 (메트)아크릴산을, 통상적인 방법에 따라 염기성 촉매의 존재하에서 반응시킴으로써 얻어지는 것 등을 들 수 있다.Examples of the epoxy (meth)acrylate include those obtained by reacting an epoxy resin and (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.
상기 에폭시(메트)아크릴레이트를 합성하기 위한 원료가 되는 에폭시 수지로는, 예를 들어 비스페놀 A 형 에폭시 수지, 비스페놀 F 형 에폭시 수지, 비스페놀 S 형 에폭시 수지, 2,2'-디알릴비스페놀 A 형 에폭시 수지, 수소 첨가 비스페놀형 에폭시 수지, 프로필렌옥사이드 부가 비스페놀 A 형 에폭시 수지, 레조르시놀형 에폭시 수지, 비페닐형 에폭시 수지, 술파이드형 에폭시 수지, 디페닐에테르형 에폭시 수지, 디시클로펜타디엔형 에폭시 수지, 나프탈렌형 에폭시 수지, 페놀노볼락형 에폭시 수지, 오르토크레졸노볼락형 에폭시 수지, 디시클로펜타디엔노볼락형 에폭시 수지, 비페닐노볼락형 에폭시 수지, 나프탈렌페놀노볼락형 에폭시 수지, 글리시딜아민형 에폭시 수지, 알킬 폴리올형 에폭시 수지, 고무 변성형 에폭시 수지, 글리시딜에스테르 화합물 등을 들 수 있다.As an epoxy resin used as a raw material for synthesizing the epoxy (meth)acrylate, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallylbisphenol A type Epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol type A epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy Resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol novolak type epoxy resin, glycy A diylamine type epoxy resin, an alkyl polyol type epoxy resin, a rubber modified type epoxy resin, a glycidyl ester compound, etc. are mentioned.
상기 비스페놀 A 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 jER828EL, jER1004 (모두 미츠비시 화학사 제조), 에피클론 850CRP (DIC 사 제조) 등을 들 수 있다.Examples of commercially available bisphenol A epoxy resins include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), Epiclon 850CRP (manufactured by DIC Corporation), and the like.
상기 비스페놀 F 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 jER806, jER4004 (모두 미츠비시 화학사 제조) 등을 들 수 있다.Examples of commercially available bisphenol F-type epoxy resins include jER806 and jER4004 (all manufactured by Mitsubishi Chemical Corporation).
상기 비스페놀 S 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 에피클론 EXA1514 (DIC 사 제조) 등을 들 수 있다.Among the above bisphenol S-type epoxy resins, commercially available ones include, for example, Epiclon EXA1514 (manufactured by DIC).
상기 2,2'-디알릴비스페놀 A 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 RE-810NM (닛폰카야쿠사 제조) 등을 들 수 있다.Among the above 2,2'-diallylbisphenol A type epoxy resins, commercially available ones include, for example, RE-810NM (manufactured by Nippon Kayaku Corporation).
상기 수소 첨가 비스페놀형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 에피클론 EXA7015 (DIC 사 제조) 등을 들 수 있다.Examples of commercially available hydrogenated bisphenol-type epoxy resins include Epiclon EXA7015 (manufactured by DIC).
상기 프로필렌옥사이드 부가 비스페놀 A 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 EP-4000S (ADEKA 사 제조) 등을 들 수 있다.Among the propylene oxide-added bisphenol A type epoxy resins, commercially available ones include, for example, EP-4000S (manufactured by ADEKA).
상기 레조르시놀형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 EX-201 (나가세켐텍스사 제조) 등을 들 수 있다.Examples of the resorcinol-type epoxy resin marketed include EX-201 (manufactured by Nagase Chemtex).
상기 비페닐형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 jER YX-4000H (미츠비시 화학사 제조) 등을 들 수 있다.Examples of commercially available biphenyl-type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
상기 술파이드형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 YSLV-50TE (신닛테츠수미킹 화학사 제조) 등을 들 수 있다.Examples of commercially available sulfide-type epoxy resins include YSLV-50TE (manufactured by Shinnittetsu Sumiking Chemical Co., Ltd.).
상기 디페닐에테르형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 YSLV-80DE (신닛테츠수미킹 화학사 제조) 등을 들 수 있다.Among the diphenyl ether type epoxy resins, commercially available ones include, for example, YSLV-80DE (manufactured by Shinnittetsu Sumiking Chemical Co., Ltd.).
상기 디시클로펜타디엔형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 EP-4088S (ADEKA 사 제조) 등을 들 수 있다.Among the above dicyclopentadiene-type epoxy resins, commercially available ones include EP-4088S (manufactured by ADEKA) and the like.
상기 나프탈렌형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 에피클론 HP4032, 에피클론 EXA-4700 (모두 DIC 사 제조) 등을 들 수 있다.Examples of commercially available naphthalene-type epoxy resins include Epiclon HP4032 and Epiclon EXA-4700 (all manufactured by DIC).
상기 페놀노볼락형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 에피클론 N-770 (DIC 사 제조) 등을 들 수 있다.Among the above phenol novolak-type epoxy resins, commercially available ones include, for example, Epiclon N-770 (manufactured by DIC).
상기 오르토크레졸노볼락형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 에피클론 N-670-EXP-S (DIC 사 제조) 등을 들 수 있다.Examples of commercially available orthocresol novolac epoxy resins include Epiclon N-670-EXP-S (manufactured by DIC).
상기 디시클로펜타디엔노볼락형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 에피클론 HP7200 (DIC 사 제조) 등을 들 수 있다.Examples of the dicyclopentadiene novolak type epoxy resins that are commercially available include Epiclon HP7200 (manufactured by DIC).
상기 비페닐노볼락형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 NC-3000P (닛폰카야쿠사 제조) 등을 들 수 있다.Examples of commercially available biphenyl novolak epoxy resins include NC-3000P (manufactured by Nippon Kayaku Corporation).
상기 나프탈렌페놀노볼락형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 ESN-165S (신닛테츠수미킹 화학사 제조) 등을 들 수 있다.Among the above naphthalenephenol novolak-type epoxy resins, commercially available ones include ESN-165S (manufactured by Shinnittetsu Sumiking Chemical Co., Ltd.) and the like.
상기 글리시딜아민형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 jER630 (미츠비시 화학사 제조), 에피클론 430 (DIC 사 제조), TETRAD-X (미츠비시 가스 화학사 제조) 등을 들 수 있다.Commercially available ones of the glycidylamine-type epoxy resins include, for example, jER630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like.
상기 알킬 폴리올형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 ZX-1542 (신닛테츠수미킹 화학사 제조), 에피클론 726 (DIC 사 제조), 에포라이트 80MFA (쿄에이샤 화학사 제조), 데나콜 EX-611 (나가세켐텍스사 제조) 등을 들 수 있다. Among the above alkyl polyol type epoxy resins, commercially available ones include, for example, ZX-1542 (manufactured by Shinnittetsu Sumiking Chemical Co., Ltd.), Epiclon 726 (manufactured by DIC Corporation), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol. EX-611 (manufactured by Nagase Chemtex), and the like.
