TWI625384B - Sealant for liquid crystal display element, upper and lower conductive materials, and liquid crystal display element - Google Patents
Sealant for liquid crystal display element, upper and lower conductive materials, and liquid crystal display element Download PDFInfo
- Publication number
- TWI625384B TWI625384B TW103139151A TW103139151A TWI625384B TW I625384 B TWI625384 B TW I625384B TW 103139151 A TW103139151 A TW 103139151A TW 103139151 A TW103139151 A TW 103139151A TW I625384 B TWI625384 B TW I625384B
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- Taiwan
- Prior art keywords
- liquid crystal
- crystal display
- display element
- meth
- sealant
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 132
- 239000004020 conductor Substances 0.000 title claims abstract description 11
- 239000000565 sealant Substances 0.000 title claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 62
- -1 caprolactone polyol Chemical class 0.000 claims abstract description 61
- 238000007789 sealing Methods 0.000 claims abstract description 55
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 235000011187 glycerol Nutrition 0.000 claims abstract description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
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- 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 14
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
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- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000516 sunscreening agent Substances 0.000 description 4
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 2
- 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- 239000006229 carbon black Substances 0.000 description 2
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
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- 230000001678 irradiating effect Effects 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
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- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
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- 125000003544 oxime group Chemical group 0.000 description 2
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- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 1
- RUVNKAUVVBCURD-UHFFFAOYSA-N 2-[[4-[2-[4-(oxiran-2-ylmethoxy)-3-prop-2-enylphenyl]propan-2-yl]-2-prop-2-enylphenoxy]methyl]oxirane Chemical compound C=1C=C(OCC2OC2)C(CC=C)=CC=1C(C)(C)C(C=C1CC=C)=CC=C1OCC1CO1 RUVNKAUVVBCURD-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- 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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- 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
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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
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- 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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- 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
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Abstract
本發明之目的在於提供一種光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 An object of the present invention is to provide a sealing agent for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element using the sealing agent for a liquid crystal display element.
本發明係含有硬化性樹脂、下述式(1)所表示之9-氧硫系聚合起始劑、及胺系增感劑之液晶顯示元件用密封劑。 The present invention contains a curable resin, 9-oxygen sulfur represented by the following formula (1) A sealing agent for a liquid crystal display element which is a polymerization initiator and an amine sensitizer.
式(1)中，n為1~6，R3為氫原子、甲基、或乙基，於n大於1之情形時，R3所表示之基或原子可相同亦可不同。A表示式-O-、-[O(CHR2CHR1)a]y-、-[O(CH2)bCO]y-、或-[O(CH2)bCO](y-1)-[O(CHR2CHR1)a]-之基，R1與R2之一者表示氫原子，另一者表示氫原子、甲基、或乙基，a為1~2，b為4~5，Q為(聚)乙二醇、(聚)丙二醇、(聚)丁二醇、甘油、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇、或己內酯多元醇之殘基，Q內之游離羥基亦可經酯化，x為大於1且不超過Q之羥基數的數目，於x大於1且不超過2之情形時，y為1~10，於x超過2之情形時，y為3~10。 In the formula (1), n is 1 to 6, and R 3 is a hydrogen atom, a methyl group or an ethyl group. When n is greater than 1, the group or atom represented by R 3 may be the same or different. A represents the formula -O-, -[O(CHR 2 CHR 1 ) a ] y -, -[O(CH 2 ) b CO] y -, or -[O(CH 2 ) b CO] (y-1) -[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, a is 1 to 2, and b is 4 ~5, Q is (poly)ethylene glycol, (poly)propylene glycol, (poly)butanediol, glycerin, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol Or the residue of the caprolactone polyol, the free hydroxyl group in Q may also be esterified, and x is a number greater than 1 and not exceeding the number of hydroxyl groups of Q. When x is greater than 1 and not more than 2, y is 1~10, when x exceeds 2, y is 3~10.
Description
本發明係關於一種光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑。又，本發明係關於一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 The present invention relates to a sealing agent for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, the present invention relates to an upper and lower conductive material and a liquid crystal display element using the sealing agent for a liquid crystal display element.
近年來，作為液晶顯示單元等液晶顯示元件之製造方法，就產距時間(tact time)縮短、使用液晶量之最佳化等觀點而言，可使用如專利文獻1、專利文獻2中所揭示之使用含有硬化性樹脂、光聚合起始劑及熱硬化劑之光熱併用硬化型之密封劑的稱為滴下方法的液晶滴下方式。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display unit, as disclosed in Patent Document 1 and Patent Document 2, from the viewpoints of shortening the tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a photocuring resin containing a curable resin, a photopolymerization initiator, and a thermosetting agent in combination with a curing agent.
於滴下方法中，首先，於2片附有電極之基板之一片藉由滴塗(dispense)而形成長方形狀之密封圖案。繼而，於密封劑未硬化之狀態將液晶之微滴滴至基板之密封框內，於真空下重疊另一片基板，並對密封部照射紫外線等光而進行暫時硬化。其後，實施加熱而進行正式硬化，製作液晶顯示元件。目前該滴下方法正成為液晶顯示元件之製造方法之主流。 In the dropping method, first, a rectangular sealing pattern is formed by dispensing on one of two substrates with electrodes attached thereto. Then, the liquid crystal droplets are dropped into the sealing frame of the substrate in a state where the sealing agent is not cured, and the other substrate is superposed under vacuum, and the sealing portion is temporarily hardened by irradiating light such as ultraviolet rays. Thereafter, heating is performed to perform main hardening, and a liquid crystal display element is produced. At present, the dropping method is becoming the mainstream of the manufacturing method of the liquid crystal display element.
且說，於行動電話、攜帶型遊戲機等各種附有液晶面板之移動機器正在普及之現代，機器之小型化為最被要求之課題。作為機器之小型化之方法，可列舉液晶顯示部之窄邊緣化，例如將密封部之位置配置於黑矩陣下(以下，亦稱為窄邊緣設計)。 In addition, various mobile devices including liquid crystal panels, such as mobile phones and portable game machines, are becoming popular, and the miniaturization of machines is the most demanding issue. As a method of downsizing the machine, a narrow edge of the liquid crystal display unit is exemplified, and for example, the position of the sealing portion is placed under a black matrix (hereinafter also referred to as a narrow edge design).
然而，於窄邊緣設計中，由於將密封劑配置於黑矩陣之正下 方，故而有如下問題：若實施滴下方法，則於使密封劑光硬化時照射之光被遮蔽，光難以到達至密封劑之內部，硬化變得不充分。若如此密封劑之硬化變得不充分，則有未硬化之密封劑成分溶出至液晶中而容易產生液晶污染之問題。 However, in the narrow edge design, because the sealant is placed directly under the black matrix However, when the dropping method is carried out, the light irradiated when the sealant is photohardened is shielded, and it is difficult for light to reach the inside of the sealant, and the hardening is insufficient. If the curing of the sealant is insufficient, the uncured sealant component is eluted into the liquid crystal to cause liquid crystal contamination.
於專利文獻3中，揭示將高感度之光聚合起始劑調配於密封劑中。然而，若僅調配高感度之光聚合起始劑，則無法使密封劑充分地光硬化。又，於專利文獻4中，揭示將高感度之光聚合起始劑與增感劑組合而調配於密封劑中。然而，由於使用增感劑，故而有容易產生液晶污染之問題。 Patent Document 3 discloses that a high-sensitivity photopolymerization initiator is formulated in a sealant. However, if only a high-sensitivity photopolymerization initiator is blended, the sealant cannot be sufficiently photocured. Further, Patent Document 4 discloses that a high-sensitivity photopolymerization initiator and a sensitizer are combined and formulated in a sealant. However, since a sensitizer is used, there is a problem that liquid crystal contamination is likely to occur.
專利文獻1：日本特開2001-133794號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-133794
專利文獻2：國際公開第02/092718號 Patent Document 2: International Publication No. 02/092718
專利文獻3：國際公開第2011/002028號 Patent Document 3: International Publication No. 2011/002028
專利文獻4：日本特開2010-286640號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2010-286640
本發明之目的在於提供一種光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 An object of the present invention is to provide a sealing agent for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element using the sealing agent for a liquid crystal display element.
本發明為含有硬化性樹脂、下述式(1)所表示之9-氧硫系聚合起始劑、及胺系增感劑之液晶顯示元件用密封劑。 The present invention is a 9-oxosulfuric acid represented by the following formula (1) containing a curable resin. A sealing agent for a liquid crystal display element which is a polymerization initiator and an amine sensitizer.
