WO2015152030A1 - Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element - Google Patents
Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element Download PDFInfo
- Publication number
- WO2015152030A1 WO2015152030A1 PCT/JP2015/059565 JP2015059565W WO2015152030A1 WO 2015152030 A1 WO2015152030 A1 WO 2015152030A1 JP 2015059565 W JP2015059565 W JP 2015059565W WO 2015152030 A1 WO2015152030 A1 WO 2015152030A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- meth
- acrylate
- crystal dropping
- group
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 76
- 238000007789 sealing Methods 0.000 title claims abstract description 70
- 239000004020 conductor Substances 0.000 title abstract 2
- -1 oxime ester compound Chemical class 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 239000003999 initiator Substances 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 101
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- 150000001875 compounds Chemical class 0.000 claims description 53
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- 239000010419 fine particle Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
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- 238000011109 contamination Methods 0.000 abstract description 18
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1341—Filling or closing of cells
- G02F1/13415—Drop filling process
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
Definitions
- the present invention relates to a sealing agent for a liquid crystal dropping method, which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods.
- a liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
- a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing.
- a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.
- the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
- the sealant is placed directly under the black matrix, so when the dripping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. If the sealant is insufficiently cured in this manner, the uncured sealant component is eluted in the liquid crystal, and the curing reaction by the eluted sealant component proceeds in the liquid crystal, resulting in liquid crystal contamination. there were.
- Patent Document 3 discloses that a highly sensitive photopolymerization initiator is blended with a sealant.
- liquid crystal contamination could not be sufficiently suppressed only by blending a highly sensitive photopolymerization initiator.
- An object of this invention is to provide the sealing compound for liquid crystal dropping methods which is excellent in photocurability and can suppress liquid-crystal contamination. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods.
- the present invention is a liquid crystal dropping method sealing agent containing a curable resin and a radical photopolymerization initiator, wherein the curable resin has a dielectric constant of 10 or more, and the radical photopolymerization initiator is polar It is a sealing agent for liquid crystal dropping method which is an oxime ester compound having a group.
- the present invention is described in detail below.
- the present inventor uses a combination of a curable resin having a dielectric constant of 10 or more and an oxime ester compound having a polar group to provide a liquid crystal drop excellent in photocurability and capable of suppressing liquid crystal contamination.
- the inventors have found that a sealing agent for a construction method can be obtained, and have completed the present invention.
- the sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
- the curable resin has a dielectric constant of 10 or more.
- the sealing agent is excellent in photocurability, and a uniform cured product can be obtained.
- the preferable lower limit of the dielectric constant of the curable resin is 11, and the more preferable lower limit is 12. The higher the dielectric constant of the curable resin is, the better, but the practical upper limit is 20.
- the dielectric constant of the said curable resin is the dielectric constant of each compound which comprises the said curable resin.
- the weight fraction in the curable resin can be measured by measuring the complex dielectric constant under the conditions of 25 ° C. and 1 MHz using an impedance analyzer (for example, “1260 type” manufactured by Solartron), and is defined by the real part. .
- an epoxy (meth) acrylate or a partial (meth) acryl-modified epoxy resin described later is preferably used.
- the epoxy resin used as a raw material for the epoxy (meth) acrylate and the partial (meth) acryl-modified epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, Biphenyl type epoxy resin, diphenyl ether type epoxy resin and the like can be mentioned.
- the sealing agent for liquid crystal dropping method of the present invention contains two or more compounds as the curable resin
- the average dielectric constant of the curable resin containing two or more compounds is preferably 10 or more. From the viewpoint of further suppressing elution into the resin, it is more preferable that the dielectric constant of all the compounds constituting the curable resin is 10 or more.
- the content of the curable resin having a dielectric constant of 10 or more in the curable resin is preferably 50% by weight or more, and 80% by weight. More preferably, it is 100% by weight.
- the curable resin preferably contains a compound having a (meth) acryloyl group, and more preferably contains a compound having 2 to 3 (meth) acryloyl groups in one molecule because of high reactivity. .
- Examples of the compound having the (meth) acryloyl group include an epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy resin, a partial (meth) acryl-modified epoxy resin, and (meth) acrylic acid. And an ester compound obtained by reacting a compound having a hydroxyl group with urethane, and a urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with isocyanate.
- the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group
- the “(meth) acryl” means acryl or methacryl
- the “(meth) acrylate” "Means acrylate or methacrylate.
- epoxy (meth) acrylate means a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid, and the “partial (meth) acrylate” is one molecule.
- 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.
- Examples of the epoxy resin used as a raw material for synthesizing the epoxy (meth) acrylate include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl bisphenol A type epoxy resin.
- Hydrogenated bisphenol type epoxy resin propylene oxide added bisphenol A type 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 Novolac epoxy resin, ortho-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Emissions phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
- Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
- Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
- Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
- Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
- Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of commercially available naphthalenephenol novolac epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
- alkyl polyol type epoxy resins examples include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX. -611 (manufactured by Nagase ChemteX Corporation).
- Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel), and the like.
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
- Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, and jER1032. (All manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.
- Examples of commercially available epoxy (meth) acrylates include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRY3603 EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical 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 Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Den
- the partial (meth) acryl-modified epoxy resin can be obtained, for example, by reacting an epoxy group of a part of an epoxy resin having two or more epoxy groups with (meth) acrylic acid.
- an epoxy resin used as the raw material of the said partial (meth) acryl modified epoxy resin what was mentioned as a raw material for synthesize
- Examples of commercially available partial (meth) acrylic-modified epoxy resins include UVACURE 1561 (manufactured by Daicel Ornex).
- ester compounds obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group examples of monofunctional compounds include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate.
- bifunctional ester compound examples include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth).
- ester compound having three or more functions examples include trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and caprolactone.
- Examples of the urethane (meth) acrylate obtained by reacting the above isocyanate with a (meth) acrylic acid derivative having a hydroxyl group include, for example, a (meth) acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups. Two equivalents can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
- isocyanate examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), and hydrogenated MDI.
- Polymeric MDI 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, Examples include 1,6,11-undecane triisocyanate.
- strand obtained by reaction of polyols, such as ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylol propane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and excess isocyanate, for example.
- polyols such as ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylol propane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and excess isocyanate, for example.
- Extended isocyanate compounds can also be used.
- Examples of the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- Hydroxyalkyl (meth) acrylates such as dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc.
- Acrylate mono (meth) acrylate or di (meth) acrylate of trivalent alcohol such as trimethylolethane, trimethylolpropane, glycerin, and epoxy (meth) acrylate such as bisphenol A type epoxy acrylate, etc. And the like.
- Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700 , Art resin N-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Industrial Co., Ltd.), U-122P, U-108A, U-340P,
- the curable resin preferably has a hydrogen bondable unit such as —OH group, —NH— group, —NH 2 group, etc. from the viewpoint of suppressing liquid crystal contamination.
- the sealing agent for liquid crystal dropping method of the present invention contains a photo radical polymerization initiator.
- the photo radical polymerization initiator is an oxime ester compound having a polar group.
- the sealing agent for liquid crystal dropping method of the present invention is excellent in photocurability by using an oxime ester compound having a polar group in combination with a curable resin having a dielectric constant of 10 or more as the photoradical polymerization initiator. , Liquid crystal contamination can be suppressed.