상기 고무 변성형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어 YR-450, YR-207 (모두 신닛테츠수미킹 화학사 제조), 에포리드 PB (다이셀사 제조) 등을 들 수 있다. Commercially available ones of the rubber-modified epoxy resins include, for example, YR-450, YR-207 (all manufactured by Shinnittetsu Sumiking Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
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 compounds, Denacol EX-147 (made by Nagase Chemtex) etc. are mentioned, for example.
상기 에폭시 수지 중 그 외에 시판되고 있는 것으로는, 예를 들어 YDC-1312, YSLV-80XY, YSLV-90CR (모두 신닛테츠수미킹 화학사 제조), XAC4151 (아사히 화성사 제조), jER1031, jER1032 (모두 미츠비시 화학사 제조), EXA-7120 (DIC 사 제조), TEPIC (닛산 화학사 제조) 등을 들 수 있다.Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Shinnittetsu Sumiking Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Chemical Co., Ltd.), jER1031, jER1032 (all Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), and the like.
상기 에폭시(메트)아크릴레이트를 제조하는 방법으로는, 구체적으로는 예를 들어, 레조르시놀형 에폭시 수지 (EX-201, 나가세켐텍스사 제조) 360 중량부와, 중합 금지제로서 p-메톡시페놀 2 중량부와, 반응 촉매로서 트리에틸아민 2 중량부와, 아크릴산 210 중량부를, 공기를 불어넣고 환류 교반하면서, 90 ℃ 에서 5 시간 반응시킴으로써 레조르시놀형 에폭시아크릴레이트를 얻을 수 있다.As a method of preparing the epoxy (meth)acrylate, specifically, for example, resorcinol-type epoxy resin (EX-201, manufactured by Nagase Chemtex) 360 parts by weight, and p-methoxy as a polymerization inhibitor Resorcinol-type epoxy acrylate can be obtained by reacting 2 parts by weight of phenol, 2 parts by weight of triethylamine, and 210 parts by weight of acrylic acid as a reaction catalyst at 90° C. for 5 hours while blowing air and stirring under reflux.
상기 에폭시(메트)아크릴레이트 중 시판되고 있는 것으로는, 예를 들어 EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (모두 다이셀·올넥스사 제조), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (모두 신나카무라 화학 공업사 제조), 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 (모두 쿄에이샤 화학사 제조), 데나콜아크릴레이트 DA-141, 데나콜아크릴레이트 DA-314, 데나콜아크릴레이트 DA-911 (모두 나가세켐텍스사 제조) 등을 들 수 있다. Among the above-mentioned epoxy (meth)acrylates, commercially available ones include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3701, EBECRYL3702, EBECRYL3701, EBECRYL3702, EBECRYL3702, all manufactured by EBECRYLX40Nx , EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shinnakamura Chemical Industries), 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 (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacholacrylate DA-141, Dena Cholacrylate DA-314, denacholacrylate DA-911 (all manufactured by Nagase Chemtex), and the like.
상기 이소시아네이트 화합물에 수산기를 갖는 (메트)아크릴산 유도체를 반응시킴으로써 얻어지는 우레탄(메트)아크릴레이트로는, 예를 들어 2 개의 이소시아네이트기를 갖는 이소시아네이트 화합물 1 당량에 대해 수산기를 갖는 (메트)아크릴산 유도체 2 당량을, 촉매량의 주석계 화합물 존재하에서 반응시킴으로써 얻을 수 있다.As the urethane (meth)acrylate obtained by reacting the isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group, for example, 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group per equivalent of an isocyanate compound having two isocyanate groups And can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
상기 우레탄(메트)아크릴레이트의 원료가 되는 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, 테트라메틸자일렌디이소시아네이트, 1,6,10-운데칸트리이소시아네이트 등을 들 수 있다. As the isocyanate compound used as the raw material of the urethane (meth)acrylate, for example, 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), hydrogen Added XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecan triisocyanate, and the like.
또, 상기 우레탄(메트)아크릴레이트의 원료가 되는 이소시아네이트로는, 예를 들어 에틸렌글리콜, 글리세린, 소르비톨, 트리메틸올프로판, (폴리)프로필렌글리콜, 카보네이트디올, 폴리에테르디올, 폴리에스테르디올, 폴리카프로락톤디올 등의 폴리올과 과잉의 이소시아네이트 화합물의 반응에 의해 얻어지는 사슬 연장된 이소시아네이트 화합물도 사용할 수 있다.In addition, as the isocyanate used as the raw material of the urethane (meth)acrylate, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycapro A chain-extended isocyanate compound obtained by reaction of a polyol such as lactonediol with an excess isocyanate compound can also be used.
상기 우레탄(메트)아크릴레이트의 원료가 되는, 수산기를 갖는 (메트)아크릴산 유도체로는, 예를 들어 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트 등의 시판품이나, 에틸렌글리콜, 프로필렌글리콜, 1,3-프로판디올, 1,3-부탄디올, 1,4-부탄디올, 폴리에틸렌글리콜 등의 2 가의 알코올의 모노(메트)아크릴레이트나, 트리메틸올에탄, 트리메틸올프로판, 글리세린 등의 3 가의 알코올의 모노(메트)아크릴레이트 또는 디(메트)아크릴레이트나, 비스페놀 A 형 에폭시아크릴레이트 등의 에폭시(메트)아크릴레이트 등을 들 수 있다.Examples of (meth)acrylic acid derivatives having a hydroxyl group, which are the raw materials for the urethane (meth)acrylate, include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4- Commercial products such as hydroxybutyl (meth)acrylate and 2-hydroxybutyl (meth)acrylate, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene Mono(meth)acrylate of dihydric alcohol such as glycol, mono(meth)acrylate or di(meth)acrylate of trihydric alcohol such as trimethylolethane, trimethylolpropane, glycerin, bisphenol A type epoxy acrylic Epoxy (meth)acrylate, such as a rate, etc. are mentioned.
상기 우레탄(메트)아크릴레이트는, 구체적으로는 예를 들어, 트리메틸올프로판 134 중량부, 중합 금지제로서 BHT 0.2 중량부, 반응 촉매로서 디부틸주석디라우릴레이트 0.01 중량부, 이소포론디이소시아네이트 666 중량부를 첨가하고, 60 ℃ 에서 환류 교반하면서 2 시간 반응시키고, 다음으로 2-하이드록시에틸아크릴레이트 51 중량부를 첨가하고, 공기를 불어넣고 환류 교반하면서 90 ℃ 에서 2 시간 반응시킴으로써 얻을 수 있다. The urethane (meth)acrylate is specifically, for example, 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, 0.01 parts by weight of dibutyltin dilaurylate as a reaction catalyst, isophorone diisocyanate It can be obtained by adding 666 parts by weight, reacting at 60°C for 2 hours while refluxing and stirring, and then adding 51 parts by weight of 2-hydroxyethylacrylate, blowing air and reacting at 90°C for 2 hours while stirring under reflux.