式(1)中，n為1~6，R3為氫原子、甲基、或乙基，於n大於1之情形時，R3所表示之基或原子可相同亦可不同。A表示式-O-、-[O(CHR2CHR1)a]y-、-[O(CH2)bCO]y-、或-[O(CH2)bCO](y-1)-[O(CHR2CHR1)a]-之基，R1與R2之一者表示氫原子，另一者表示氫原子、甲基、或乙基，a為1~2，b為4~5，Q為(聚)乙二醇、(聚)丙二醇、(聚)丁二醇、甘油、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇、或己內酯多元醇之殘基，Q內之游離羥基亦可經酯化，x為大於1且不超過Q之羥基數的數目，於x大於1且不超過2之情形時，y為1~10，於x超過2之情形時，y為3~10。 In the formula (1), n is 1 to 6, and R 3 is a hydrogen atom, a methyl group or an ethyl group. When n is greater than 1, the group or atom represented by R 3 may be the same or different. A represents the formula -O-, -[O(CHR 2 CHR 1 ) a ] y -, -[O(CH 2 ) b CO] y -, or -[O(CH 2 ) b CO] (y-1) -[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, a is 1 to 2, and b is 4 ~5, Q is (poly)ethylene glycol, (poly)propylene glycol, (poly)butanediol, glycerin, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol Or the residue of the caprolactone polyol, the free hydroxyl group in Q may also be esterified, and x is a number greater than 1 and not exceeding the number of hydroxyl groups of Q. When x is greater than 1 and not more than 2, y is 1~10, when x exceeds 2, y is 3~10.
本發明人等發現，令人驚訝的是，具有特定之結構之化合物對液晶之污染性低，且光反應性優異。因此，本發明者人等發現：藉由調配該化合物作為光聚合起始劑，可獲得光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑，從而完成本發明。 The present inventors have found that, surprisingly, a compound having a specific structure is low in contamination to liquid crystals and excellent in photoreactivity. Therefore, the inventors of the present invention have found that a compound for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination can be obtained by blending the compound as a photopolymerization initiator.
本發明之液晶顯示元件用密封劑含有上述式(1)所表示之9-氧硫系聚合起始劑。藉由將上述式(1)所表示之9-氧硫系聚合起始劑與胺系增感劑組合而含有，本發明之液晶顯示元件用密封劑成為高感度而光硬化性優異、且可抑制液晶污染者。 The sealant for liquid crystal display elements of the present invention contains 9-oxosulfur represented by the above formula (1) It is a polymerization initiator. By the 9-oxosulfur represented by the above formula (1) The polymerization initiator is contained in combination with an amine sensitizer, and the sealing agent for liquid crystal display elements of the present invention has high sensitivity and is excellent in photocurability, and can suppress liquid crystal contamination.
上述式(1)中，x為大於1且不超過Q之羥基數的數目，較佳之下限為2，較佳之上限為6。若上述x未達2，則存在引起液晶污染之情形。若上述x超過6，則存在黏度增高而難以使用之情形。 In the above formula (1), x is a number of hydroxyl groups greater than 1 and not exceeding Q, and a lower limit is preferably 2, and a preferred upper limit is 6. If the above x is less than 2, there is a case where liquid crystal contamination is caused. When the above x exceeds 6, the viscosity is increased and it is difficult to use.
上述式(1)所表示之9-氧硫系聚合起始劑中，較佳為上述式(1)中之n為1，R3為氫原子，A為式-O-之基。 9-oxosulfur represented by the above formula (1) In the polymerization initiator, it is preferred that n in the above formula (1) is 1, R 3 is a hydrogen atom, and A is a group of the formula -O-.
上述式(1)中之Q較佳為聚丁二醇之殘基。 Q in the above formula (1) is preferably a residue of polytetramethylene glycol.
又，於Q內之游離羥基經酯化之情形時，上述式(1)所表示之9-氧硫系聚合起始劑較佳為低級脂肪酸酯。 Further, in the case where the free hydroxyl group in Q is esterified, the 9-oxygen sulfur represented by the above formula (1) The polymerization initiator is preferably a lower fatty acid ester.
上述式(1)中，A-Q之分子量之較佳之下限為100，較佳之上限為2000。若A-Q之分子量未達100，則存在引起液晶污染之情形。若A-Q之分子量超過2000，則存在黏度變得過高而難以使用之情形。 In the above formula (1), a preferred lower limit of the molecular weight of A-Q is 100, and a preferred upper limit is 2000. If the molecular weight of A-Q is less than 100, there is a case where liquid crystal contamination is caused. When the molecular weight of A-Q exceeds 2,000, the viscosity becomes too high and it is difficult to use.
作為製造上述式(1)所表示之9-氧硫系聚合起始劑之方法，具體而言，例如可列舉使羧基甲氧基9-氧硫與聚乙二醇反應之方法等。 As the production of 9-oxosulfur represented by the above formula (1) The method of polymerizing the initiator, specifically, for example, carboxymethoxy 9-oxosulfide A method of reacting with polyethylene glycol, and the like.
本發明之液晶顯示元件用密封劑100重量份中之上述式(1)所表示之9-氧硫系聚合起始劑之含量的較佳之下限為0.1重量份，較佳之上限為10重量份。若上述式(1)所表示之9-氧硫系聚合起始劑之含量未達0.1重量份，則存在未充分地進行所獲得之液晶顯示元件用密封劑之光聚合之情形。若上述式(1)所表示之9-氧硫系聚合起始劑之含量超過10重量份，則存在未反應之式(1)所表示之9-氧硫系聚合起始劑大量殘留，所獲得之液晶顯示元件用密封劑成為耐候性或保存穩定性差者，或產生液晶污染之情形。上述式(1)所表示之9-氧硫 系聚合起始劑之含量的更佳之下限為0.3重量份，更佳之上限為7重量份。 9-oxosulfuric acid represented by the above formula (1) in 100 parts by weight of the sealant for a liquid crystal display device of the present invention A preferred lower limit of the content of the polymerization initiator is 0.1 part by weight, preferably 10 parts by weight. If the 9-oxygen sulfur represented by the above formula (1) When the content of the polymerization initiator is less than 0.1 part by weight, photopolymerization of the obtained sealing agent for liquid crystal display elements may not be sufficiently performed. If the 9-oxygen sulfur represented by the above formula (1) When the content of the polymerization initiator is more than 10 parts by weight, there is an unreacted 9-oxosulfur represented by the formula (1) A large amount of the polymerization initiator remains, and the obtained sealant for a liquid crystal display element is inferior in weather resistance or storage stability, or liquid crystal contamination occurs. 9-oxosulfur represented by the above formula (1) A more preferred lower limit of the content of the polymerization initiator is 0.3 parts by weight, and a more preferred upper limit is 7 parts by weight.
本發明之液晶顯示元件用密封劑含有胺系增感劑。作為上述胺系增感劑，例如可列舉：下述式(2)所表示之化合物、4,4'-雙(二乙胺基)二苯甲酮、2-二甲胺基-苯甲酸乙酯、4-(二甲胺基)苯甲酸乙酯、4-二甲胺基苯甲酸2-乙基己酯、4-(二甲胺基)苯甲酸異戊酯、4-(二甲胺基) 苯甲酸丁氧基乙酯等。其中，就所獲得之液晶顯示元件用密封劑成為硬化性優異者而言，較佳為下述式(2)所表示之化合物(以下，亦稱為「式(2)所表示之胺系增感劑」)。 The sealing agent for liquid crystal display elements of this invention contains an amine type sensitizer. Examples of the amine-based sensitizer include a compound represented by the following formula (2), 4,4′-bis(diethylamino)benzophenone, and 2-dimethylamino-benzoic acid B. Ester, ethyl 4-(dimethylamino)benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, isoamyl 4-(dimethylamino)benzoate, 4-(dimethylamine) base) Butyloxy benzoate and the like. In the case where the sealant for a liquid crystal display device obtained is excellent in curability, the compound represented by the following formula (2) is preferable (hereinafter, also referred to as "the amine compound represented by the formula (2)). Sensation").
式(2)中，z表示1以上之整數，P為(聚)乙二醇、(聚)丙二醇、(聚)丁二醇、甘油、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇、或己內酯多元醇之殘基。 In the formula (2), z represents an integer of 1 or more, and P is (poly)ethylene glycol, (poly)propylene glycol, (poly)butanediol, glycerin, trimethylolpropane, di-trimethylolpropane, Residues of pentaerythritol, dipentaerythritol, or caprolactone polyol.
上述式(2)中，z表示1以上之整數，較佳之下限為2，較佳之上限為6。若上述z未達2，則存在引起液晶污染之情形。若上述z超過6，則存在黏度增高而難以使用之情形。 In the above formula (2), z represents an integer of 1 or more, and a preferred lower limit is 2, and a preferred upper limit is 6. If the above z is less than 2, there is a case where liquid crystal contamination is caused. When the above z exceeds 6, there is a case where the viscosity is increased and it is difficult to use.
上述式(2)中，P為(聚)乙二醇、(聚)丙二醇、(聚)丁二醇、甘油、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇、或己內酯多元醇之殘基。 In the above formula (2), P is (poly)ethylene glycol, (poly)propylene glycol, (poly)butanediol, glycerin, trimethylolpropane, di-trimethylolpropane, pentaerythritol, two Residue of pentaerythritol or caprolactone polyol.
上述式(2)中之P之分子量之較佳之下限為100，較佳之上限為2000。若P之分子量未達100，則存在引起液晶污染之情形。若P之分子量超過2000，則存在黏度變得過高而難以使用之情形。 A preferred lower limit of the molecular weight of P in the above formula (2) is 100, and a preferred upper limit is 2000. If the molecular weight of P is less than 100, there is a case where liquid crystal contamination is caused. When the molecular weight of P exceeds 2,000, the viscosity becomes too high and it is difficult to use.