- the polar group of the oxime ester compound having a polar group is preferably at least one selected from the group consisting of —OH group, —COOH group, —SH group, —CONH 2 group, and —NH 2 group. .
- the —OH group is more preferable because the compatibility with the liquid crystal becomes low.
- the oxime ester compound having a polar group is preferably a compound represented by the following formula (1).
- X represents an alkylene group having 1 to 6 carbon atoms.
- examples of the alkylene group having 1 to 6 carbon atoms represented by X include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a 1-ethylethylene group, Examples thereof include an n-pentylene group and an n-hexylene group. Of these, an ethylene group is preferable.
- the content of the oxime ester compound having a polar group is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the oxime ester compound having a polar group is less than 0.1 parts by weight, the photocuring reaction of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed. If the content of the oxime ester compound having a polar group exceeds 10 parts by weight, the resulting liquid crystal dropping method sealing agent may be inferior in weather resistance and storage stability, or liquid crystal contamination may occur.
- the minimum with more preferable content of the oxime ester compound which has the said polar group is 0.5 weight part, and a more preferable upper limit is 5 weight part.
- the sealing agent for liquid crystal dropping method of the present invention may contain other photoradical polymerization initiator as the photoradical polymerization initiator in addition to the oxime ester compound having the polar group. From the viewpoint of achieving both the effect of suppressing liquid crystal contamination, it is preferable that no other radical photopolymerization initiator is contained.
- the sealing agent for liquid crystal dropping method of the present invention preferably contains a sensitizer.
- the liquid crystal dropping method sealing agent of the present invention can provide a liquid crystal dropping method sealing agent with high sensitivity and more excellent photocurability.
- the sensitizer preferably has a sufficient light absorption band in the ultraviolet / visible region, at least selected from the group consisting of a benzophenone skeleton, an anthracene skeleton, an anthraquinone skeleton, a coumarin skeleton, a thioxanthone skeleton, and a phthalocyanine skeleton. It is preferable to contain a compound having one kind of skeleton, and it is more preferred to contain a compound having at least one kind of skeleton selected from the group consisting of an anthracene skeleton, an anthraquinone skeleton, and a thioxanthone skeleton.
- Examples of the compound having a benzophenone skeleton include benzophenone, 2,4-dichlorobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.
- Examples of the compound having an anthracene skeleton include 9,10-dibutoxyanthracene, 9,10-diproxyanthraquinone, and 9,10-ethoxyanthraquinone.
- Examples of the compound having an anthraquinone skeleton include 2-ethylanthraquinone, 1-methylanthraquinone, 1,4-dihydroxyanthraquinone, 2- (2-hydroxyethoxy) -anthraquinone and the like.
- Examples of the compound having a coumarin skeleton include 7-diethylamino-4-methylcoumarin.
- Examples of the compound having a thioxanthone skeleton include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and the like.
- the compound having a phthalocyanine skeleton examples include phthalocyanine.
- the resulting sealant for liquid crystal dropping method is particularly excellent in light-curing part curability, so that 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis At least one of (diethylamino) benzophenone is preferred.
- the content of the sensitizer is such that a preferred lower limit is 2 parts by weight and a preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the photopolymerization initiator. If the content of the sensitizer is less than 2 parts by weight, the effect of further improving the photocurability of the obtained liquid crystal dropping method sealing agent may not be sufficiently exhibited. When the content of the sensitizer exceeds 50 parts by weight, liquid crystal contamination may occur.
- the minimum with more preferable content of the said sensitizer is 5 weight part, and a more preferable upper limit is 40 weight part.
- the sealing agent for liquid crystal dropping method of the present invention may contain a thermal radical polymerization initiator.
- a thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
- an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
- the polymer azo compound means a compound having an azo group and generating a radical by heat and having a number average molecular weight of 300 or more.
- the preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000.
- the number average molecular weight of the polymer azo initiator is less than 1000, the polymer azo initiator may adversely affect the liquid crystal.
- the number average molecular weight of the polymeric azo initiator exceeds 300,000, mixing with the curable resin may be difficult.
- the more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
- the said number average molecular weight is a value calculated
- GPC gel permeation chromatography
- Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
- polymer azo initiator examples include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
- polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group those having a polyethylene oxide structure are preferable.
- Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
- Examples of azo compounds that are not a polymer include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
- organic peroxide examples include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
- the content of the thermal radical polymerization initiator is preferably 0.05 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
- the thermosetting reaction of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed.
- content of the said thermal radical polymerization initiator exceeds 10 weight part, the sealing compound for liquid crystal dropping methods obtained may cause liquid crystal contamination.
- the minimum with more preferable content of the said thermal radical polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
- the sealing agent for liquid crystal dropping method of the present invention may contain a thermosetting agent.
- thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
- organic acid hydrazide examples include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
- organic acid hydrazides examples include, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.
- the content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit.
- the content of the thermosetting agent is less than 1 part by weight, the resulting sealing agent for liquid crystal dropping method may not be sufficiently cured.
- content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability
- the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
- the sealing agent for liquid crystal dropping method of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesiveness due to the stress dispersion effect, improving the coefficient of linear expansion, and further improving the moisture resistance of the cured product. preferable.
- the filler examples 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, water Inorganic fillers such as aluminum oxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned. These fillers may be used alone or in combination of two or more.
- the minimum with preferable content of the said filler in 100 weight part of whole sealing compound for liquid crystal dropping methods of this invention is 10 weight part, and a preferable upper limit is 70 weight part.
- a preferable upper limit is 70 weight part.
- content of the filler is less than 10 parts by weight, effects such as improvement of adhesiveness may not be sufficiently exhibited.
- content of the said filler exceeds 70 weight part, the sealing compound for liquid crystal dropping methods obtained may have a viscosity too high, and may become inferior to applicability
- the minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
- the sealing agent for liquid crystal dropping method of the present invention preferably contains a silane coupling agent.
- the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
- silane coupling agent since it is excellent in the effect which improves adhesiveness with a board
- -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used.
- These silane coupling agents may be used alone or in combination of two or more.
- the minimum with preferable content of the said silane coupling agent in 100 weight part of sealing agents for liquid crystal dropping methods of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part.
- a preferable upper limit is 10 weight part.
- content of the silane coupling agent is less than 0.1 parts by weight, effects such as improvement of adhesiveness may not be sufficiently exhibited.
- content of the said silane coupling agent exceeds 10 weight part, the sealing compound for liquid crystal dropping methods obtained may cause liquid-crystal contamination.
- the minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.
- the sealing agent for liquid crystal dropping method of the present invention may contain a light shielding agent.
- the sealing compound for liquid crystal dropping methods of this invention can be used suitably as a light shielding sealing agent.
- the light-shielding agent examples include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferred because of its high insulating properties.
- the above-mentioned 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, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
- the liquid crystal display device manufactured using the sealing agent for liquid crystal dropping method of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has a high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
- titanium black examples include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like. Can be mentioned.
- the preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
- the preferred lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferred upper limit is 3 ⁇ ⁇ cm, the more preferred lower limit is 1 ⁇ ⁇ cm, and the more preferred upper limit is 2.5 ⁇ ⁇ cm.
- the primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 ⁇ m.