상기 우레탄(메트)아크릴레이트 중 시판되고 있는 것으로는, 예를 들어 M-1100, M-1200, M-1210, M-1600 (모두 동아합성사 제조), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (모두 다이셀·올넥스사 제조), 아트레진 UN-9000H, 아트레진 UN-9000A, 아트레진 UN-7100, 아트레진 UN-1255, 아트레진 UN-330, 아트레진 UN-3320HB, 아트레진 UN-1200TPK, 아트레진 SH-500B (모두 네가미공업사 제조), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (모두 신나카무라 화학 공업사 제조), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (모두 쿄에이샤 화학사 제조) 등을 들 수 있다.Among the urethane (meth)acrylates that are commercially available, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Dong-A Synthetic Corporation), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803 , EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (all manufactured by Atresin UN-7100A, Atresin UN-7100A, Atresin UN-9000H) Resin UN-1255, Atresin UN-330, Atresin UN-3320HB, Atresin UN-1200TPK, Atresin SH-500B (all manufactured by Negami Industries), U-122P, U-108A, U-340P, U- 4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shinnakamura Chemical ), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemicals), and the like.
상기 경화성 수지는, 얻어지는 액정 표시 소자용 시일제의 접착성을 향상시키는 것을 목적으로 해, 추가로 에폭시 수지를 함유하는 것이 바람직하다. 상기 에폭시 수지로는, 예를 들어 상기 에폭시(메트)아크릴레이트를 합성하기 위한 원료가 되는 에폭시 수지나, 부분 (메트)아크릴 변성 에폭시 수지 등을 들 수 있다.It is preferable that the said curable resin further contains an epoxy resin for the purpose of improving the adhesiveness of the sealing agent for liquid crystal display elements obtained. Examples of the epoxy resin include an epoxy resin used as a raw material for synthesizing the epoxy (meth)acrylate, and a partially (meth)acrylic modified epoxy resin.
또한, 본 명세서에 있어서 상기 부분 (메트)아크릴 변성 에폭시 수지란, 1 분자 중에 에폭시기와 (메트)아크릴로일옥시기를 각각 1 개 이상 갖는 수지를 의미하고, 예를 들어 2 개 이상의 에폭시 수지의 일부분의 에폭시기를 (메트)아크릴산과 반응시킴으로써 얻을 수 있다.In addition, in the present specification, the partial (meth)acrylic-modified epoxy resin means a resin having at least one epoxy group and at least one (meth)acryloyloxy group in one molecule, for example, a part of at least two epoxy resins It can be obtained by reacting an epoxy group of (meth)acrylic acid.
본 발명의 액정 표시 소자용 시일제가 상기 에폭시 수지를 함유하는 경우, (메트)아크릴로일옥시기와 에폭시기의 비가 30 : 70 ∼ 95 : 5 가 되도록 상기 (메트)아크릴 수지와 상기 에폭시 수지를 배합하는 것이 바람직하다. (메트)아크릴로일옥시기의 비율이 30 % 미만이면, (메트)아크릴로일옥시기의 중합이 완료되어도 미경화의 에폭시 수지 성분이 많이 존재하기 때문에 액정 오염이 발생하는 경우가 있다. (메트)아크릴로일옥시기의 비율이 95 % 를 초과하면, 얻어지는 액정 표시 소자용 시일제가 접착성이 열등한 것이 되는 경우가 있다. When the sealing agent for a liquid crystal display device of the present invention contains the epoxy resin, mixing the (meth)acrylic resin and the epoxy resin so that the ratio of the (meth)acryloyloxy group and the epoxy group is 30:70 to 95:5. It is desirable. If the proportion of the (meth)acryloyloxy group is less than 30%, even when the polymerization of the (meth)acryloyloxy group is completed, since many uncured epoxy resin components exist, liquid crystal contamination may occur. When the proportion of the (meth)acryloyloxy group exceeds 95%, the obtained sealing agent for a liquid crystal display device may be inferior in adhesiveness.
상기 경화성 수지는, 액정 오염을 억제하는 점에서, -OH 기, -NH- 기, -NH2 기 등의 수소 결합성의 유닛을 갖는 것이 바람직하다.From the viewpoint of suppressing liquid crystal contamination, the curable resin preferably has hydrogen bonding units such as -OH group, -NH- group, and -NH 2 group.
또, 상기 (메트)아크릴 수지는, 반응성이 높다는 점에서 분자 중에 (메트)아크릴로일옥시기를 2 ∼ 3 개 갖는 것이 바람직하다. Moreover, it is preferable that the said (meth)acrylic resin has 2 to 3 (meth)acryloyloxy groups in a molecule|numerator from the point of high reactivity.
본 발명의 액정 표시 소자용 시일제는, 열 라디칼 중합 개시제를 함유해도 된다. The sealing agent for liquid crystal display elements of this invention may contain a thermal radical polymerization initiator.
상기 열 라디칼 중합 개시제로는, 예를 들어 아조 화합물, 유기 과산화물 등으로 이루어지는 것을 들 수 있다. 그 중에서도, 고분자 아조 화합물로 이루어지는 개시제 (이하, 「고분자 아조 개시제」라고도 한다) 가 바람직하다.Examples of the thermal radical polymerization initiator include those made of an azo compound and an organic peroxide. Among them, an initiator made of a high molecular azo compound (hereinafter, also referred to as a "polymer azo initiator") is preferable.
또한, 본 명세서에 있어서 고분자 아조 개시제란, 아조기를 갖고, 열에 의해 (메트)아크릴로일옥시기를 경화시킬 수 있는 라디칼을 생성하는, 수평균 분자량이 300 이상인 화합물을 의미한다. In addition, in the present specification, the polymeric azo initiator refers to a compound having an azo group and a number average molecular weight of 300 or more, which generates a radical capable of curing a (meth)acryloyloxy group by heat.
상기 고분자 아조 개시제의 수평균 분자량의 바람직한 하한은 1000, 바람직한 상한은 30만이다. 상기 고분자 아조 개시제의 수평균 분자량이 1000 미만이면, 고분자 아조 개시제가 액정에 악영향을 주는 경우가 있다. 상기 고분자 아조 개시제의 수평균 분자량이 30만을 초과하면, 경화성 수지에의 혼합이 곤란해지는 경우가 있다. 상기 고분자 아조 개시제의 수평균 분자량의 보다 바람직한 하한은 5000, 보다 바람직한 상한은 10만이고, 더 바람직한 하한은 1만, 더 바람직한 상한은 9만이다.The preferred lower limit of the number average molecular weight of the polymer azo initiator is 1000, and the preferred upper limit is 300,000. If the number average molecular weight of the polymeric azo initiator is less than 1000, the polymeric azo initiator may adversely affect the liquid crystal. When the number average molecular weight of the polymeric azo initiator exceeds 300,000, mixing with the curable resin may become difficult. A more preferable lower limit of the number average molecular weight of the polymer azo initiator is 5000, a more preferable upper limit is 100,000, a more preferable lower limit is 10,000, and a more preferable upper limit is 90,000.
또한, 본 명세서에 있어서, 상기 수평균 분자량은, 겔 퍼미에이션 크로마토그래피 (GPC) 로 측정을 실시하고, 폴리스티렌 환산에 의해 구해지는 값이다. GPC 에 의해 폴리스티렌 환산에 의한 수평균 분자량을 측정할 때의 칼럼으로는, 예를 들어 Shodex LF-804 (쇼와 전공사 제조) 등을 들 수 있다. In addition, in this specification, the said number average molecular weight is a value measured by gel permeation chromatography (GPC) and calculated|required by polystyrene conversion. As a column for measuring the number average molecular weight in terms of polystyrene by GPC, Shodex LF-804 (made by Showa Electric Corporation), etc. are mentioned, for example.