上述式(2)所表示之胺系增感劑中，較佳為式(2)中之z為2，P為聚乙二醇之殘基。 In the amine-based sensitizer represented by the above formula (2), it is preferred that z in the formula (2) is 2, and P is a residue of polyethylene glycol.
作為製造上述式(2)所表示之胺系增感劑之方法，具體而言，例如可列舉使4-(二甲胺基)苯甲醯氯與聚環氧乙烷反應之方法等。 Specific examples of the method for producing the amine-based sensitizer represented by the above formula (2) include a method of reacting 4-(dimethylamino)benzimidyl chloride with polyethylene oxide.
本發明之液晶顯示元件用密封劑100重量份中之上述胺系增感劑之含量的較佳之下限為0.1重量份，較佳之上限為10重量份。若上述胺系增感劑之含量未達0.1重量份，則存在所獲得之液晶顯示元件用密封劑成為光硬化性差者，而產生液晶污染之情形。若上述胺系增感劑之含量超過10重量份，則存在產生因胺系增感劑所導致之液晶污染之情形。上述胺系增感劑之含量之更佳之下限為0.3重量份，更佳之上限為7重量份。 A preferred lower limit of the content of the amine-based sensitizer in 100 parts by weight of the sealant for a liquid crystal display device of the present invention is 0.1 part by weight, preferably 10 parts by weight. When the content of the above-mentioned amine-based sensitizer is less than 0.1 part by weight, the obtained sealing agent for a liquid crystal display element may be inferior in photocurability, and liquid crystal contamination may occur. When the content of the above amine-based sensitizer exceeds 10 parts by weight, liquid crystal contamination due to the amine-based sensitizer may occur. A more preferred lower limit of the content of the above amine-based sensitizer is 0.3 parts by weight, and a more preferred upper limit is 7 parts by weight.
關於上述式(1)所表示之9-氧硫系聚合起始劑與上述胺系增感劑之含有比例，以重量比計，較佳為式(1)所表示之9-氧硫系聚合起始劑：胺系增感劑=1：0.05~1：5。藉由使上述式(1)所表示之9-氧硫系聚合起始劑與上述胺系增感劑之含有比例為該範圍內，本發明之液晶顯示元件用密封劑成為抑制液晶污染之效果、及光硬化性尤其優異者。上述式(1)所表示之9-氧硫系聚合起始劑與上述胺系增感劑之含有比例更佳為式(1)所表示之9-氧硫系聚合起始劑：胺系增感劑=1：0.1~1：2。 About 9-oxosulfur represented by the above formula (1) The content ratio of the polymerization initiator to the above amine sensitizer is preferably 9-oxosulfur represented by the formula (1) by weight ratio. Polymerization initiator: amine sensitizer = 1:0.05~1:5. By causing 9-oxosulfuric represented by the above formula (1) The content ratio of the polymerization initiator to the amine sensitizer is within this range, and the sealing agent for a liquid crystal display device of the present invention is excellent in suppressing liquid crystal contamination and is excellent in photocurability. 9-oxosulfur represented by the above formula (1) The content ratio of the polymerization initiator to the above amine sensitizer is more preferably 9-oxosulfur represented by the formula (1) Polymerization initiator: amine sensitizer = 1: 0.1 ~ 1:2.
本發明之液晶顯示元件用密封劑含有硬化性樹脂。 The sealing agent for liquid crystal display elements of this invention contains a curable resin.
上述硬化性樹脂較佳為含有(甲基)丙烯酸樹脂。 The curable resin preferably contains a (meth)acrylic resin.
作為上述(甲基)丙烯酸樹脂，例如可列舉：藉由使具有羥基之化合物與(甲基)丙烯酸反應而獲得之酯化合物、藉由使(甲基)丙烯酸與環氧化合物反應而獲得之環氧(甲基)丙烯酸酯、藉由使具有羥基之(甲基)丙烯酸衍生物與異氰酸酯化合物反應而獲得之(甲基)丙烯酸胺酯(urethane(meth)acrylate)等。其中，較佳為環氧(甲基)丙烯酸酯。再者，於本說明書中，上述所謂「(甲基)丙烯酸」，係指丙烯酸或甲基丙烯酸，上述所謂「(甲基)丙烯酸樹脂」，係指具有丙烯醯基或甲基丙烯醯基(以下，亦合併稱為「(甲基)丙烯醯基」)之樹脂。又，上述所謂「(甲基)丙烯酸酯」，係指丙烯酸酯或甲基丙烯酸酯。進而，上述所謂「環氧(甲基)丙烯酸酯」，表示使環氧樹脂中之所有環氧基 與(甲基)丙烯酸反應而成之化合物。 Examples of the (meth)acrylic resin include an ester compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, and a ring obtained by reacting (meth)acrylic acid with an epoxy compound. Oxy (meth) acrylate, urethane (meth) acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound. Among them, epoxy (meth) acrylate is preferred. In the present specification, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylic resin" means having an acrylonitrile group or a methacrylic acid group ( Hereinafter, a resin called "(meth)acrylonitrile" is also incorporated. Moreover, the above-mentioned "(meth) acrylate" means acrylate or methacrylate. Further, the above-mentioned "epoxy (meth) acrylate" means all epoxy groups in the epoxy resin. A compound formed by reacting with (meth)acrylic acid.
作為上述酯化合物中之單官能者，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸苄酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、醯亞胺(甲基)丙烯酸酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸二甲胺基乙酯、琥珀酸2-(甲基)丙烯醯氧基乙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯2-羥基丙酯、(甲基)丙烯酸縮水甘油酯、磷酸2-(甲基)丙烯醯氧基乙酯等。 Examples of the monofunctional ones of the above ester compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (methyl). ) 2-hydroxybutyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid Fatty ester, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth) acrylate, (methyl) ) 2-ethoxyethyl acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate , phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, (meth) acrylate 2, 2,2-trifluoroethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, quinone imine (methyl) Acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) propylene N-butyl acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate Myristyl ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, ( Diethylaminoethyl methacrylate, dimethylaminoethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl succinate, 2-(methyl) hexahydrophthalate Propylene methoxyethyl ester, 2-(methyl) propylene methoxyethyl phthalate 2-hydroxypropyl ester, glycidyl (meth) acrylate, 2-(methyl) propylene methoxy ethoxylate Ester and the like.
又，作為上述酯化合物中之二官能者，例如可列舉：1,4-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸 酯、聚乙二醇二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、二(甲基)丙烯酸二羥甲基二環戊二烯酯、1,3-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷改質異氰尿酸二(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、碳酸酯二醇二(甲基)丙烯酸酯、聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己內酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。 Further, examples of the difunctional one of the above ester compounds include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, and 1,6- Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, 2-n-butyl-2-ethyl -1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol (meth)acrylate, ethylene glycol di(a) Acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylic acid Ester, polyethylene glycol di(meth) acrylate, propylene oxide addition bisphenol A di(meth) acrylate, ethylene oxide addition bisphenol A di(meth) acrylate, epoxy B Alkane addition of bisphenol F di(meth)acrylate, di(hydroxy)dicyclopentadienyl di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol Di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-hydroxy-3-(methyl)propenyloxypropyl ester, carbonate II Alcohol di(meth)acrylate, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, polycaprolactone diol di(meth) acrylate, polybutylene Olediol di(meth)acrylate or the like.
又，作為上述酯化合物中之三官能以上者，例如可列舉：新戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成異氰尿酸三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、三(甲基)丙烯酸甘油酯、環氧丙烷加成三(甲基)丙烯酸甘油酯、磷酸三(甲基)丙烯醯氧基乙酯等。 Further, examples of the trifunctional or higher of the above ester compounds include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and propylene oxide addition tris. Propane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, epoxy B Alkane addition of tris(meth)acrylate isocyanurate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, di-trimethylolpropane tetra (a) Acrylate, neopentyl alcohol tetra(meth)acrylate, tris(meth)acrylate, propylene oxide addition tris(meth)acrylate, tris(meth)acryloxyl phosphate Ethyl ester and the like.
作為上述環氧(甲基)丙烯酸酯，例如可列舉藉由使環氧樹脂與(甲基)丙烯酸依據常法於鹼性觸媒之存在下進行反應而獲得者等。 Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy resin with (meth)acrylic acid in the presence of a basic catalyst according to a usual method.
作為成為用於合成上述環氧(甲基)丙烯酸酯之原料之環氧樹脂，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、2,2'-二烯丙基雙酚A型環氧樹脂、氫化雙酚型環氧樹脂、環氧丙烷加成雙酚A型環氧樹脂、間苯二酚型環氧樹脂、聯苯型環氧樹脂、硫化物型環氧樹脂、二苯醚型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、二環戊二烯酚醛清漆型環氧樹脂、聯苯酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、縮水甘油胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧樹 脂、縮水甘油酯化合物等。 Examples of the epoxy resin used as a raw material for synthesizing the above epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin, and 2 , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy Resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber Modified epoxy tree Lipid, glycidyl ester compound, and the like.