- the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained liquid crystal dropping method sealing agent are greatly increased, and workability may be deteriorated.
- the primary particle diameter of the light-shielding agent exceeds 5 ⁇ m, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated.
- the more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
- the primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
- the preferable lower limit of the content of the light shielding agent in 100 parts by weight of the sealing agent for liquid crystal dropping method 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 obtained sealing agent for liquid crystal dropping method to the substrate and the strength after curing may be lowered, or the drawing property may be lowered.
- the more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
- a method for producing the sealing agent for liquid crystal dropping method of the present invention for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light
- a vertical conduction material can be produced by blending conductive fine particles with the sealant for the liquid crystal dropping method of the present invention.
- Such a vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
- the conductive fine particles a metal ball, a resin fine particle formed with a conductive metal layer on the surface, or the like can be used.
- the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
- the liquid crystal display element using the sealing agent for liquid crystal dropping method of the present invention or the vertical conduction material of the present invention is also one aspect of the present invention.
- the sealing agent for the liquid crystal dropping method of the present invention is applied to one of two transparent substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate.
- the process of forming a rectangular seal pattern by screen printing, dispenser application, etc., the liquid crystal drop method sealing agent of the present invention is uncured, and liquid crystal microdrops are dropped on the entire surface of the transparent substrate and applied immediately.
- a step of superimposing another substrate on the substrate, a step of irradiating the seal pattern portion of the sealant for the liquid crystal dropping method of the present invention with light such as ultraviolet rays, and the step of pre-curing the sealant, and a pre-cured sealant The method etc. which have the process of heating this and making it harden
- the sealing compound for liquid crystal dropping methods which can be excellent in photocurability and can suppress liquid crystal contamination can be provided.
- the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods can be provided.
- Example 1 As curable resin, 40 parts by weight of bisphenol A type epoxy acrylate (manufactured by Daicel Ornex Co., Ltd., “EBECRYL 3700”, dielectric constant 14), and partially acrylic modified bisphenol A type epoxy resin (manufactured by Daicel Ornex Co., Ltd., “UVACURE 1561”) Dielectric constant 13) 20 parts by weight, 1 part by weight of a compound represented by the following formula (2) (produced by ADEKA, “NCI-930”) as a radical photopolymerization initiator, and adipic acid dihydrazide as a thermosetting agent 3 parts by weight (manufactured by Otsuka Chemical Co., Ltd., “ADH”), 15 parts by weight of silica (manufactured by Admatechs, “Admafine SO-C2”) as a filler, and talc (manufactured by Nippon Talc Co., Ltd., “Nanoace D600” ]) 5 parts
- Examples 2 to 11, Comparative Examples 1 to 5 According to the blending ratios described in Tables 1 and 2, each material was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., “Awatori Netaro”) in the same manner as in Example 1, and then 3 more The sealing agents for the liquid crystal dropping method of Examples 2 to 11 and Comparative Examples 1 to 5 were prepared by mixing using a roll.
- the “compound represented by the formula (3)” described in Tables 1 and 2 is a compound represented by the following formula (3)
- the “compound represented by the formula (4)” It is a compound represented by following formula (4).
- the partial acrylic modified phenol novolac type epoxy resins in Tables 1 and 2 were prepared by the following method. That is, 190 g of phenol novolac type epoxy resin (manufactured by DIC, “N-770”) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to this solution to obtain a uniform solution. After 35 g of acrylic acid was added dropwise to the obtained solution under reflux stirring over 2 hours, the mixture was further stirred under reflux for 6 hours. By removing toluene, a partially acrylic-modified phenol novolac epoxy resin (dielectric constant 9) in which 50 mol% of the epoxy group of the phenol novolac epoxy resin was modified to an acrylic group was obtained.
- Liquid crystal contamination 1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of each liquid crystal dropping method sealant obtained in the examples and comparative examples, and two rubbed orientations are obtained. It applied with a dispenser so that the line width of a sealing agent might be set to 1 mm to one of a film
- liquid crystal Chisso, “JC-5004LA”
- a metal halide lamp was used to irradiate 100 mW / cm 2 of ultraviolet rays for 30 seconds to cure the sealant, and further heated at 120 ° C. for 1 hour to obtain a liquid crystal display element.
- liquid crystal alignment disorder near the sealant was confirmed by observation with an optical microscope.
- the liquid crystal alignment disorder is judged from the color unevenness of the display part. Depending on the degree of the color unevenness, “ ⁇ ” indicates that there is no color unevenness, “ ⁇ ” indicates that the color unevenness is slight, and “color unevenness”.
- the liquid crystal contamination property was evaluated as “ ⁇ ” when there was a slight amount of color, and “X” when there was considerable color unevenness.
- liquid crystal display elements with the evaluations “ ⁇ ” and “O” are at a level where there is no problem in practical use, and “ ⁇ ” is a level at which the display design of the liquid crystal display element may cause a problem. "Is a level that can not be put into practical use.
- the sealing compound for liquid crystal dropping methods which can be excellent in photocurability and can suppress liquid crystal contamination can be provided.
- the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods can be provided.
Abstract
One purpose of the present invention is to provide a sealing agent for liquid crystal dropping methods, which has excellent photocurability and is capable of suppressing liquid crystal contamination. Another purpose of the present invention is to provide: a vertically conducting material which is obtained using the sealing agent for liquid crystal dropping methods; and a liquid crystal display element.
The present invention is a sealing agent for liquid crystal dropping methods, which contains a curable resin and a radical photopolymerization initiator. The curable resin has a dielectric constant of 10 or more. The radical photopolymerization initiator is an oxime ester compound having a polar group.
Description
本発明は、光硬化性に優れ、かつ、液晶汚染を抑制することができる液晶滴下工法用シール剤に関する。また、本発明は、該液晶滴下工法用シール剤を用いてなる上下導通材料及び液晶表示素子に関する。
The present invention relates to a sealing agent for a liquid crystal dropping method, which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods.
近年、液晶表示セル等の液晶表示素子の製造方法としては、タクトタイム短縮、使用液晶量の最適化といった観点から、特許文献１、特許文献２に開示されているような、硬化性樹脂と光重合開始剤と熱硬化剤とを含有する光熱併用硬化型のシール剤を用いた滴下工法と呼ばれる液晶滴下方式が用いられている。
滴下工法では、まず、２枚の電極付き透明基板の一方に、ディスペンスにより長方形状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下し、すぐに他方の透明基板を重ね合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、液晶アニール時に加熱して本硬化を行い、液晶表示素子を作製する。基板の貼り合わせを減圧下で行うようにすれば、極めて高い効率で液晶表示素子を製造することができ、現在この滴下工法が液晶表示素子の製造方法の主流となっている。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin and a light as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.
滴下工法では、まず、２枚の電極付き透明基板の一方に、ディスペンスにより長方形状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下し、すぐに他方の透明基板を重ね合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、液晶アニール時に加熱して本硬化を行い、液晶表示素子を作製する。基板の貼り合わせを減圧下で行うようにすれば、極めて高い効率で液晶表示素子を製造することができ、現在この滴下工法が液晶表示素子の製造方法の主流となっている。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin and a light as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.