상기 고분자 아조 개시제로는, 예를 들어 아조기를 개재하여 폴리알킬렌옥사이드나 폴리디메틸실록산 등의 유닛이 복수 결합한 구조를 갖는 것을 들 수 있다.Examples of the polymeric azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded through an azo group.
상기 아조기를 개재하여 폴리알킬렌옥사이드 등의 유닛이 복수 결합한 구조를 갖는 고분자 아조 개시제로는, 폴리에틸렌옥사이드 구조를 갖는 것이 바람직하다. 이와 같은 고분자 아조 개시제로는, 예를 들어 4,4'-아조비스(4-시아노펜탄산) 과 폴리알킬렌글리콜의 중축합물이나, 4,4'-아조비스(4-시아노펜탄산) 과 말단 아미노기를 갖는 폴리디메틸실록산의 중축합물 등을 들 수 있고, 구체적으로는 예를 들어 VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (모두 와코쥰야쿠 공업사 제조) 등을 들 수 있다.As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded through the azo group, it is preferable to have a polyethylene oxide structure. As such a polymeric azo initiator, for example, a polycondensate of 4,4'-azobis(4-cyanopentanoic acid) and polyalkylene glycol, or 4,4'-azobis(4-cyanopentanoic acid) and Polycondensates of polydimethylsiloxane having a terminal amino group, etc., specifically, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.), etc. Can be mentioned.
또, 고분자가 아닌 아조 화합물의 예로는 V-65, V-501 (모두 와코쥰야쿠 공업사 제조) 등을 들 수 있다.Further, examples of azo compounds that are not polymers include V-65 and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.), and the like.
상기 유기 과산화물로는, 예를 들어 케톤퍼옥사이드, 퍼옥시케탈, 하이드로퍼옥사이드, 디알킬퍼옥사이드, 퍼옥시에스테르, 디아실퍼옥사이드, 퍼옥시디카보네이트 등을 들 수 있다.Examples of the organic peroxide include ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, peroxy dicarbonate, and the like.
상기 열 라디칼 중합 개시제의 함유량은, 경화성 수지 100 중량부에 대해, 바람직한 하한이 0.05 중량부, 바람직한 상한이 10 중량부이다. 상기 열 라디칼 중합 개시제의 함유량이 0.05 중량부 미만이면, 얻어지는 액정 표시 소자용 시일제의 열 중합이 충분히 진행되지 않는 경우가 있다. 상기 열 라디칼 중합 개시제의 함유량이 10 중량부를 초과하면, 미반응의 열 라디칼 중합 개시제에 의해 액정 오염이 생기는 경우가 있다. 상기 열 라디칼 중합 개시제의 함유량의 보다 바람직한 하한은 0.1 중량부, 보다 바람직한 상한은 5 중량부이다.The content of the thermal radical polymerization initiator is a preferable lower limit of 0.05 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermal radical polymerization initiator is less than 0.05 parts by weight, thermal polymerization of the obtained sealing agent for a liquid crystal display device may not sufficiently proceed. When the content of the thermal radical polymerization initiator exceeds 10 parts by weight, liquid crystal contamination may be caused by an unreacted thermal radical polymerization initiator. A more preferable lower limit of the content of the thermal radical polymerization initiator is 0.1 parts by weight, and a more preferable upper limit is 5 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 열 경화제를 함유해도 된다.The sealing agent for liquid crystal display elements of this invention may contain a thermosetting agent.
상기 열 경화제로는, 예를 들어 유기산 하이드라지드, 이미다졸 유도체, 아민 화합물, 다가 페놀계 화합물, 산 무수물 등을 들 수 있다. 그 중에서도, 유기산 하이드라지드가 바람직하게 사용된다.Examples of the thermal curing agent include organic acid hydrazide, imidazole derivatives, amine compounds, polyhydric phenolic compounds, and acid anhydrides. Among them, organic acid hydrazide is preferably used.
상기 유기산 하이드라지드로는, 예를 들어 세바스산디하이드라지드, 이소프탈산디하이드라지드, 아디프산디하이드라지드, 말론산디하이드라지드 등을 들 수 있다.Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide.
상기 유기산 하이드라지드 중 시판되고 있는 것으로는, 예를 들어 SDH, ADH (모두 오오츠카 화학사 제조), 아미큐어 VDH, 아미큐어 VDH-J, 아미큐어 UDH, 아미큐어 UDH-J (모두 아지노모토 파인 테크노사 제조) 등을 들 수 있다. Among the organic acid hydrazides that are commercially available, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all of Ajinomoto Fine Techno Co., Ltd.) Manufacturing) and the like.
상기 열 경화제의 함유량은, 상기 경화성 수지 100 중량부에 대해, 바람직한 하한이 1 중량부, 바람직한 상한이 50 중량부이다. 상기 열 경화제의 함유량이 1 중량부 미만이면, 얻어지는 액정 표시 소자용 시일제를 충분히 열 경화시킬 수 없는 경우가 있다. 상기 열 경화제의 함유량이 50 중량부를 초과하면, 얻어지는 액정 표시 소자용 시일제의 점도가 높아져, 도포성이 나빠지는 경우가 있다. 상기 열 경화제의 함유량의 보다 바람직한 상한은 30 중량부이다.The content of the thermal curing agent is a preferable lower limit of 1 part by weight and a preferable upper limit of 50 parts by weight per 100 parts by weight of the curable resin. When the content of the thermal curing agent is less than 1 part by weight, the obtained sealing agent for a liquid crystal display element cannot be sufficiently thermally cured in some cases. When the content of the thermal curing agent exceeds 50 parts by weight, the viscosity of the obtained sealing agent for a liquid crystal display device increases, and the coating property may be deteriorated. A more preferable upper limit of the content of the thermal curing agent is 30 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 점도의 향상, 응력 분산 효과에 의한 접착성의 개선, 선팽창률의 개선, 경화물의 내습성의 추가적인 향상 등을 목적으로 해 충전제를 함유하는 것이 바람직하다.The sealing agent for a liquid crystal display device of the present invention preferably contains a filler for the purpose of improving viscosity, improving adhesion due to a stress dispersion effect, improving linear expansion coefficient, and further improving moisture resistance of a cured product.
상기 충전제로는, 예를 들어 탤크, 석면, 실리카, 규조토, 스멕타이트, 벤토나이트, 탄산칼슘, 탄산마그네슘, 알루미나, 몬모릴로나이트, 산화아연, 산화철, 산화마그네슘, 산화주석, 산화티탄, 수산화마그네슘, 수산화알루미늄, 유리비즈, 질화규소, 황산바륨, 석고, 규산칼슘, 세리사이트 활성 백토, 질화알루미늄 등의 무기 충전제나, 폴리에스테르 미립자, 폴리우레탄 미립자, 비닐 중합체 미립자, 아크릴 중합체 미립자 등의 유기 충전제를 들 수 있다. 이들 충전제는 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다.Examples of the filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, Inorganic fillers such as glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, and aluminum nitride, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles. These fillers may be used alone or in combination of two or more.