作為上述雙酚A型環氧樹脂中之市售者，例如可列舉：jER828EL、jER1004(均為三菱化學公司製造)、Epiclon 850CRP(DIC公司製造)等。 The commercially available ones of the bisphenol A type epoxy resins include, for example, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), and Epiclon 850CRP (manufactured by DIC Corporation).
作為上述雙酚F型環氧樹脂中之市售者，例如可列舉jER806、jER4004(均為三菱化學公司製造)等。 For example, jER806 and jER4004 (all manufactured by Mitsubishi Chemical Corporation) and the like are mentioned as a commercial product of the bisphenol F-type epoxy resin.
作為上述雙酚S型環氧樹脂中之市售者，例如可列舉Epiclon EXA1514(DIC公司製造)等。 As a commercial item of the said bisphenol S type epoxy resin, Epiclon EXA1514 (made by the DIC company) etc. are mentioned, for example.
作為上述2,2'-二烯丙基雙酚A型環氧樹脂中之市售者，例如可列舉RE-810NM(日本化藥公司製造)等。 The commercially available one of the 2,2'-diallyl bisphenol A type epoxy resins is, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
作為上述氫化雙酚型環氧樹脂中之市售者，例如可列舉Epiclon EXA7015(DIC公司製造)等。 As a commercial item of the said hydrogenated bisphenol type epoxy resin, Epiclon EXA7015 (made by the DIC company) etc. are mentioned, for example.
作為上述環氧丙烷加成雙酚A型環氧樹脂中之市售者，例如可列舉：EP-4000S(ADEKA公司製造)等。 The commercially available one of the above-mentioned propylene oxide-added bisphenol A-type epoxy resins is, for example, EP-4000S (manufactured by Adeka Co., Ltd.).
作為上述間苯二酚型環氧樹脂中之市售者，例如可列舉EX-201(Nagase chemteX公司製造)等。 The commercially available one of the resorcinol-type epoxy resins is, for example, EX-201 (manufactured by Nagase ChemteX Co., Ltd.).
作為上述聯苯型環氧樹脂中之市售者，例如可列舉jERYX-4000H(三菱化學公司製造)等。 As a commercial item of the above-mentioned biphenyl type epoxy resin, jERYX-4000H (made by Mitsubishi Chemical Corporation), etc. are mentioned, for example.
作為上述硫化物型環氧樹脂中之市售者，例如可列舉YSLV-50TE(新日鐵住金化學公司製造)等。 For example, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like can be mentioned as a commercially available one of the above-mentioned sulfide-type epoxy resins.
作為上述二苯醚型環氧樹脂中之市售者，例如可列舉YSLV-80DE(新日鐵住金化學公司製造)等。 For example, YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like can be cited as a commercially available one of the above-mentioned diphenyl ether type epoxy resins.
作為上述二環戊二烯型環氧樹脂中之市售者，例如可列舉EP-4088S(ADEKA公司製造)等。 The commercially available one of the above-mentioned dicyclopentadiene type epoxy resins is, for example, EP-4088S (manufactured by Adeka Co., Ltd.).
作為上述萘型環氧樹脂中之市售者，例如可列舉Epiclon HP4032、Epiclon EX A-4700(均為DIC公司製造)等。 As a commercial one of the said naphthalene type epoxy resins, Epiclon HP4032 and Epiclon are mentioned, for example. EX A-4700 (both manufactured by DIC Corporation).
作為上述苯酚酚醛清漆型環氧樹脂中之市售者，例如可列舉Epiclon N-770(DIC公司製造)等。 As a commercial item of the above-mentioned phenol novolak type epoxy resin, Epiclon N-770 (made by the DIC company) etc. are mentioned, for example.
作為上述鄰甲酚酚醛清漆型環氧樹脂中之市售者，例如可列舉Epiclon N-670-EXP-S(DIC公司製造)等。 As a commercial item of the above-mentioned o-cresol novolak-type epoxy resin, Epiclon N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.
作為上述二環戊二烯酚醛清漆型環氧樹脂中之市售者，例如可列舉Epiclon HP7200(DIC公司製造)等。 The commercially available one of the above-mentioned dicyclopentadiene novolac type epoxy resins is Epiclon HP7200 (manufactured by DIC Corporation).
作為上述聯苯酚醛清漆型環氧樹脂中之市售者，例如可列舉NC-3000P(日本化藥公司製造)等。 The commercially available one of the above-mentioned biphenyl novolak type epoxy resins is, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
作為上述萘酚酚醛清漆型環氧樹脂中之市售者，例如可列舉ESN-165S(新日鐵住金化學公司製造)等。 As a commercial item of the above-mentioned naphthol novolac type epoxy resin, ESN-165S (made by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc. are mentioned, for example.
作為上述縮水甘油胺型環氧樹脂中之市售者，例如可列舉：jER630(三菱化學公司製造)、Epiclon 430(DIC公司製造)、TETRAD-X(三菱瓦斯化學公司製造)等。 For example, jER630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like are mentioned as a commercially available product of the glycidylamine type epoxy resin.
作為上述烷基多元醇型環氧樹脂中之市售者，例如可列舉：ZX-1542(新日鐵住金化學公司製造)、Epiclon 726(DIC公司製造)、Epolight 80MFA(共榮社化學公司製造)、Denacol EX-611(Nagase chemteX公司製造)等。 For example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epiclon 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) are mentioned as a commercial product of the above-mentioned alkyl polyol type epoxy resin. ), Denacol EX-611 (manufactured by Nagase ChemteX), and the like.
作為上述橡膠改質型環氧樹脂中之市售者，例如可列舉：YR-450、YR-207(均為新日鐵住金化學公司製造)、Epolead PB(Daicel公司製造)等。 For example, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Co., Ltd.), and the like are mentioned as a commercially available one of the rubber-modified epoxy resins.
作為上述縮水甘油酯化合物中之市售者，例如可列舉Denacol EX-147(Nagase chemteX公司製造)等。 As a commercial one of the above-mentioned glycidyl ester compounds, for example, Denacol EX-147 (manufactured by Nagase ChemteX Co., Ltd.) or the like can be mentioned.
作為上述環氧樹脂中之其他市售者，例如可列舉：YDC-1312、YSLV-80XY、YSLV-90CR(均為新日鐵住金化學公司製造)、XAC4151(旭化成公司製造)、jER1031、jER1032(均為三菱化學公司製造)、EXA-7120(DIC 公司製造)、TEPIC(日產化學公司製造)等。 Other commercially available ones of the above-mentioned epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, and jER1032 ( All manufactured by Mitsubishi Chemical Corporation), EXA-7120 (DIC Made by the company), TEPIC (manufactured by Nissan Chemical Co., Ltd.), etc.
作為製造上述環氧(甲基)丙烯酸酯之方法，具體而言，例如可藉由一面對間苯二酚型環氧樹脂(EX-201，Nagase chemteX公司製造)360重量份、作為聚合抑制劑之對甲氧基苯酚2重量份、作為反應觸媒之三乙胺2重量份、及丙烯酸210重量份吹送空氣而進行回流攪拌，一面於90℃使之反應5小時，而獲得間苯二酚型環氧丙烯酸酯。 As a method of producing the above-mentioned epoxy (meth) acrylate, specifically, for example, it can be inhibited by polymerization by 360 parts by weight of a resorcinol type epoxy resin (EX-201, manufactured by Nagase ChemteX Co., Ltd.). 2 parts by weight of a p-methoxyphenol, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid were mixed under reflux, and reacted at 90 ° C for 5 hours to obtain isophthalic acid. Phenolic epoxy acrylate.
作為上述環氧(甲基)丙烯酸酯中之市售者，例如可列舉：EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182(均為Daicel-Allnex公司製造)、EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020(均為新中村化學工業公司製造)、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(均為共榮社化學公司製造)、Denacol Acrylate DA-141、Denacol Acrylate DA-314、Denacol Acrylate DA-911(均為Nagase chemteX公司製造)等。 As a commercially available one of the above-mentioned epoxy (meth) acrylates, for example, EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3102, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX 63182 (both are Daicel-Allnex) Made by the company), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 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 Kyoei Chemical Co., Ltd.), Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all manufactured by Nagase Chemtech X), and the like.
作為上述藉由使具有羥基之(甲基)丙烯酸衍生物與異氰酸酯化合物反應而獲得之(甲基)丙烯酸胺酯，例如可藉由相對於具有2個異氰酸酯基之異氰酸酯化合物1當量，使具有羥基之(甲基)丙烯酸衍生物2當量於觸媒量之錫系化合物存在下反應而獲得。 As the above-mentioned (meth)acrylic acid ester obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound, for example, it can have a hydroxyl group by being equivalent to 1 equivalent of an isocyanate compound having 2 isocyanate groups. The (meth)acrylic acid derivative is obtained by reacting 2 equivalents in the presence of a catalyst amount of a tin-based compound.