ところで、携帯電話、携帯ゲーム機等、各種液晶パネル付きモバイル機器が普及している現代において、装置の小型化は最も求められている課題である。装置の小型化の手法としては、液晶表示部の狭額縁化が挙げられ、例えば、シール部の位置をブラックマトリックス下に配置することが行われている（以下、狭額縁設計ともいう）。
By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of devices is the most demanded issue. As a method for reducing the size of the apparatus, there is a narrow frame of the liquid crystal display unit. For example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
しかしながら、狭額縁設計ではシール剤がブラックマトリックスの直下に配置されるため、滴下工法を行うと、シール剤を光硬化させる際に照射した光が遮られ、シール剤の内部まで光が到達せず硬化が不充分となるという問題があった。このようにシール剤の硬化が不充分となると、未硬化のシール剤成分が液晶中に溶出し、溶出したシール剤成分による硬化反応が液晶中において進行することで液晶汚染が発生するという問題があった。
However, in the narrow frame design, the sealant is placed directly under the black matrix, so when the dripping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. If the sealant is insufficiently cured in this manner, the uncured sealant component is eluted in the liquid crystal, and the curing reaction by the eluted sealant component proceeds in the liquid crystal, resulting in liquid crystal contamination. there were.
液晶汚染を抑制する方法として、特許文献３には、シール剤に高感度の光重合開始剤を配合することが開示されている。しかしながら、高感度の光重合開始剤を配合しただけでは、充分に液晶汚染を抑制することができなかった。
As a method for suppressing liquid crystal contamination, Patent Document 3 discloses that a highly sensitive photopolymerization initiator is blended with a sealant. However, liquid crystal contamination could not be sufficiently suppressed only by blending a highly sensitive photopolymerization initiator.
本発明は、光硬化性に優れ、かつ、液晶汚染を抑制することができる液晶滴下工法用シール剤を提供することを目的とする。また、本発明は、該液晶滴下工法用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することを目的とする。
An object of this invention is to provide the sealing compound for liquid crystal dropping methods which is excellent in photocurability and can suppress liquid-crystal contamination. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods.
本発明は、硬化性樹脂と光ラジカル重合開始剤とを含有する液晶滴下工法用シール剤であって、上記硬化性樹脂は、誘電率が１０以上であり、上記光ラジカル重合開始剤は、極性基を有するオキシムエステル化合物である液晶滴下工法用シール剤である。
以下に本発明を詳述する。 The present invention is a liquid crystal dropping method sealing agent containing a curable resin and a radical photopolymerization initiator, wherein the curable resin has a dielectric constant of 10 or more, and the radical photopolymerization initiator is polar It is a sealing agent for liquid crystal dropping method which is an oxime ester compound having a group.
The present invention is described in detail below.
以下に本発明を詳述する。 The present invention is a liquid crystal dropping method sealing agent containing a curable resin and a radical photopolymerization initiator, wherein the curable resin has a dielectric constant of 10 or more, and the radical photopolymerization initiator is polar It is a sealing agent for liquid crystal dropping method which is an oxime ester compound having a group.
The present invention is described in detail below.
本発明者は、誘電率が１０以上である硬化性樹脂と、極性基を有するオキシムエステル化合物とを組み合わせて用いることにより、光硬化性に優れ、かつ、液晶汚染を抑制することができる液晶滴下工法用シール剤を得ることができることを見出し、本発明を完成させるに至った。
The present inventor uses a combination of a curable resin having a dielectric constant of 10 or more and an oxime ester compound having a polar group to provide a liquid crystal drop excellent in photocurability and capable of suppressing liquid crystal contamination. The inventors have found that a sealing agent for a construction method can be obtained, and have completed the present invention.
本発明の液晶滴下工法用シール剤は、硬化性樹脂を含有する。
上記硬化性樹脂は、誘電率が１０以上である。上記硬化性樹脂は、誘電率が１０以上であることにより、液晶へ溶出しにくいものとなり、更に、後述する極性基を有するオキシムエステル化合物との相溶性が高くなって、得られる液晶滴下工法用シール剤が光硬化性に優れるものとなり、かつ、均一な硬化物を得ることができる。上記硬化性樹脂の誘電率の好ましい下限は１１、より好ましい下限は１２である。また、上記硬化性樹脂の誘電率は、高ければ高いほどがよいが、実質的な上限は２０である。
なお、本発明の液晶滴下工法用シール剤が、上記硬化性樹脂として２種以上の化合物を含有する場合、上記硬化性樹脂の誘電率は、上記硬化性樹脂を構成するそれぞれの化合物の誘電率と硬化性樹脂中における重量分率とから算出できる。
上記「誘電率」は、インピーダンスアナライザー（例えば、ソーラトロン社製、「１２６０型」等）を用いて２５℃、１ＭＨｚの条件で複素比誘電率を測定することにより測定でき、実数部で定義される。 The sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
The curable resin has a dielectric constant of 10 or more. When the above curable resin has a dielectric constant of 10 or more, it becomes difficult to elute into the liquid crystal, and the compatibility with the oxime ester compound having a polar group described later is further increased. The sealing agent is excellent in photocurability, and a uniform cured product can be obtained. The preferable lower limit of the dielectric constant of the curable resin is 11, and the more preferable lower limit is 12. The higher the dielectric constant of the curable resin is, the better, but the practical upper limit is 20.
In addition, when the sealing compound for liquid crystal dropping method of this invention contains 2 or more types of compounds as said curable resin, the dielectric constant of the said curable resin is the dielectric constant of each compound which comprises the said curable resin. And the weight fraction in the curable resin.
The above-mentioned “dielectric constant” can be measured by measuring the complex dielectric constant under the conditions of 25 ° C. and 1 MHz using an impedance analyzer (for example, “1260 type” manufactured by Solartron), and is defined by the real part. .
上記硬化性樹脂は、誘電率が１０以上である。上記硬化性樹脂は、誘電率が１０以上であることにより、液晶へ溶出しにくいものとなり、更に、後述する極性基を有するオキシムエステル化合物との相溶性が高くなって、得られる液晶滴下工法用シール剤が光硬化性に優れるものとなり、かつ、均一な硬化物を得ることができる。上記硬化性樹脂の誘電率の好ましい下限は１１、より好ましい下限は１２である。また、上記硬化性樹脂の誘電率は、高ければ高いほどがよいが、実質的な上限は２０である。
なお、本発明の液晶滴下工法用シール剤が、上記硬化性樹脂として２種以上の化合物を含有する場合、上記硬化性樹脂の誘電率は、上記硬化性樹脂を構成するそれぞれの化合物の誘電率と硬化性樹脂中における重量分率とから算出できる。
上記「誘電率」は、インピーダンスアナライザー（例えば、ソーラトロン社製、「１２６０型」等）を用いて２５℃、１ＭＨｚの条件で複素比誘電率を測定することにより測定でき、実数部で定義される。 The sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
The curable resin has a dielectric constant of 10 or more. When the above curable resin has a dielectric constant of 10 or more, it becomes difficult to elute into the liquid crystal, and the compatibility with the oxime ester compound having a polar group described later is further increased. The sealing agent is excellent in photocurability, and a uniform cured product can be obtained. The preferable lower limit of the dielectric constant of the curable resin is 11, and the more preferable lower limit is 12. The higher the dielectric constant of the curable resin is, the better, but the practical upper limit is 20.