본 발명의 액정 표시 소자용 시일제 100 중량부 중에 있어서의 상기 충전제의 함유량의 바람직한 하한은 10 중량부, 바람직한 상한은 70 중량부이다. 상기 충전제의 함유량이 10 중량부 미만이면, 접착성 개선 등의 효과가 충분히 발휘되지 않는 경우가 있다. 상기 충전제의 함유량이 70 중량부를 초과하면, 얻어지는 액정 표시 소자용 시일제의 점도가 높아져, 도포성이 나빠지는 경우가 있다. 상기 충전제의 함유량의 보다 바람직한 하한은 20 중량부, 보다 바람직한 상한은 60 중량부이다.A preferable lower limit of the content of the filler in 100 parts by weight of the sealing agent for a liquid crystal display device of the present invention is 10 parts by weight, and a preferable upper limit is 70 parts by weight. When the content of the filler is less than 10 parts by weight, effects such as improvement in adhesion may not be sufficiently exhibited. When the content of the filler exceeds 70 parts by weight, the viscosity of the obtained sealing agent for a liquid crystal display device increases, and the coating property may deteriorate. A more preferable lower limit of the content of the filler is 20 parts by weight, and a more preferable upper limit is 60 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 agent for liquid crystal display elements of this invention contains a silane coupling agent. The silane coupling agent mainly serves as an adhesion aid for good adhesion between the sealing agent and the substrate.
상기 실란 커플링제로는, 기판 등과의 접착성을 향상시키는 효과가 우수하고, 경화성 수지와 화학 결합함으로써 액정 중에의 경화성 수지의 유출을 억제할 수 있으므로, 예를 들어 3-아미노프로필트리메톡시실란, 3-메르캅토프로필트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-이소시아네이트프로필트리메톡시실란 등이 바람직하게 사용된다. 이들 실란 커플링제는 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다. The silane coupling agent has an excellent effect of improving adhesion to a substrate, etc., and can suppress the outflow of the curable resin into the liquid crystal by chemical bonding with the curable resin. For example, 3-aminopropyltrimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and the like are preferably used. These silane coupling agents may be used alone or in combination of two or more.
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 0.1 중량부 미만이면, 실란 커플링제를 배합하는 것에 의한 효과가 충분히 발휘되지 않는 경우가 있다. 상기 실란 커플링제의 함유량이 10 중량부를 초과하면, 얻어지는 액정 표시 소자용 시일제가 액정 오염을 일으키는 경우가 있다. 상기 실란 커플링제의 함유량의 보다 바람직한 하한은 0.3 중량부, 보다 바람직한 상한은 5 중량부이다.A preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealing agent for a liquid crystal display device of the present invention is 0.1 parts by weight, and a preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is less than 0.1 part by weight, the effect of blending the silane coupling agent may not be sufficiently exhibited. When the content of the silane coupling agent exceeds 10 parts by weight, the obtained sealing agent for a liquid crystal display element may cause liquid crystal contamination. A more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 차광제를 함유해도 된다. 상기 차광제를 함유함으로써, 본 발명의 액정 표시 소자용 시일제는, 차광 시일제로서 바람직하게 사용할 수 있다.The sealing agent for liquid crystal display elements of this invention may contain a light shielding agent. By containing the said light-shielding agent, the sealing agent for liquid crystal display elements of this invention can be used suitably as a light-shielding sealing agent.
상기 차광제로는, 예를 들어 산화철, 티탄 블랙, 아닐린 블랙, 시아닌 블랙, 플러렌, 카본 블랙, 수지 피복형 카본 블랙 등을 들 수 있다. 그 중에서도, 티탄 블랙이 바람직하다.Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferable.
상기 티탄 블랙은, 파장 300 ∼ 800 ㎚ 의 광에 대한 평균 투과율과 비교해, 자외선 영역 부근, 특히 파장 370 ∼ 450 ㎚ 의 광에 대한 투과율이 높아지는 물질이다. 즉, 상기 티탄 블랙은, 가시광 영역의 파장의 광을 충분히 차폐함으로써 본 발명의 액정 표시 소자용 시일제에 차광성을 부여하는 한편, 자외선 영역 부근의 파장의 광은 투과시키는 성질을 갖는 차광제이다. 본 발명의 액정 표시 소자용 시일제에 함유되는 차광제로는, 절연성이 높은 물질이 바람직하고, 절연성이 높은 차광제로서도 티탄 블랙이 바람직하다.The titanium black is a material whose transmittance is increased in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared with the average transmittance for light having a wavelength of 300 to 800 nm. That is, the titanium black is a light-shielding agent having a property of providing light-shielding property to the sealing agent for a liquid crystal display device of the present invention by sufficiently shielding light of a wavelength in the visible region, while transmitting light in a wavelength in the vicinity of the ultraviolet region. . As the light shielding agent contained in the sealing agent for a liquid crystal display device of the present invention, a material having high insulating properties is preferred, and titanium black is also preferred as a light shielding agent having high insulation properties.
상기 티탄 블랙은, 표면 처리되어 있지 않은 것이라도 충분한 효과를 발휘하지만, 표면이 커플링제 등의 유기 성분으로 처리되어 있는 것이나, 산화규소, 산화티탄, 산화게르마늄, 산화알루미늄, 산화지르코늄, 산화마그네슘 등의 무기 성분으로 피복되어 있는 것 등, 표면 처리된 티탄 블랙을 사용할 수도 있다. 그 중에서도, 유기 성분으로 처리되어 있는 것은, 보다 절연성을 향상시킬 수 있는 점에서 바람직하다.The titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. It is also possible to use surface-treated titanium black, such as those coated with an inorganic component of. Among them, what has been treated with an organic component is preferable from the viewpoint of being able to further improve the insulating properties.
또, 차광제로서 상기 티탄 블랙을 함유하는 본 발명의 액정 표시 소자용 시일제를 이용하여 제조한 액정 표시 소자는, 충분한 차광성을 가지므로, 광의 누출이 없어 높은 콘트라스트를 가져, 우수한 화상 표시 품질을 갖는 액정 표시 소자를 실현할 수 있다. In addition, the liquid crystal display device manufactured by using the sealing agent for a liquid crystal display device of the present invention containing the titanium black as a light shielding agent has sufficient light shielding property, and therefore has high contrast without leakage of light, and excellent image display quality. It is possible to realize a liquid crystal display device having.
상기 티탄 블랙 중 시판되고 있는 것으로는, 예를 들어 12S, 13M, 13M-C, 13R-N, 14M-C (모두 미츠비시 메트리얼사 제조), 틸락 D (아코 화성사 제조) 등을 들 수 있다.Among the above titanium blacks, commercially available ones include, for example, 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials), Tilak D (manufactured by Ako Hwaseong), and the like. .
상기 티탄 블랙의 비표면적의 바람직한 하한은 13 ㎡/g, 바람직한 상한은 30 ㎡/g 이고, 보다 바람직한 하한은 15 ㎡/g, 보다 바람직한 상한은 25 ㎡/g 이다.A preferable lower limit of the specific surface area of the titanium black is 13 m 2 /g, a preferable upper limit is 30 m 2 /g, a more preferable lower limit is 15 m 2 /g, and a more preferable upper limit is 25 m 2 /g.