作為成為上述(甲基)丙烯酸胺酯之原料之異氰酸酯化合物，例如可列舉：異佛酮二異氰酸酯、2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯(MDI)、氫化MDI、聚合MDI、1,5-萘二 異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯(XDI)、氫化XDI、離胺酸二異氰酸酯(lysine diisocyanate)、三苯基甲烷三異氰酸酯、硫代磷酸三(異氰酸酯基苯基)酯、四甲基二甲苯二異氰酸酯、1,6,10-十一烷三異氰酸酯等。 Examples of the isocyanate compound which is a raw material of the above (meth)acrylic acid amide include isophorone diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, and hexa Methyl diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene Isocyanate, norbornane diisocyanate, tolidine diisocyanate, benzodimethyl diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(thiocyanate) Phenyl phenyl) ester, tetramethyl xylene diisocyanate, 1,6,10-undecane triisocyanate, and the like.
又，作為成為上述(甲基)丙烯酸胺酯之原料之異氰酸酯，例如亦可使用藉由使乙二醇、甘油、山梨糖醇、三羥甲基丙烷、(聚)丙二醇、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等多元醇與過量之異氰酸酯化合物之反應而獲得的經鏈延長之異氰酸酯化合物。 Further, as the isocyanate which is a raw material of the above (meth)acrylic acid amide, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, or the like may be used. A chain-extended isocyanate compound obtained by reacting a polyhydric alcohol such as a polyether diol, a polyester diol or a polycaprolactone diol with an excess of an isocyanate compound.
作為成為上述(甲基)丙烯酸胺酯之原料之具有羥基之(甲基)丙烯酸衍生物，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基丁酯等之市售品，或乙二醇、丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、聚乙二醇等二元醇之單(甲基)丙烯酸酯，或三羥甲基乙烷、三羥甲基丙烷、甘油等三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯，或雙酚A型環氧丙烯酸酯等環氧(甲基)丙烯酸酯等。 Examples of the (meth)acrylic acid derivative having a hydroxyl group which is a raw material of the above (meth)acrylic acid amide include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. A commercially available product of 4-hydroxybutyl (meth)acrylate or 2-hydroxybutyl (meth)acrylate, or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1, a mono(meth)acrylate of a glycol such as 4-butanediol or polyethylene glycol, or a mono(meth)acrylate of a triol such as trimethylolethane, trimethylolpropane or glycerin Or an epoxy (meth) acrylate such as di(meth)acrylate or bisphenol A epoxy acrylate.
具體而言，上述(甲基)丙烯酸胺酯例如可藉由如下方式而獲得：添加三羥甲基丙烷134重量份、作為聚合抑制劑之BHT 0.2重量份、作為反應觸媒之二月桂酸二丁基錫0.01重量份、及異佛酮二異氰酸酯666重量份，一面於60℃進行回流攪拌，一面使之反應2小時，繼而，添加丙烯酸2-羥基乙酯51重量份，一面吹送空氣而進行回流攪拌，一面於90℃使之反應2小時。 Specifically, the above (meth)acrylic acid amide can be obtained, for example, by adding 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, and dilauric acid as a reaction catalyst. 0.01 parts by weight of butyltin and 666 parts by weight of isophorone diisocyanate were reacted under reflux at 60 ° C for 2 hours, and then 51 parts by weight of 2-hydroxyethyl acrylate was added thereto, and air was blown and refluxed. The reaction was allowed to proceed at 90 ° C for 2 hours.
作為上述(甲基)丙烯酸胺酯中之市售者，例如可列舉：M-1100、M-1200、M-1210、M-1600(均為東亞合成公司製造)、EBECRYL230、EBECRYL270、EBECRYL4858、EBECRYL8402、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、 EBECRYL1290、EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、EBECRYL2220(均為Daicel-Allnex公司製造)、Artresin UN-9000H、Artresin UN-9000A、Artresin UN-7100、Artresin UN-1255、Artresin UN-330、Artresin UN-3320HB、Artresin UN-1200TPK、Artresin SH-500B(均為根上工業公司製造)、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(均為新中村化學工業公司製造)、AH-600、AT-600、UA-306H、AI-600、UA-101T、UA-101I、UA-306T、UA-306I(均為共榮社化學公司製造)等。 For example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402 are exemplified as the commercially available (meth) acrylate. , EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL12129, EBECRYL482, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (all manufactured by Daicel-Allnex), Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Gensal Industries, Inc.), 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 Shin-Nakamura Chemical Industry Co., Ltd.), AH-600, AT-600, UA -306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.).
為了提高所獲得之液晶顯示元件用密封劑之接著性，上述硬化性樹脂較佳為進而含有環氧樹脂。作為上述環氧樹脂，例如可列舉成為用於合成上述環氧(甲基)丙烯酸酯之原料之環氧樹脂、或部分(甲基)丙烯醯基改質環氧樹脂等。 In order to improve the adhesiveness of the obtained sealing compound for liquid crystal display elements, it is preferable that the said curable resin further contains an epoxy resin. Examples of the epoxy resin include an epoxy resin used as a raw material for synthesizing the above epoxy (meth)acrylate, or a partially (meth)acrylonitrile-based modified epoxy resin.
再者，於本說明書中，上述所謂部分(甲基)丙烯醯基改質環氧樹脂，係指1分子中具有各1個以上之環氧基與(甲基)丙烯醯氧基之樹脂，例如可藉由使2個以上之環氧樹脂之一部分之環氧基與(甲基)丙烯酸反應而獲得。 In the present specification, the above-mentioned partial (meth) acrylonitrile-based modified epoxy resin refers to a resin having one or more epoxy groups and (meth) acryloxy group in one molecule. For example, it can be obtained by reacting an epoxy group which is a part of two or more epoxy resins with (meth)acrylic acid.
於本發明之液晶顯示元件用密封劑含有上述環氧樹脂之情形時，較佳為以使(甲基)丙烯醯氧基與環氧基之比成為30：70~95：5之方式調配上述(甲基)丙烯酸樹脂與上述環氧樹脂。若(甲基)丙烯醯氧基之比率未達30%，則存在如下情形：由於即便(甲基)丙烯醯氧基之聚合結束亦大量存在未硬化之環氧樹脂成分，故而產生液晶污染。若(甲基)丙烯醯氧基之比率超過95%，則存在所獲得之液晶顯示元件用密封劑成為接著性差者之情 形。 In the case where the sealing agent for a liquid crystal display device of the present invention contains the above epoxy resin, it is preferred to blend the above ratio of (meth)acryloxyloxy group to epoxy group to be 30:70 to 95:5. (Meth)acrylic resin and the above epoxy resin. When the ratio of the (meth) propylene oxime group is less than 30%, there is a case where liquid crystal contamination occurs due to the large amount of uncured epoxy resin component even after the polymerization of the (meth) propylene oxime group is completed. When the ratio of the (meth) propylene decyloxy group exceeds 95%, the obtained sealing agent for a liquid crystal display element has a poor adhesion property. shape.
就抑制液晶污染之觀點而言，上述硬化性樹脂較佳為-OH基、-NH-基、-NH2基等具有氫鍵性之單元者。 In view of suppressing liquid crystal contamination, the curable resin is preferably a unit having hydrogen bonding properties such as an -OH group, a -NH- group, or a -NH 2 group.
又，就反應性之程度而言，上述(甲基)丙烯酸系樹脂較佳為分子中具有2~3個(甲基)丙烯醯氧基者。 Moreover, as for the degree of reactivity, the (meth)acrylic resin preferably has 2 to 3 (meth) acryloxy groups in the molecule.
本發明之液晶顯示元件用密封劑亦可含有熱自由基聚合起始劑。 The sealant for a liquid crystal display element of the present invention may further contain a thermal radical polymerization initiator.
作為上述熱自由基聚合起始劑，例如可列舉由偶氮化合物、有機過氧化物等所構成者。其中，較佳為由高分子偶氮化合物所構成之起始劑(以下，亦稱為「高分子偶氮起始劑」)。 Examples of the thermal radical polymerization initiator include those composed of an azo compound, an organic peroxide, and the like. Among them, an initiator (hereinafter also referred to as "polymer azo initiator") composed of a polymer azo compound is preferred.
再者，於本說明書中，所謂高分子偶氮起始劑，係指具有偶氮基、且藉由熱而產生可使(甲基)丙烯醯氧基硬化之自由基之數量平均分子量為300以上之化合物。 In the present specification, the term "polymer azo initiator" means a radical having an azo group and which generates a radical capable of hardening a (meth) propylene oxime by heat, and has a number average molecular weight of 300. The above compounds.
上述高分子偶氮起始劑之數量平均分子量之較佳之下限為1000，較佳之上限為30萬。若上述高分子偶氮起始劑之數量平均分子量未達1000，則存在高分子偶氮起始劑對液晶造成不良影響之情形。若上述高分子偶氮起始劑之數量平均分子量超過30萬，則存在難以混合至硬化性樹脂中之情形。上述高分子偶氮起始劑之數量平均分子量之更佳之下限為5000，更佳之上限為10萬，進而較佳之下限為1萬，進而較佳之上限為9萬。 A preferred lower limit of the number average molecular weight of the above polymer azo initiator is 1000, and a preferred upper limit is 300,000. If the number average molecular weight of the above polymer azo initiator is less than 1,000, the polymer azo initiator may adversely affect the liquid crystal. When the number average molecular weight of the above polymer azo initiator is more than 300,000, it may be difficult to mix into the curable resin. The lower limit of the number average molecular weight of the above polymer azo initiator is 5,000, more preferably 100,000, and still more preferably 10,000, and further preferably 90,000.