In addition, when the sealing compound for liquid crystal dropping method of this invention contains 2 or more types of compounds as said curable resin, the dielectric constant of the said curable resin is the dielectric constant of each compound which comprises the said curable resin. And the weight fraction in the curable resin.
The above-mentioned “dielectric constant” can be measured by measuring the complex dielectric constant under the conditions of 25 ° C. and 1 MHz using an impedance analyzer (for example, “1260 type” manufactured by Solartron), and is defined by the real part. .
誘電率が１０以上の硬化性樹脂としては、後述するエポキシ（メタ）アクリレートや部分（メタ）アクリル変性エポキシ樹脂が好適に用いられる。上記エポキシ（メタ）アクリレートや上記部分（メタ）アクリル変性エポキシ樹脂の原料となるエポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂等が挙げられる。
As the curable resin having a dielectric constant of 10 or more, an epoxy (meth) acrylate or a partial (meth) acryl-modified epoxy resin described later is preferably used. Examples of the epoxy resin used as a raw material for the epoxy (meth) acrylate and the partial (meth) acryl-modified epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, Biphenyl type epoxy resin, diphenyl ether type epoxy resin and the like can be mentioned.
本発明の液晶滴下工法用シール剤が、上記硬化性樹脂として２種以上の化合物を含有する場合、２種以上を配合した硬化性樹脂の平均の誘電率が１０以上であることが好ましく、液晶への溶出をより抑制する観点から、上記硬化性樹脂を構成する全ての化合物の誘電率が１０以上であることがより好ましい。
また、上記硬化性樹脂として２種以上の化合物を含有する場合、硬化性樹脂中における上記誘電率が１０以上の硬化性樹脂の含有割合は、５０重量％以上であることが好ましく、８０重量％以上であることがより好ましく、１００重量％であることが最も好ましい。 When the sealing agent for liquid crystal dropping method of the present invention contains two or more compounds as the curable resin, the average dielectric constant of the curable resin containing two or more compounds is preferably 10 or more. From the viewpoint of further suppressing elution into the resin, it is more preferable that the dielectric constant of all the compounds constituting the curable resin is 10 or more.
When the curable resin contains two or more compounds, the content of the curable resin having a dielectric constant of 10 or more in the curable resin is preferably 50% by weight or more, and 80% by weight. More preferably, it is 100% by weight.
また、上記硬化性樹脂として２種以上の化合物を含有する場合、硬化性樹脂中における上記誘電率が１０以上の硬化性樹脂の含有割合は、５０重量％以上であることが好ましく、８０重量％以上であることがより好ましく、１００重量％であることが最も好ましい。 When the sealing agent for liquid crystal dropping method of the present invention contains two or more compounds as the curable resin, the average dielectric constant of the curable resin containing two or more compounds is preferably 10 or more. From the viewpoint of further suppressing elution into the resin, it is more preferable that the dielectric constant of all the compounds constituting the curable resin is 10 or more.
When the curable resin contains two or more compounds, the content of the curable resin having a dielectric constant of 10 or more in the curable resin is preferably 50% by weight or more, and 80% by weight. More preferably, it is 100% by weight.
上記硬化性樹脂は、（メタ）アクリロイル基を有する化合物を含有することが好ましく、反応性の高さから１分子中に（メタ）アクリロイル基を２～３個有する化合物を含有することがより好ましい。
The curable resin preferably contains a compound having a (meth) acryloyl group, and more preferably contains a compound having 2 to 3 (meth) acryloyl groups in one molecule because of high reactivity. .
上記（メタ）アクリロイル基を有する化合物としては、例えば、（メタ）アクリル酸とエポキシ樹脂とを反応させることにより得られるエポキシ（メタ）アクリレートや部分（メタ）アクリル変性エポキシ樹脂、（メタ）アクリル酸に水酸基を有する化合物を反応させることにより得られるエステル化合物、イソシアネートに水酸基を有する（メタ）アクリル酸誘導体を反応させることにより得られるウレタン（メタ）アクリレート等が挙げられる。なかでも、高い誘電率を得やすいことから、エポキシ（メタ）アクリレート及び／又は部分（メタ）アクリル変性エポキシ樹脂を含有することがより好ましく、エポキシ（メタ）アクリレートを含有することが更に好ましい。
なお、本明細書において、上記「（メタ）アクリロイル基」とは、アクリロイル基又はメタクリロイル基を意味し、上記「（メタ）アクリル」とは、アクリル又はメタクリルを意味し、上記「（メタ）アクリレート」とは、アクリレート又はメタクリレートを意味する。また、上記「エポキシ（メタ）アクリレート」とは、エポキシ樹脂中の全てのエポキシ基を（メタ）アクリル酸と反応させた化合物のことを表し、上記「部分（メタ）アクリレート」とは、１分子中にエポキシ基と（メタ）アクリロイル基とをそれぞれ１つ以上有する樹脂を表す。 Examples of the compound having the (meth) acryloyl group include an epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy resin, a partial (meth) acryl-modified epoxy resin, and (meth) acrylic acid. And an ester compound obtained by reacting a compound having a hydroxyl group with urethane, and a urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with isocyanate. Especially, since it is easy to obtain a high dielectric constant, it is more preferable to contain an epoxy (meth) acrylate and / or a partial (meth) acryl modified epoxy resin, and it is still more preferable to contain an epoxy (meth) acrylate.
In the present specification, the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group, the “(meth) acryl” means acryl or methacryl, and the “(meth) acrylate” "Means acrylate or methacrylate. The “epoxy (meth) acrylate” means a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid, and the “partial (meth) acrylate” is one molecule. A resin having one or more epoxy groups and one or more (meth) acryloyl groups therein.
なお、本明細書において、上記「（メタ）アクリロイル基」とは、アクリロイル基又はメタクリロイル基を意味し、上記「（メタ）アクリル」とは、アクリル又はメタクリルを意味し、上記「（メタ）アクリレート」とは、アクリレート又はメタクリレートを意味する。また、上記「エポキシ（メタ）アクリレート」とは、エポキシ樹脂中の全てのエポキシ基を（メタ）アクリル酸と反応させた化合物のことを表し、上記「部分（メタ）アクリレート」とは、１分子中にエポキシ基と（メタ）アクリロイル基とをそれぞれ１つ以上有する樹脂を表す。 Examples of the compound having the (meth) acryloyl group include an epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy resin, a partial (meth) acryl-modified epoxy resin, and (meth) acrylic acid. And an ester compound obtained by reacting a compound having a hydroxyl group with urethane, and a urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with isocyanate. Especially, since it is easy to obtain a high dielectric constant, it is more preferable to contain an epoxy (meth) acrylate and / or a partial (meth) acryl modified epoxy resin, and it is still more preferable to contain an epoxy (meth) acrylate.
In the present specification, the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group, the “(meth) acryl” means acryl or methacryl, and the “(meth) acrylate” "Means acrylate or methacrylate. The “epoxy (meth) acrylate” means a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid, and the “partial (meth) acrylate” is one molecule. A resin having one or more epoxy groups and one or more (meth) acryloyl groups therein.
上記エポキシ（メタ）アクリレートとしては、例えば、エポキシ樹脂と（メタ）アクリル酸とを、常法に従って塩基性触媒の存在下で反応することにより得られるもの等が挙げられる。
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.