또, 상기 티탄 블랙의 체적 저항의 바람직한 하한은 0.5 Ω·㎝, 바람직한 상한은 3 Ω·㎝ 이고, 보다 바람직한 하한은 1 Ω·㎝, 보다 바람직한 상한은 2.5 Ω·㎝ 이다.In addition, a preferable lower limit of the volume resistance of the titanium black is 0.5 Ω·cm, a preferable upper limit is 3 Ω·cm, a more preferable lower limit is 1 Ω·cm, and a more preferable upper limit is 2.5 Ω·cm.
상기 차광제의 1 차 입자경은, 액정 표시 소자의 기판간의 거리 이하이면 특별히 한정되지 않지만, 바람직한 하한은 1 ㎚, 바람직한 상한은 5 ㎛ 이다. 상기 차광제의 1 차 입자경이 1 ㎚ 미만이면, 얻어지는 액정 표시 소자용 시일제의 점도나 틱소트로피가 크게 증대해 버려, 작업성이 나빠지는 경우가 있다. 상기 차광제의 1 차 입자경이 5 ㎛ 를 초과하면, 얻어지는 액정 표시 소자용 시일제의 기판에 대한 도포성이 나빠지는 경우가 있다. 상기 차광제의 1 차 입자경의 보다 바람직한 하한은 5 ㎚, 보다 바람직한 상한은 200 ㎚, 더 바람직한 하한은 10 ㎚, 더 바람직한 상한은 100 ㎚ 이다.The primary particle diameter of the light-shielding agent is not particularly limited as long as it is less than or equal to the distance between the substrates of the liquid crystal display device, but the preferred lower limit is 1 nm, and the preferred upper limit is 5 µm. When the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained sealing agent for a liquid crystal display device will greatly increase, and workability may deteriorate. When the primary particle diameter of the light shielding agent exceeds 5 µm, the coating property of the obtained sealing agent for a liquid crystal display device to the substrate may be deteriorated. A more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, a more preferable upper limit is 200 nm, a more preferable lower limit is 10 nm, and a more preferable upper limit is 100 nm.
본 발명의 액정 표시 소자용 시일제 100 중량부 중에 있어서의 상기 차광제의 함유량의 바람직한 하한은 5 중량부, 바람직한 상한은 80 중량부이다. 상기 차광제의 함유량이 5 중량부 미만이면, 충분한 차광성이 얻어지지 않는 경우가 있다. 상기 차광제의 함유량이 80 중량부를 초과하면, 얻어지는 액정 표시 소자용 시일제의 기판에 대한 밀착성이나 경화 후의 강도가 저하되거나, 묘화성이 저하되거나 하는 경우가 있다. 상기 차광제의 함유량의 보다 바람직한 하한은 10 중량부, 보다 바람직한 상한은 70 중량부이고, 더 바람직한 하한은 30 중량부, 더 바람직한 상한은 60 중량부이다.The preferable lower limit of the content of the light shielding agent in 100 parts by weight of the sealing agent for a liquid crystal display device of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. If the content of the light-shielding agent is less than 5 parts by weight, sufficient light-shielding properties may not be obtained. When the content of the light-shielding agent exceeds 80 parts by weight, the adhesion of the resulting liquid crystal display element sealing agent to the substrate and the strength after curing may decrease, or the drawing property may decrease. A more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.
본 발명의 액정 표시 소자용 시일제를 제조하는 방법으로는, 예를 들어 호모디스퍼, 호모믹서, 만능 믹서, 플래니터리 믹서, 니더, 3 단 롤 등의 혼합기를 이용하여, 경화성 수지와, 티오크산톤계 중합 개시제와, 아민계 증감제와, 필요에 따라 첨가하는 실란 커플링제 등의 첨가제를 혼합하는 방법 등을 들 수 있다.As a method of manufacturing the sealing agent for a liquid crystal display device of the present invention, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-stage roll, a curable resin and, A method of mixing an additive such as a thioxanthone polymerization initiator, an amine-based sensitizer, and a silane coupling agent added as needed, etc. are mentioned.
본 발명의 액정 표시 소자용 시일제에, 도전성 미립자를 배합함으로써, 상하 도통 재료를 제조할 수 있다. 이와 같은 본 발명의 액정 표시 소자용 시일제와 도전성 미립자를 함유하는 상하 도통 재료도 또한, 본 발명의 하나이다.The upper and lower conduction materials can be produced by blending conductive fine particles into the sealing agent for a liquid crystal display device of the present invention. The upper and lower conduction material containing such a sealing agent for a liquid crystal display device of the present invention and conductive fine particles is also one of the present 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 가능하므로 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, or the like can be used. Among them, it is preferable that a conductive metal layer is formed on the surface of the resin fine particles because 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 시일제, 또는 본 발명의 상하 도통 재료를 이용하여 제조되는 액정 표시 소자도 또, 본 발명의 하나이다.A liquid crystal display device manufactured using the sealing agent for a liquid crystal display device of the present invention or the upper and lower conduction material of the present invention is also one of the present invention.
본 발명의 액정 표시 소자를 제조하는 방법으로는, 예를 들어 ITO 박막 등의 전극이 형성된 유리 기판이나 폴리에틸렌테레프탈레이트 기판 등의 2 장의 기판의 일방에, 본 발명의 액정 표시 소자용 시일제 등을 스크린 인쇄, 디스펜서 도포 등에 의해 장방형상의 시일 패턴을 형성하는 공정, 본 발명의 액정 표시 소자용 시일제 등이 미경화 상태에서 액정의 미소 방울을 기판의 시일 프레임 내에 적하 도포하고, 진공하에서 별도의 기판을 중첩하는 공정, 및 본 발명의 액정 표시 소자용 시일제 등의 시일 패턴 부분에 자외선 등의 광을 조사해 시일제를 가경화시키는 공정, 및 가경화시킨 시일제를 가열하여 본경화시키는 공정을 갖는 방법 등을 들 수 있다.As a method of manufacturing a liquid crystal display device of the present invention, for example, a sealing agent for a liquid crystal display device of the present invention is applied to one of two substrates, such as a glass substrate or a polyethylene terephthalate substrate on which an electrode such as an ITO thin film is formed. Process of forming a rectangular seal pattern by screen printing, dispenser application, etc., while the sealing agent for a liquid crystal display device of the present invention is uncured, droplets of liquid crystal are applied dropwise into the seal frame of the substrate, and a separate substrate under vacuum A method having a step of superimposing, and a step of temporally curing the sealing agent by irradiating light such as ultraviolet rays to the sealing pattern portion of the sealing agent for a liquid crystal display device of the present invention, and a step of heating the temporarily cured sealing agent to be cured Etc. are mentioned.
본 발명에 의하면, 광 경화성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제를 제공할 수 있다. 또, 본 발명에 의하면, 그 액정 표시 소자용 시일제를 이용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공할 수 있다.ADVANTAGE OF THE INVENTION According to this invention, it is excellent in photocurability and can provide the sealing agent for liquid crystal display elements which can suppress liquid crystal contamination. Further, according to the present invention, it is possible to provide a vertical conduction material and a liquid crystal display element formed by using the sealing agent for a liquid crystal display element.
이하에 실시예를 들어 본 발명을 더 상세하게 설명하지만, 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.