再者，於本說明書中，上述數量平均分子量係藉由凝膠滲透層析法(GPC)進行測定，並藉由聚苯乙烯換算而求出之值。作為藉由GPC測定由聚苯乙烯換算而得之數量平均分子量時之管柱，例如可列舉Shodex LF-804(昭和電工公司製造)等。 In the present specification, the above-mentioned number average molecular weight is measured by gel permeation chromatography (GPC) and is determined by polystyrene conversion. As a column for measuring the number average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) or the like can be mentioned.
作為上述高分子偶氮起始劑，例如可列舉具有經由偶氮基而 鍵結有複數個聚環氧烷或聚二甲基矽氧烷等單元之結構者。 The polymer azo initiator is exemplified by an azo group. The structure of a plurality of units such as polyalkylene oxide or polydimethyl siloxane is bonded.
作為上述具有經由偶氮基而鍵結有複數個聚環氧烷等單元之結構之高分子偶氮起始劑，較佳為具有聚環氧乙烷結構者。作為此種高分子偶氮起始劑，例如可列舉：4,4'-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之聚縮合物、或4,4'-偶氮雙(4-氰基戊酸)與具有末端胺基之聚二甲基矽氧烷之聚縮合物等，具體而言，例如可列舉：VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001(均為和光純藥工業公司製造)等。 The polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group is preferably a polyethylene oxide structure. Examples of such a polymer azo initiator include a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-even. A polycondensate of nitrogen bis(4-cyanovaleric acid) and a polydimethyl siloxane having a terminal amine group, and the like, specifically, for example, VPE-0201, VPE-0401, VPE-0601, VPS -0501, VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.
又，作為非高分子之偶氮化合物之例，可列舉：V-65、V-501(均為和光純藥工業公司製造)等。 In addition, examples of the non-polymer azo compound include V-65 and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.).
作為上述有機過氧化物，例如可列舉：過氧化酮、過氧縮酮、過氧化氫、過氧化二烷基、過氧酯、過氧化二醯基、過氧化二碳酸酯等。 Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, dinonyl peroxide, and peroxydicarbonate.
關於上述熱自由基聚合起始劑之含量，相對於硬化性樹脂100重量份，較佳之下限為0.05重量份，較佳之上限為10重量份。若上述熱自由基聚合起始劑之含量未達0.05重量份，則存在未充分地進行所獲得之液晶顯示元件用密封劑之熱聚合之情形。若上述熱自由基聚合起始劑之含量超過10重量份，則存在因未反應之熱自由基聚合起始劑而產生液晶污染之情形。上述熱自由基聚合起始劑之含量之更佳之下限為0.1重量份，更佳之上限為5重量份。 The content of the thermal radical polymerization initiator is preferably 0.05 parts by weight, and preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned thermal radical polymerization initiator is less than 0.05 part by weight, thermal polymerization of the obtained sealing compound for liquid crystal display elements may not be sufficiently performed. When the content of the above thermal radical polymerization initiator exceeds 10 parts by weight, liquid crystal contamination may occur due to an unreacted thermal radical polymerization initiator. A more preferred lower limit of the content of the above thermal radical polymerization initiator is 0.1 part by weight, and a more preferred upper limit is 5 parts by weight.
本發明之液晶顯示元件用密封劑亦可含有熱硬化劑。 The sealant for a liquid crystal display element of the present invention may further contain a heat hardener.
作為上述熱硬化劑，例如可列舉：有機酸醯肼、咪唑衍生物、胺化合物、多酚系化合物、酸酐等。其中，可較佳地使用有機酸醯肼。 Examples of the above-mentioned thermosetting agent include an organic acid hydrazine, an imidazole derivative, an amine compound, a polyphenol compound, and an acid anhydride. Among them, organic acid hydrazine can be preferably used.
作為上述有機酸醯肼，例如可列舉：癸二酸二醯肼、間苯二甲酸二醯肼、己二酸二醯肼、丙二酸二醯肼等。 Examples of the organic acid hydrazine include diindole azelaic acid, diterpene isophthalate, diammonium adipate, and diammonium malonate.
作為上述有機酸醯肼中之市售者，例如可列舉：SDH、ADH(均為大塚化學公司製造)、Amicure VDH、Amicure VDN-J、Amicure UDH、Amicure UDH-J(均為Ajinomoto Fine-Techno公司製造)等。 For example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDN-J, Amicure UDH, and Amicure are mentioned as a commercial product of the above-mentioned organic bismuth. UDH-J (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) and the like.
關於上述熱硬化劑之含量，相對於上述硬化性樹脂100重量份，較佳之下限為1重量份，較佳之上限為50重量份。若上述熱硬化劑之含量未達1重量份，則存在無法使所獲得之液晶顯示元件用密封劑充分地熱硬化之情形。若上述熱硬化劑之含量超過50重量份，則存在所獲得之液晶顯示元件用密封劑之黏度增高而塗佈性變差之情形。上述熱硬化劑之含量之更佳之上限為30重量份。 The content of the above-mentioned thermosetting agent is preferably 1 part by weight, and preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned thermosetting agent is less than 1 part by weight, the obtained sealing agent for liquid crystal display elements cannot be sufficiently thermally cured. When the content of the above-mentioned heat-hardening agent is more than 50 parts by weight, the viscosity of the obtained sealing compound for liquid crystal display elements is increased, and the coating property is deteriorated. A more preferable upper limit of the content of the above-mentioned thermosetting agent is 30 parts by weight.
以黏度之提高、由應力分散效果所引起之接著性之改善、線膨脹率之改善、硬化物之耐濕性之進一步之提高等為目的，本發明之液晶顯示元件用密封劑較佳為含有填充劑。 The sealing agent for a liquid crystal display element of the present invention preferably contains the viscosity, the improvement of the adhesion due to the stress dispersion effect, the improvement of the linear expansion ratio, and the further improvement of the moisture resistance of the cured product. Filler.
作為上述填充劑，例如可列舉：滑石、石棉、二氧化矽、矽藻土、膨潤石(smectite)、膨土(bentonite)、碳酸鈣、碳酸鎂、氧化鋁、蒙脫石、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、氫氧化鎂、氫氧化鋁、玻璃珠、氮化矽、硫酸鋇、石膏、矽酸鈣、絹雲母、活性白土、氮化鋁等無機填充劑，或聚酯微粒子、聚胺酯微粒子、乙烯基聚合物微粒子、丙烯酸系聚合物微粒子等有機填充劑。該等填充劑可單獨使用，亦可併用兩種以上。 Examples of the filler include talc, asbestos, cerium oxide, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, and oxidation. Inorganic fillers such as iron, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, tantalum nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, or the like, or An organic filler such as polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, or acrylic polymer microparticles. These fillers may be used singly or in combination of two or more.
本發明之液晶顯示元件用密封劑100重量份中之上述填充劑之含量的較佳之下限為10重量份，較佳之上限為70重量份。若上述填充劑之含量未達10重量份，則存在未充分地發揮接著性之改善等效果之情形。若上述填充劑之含量超過70重量份，則存在所獲得之液晶顯示元件用密封劑之黏度增高而塗佈性變差之情形。上述填充劑之含量之更佳之下限為20重量份，更佳之上限為60重量份。 A preferred lower limit of the content of the above filler in 100 parts by weight of the sealant for a liquid crystal display device of the present invention is 10 parts by weight, and preferably the upper limit is 70 parts by weight. When the content of the filler is less than 10 parts by weight, the effect of improving the adhesion is not sufficiently exhibited. When the content of the above-mentioned filler is more than 70 parts by weight, the viscosity of the obtained sealant for a liquid crystal display element is increased, and the coatability is deteriorated. A more preferred lower limit of the content of the above filler is 20 parts by weight, and a more preferred upper limit is 60 parts by weight.
本發明之液晶顯示元件用密封劑較佳為含有矽烷偶合劑。上述矽烷偶合劑主要具有作為用於良好地接著密封劑與基板等之接著助劑之 作用。 The sealing agent for liquid crystal display elements of the present invention preferably contains a decane coupling agent. The above decane coupling agent mainly has a bonding aid for well adhering a sealant to a substrate or the like. effect.
作為上述矽烷偶合劑，就提高與基板等之接著性之效果優異，且可藉由與硬化性樹脂進行化學鍵結而抑制硬化性樹脂向液晶中之流出而言，例如可較佳地使用3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷等。該等矽烷偶合劑可單獨使用，亦可併用兩種以上。 The decane coupling agent is excellent in the effect of improving adhesion to a substrate or the like, and can be used to inhibit the flow of the curable resin into the liquid crystal by chemical bonding with the curable resin. For example, it is preferable to use 3- Aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, and the like. These decane coupling agents may be used singly or in combination of two or more.