上記エポキシ（メタ）アクリレートを合成するための原料となるエポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、２，２’－ジアリルビスフェノールＡ型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スルフィド型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンフェノールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、アルキルポリオール型エポキシ樹脂、ゴム変性型エポキシ樹脂、グリシジルエステル化合物等が挙げられる。
Examples of the epoxy resin used as a raw material for synthesizing the epoxy (meth) acrylate include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl bisphenol A type epoxy resin. , Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type 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 Novolac epoxy resin, ortho-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Emissions phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
上記ビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ８０８、ｊＥＲ８２８ＥＬ、ｊＥＲ１００４（いずれも三菱化学社製）、エピクロン８５０ＣＲＰ（ＤＩＣ社製）等が挙げられる。
上記ビスフェノールＦ型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ８０６、ｊＥＲ４００４（いずれも三菱化学社製）等が挙げられる。
上記ビスフェノールＳ型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＥＸＡ１５１４（ＤＩＣ社製）等が挙げられる。
上記２，２’－ジアリルビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ＲＥ－８１０ＮＭ（日本化薬社製）等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＥＸＡ７０１５（ＤＩＣ社製）等が挙げられる。
上記プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＰ－４０００Ｓ（ＡＤＥＫＡ社製）等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＸ－２０１（ナガセケムテックス社製）等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲＹＸ－４０００Ｈ（三菱化学社製）等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＳＬＶ－５０ＴＥ（新日鐵住金化学社製）等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＳＬＶ－８０ＤＥ（新日鐵住金化学社製）等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＰ－４０８８Ｓ（ＡＤＥＫＡ社製）等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＨＰ４０３２、エピクロンＥＸＡ－４７００（いずれもＤＩＣ社製）等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＮ－７７０（ＤＩＣ社製）等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＮ－６７０－ＥＸＰ－Ｓ（ＤＩＣ社製）等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＨＰ７２００（ＤＩＣ社製）等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ＮＣ－３０００Ｐ（日本化薬社製）等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＳＮ－１６５Ｓ（新日鐵住金化学社製）等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ６３０（三菱化学社製）、エピクロン４３０（ＤＩＣ社製）、ＴＥＴＲＡＤ－Ｘ（三菱ガス化学社製）等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ＺＸ－１５４２（新日鐵住金化学社製）、エピクロン７２６（ＤＩＣ社製）、エポライト８０ＭＦＡ（共栄社化学社製）、デナコールＥＸ－６１１（ナガセケムテックス社製）等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＲ－４５０、ＹＲ－２０７（いずれも新日鐵住金化学社製）、エポリードＰＢ（ダイセル社製）等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールＥＸ－１４７（ナガセケムテックス社製）等が挙げられる。
上記エポキシ樹脂のうちその他に市販されているものとしては、例えば、ＹＤＣ－１３１２、ＹＳＬＶ－８０ＸＹ、ＹＳＬＶ－９０ＣＲ（いずれも新日鐵住金化学社製）、ＸＡＣ４１５１（旭化成社製）、ｊＥＲ１０３１、ｊＥＲ１０３２（いずれも三菱化学社製）、ＥＸＡ－７１２０（ＤＩＣ社製）、ＴＥＰＩＣ（日産化学社製）等が挙げられる。 As what is marketed among the said bisphenol A type epoxy resins, jER808, jER828EL, jER1004 (all are the Mitsubishi Chemical company make), Epiklon 850CRP (made by DIC company), etc. are mentioned, for example.
As what is marketed among the said bisphenol F-type epoxy resins, jER806, jER4004 (all are the Mitsubishi Chemical company make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include jERYX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalenephenol novolac epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX. -611 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, and jER1032. (All manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.
上記ビスフェノールＦ型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ８０６、ｊＥＲ４００４（いずれも三菱化学社製）等が挙げられる。
上記ビスフェノールＳ型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＥＸＡ１５１４（ＤＩＣ社製）等が挙げられる。
上記２，２’－ジアリルビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ＲＥ－８１０ＮＭ（日本化薬社製）等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＥＸＡ７０１５（ＤＩＣ社製）等が挙げられる。
上記プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＰ－４０００Ｓ（ＡＤＥＫＡ社製）等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＸ－２０１（ナガセケムテックス社製）等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲＹＸ－４０００Ｈ（三菱化学社製）等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＳＬＶ－５０ＴＥ（新日鐵住金化学社製）等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＳＬＶ－８０ＤＥ（新日鐵住金化学社製）等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＰ－４０８８Ｓ（ＡＤＥＫＡ社製）等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＨＰ４０３２、エピクロンＥＸＡ－４７００（いずれもＤＩＣ社製）等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＮ－７７０（ＤＩＣ社製）等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＮ－６７０－ＥＸＰ－Ｓ（ＤＩＣ社製）等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＨＰ７２００（ＤＩＣ社製）等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ＮＣ－３０００Ｐ（日本化薬社製）等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＳＮ－１６５Ｓ（新日鐵住金化学社製）等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、ｊＥＲ６３０（三菱化学社製）、エピクロン４３０（ＤＩＣ社製）、ＴＥＴＲＡＤ－Ｘ（三菱ガス化学社製）等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ＺＸ－１５４２（新日鐵住金化学社製）、エピクロン７２６（ＤＩＣ社製）、エポライト８０ＭＦＡ（共栄社化学社製）、デナコールＥＸ－６１１（ナガセケムテックス社製）等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＲ－４５０、ＹＲ－２０７（いずれも新日鐵住金化学社製）、エポリードＰＢ（ダイセル社製）等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールＥＸ－１４７（ナガセケムテックス社製）等が挙げられる。
上記エポキシ樹脂のうちその他に市販されているものとしては、例えば、ＹＤＣ－１３１２、ＹＳＬＶ－８０ＸＹ、ＹＳＬＶ－９０ＣＲ（いずれも新日鐵住金化学社製）、ＸＡＣ４１５１（旭化成社製）、ｊＥＲ１０３１、ｊＥＲ１０３２（いずれも三菱化学社製）、ＥＸＡ－７１２０（ＤＩＣ社製）、ＴＥＰＩＣ（日産化学社製）等が挙げられる。 As what is marketed among the said bisphenol A type epoxy resins, jER808, jER828EL, jER1004 (all are the Mitsubishi Chemical company make), Epiklon 850CRP (made by DIC company), etc. are mentioned, for example.
As what is marketed among the said bisphenol F-type epoxy resins, jER806, jER4004 (all are the Mitsubishi Chemical company make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include jERYX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalenephenol novolac epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX. -611 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, and jER1032. (All manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.