(실시예 1 ∼ 13, 비교예 1 ∼ 5)(Examples 1 to 13, Comparative Examples 1 to 5)
표 1, 2 에 기재된 배합비에 따라, 각 재료를, 유성식 교반기 (싱키사 제조, 「아와토리렌타로」) 를 이용하여 혼합한 후, 추가로 3 단 롤을 이용하여 혼합함으로써 실시예 1 ∼ 13, 비교예 1 ∼ 5 의 각 액정 표시 소자용 시일제를 조제하였다. According to the blending ratios shown in Tables 1 and 2, each material was mixed using a planetary stirrer (manufactured by Shinki, ``Awatori Rentaro''), and then further mixed using a three-stage roll, Examples 1 to 13, the sealing agent for each liquid crystal display element of Comparative Examples 1-5 was prepared.
<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 of the sealing agents for liquid crystal display elements obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.
(광 경화성)(Photocurable)
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제 100 중량부에 스페이서 미립자 (세키스이 화학 공업사 제조, 「마이크로펄 SI-H050」) 1 중량부를 분산시킨 것을 유리 기판 상에 도포하고, 그 기판에 동일 사이즈의 유리 기판을 중첩하고, 다음으로 메탈 할라이드 램프를 이용하여 100 ㎽/㎠ 의 광을 10 초 조사해, 광 경화성 시험편을 제작하였다. 광 조사는 컷 필터가 없는 경우와 400 ㎚ 컷 필터가 있는 경우의 2 패턴을 실시하고, 각각에 대해 3 장의 시험편을 제작하였다. 적외 분광 장치 (BIORAD 사 제조, 「FTS3000」) 를 사용하여, (메트)아크릴로일기 유래 피크의 광 조사 전후에서의 변화량을 측정함으로써 광 경화성의 평가를 실시하였다. 광 조사 후에 (메트)아크릴로일기 유래의 피크가 90 % 이상 감소한 경우를 「◎」, 광 조사 후에 (메트)아크릴로일기 유래의 피크가 80 % 이상 90 % 미만 감소한 경우를 「○」, 광 조사 후에 (메트)아크릴로일기 유래의 피크가 70 % 이상 80 % 미만 감소한 경우를 「△」, 광 조사 후의 (메트)아크릴로일기 유래의 피크의 감소가 70 % 미만인 경우를 「×」 로 해서 광 경화성을 평가하였다.1 part by weight of spacer microparticles (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SI-H050") dispersed in 100 parts by weight of the sealing agent for each liquid crystal display device obtained in Examples and Comparative Examples was applied onto a glass substrate, and the substrate A glass substrate of the same size was superimposed on, and then 100 mW/cm 2 of light was irradiated for 10 seconds using a metal halide lamp to prepare a photocurable test piece. The light irradiation performed 2 patterns in the case where there was no cut filter and the case where there was a 400 nm cut filter, and three test pieces were produced for each. Photocurability was evaluated by measuring the amount of change before and after light irradiation of the (meth)acryloyl group-derived peak using an infrared spectroscopic apparatus (manufactured by BIORAD, "FTS3000"). When the peak derived from the (meth)acryloyl group decreases by 90% or more after irradiation with light, "◎", and "○" when the peak derived from the (meth)acryloyl group decreases by 80% or more and less than 90% after light irradiation, light After irradiation, the case where the peak derived from the (meth)acryloyl group decreased by 70% or more and less than 80% was designated as "△", and the case where the decrease in the peak derived from the (meth)acryloyl group after irradiation was less than 70% was represented as "x" Photocurability was evaluated.
또한, (메트)아크릴로일기 유래 피크의 광 조사 전후에서의 변화량은, 3 장의 시험편으로부터 얻어진 평균값을 취하였다.In addition, the amount of change in the (meth)acryloyl group-derived peak before and after irradiation with light took the average value obtained from three test pieces.
(액정 오염성)(Liquid crystal contamination)
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제 100 중량부에 스페이서 미립자 (세키스이 화학 공업사 제조, 「마이크로펄 SI-H050」) 1 중량부를 분산시키고, 액정 표시 소자용 시일제로서, 2 장의 러빙이 완료된 배향막 및 투명 전극이 형성된 기판의 일방에 시일제의 선폭이 1 ㎜ 가 되도록 디스펜서로 도포하였다. 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of the sealing agent for each liquid crystal display device obtained in Examples and Comparative Examples, and as a sealing agent for a liquid crystal display device, 2 The sheet was coated with a dispenser so that the line width of the sealing agent was 1 mm on one side of the substrate on which the rubbing was completed and the transparent electrode was formed.
계속해서 액정 (칫소사 제조, 「JC-5004LA」) 의 미소 방울을 투명 전극이 형성된 기판의 시일제의 프레임 내 전체면에 적하 도포하고, 바로 다른 일방의 투명 전극이 형성된 컬러 필터 기판을 첩합 (貼合) 하고, 시일제 부분에 메탈 할라이드 램프를 이용하여 100 ㎽/㎠ 의 자외선을 30 초 조사해 경화시키고, 추가로 120 ℃ 에서 1 시간 가열하여 액정 표시 소자를 얻었다. 광 조사는 컷 필터가 없는 경우와 400 ㎚ 컷 필터가 있는 경우의 2 패턴을 실시하고, 각각에 대해 3 장의 액정 표시 소자를 제작하였다.Subsequently, microdroplets of a liquid crystal (manufactured by Chisso Corporation, ``JC-5004LA'') were applied dropwise to the entire surface of the frame of the sealing agent of the substrate on which the transparent electrode was formed, and immediately pasted the color filter substrate on which the other transparent electrode was formed ( It was made to cure by irradiating 100 mW/cm<2> ultraviolet-ray for 30 seconds using a metal halide lamp to the sealing agent part, and further heated at 120 degreeC for 1 hour, and obtained the liquid crystal display element. The light irradiation performed 2 patterns in the case where there was no cut filter and the case where there was a 400 nm cut filter, and three liquid crystal display elements were produced for each.
얻어진 액정 표시 소자에 대해, 60 ℃ 에서 1000 시간 전압 인가 상태로 한 후의 시일제 부근의 액정 오염을 육안에 의해 확인하였다.With respect to the obtained liquid crystal display element, liquid crystal contamination in the vicinity of the sealing agent after the voltage was applied at 60°C for 1000 hours was visually confirmed.
액정 오염은, 3 장의 액정 표시 소자의 색 불균일에 의해 판단하고 있고, 색 불균일의 정도에 따라, 모든 액정 표시 소자에 대해 색 불균일이 전혀 없는 경우를 「◎」, 적어도 1 장의 액정 표시 소자에 색 불균일이 희미하게 있는 경우를 「○」, 적어도 1 장의 액정 표시 소자에 색 불균일이 조금 있는 경우를 「△」, 적어도 1 장의 액정 표시 소자에 색 불균일이 상당히 있는 경우를 「×」로 해서 액정 오염성을 평가하였다. Liquid crystal contamination is judged by the color non-uniformity of three liquid crystal display elements, and according to the degree of color non-uniformity, ``◎'' when there is no color non-uniformity at all for all liquid crystal display elements, and at least one liquid crystal display element has color Liquid crystal contamination by setting ``○'' for faint unevenness, ``△'' for slight color unevenness in at least one liquid crystal display element, and ``x'' for significant color unevenness in at least one liquid crystal display element Was evaluated.