本發明之液晶顯示元件用密封劑100重量份中之上述矽烷偶合劑之含量的較佳之下限為0.1重量份，較佳之上限為10重量份。若上述矽烷偶合劑之含量未達0.1重量份，則存在未充分地發揮由調配矽烷偶合劑所產生之效果之情形。若上述矽烷偶合劑之含量超過10重量份，則存在所獲得之液晶顯示元件用密封劑引起液晶污染之情形。上述矽烷偶合劑之含量之更佳之下限為0.3重量份，更佳之上限為5重量份。 A preferred lower limit of the content of the above decane coupling agent in 100 parts by weight of the sealing agent for a liquid crystal display device of the present invention is 0.1 part by weight, preferably 10 parts by weight. When the content of the above decane coupling agent is less than 0.1 part by weight, the effect produced by the preparation of the decane coupling agent may not be sufficiently exhibited. When the content of the above decane coupling agent exceeds 10 parts by weight, the obtained sealing agent for a liquid crystal display element may cause liquid crystal contamination. A more preferred lower limit of the content of the above decane coupling agent is 0.3 parts by weight, and a more preferred upper limit is 5 parts by weight.
本發明之液晶顯示元件用密封劑亦可含有遮光劑。藉由含有上述遮光劑，本發明之液晶顯示元件用密封劑可較佳地用作遮光密封劑。 The sealing agent for liquid crystal display elements of this invention may also contain an opacifier. The sealing agent for a liquid crystal display element of the present invention can be preferably used as a light-shielding sealant by containing the above-mentioned sunscreen agent.
作為上述遮光劑，例如可列舉：氧化鐵、鈦黑、苯胺黑、花青黑、富勒烯、碳黑、樹脂被覆型碳黑等。其中，較佳為鈦黑。 Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferred.
上述鈦黑係與對波長300~800nm之光之平均透過率相比，對紫外線區域附近、尤其是波長370~450nm之光之透過率增高之物質。即，上述鈦黑係具有如下性質之遮光劑：藉由充分地遮蔽可見光區域之波長之光，而對本發明之液晶顯示元件用密封劑賦予遮光性，另一方面，使紫外線區域附近之波長之光透過。作為本發明之液晶顯示元件用密封劑中所含之遮光劑，較佳為絕緣性較高之物質，作為絕緣性較高之遮光劑，亦較佳為鈦黑。 The titanium black is a substance having a higher transmittance to light in the vicinity of the ultraviolet region, particularly at a wavelength of 370 to 450 nm, compared with the average transmittance of light having a wavelength of 300 to 800 nm. In other words, the titanium black has a light-shielding agent having a light-shielding property to the sealing agent for a liquid crystal display element of the present invention while sufficiently shielding light of a wavelength in the visible light region, and a wavelength near the ultraviolet region is provided. Light passes through. The light-shielding agent contained in the sealing agent for liquid crystal display elements of the present invention is preferably a material having high insulating properties, and is preferably a titanium black as a light-shielding agent having high insulating properties.
上述鈦黑即便為未經表面處理者亦發揮充分之效果，但亦可使用表面經偶合劑等有機成分處理者，或經氧化矽、氧化鈦、氧化鍺、氧 化鋁、氧化鋯、氧化鎂等無機成分被覆者等經表面處理之鈦黑。其中，就可進一步提高絕緣性之觀點而言，較佳為經有機成分處理者。 The titanium black described above may exhibit sufficient effects even if it is not surface-treated, but may be treated with an organic component such as a surface coupler or cerium oxide, titanium oxide, cerium oxide or oxygen. A surface-treated titanium black such as an inorganic component such as aluminum, zirconia or magnesia. Among them, from the viewpoint of further improving the insulating property, it is preferred to be treated by an organic component.
又，使用含有上述鈦黑作為遮光劑之本發明之液晶顯示元件用密封劑而製造的液晶顯示元件由於具有充分之遮光性，故而可實現無光之漏出，具有較高之對比度，而具有優異之圖像顯示品質之液晶顯示元件。 In addition, since the liquid crystal display element produced by using the sealing agent for liquid crystal display elements of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding property, it can realize light-free leakage and has high contrast and excellent The image shows the quality of the liquid crystal display element.
作為上述鈦黑中之市售者，例如可列舉：12S、13M、13M-C、13R-N、14M-C(均為Mitsubishi Materials公司製造)、Tilack D(赤穗化成公司製造)等。 For example, 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Co., Ltd.), Tilack D (manufactured by Ako Chemical Co., Ltd.), and the like are mentioned.
上述鈦黑之比表面積之較佳下限為13m2/g，較佳上限為30m2/g，更佳下限為15m2/g，更佳上限為25m2/g。 A preferred lower limit of the specific surface area of the above titanium black is 13 m 2 /g, a preferred upper limit is 30 m 2 /g, a more preferred lower limit is 15 m 2 /g, and a more preferred upper limit is 25 m 2 /g.
又，上述鈦黑之體積電阻之較佳下限為0.5Ω．cm，較佳上限為3Ω．cm，更佳下限為1Ω．cm，更佳上限為2.5Ω．cm。 Moreover, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω. Cm, the upper limit is 3Ω. Cm, the lower limit is 1Ω. Cm, the upper limit is 2.5Ω. Cm.
上述遮光劑之一次粒徑只要為液晶顯示元件之基板間之距離以下，則並無特別限定，較佳之下限為1nm，較佳之上限為5μm。若上述遮光劑之一次粒徑未達1nm，則存在所獲得之液晶顯示元件用密封劑之黏度或搖變性大幅增大，作業性變差之情形。若上述遮光劑之一次粒徑超過5μm，則存在所獲得之液晶顯示元件用密封劑向基板之塗佈性變差之情形。上述遮光劑之一次粒徑之更佳之下限為5nm，更佳之上限為200nm，進而較佳之下限為10nm，進而較佳之上限為100nm。 The primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display device. A preferred lower limit is 1 nm, and a preferred upper limit is 5 μm. When the primary particle diameter of the above-mentioned light-shielding agent is less than 1 nm, the viscosity or the shakeability of the obtained sealing agent for a liquid crystal display element is greatly increased, and the workability is deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the coating property of the obtained liquid crystal display element sealing agent to the substrate may be deteriorated. A more preferred lower limit of the primary particle diameter of the above-mentioned opacifier is 5 nm, more preferably an upper limit of 200 nm, further preferably a lower limit of 10 nm, and further preferably an upper limit of 100 nm.
本發明之液晶顯示元件用密封劑100重量份中之上述遮光劑之含量的較佳之下限為5重量份，較佳之上限為80重量份。若上述遮光劑之含量未達5重量份，則存在無法獲得充分之遮光性之情形。若上述遮光劑之含量超過80重量份，則存在所獲得之液晶顯示元件用密封劑對基板之密接性或硬化後之強度降低、或描繪性降低之情形。上述遮光劑之含量之更佳之下限為10重量份，更佳之上限為70重量份，進而較佳之下限為 30重量份，進而較佳之上限為60重量份。 A preferred lower limit of the content of the above-mentioned sunscreen agent in 100 parts by weight of the sealant for a liquid crystal display device of the present invention is 5 parts by weight, and preferably the upper limit is 80 parts by weight. When the content of the above-mentioned sunscreen agent is less than 5 parts by weight, sufficient light-shielding properties may not be obtained. When the content of the above-mentioned light-shielding agent is more than 80 parts by weight, the adhesiveness of the obtained liquid crystal display element sealing agent to the substrate may be lowered or the strength after curing may be lowered or the drawability may be lowered. A lower limit of the content of the above-mentioned sunscreen agent is preferably 10 parts by weight, more preferably 70 parts by weight, and further preferably a lower limit is 30 parts by weight, and further preferably, the upper limit is 60 parts by weight.
作為製造本發明之液晶顯示元件用密封劑之方法，例如可列舉如下方法等：使用勻相分散機、均質攪拌機、萬能攪拌機、行星式攪拌機、捏合機、3輥混練機等混合機而混合硬化性樹脂、9-氧硫系聚合起始劑、胺系增感劑、及視需要添加之矽烷偶合劑等添加劑。 As a method of producing the sealing agent for liquid crystal display elements of the present invention, for example, a method such as a homogeneous phase disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll kneader can be used for mixing and hardening. Resin, 9-oxosulfur An additive such as a polymerization initiator, an amine sensitizer, and a decane coupling agent to be added as needed.
藉由在本發明之液晶顯示元件用密封劑中調配導電性微粒子，可製造上下導通材料。此種含有本發明之液晶顯示元件用密封劑與導電性微粒子之上下導通材料亦為本發明之一。 By disposing the conductive fine particles in the sealant for liquid crystal display elements of the present invention, the upper and lower conductive materials can be produced. Such a sealing agent for a liquid crystal display element of the present invention and an upper conductive material for conductive fine particles are also one of the inventions.
作為上述導電性微粒子，可使用金屬球、於樹脂微粒子之表面形成有導電金屬層者等。其中，於樹脂微粒子之表面形成有導電金屬層者因樹脂微粒子之優異之彈性，可不損傷透明基板等而進行導電連接，故而較佳。 As the conductive fine particles, a metal ball or a conductive metal layer formed on the surface of the resin fine particles can be used. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are excellent in elasticity due to the resin fine particles, and can be electrically connected without damaging the transparent substrate or the like.
使用本發明之液晶顯示元件用密封劑、或本發明之上下導通材料而製造之液晶顯示元件亦為本發明之一。 A liquid crystal display element produced by using the sealing agent for a liquid crystal display element of the present invention or the underlying conductive material of the present invention is also one of the inventions.