上記エポキシ（メタ）アクリレートのうち市販されているものとしては、例えば、ＥＢＥＣＲＹＬ８６０、ＥＢＥＣＲＹＬ３２００、ＥＢＥＣＲＹＬ３２０１、ＥＢＥＣＲＹＬ３４１２、ＥＢＥＣＲＹＬ３６００、ＥＢＥＣＲＹＬ３７００、ＥＢＥＣＲＹＬ３７０１、ＥＢＥＣＲＹＬ３７０２、ＥＢＥＣＲＹＬ３７０３、ＥＢＥＣＲＹＬ３８００、ＥＢＥＣＲＹＬ６０４０、ＥＢＥＣＲＹＬＲＤＸ６３１８２（いずれもダイセル・オルネクス社製）、ＥＡ－１０１０、ＥＡ－１０２０、ＥＡ－５３２３、ＥＡ－５５２０、ＥＡ－ＣＨＤ、ＥＭＡ－１０２０（いずれも新中村化学工業社製）、エポキシエステルＭ－６００Ａ、エポキシエステル４０ＥＭ、エポキシエステル７０ＰＡ、エポキシエステル２００ＰＡ、エポキシエステル８０ＭＦＡ、エポキシエステル３００２Ｍ、エポキシエステル３００２Ａ、エポキシエステル１６００Ａ、エポキシエステル３０００Ｍ、エポキシエステル３０００Ａ、エポキシエステル２００ＥＡ、エポキシエステル４００ＥＡ（いずれも共栄社化学社製）、デナコールアクリレートＤＡ－１４１、デナコールアクリレートＤＡ－３１４、デナコールアクリレートＤＡ－９１１（いずれもナガセケムテックス社製）等が挙げられる。
Examples of commercially available epoxy (meth) acrylates include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRY3603 EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical 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 Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911 (all manufactured by Nagase ChemteX Corporation).
上記部分（メタ）アクリル変性エポキシ樹脂は、例えば、２つ以上のエポキシ基を有するエポキシ樹脂の一部分のエポキシ基を、（メタ）アクリル酸と反応させることによって得ることができる。
上記部分（メタ）アクリル変性エポキシ樹脂の原料となるエポキシ樹脂としては、上記エポキシ（メタ）アクリレートを合成するための原料として挙げたもの等が挙げられる。 The partial (meth) acryl-modified epoxy resin can be obtained, for example, by reacting an epoxy group of a part of an epoxy resin having two or more epoxy groups with (meth) acrylic acid.
As an epoxy resin used as the raw material of the said partial (meth) acryl modified epoxy resin, what was mentioned as a raw material for synthesize | combining the said epoxy (meth) acrylate, etc. are mentioned.
上記部分（メタ）アクリル変性エポキシ樹脂の原料となるエポキシ樹脂としては、上記エポキシ（メタ）アクリレートを合成するための原料として挙げたもの等が挙げられる。 The partial (meth) acryl-modified epoxy resin can be obtained, for example, by reacting an epoxy group of a part of an epoxy resin having two or more epoxy groups with (meth) acrylic acid.
As an epoxy resin used as the raw material of the said partial (meth) acryl modified epoxy resin, what was mentioned as a raw material for synthesize | combining the said epoxy (meth) acrylate, etc. are mentioned.
上記部分（メタ）アクリル変性エポキシ樹脂のうち、市販されているものとしては、例えば、ＵＶＡＣＵＲＥ１５６１（ダイセル・オルネクス社製）が挙げられる。
Examples of commercially available partial (meth) acrylic-modified epoxy resins include UVACURE 1561 (manufactured by Daicel Ornex).
上記（メタ）アクリル酸に水酸基を有する化合物を反応させることにより得られるエステル化合物のうち単官能のものとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、イミド（メタ）アクリレート、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチル２－ヒドロキシプロピルフタレート、グリシジル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルホスフェート等が挙げられる。
Among the ester compounds obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group, examples of monofunctional compounds include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate. , N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate , Isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopenteni (Meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxy Ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, tetrahydrofur Furyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, dimethylaminoethyl ( (Meth) acrylate, diethylaminoethyl (meth) acrylate, imide (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyl Examples include loxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, and the like.
また、上記エステル化合物のうち２官能のものとしては、例えば、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、２－ｎ－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、エチレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、プロピレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＦジ（メタ）アクリレート、ジメチロールジシクロペンタジエニルジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキシド変性イソシアヌル酸ジ（メタ）アクリレート、２－ヒドロキシ－３－（メタ）アクリロイロキシプロピル（メタ）アクリレート、カーボネートジオールジ（メタ）アクリレート、ポリエーテルジオールジ（メタ）アクリレート、ポリエステルジオールジ（メタ）アクリレート、ポリカプロラクトンジオールジ（メタ）アクリレート、ポリブタジエンジオールジ（メタ）アクリレート等が挙げられる。
Examples of the bifunctional ester compound include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth). Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (Meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) ) Acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) acrylate Etc. The.
また、上記エステル化合物のうち３官能以上のものとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、カプロラクトン変性トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、エチレンオキシド付加イソシアヌル酸トリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、プロピレンオキシド付加グリセリントリ（メタ）アクリレート、トリス（メタ）アクリロイルオキシエチルフォスフェート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。
Examples of the ester compound having three or more functions include trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and caprolactone. Modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, tris (meth) acryloyl Oxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.
上記イソシアネートに水酸基を有する（メタ）アクリル酸誘導体を反応させることにより得られるウレタン（メタ）アクリレートとしては、例えば、２つのイソシアネート基を有する化合物１当量に対して水酸基を有する（メタ）アクリル酸誘導体２当量を、触媒量のスズ系化合物存在下で反応させることによって得ることができる。
Examples of the urethane (meth) acrylate obtained by reacting the above isocyanate with a (meth) acrylic acid derivative having a hydroxyl group include, for example, a (meth) acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups. Two equivalents can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
上記イソシアネートとしては、例えば、イソホロンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート（ＭＤＩ）、水添ＭＤＩ、ポリメリックＭＤＩ、１，５－ナフタレンジイソシアネート、ノルボルナンジイソシアネート、トリジンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）、水添ＸＤＩ、リジンジイソシアネート、トリフェニルメタントリイソシアネート、トリス（イソシアネートフェニル）チオフォスフェート、テトラメチルキシレンジイソシアネート、１，６，１１－ウンデカントリイソシアネート等が挙げられる。
Examples of the isocyanate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), and hydrogenated MDI. , Polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, Examples include 1,6,11-undecane triisocyanate.
また、上記イソシアネートとしては、例えば、エチレングリコール、プロピレングリコール、グリセリン、ソルビトール、トリメチロールプロパン、カーボネートジオール、ポリエーテルジオール、ポリエステルジオール、ポリカプロラクトンジオール等のポリオールと過剰のイソシアネートとの反応により得られる鎖延長されたイソシアネート化合物も使用することができる。
Moreover, as said isocyanate, the chain | strand obtained by reaction of polyols, such as ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylol propane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and excess isocyanate, for example. Extended isocyanate compounds can also be used.
上記水酸基を有する（メタ）アクリル酸誘導体としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートや、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ポリエチレングリコール等の二価のアルコールのモノ（メタ）アクリレートや、トリメチロールエタン、トリメチロールプロパン、グリセリン等の三価のアルコールのモノ（メタ）アクリレート又はジ（メタ）アクリレートや、ビスフェノールＡ型エポキシアクリレート等のエポキシ（メタ）アクリレート等が挙げられる。
Examples of the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Hydroxyalkyl (meth) acrylates such as dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc. Acrylate, mono (meth) acrylate or di (meth) acrylate of trivalent alcohol such as trimethylolethane, trimethylolpropane, glycerin, and epoxy (meth) acrylate such as bisphenol A type epoxy acrylate, etc. And the like.