또한, 평가가 「◎」, 「○」인 액정 표시 소자는 실용에 전혀 문제가 없는 레벨이다.In addition, a liquid crystal display element whose evaluation is "◎" and "○" is a level without any problem in practical use.
산업상 이용가능성 Industrial applicability
본 발명에 의하면, 광 경화성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제를 제공할 수 있다. 또, 본 발명에 의하면, 그 액정 표시 소자용 시일제를 이용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공할 수 있다.ADVANTAGE OF THE INVENTION According to this invention, it is excellent in photocurability and can provide the sealing agent for liquid crystal display elements which can suppress liquid crystal contamination. Further, according to the present invention, it is possible to provide a vertical conduction material and a liquid crystal display element formed by using the sealing agent for a liquid crystal display element.
Claims (10)
[화학식 1]
[식 (1) 중, n 은, 1 ∼ 6 이고, R3 은, 수소 원자, 메틸기, 또는 에틸기이고, n 이 1 보다 큰 경우, R3 으로 나타내는 기 또는 원자는, 동일해도 되고, 상이해도 된다. A 는, 식 -O-, -[O(CHR2CHR1)a]y-, -[O(CH2)bCO]y-, 또는 -[O(CH2)bCO](y-1)-[O(CHR2CHR1)a]- 의 기를 나타내고, R1 과 R2 의 일방은, 수소 원자를 나타내고, 타방은, 수소 원자, 메틸기, 또는 에틸기를 나타내고, a 는, 1 ∼ 2 이고, b 는, 4 ∼ 5 이고, Q 는, (폴리)에틸렌글리콜, (폴리)프로필렌글리콜, (폴리)부틸렌글리콜, 글리세린, 트리메틸올프로판, 디트리메틸올프로판, 펜타에리트리톨, 디펜타에리트리톨, 또는 카프로락톤 폴리올의 잔기이고, Q 내의 유리 하이드록실기가 에스테르화되어 있어도 되고, x 는, 1 보다 크고, Q 의 수산기의 수를 초과하지 않는 수이고, x 가 1 보다 크고, 2 를 초과하지 않는 경우, y 는 1 ∼ 10 이고, x 가 2 를 초과하는 경우, y 는 3 ∼ 10 임].A sealing agent for a liquid crystal display device comprising a curable resin, a thioxanthone polymerization initiator represented by the following formula (1), and an amine sensitizer:
[Formula 1]
[In formula (1), n is 1 to 6, R 3 is a hydrogen atom, a methyl group, or an ethyl group, and when n is greater than 1, the group or atom represented by R 3 may be the same or different do. A is the formula -O-, -[O(CHR 2 CHR 1 ) a ] y -, -[O(CH 2 ) b CO] y -, or -[O(CH 2 ) b CO] (y-1 ) Represents a group of -[O(CHR 2 CHR 1 ) a ]-, one of R 1 and R 2 represents a hydrogen atom, the other represents a hydrogen atom, a methyl group, or an ethyl group, and a represents 1 to 2 , B is 4 to 5, Q is (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaeryth It is a residue of lithol or caprolactone polyol, and the free hydroxyl group in Q may be esterified, x is a number greater than 1 and not exceeding the number of hydroxyl groups in Q, x is greater than 1, and 2 When not exceeding, y is 1-10, when x exceeds 2, y is 3-10].
식 (1) 중의 n 이 1 이고, R3 이 수소 원자이고, A 가 식 -O- 의 기인 것을 특징으로 하는 액정 표시 소자용 시일제.The method of claim 1,
The sealing agent for a liquid crystal display element characterized in that n in formula (1) is 1, R 3 is a hydrogen atom, and A is a group of formula -O-.
식 (1) 중의 Q 가 폴리부틸렌글리콜의 잔기인 것을 특징으로 하는 액정 표시 소자용 시일제.The method according to claim 1 or 2,
A sealing agent for a liquid crystal display device, wherein Q in formula (1) is a residue of polybutylene glycol.
아민계 증감제는, 하기 식 (2) 로 나타내는 화합물인 것을 특징으로 하는 액정 표시 소자용 시일제:
[화학식 2]
[식 (2) 중, z 는, 1 이상의 정수를 나타내고, P 는, (폴리)에틸렌글리콜, (폴리)프로필렌글리콜, (폴리)부틸렌글리콜, 글리세린, 트리메틸올프로판, 디트리메틸올프로판, 펜타에리트리톨, 디펜타에리트리톨, 또는 카프로락톤 폴리올의 잔기임].The method according to claim 1 or 2,
The amine-based sensitizer is a compound represented by the following formula (2), wherein the sealing agent for a liquid crystal display device:
[Formula 2]
[In formula (2), z represents an integer of 1 or more, and P is (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, penta Is a residue of erythritol, dipentaerythritol, or caprolactone polyol].
식 (2) 중의 z 가 2 이고, P 가 폴리에틸렌글리콜의 잔기인 것을 특징으로 하는 액정 표시 소자용 시일제.The method of claim 4,
The sealing agent for a liquid crystal display element characterized in that z in Formula (2) is 2, and P is a residue of polyethylene glycol.
액정 표시 소자용 시일제 100 중량부 중에 있어서의 식 (1) 로 나타내는 티오크산톤계 중합 개시제의 함유량이 0.1 ∼ 10 중량부인 것을 특징으로 하는 액정 표시 소자용 시일제.The method according to claim 1 or 2,
A sealing agent for a liquid crystal display device, wherein the content of the thioxanthone-based polymerization initiator represented by formula (1) in 100 parts by weight of the sealing agent for a liquid crystal display device is 0.1 to 10 parts by weight.
식 (1) 로 나타내는 티오크산톤계 중합 개시제와 아민계 증감제의 함유 비율이, 중량비로, 식 (1) 로 나타내는 티오크산톤계 중합 개시제 : 아민계 증감제 = 1 : 0.05 ∼ 1 : 5 인 것을 특징으로 하는 액정 표시 소자용 시일제.The method according to claim 1 or 2,
The content ratio of the thioxanthone-based polymerization initiator represented by formula (1) and the amine-based sensitizer is by weight ratio, and the thioxanthone-based polymerization initiator represented by formula (1): amine-based sensitizer=1:0.05-1:5 A sealing agent for a liquid crystal display device, characterized in that it is.
차광제를 함유하는 것을 특징으로 하는 액정 표시 소자용 시일제.The method according to claim 1 or 2,
A sealing agent for a liquid crystal display device comprising a light shielding agent.
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WO2014192880A1 (en) * | 2013-05-31 | 2014-12-04 | 積水化学工業株式会社 | Sealing agent for display elements |
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2014
- 2014-11-10 KR KR1020157031377A patent/KR102240965B1/en active IP Right Grant
- 2014-11-10 JP JP2014556282A patent/JP5759638B1/en active Active
- 2014-11-10 WO PCT/JP2014/079685 patent/WO2015072415A1/en active Application Filing
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CN105579898A (en) | 2016-05-11 |
JPWO2015072415A1 (en) | 2017-03-16 |
JP5759638B1 (en) | 2015-08-05 |
CN105579898B (en) | 2017-07-21 |
WO2015072415A1 (en) | 2015-05-21 |
KR20160082940A (en) | 2016-07-11 |
TW201522593A (en) | 2015-06-16 |
TWI625384B (en) | 2018-06-01 |
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