作為製造本發明之液晶顯示元件之方法，例如可列舉具有如下步驟之方法等：於附有ITO薄膜等電極之玻璃基板或聚對苯二甲酸乙二酯基板等2片基板之一片藉由網版印刷、分注器塗佈等使本發明之液晶顯示元件用密封劑等形成長方形狀之密封圖案；於本發明之液晶顯示元件用密封劑等未硬化之狀態將液晶之微滴滴下塗佈至基板之密封框內，於真空下重疊另一基板；及對本發明之液晶顯示元件用密封劑等之密封圖案部分照射紫外線等光而使密封劑暫時硬化；及加熱暫時硬化之密封劑而使之正式硬化。 The method for producing the liquid crystal display device of the present invention includes, for example, a method of the following steps: one of two substrates such as a glass substrate or a polyethylene terephthalate substrate having an electrode such as an ITO film; A sealant for a liquid crystal display device of the present invention is formed into a rectangular seal pattern by a sealant or the like, and the liquid crystal droplets are dripped in a state in which the sealant for a liquid crystal display device of the present invention is not cured. In the sealing frame of the substrate, the other substrate is superposed under vacuum; and the sealing pattern portion such as the sealing agent for a liquid crystal display element of the present invention is irradiated with ultraviolet light or the like to temporarily cure the sealing agent; and the temporarily hardened sealing agent is heated. Formally hardened.
根據本發明，可提供一種光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示 元件用密封劑而成之上下導通材料及液晶顯示元件。 According to the present invention, it is possible to provide a sealing agent for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, according to the present invention, it is possible to provide a liquid crystal display using the same The component is made of a sealing agent to form an upper conductive material and a liquid crystal display element.
以下揭示實施例更詳細地說明本發明，但本發明並不僅限定於該等實施例。 The invention is illustrated in more detail in the following examples, but the invention is not limited to the examples.
(實施例1~13、比較例1~5) (Examples 1 to 13 and Comparative Examples 1 to 5)
依據表1、2中所記載之調配比，使用行星式攪拌機(Thinky公司製造之「脫泡練太郎」)而混合各材料後，進而使用3輥混練機進行混合，藉此製備實施例1~13、比較例1~5之各液晶顯示元件用密封劑。 According to the blending ratios shown in Tables 1 and 2, each material was mixed using a planetary mixer ("Defoaming Rantaro" manufactured by Thinky Co., Ltd.), and then mixed using a three-roll kneader to prepare Example 1~ 13. The sealing agent for each liquid crystal display element of Comparative Examples 1 to 5.
<評價> <evaluation>
對實施例及比較例中獲得之各液晶顯示元件用密封劑進行以下之評價。將結果示於表1、2。 The following evaluations were performed on the respective sealing agents for liquid crystal display elements obtained in the examples and the comparative examples. The results are shown in Tables 1 and 2.
(光硬化性) (photohardenability)
將於實施例及比較例中獲得之各液晶顯示元件用密封劑100重量份中分散有間隔物微粒子(積水化學工業公司製造之「Micropearl SI-H050」)1重量份者塗佈於玻璃基板上，使同尺寸之玻璃基板重疊於該基板，繼而，使用金屬鹵化物燈照射100mW/cm2之光10秒，而製作光硬化性試片。光照射係進行無截止濾光片(cut filter)之情形與有400nm截止濾光片之情形之2種模式，並對各情形製作3片試片。使用紅外分光裝置(BIORAD公司製造之「FTS3000」)，測定源自(甲基)丙烯醯基之峰值之光照射前後之變化量，藉此進行光硬化性之評價。將於光照射後源自(甲基)丙烯醯基之峰值減少90%以上之情形評價為「◎」，將於光照射後源自(甲基)丙烯醯基之峰值 減少80%以上且未達90%之情形評價為「○」，將於光照射後源自(甲基)丙烯醯基之峰值減少70%以上且未達80%之情形評價為「△」，將於光照射後源自(甲基)丙烯醯基之峰值之減少未達70%之情形評價為「×」而評價光硬化性。 1 part by weight of spacer fine particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Co., Ltd.) was dispersed on a glass substrate in 100 parts by weight of each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples. The glass substrate of the same size was placed on the substrate, and then light of 100 mW/cm 2 was irradiated for 10 seconds using a metal halide lamp to prepare a photocurable test piece. The light irradiation system was performed in two cases of a cut filter and a 400 nm cut filter, and three test pieces were produced for each case. The amount of change before and after the irradiation of light from the peak of the (meth) acrylonitrile group was measured using an infrared spectroscopic device ("FTS3000" manufactured by BIORAD Co., Ltd.), whereby the photocurability was evaluated. The case where the peak of the (meth) acrylonitrile group was reduced by 90% or more after light irradiation was evaluated as "?", and the peak derived from the (meth) acrylonitrile group after light irradiation was reduced by 80% or more. The case of 90% is evaluated as "○", and the value derived from the (meth) acrylonitrile group after the light irradiation is reduced by 70% or more and less than 80% is evaluated as "△", which will be sourced after light irradiation. The photocurability was evaluated by evaluating "x" from the case where the decrease in the peak of the (meth) acrylonitrile group was less than 70%.
再者，源自(甲基)丙烯醯基之峰值之光照射前後的變化量係取由3片試片獲得之平均值。 Further, the amount of change before and after the light irradiation from the peak of the (meth) acrylonitrile group was obtained by taking the average value of the three test pieces.
(液晶污染性) (liquid crystal contamination)
使間隔物微粒子(積水化學工業公司製造之「Micropearl SI-H050」)1重量份分散於實施例及比較例中獲得之各液晶顯示元件用密封劑100重量份，以作為液晶顯示元件用密封劑，於2片已摩擦之配向膜及附有透明電極之基板之一片上以使密封劑之線寬成為1mm的方式利用分注器進行塗佈。 1 part by weight of the spacer fine particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Co., Ltd.) was dispersed in 100 parts by weight of each of the sealing agents for liquid crystal display elements obtained in the examples and the comparative examples, and used as a sealing agent for liquid crystal display elements. The coating was applied by means of a dispenser on one of the two rubbed alignment films and one of the substrates on which the transparent electrodes were attached so that the line width of the sealant became 1 mm.
繼而將液晶(Chisso公司製造之「JC-5004LA」)之微滴滴下塗佈於附有透明電極之基板的密封劑之框內整個面上，並立即貼合另一片附有透明電極之彩色濾光片基板，對密封劑部分使用金屬鹵化物燈照射100mW/cm2之紫外線30秒而使之硬化，進而以120℃加熱1小時而獲得液晶顯示元件。光照射係進行無截止濾光片之情形與有400nm截止濾光片之情形之2種模式，並對各情形製作3片液晶顯示元件。 Then, droplets of liquid crystal ("JC-5004LA" manufactured by Chisso Co., Ltd.) were dropped on the entire surface of the sealant of the substrate with the transparent electrode, and another color filter with a transparent electrode was immediately attached. The light-film substrate was obtained by irradiating the sealant portion with a metal halide lamp with ultraviolet rays of 100 mW/cm 2 for 30 seconds to be hardened, and further heating at 120 ° C for 1 hour to obtain a liquid crystal display element. The light irradiation system was performed in the case of a non-cut filter and in the case of a 400 nm cut filter, and three liquid crystal display elements were produced for each case.
對所獲得之液晶顯示元件藉由目測確認設為於60℃施加電壓1000小時之狀態後之密封劑附近之液晶污染。 The liquid crystal display element obtained was visually confirmed to have liquid crystal contamination in the vicinity of the sealant after the voltage was applied at 60 ° C for 1,000 hours.
液晶污染係藉由3片液晶顯示元件之色不均進行判斷，根據色不均之程度，將所有液晶顯示元件完全無色不均之情形評價為「◎」，將至少1片液晶顯示元件略微有色不均之情形評價為「○」，將至少1片液晶顯示元件有稍許色不均之情形評價為「△」，將至少1片液晶顯示元件有相當多色不均之情形評價為「×」而評價液晶污染性。 The liquid crystal contamination is judged by the color unevenness of the three liquid crystal display elements, and the case where all the liquid crystal display elements are completely colorless unevenly is evaluated as "◎" according to the degree of color unevenness, and at least one liquid crystal display element is slightly colored. The case of unevenness was evaluated as "○", and the case where at least one liquid crystal display element had a slight color unevenness was evaluated as "Δ", and the case where at least one liquid crystal display element had a considerable color unevenness was evaluated as "×". The liquid crystal contamination was evaluated.
再者，評價為「◎」、「○」之液晶顯示元件係於實用方面完全無問題之等級。 In addition, the liquid crystal display elements evaluated as "◎" and "○" are at a level that is practically problem-free.
[產業上之可利用性] [Industrial availability]
根據本發明，可提供一種光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 According to the present invention, it is possible to provide a sealing agent for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element using the sealing agent for a liquid crystal display element.
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| 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 |
| JP6554040B2 (en) | 2016-01-25 | 2019-07-31 | 三井化学株式会社 | Liquid crystal display panel and method for manufacturing liquid crystal display panel |
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| JP7000164B2 (en) * | 2016-12-16 | 2022-01-19 | 積水化学工業株式会社 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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