上記ウレタン（メタ）アクリレートのうち市販されているものとしては、例えば、Ｍ－１１００、Ｍ－１２００、Ｍ－１２１０、Ｍ－１６００（いずれも東亞合成社製）、ＥＢＥＣＲＹＬ２３０、ＥＢＥＣＲＹＬ２７０、ＥＢＥＣＲＹＬ４８５８、ＥＢＥＣＲＹＬ８４０２、ＥＢＥＣＲＹＬ８８０４、ＥＢＥＣＲＹＬ８８０３、ＥＢＥＣＲＹＬ８８０７、ＥＢＥＣＲＹＬ９２６０、ＥＢＥＣＲＹＬ１２９０、ＥＢＥＣＲＹＬ５１２９、ＥＢＥＣＲＹＬ４８４２、ＥＢＥＣＲＹＬ２１０、ＥＢＥＣＲＹＬ４８２７、ＥＢＥＣＲＹＬ６７００、ＥＢＥＣＲＹＬ２２０、ＥＢＥＣＲＹＬ２２２０（いずれもダイセル・オルネクス社製）、アートレジンＵＮ－９０００Ｈ、アートレジンＵＮ－９０００Ａ、アートレジンＵＮ－７１００、アートレジンＵＮ－１２５５、アートレジンＵＮ－３３０、アートレジンＵＮ－３３２０ＨＢ、アートレジンＵＮ－１２００ＴＰＫ、アートレジンＳＨ－５００Ｂ（いずれも根上工業社製）、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（いずれも新中村化学工業社製）、ＡＨ－６００、ＡＴ－６００、ＵＡ－３０６Ｈ、ＡＩ－６００、ＵＡ－１０１Ｔ、ＵＡ－１０１Ｉ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ（いずれも共栄社化学社製）等が挙げられる。
Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL6700, EBECRYL6700 , Art resin N-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Industrial Co., Ltd.), 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 Shin-Nakamura Chemical Industries ), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, A-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.).
上記硬化性樹脂は、液晶汚染を抑える点で、－ＯＨ基、－ＮＨ－基、－ＮＨ２基等の水素結合性のユニットを有するものが好ましい。
The curable resin preferably has a hydrogen bondable unit such as —OH group, —NH— group, —NH 2 group, etc. from the viewpoint of suppressing liquid crystal contamination.
本発明の液晶滴下工法用シール剤は、光ラジカル重合開始剤を含有する。
上記光ラジカル重合開始剤は、極性基を有するオキシムエステル化合物である。本発明の液晶滴下工法用シール剤は、上記光ラジカル重合開始剤として、極性基を有するオキシムエステル化合物を上記誘電率が１０以上である硬化性樹脂と組み合わせて用いることにより、光硬化性に優れ、液晶汚染を抑制することができるものとなる。 The sealing agent for liquid crystal dropping method of the present invention contains a photo radical polymerization initiator.
The photo radical polymerization initiator is an oxime ester compound having a polar group. The sealing agent for liquid crystal dropping method of the present invention is excellent in photocurability by using an oxime ester compound having a polar group in combination with a curable resin having a dielectric constant of 10 or more as the photoradical polymerization initiator. , Liquid crystal contamination can be suppressed.
上記光ラジカル重合開始剤は、極性基を有するオキシムエステル化合物である。本発明の液晶滴下工法用シール剤は、上記光ラジカル重合開始剤として、極性基を有するオキシムエステル化合物を上記誘電率が１０以上である硬化性樹脂と組み合わせて用いることにより、光硬化性に優れ、液晶汚染を抑制することができるものとなる。 The sealing agent for liquid crystal dropping method of the present invention contains a photo radical polymerization initiator.
The photo radical polymerization initiator is an oxime ester compound having a polar group. The sealing agent for liquid crystal dropping method of the present invention is excellent in photocurability by using an oxime ester compound having a polar group in combination with a curable resin having a dielectric constant of 10 or more as the photoradical polymerization initiator. , Liquid crystal contamination can be suppressed.
上記極性基を有するオキシムエステル化合物の極性基は、－ＯＨ基、－ＣＯＯＨ基、－ＳＨ基、－ＣＯＮＨ２基、及び、－ＮＨ２基からなる群より選択される少なくとも一種であることが好ましい。なかでも、液晶との相溶性が低くなることから、－ＯＨ基がより好ましい。
The polar group of the oxime ester compound having a polar group is preferably at least one selected from the group consisting of —OH group, —COOH group, —SH group, —CONH 2 group, and —NH 2 group. . Among them, the —OH group is more preferable because the compatibility with the liquid crystal becomes low.
上記極性基を有するオキシムエステル化合物としては、具体的には、下記式（１）で表される化合物が好ましい。
Specifically, the oxime ester compound having a polar group is preferably a compound represented by the following formula (1).
式（１）中、Ｘは、炭素数１～６のアルキレン基を表す。
式（１）中、Ｘで表される炭素数１～６のアルキレン基としては、例えば、メチレン基、エチレン基、ｎ－プロピレン基、イソプロピレン基、ｎ－ブチレン基、１－エチルエチレン基、ｎ－ペンチレン基、ｎ－へキシレン基等が挙げられる。なかでも、エチレン基が好ましい。 In the formula (1), X represents an alkylene group having 1 to 6 carbon atoms.
In the formula (1), examples of the alkylene group having 1 to 6 carbon atoms represented by X include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a 1-ethylethylene group, Examples thereof include an n-pentylene group and an n-hexylene group. Of these, an ethylene group is preferable.
式（１）中、Ｘで表される炭素数１～６のアルキレン基としては、例えば、メチレン基、エチレン基、ｎ－プロピレン基、イソプロピレン基、ｎ－ブチレン基、１－エチルエチレン基、ｎ－ペンチレン基、ｎ－へキシレン基等が挙げられる。なかでも、エチレン基が好ましい。 In the formula (1), X represents an alkylene group having 1 to 6 carbon atoms.
In the formula (1), examples of the alkylene group having 1 to 6 carbon atoms represented by X include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a 1-ethylethylene group, Examples thereof include an n-pentylene group and an n-hexylene group. Of these, an ethylene group is preferable.
上記極性基を有するオキシムエステル化合物の含有量は、硬化性樹脂１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が１０重量部である。上記極性基を有するオキシムエステル化合物の含有量が０．１重量部未満であると、得られる液晶滴下工法用シール剤の光硬化反応が充分に進行しないことがある。上記極性基を有するオキシムエステル化合物の含有量が１０重量部を超えると、得られる液晶滴下工法用シール剤が耐候性や保存安定性に劣るものとなったり、液晶汚染が生じたりすることがある。上記極性基を有するオキシムエステル化合物の含有量のより好ましい下限は０．５重量部、より好ましい上限は５重量部である。
The content of the oxime ester compound having a polar group is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the oxime ester compound having a polar group is less than 0.1 parts by weight, the photocuring reaction of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed. If the content of the oxime ester compound having a polar group exceeds 10 parts by weight, the resulting liquid crystal dropping method sealing agent may be inferior in weather resistance and storage stability, or liquid crystal contamination may occur. . The minimum with more preferable content of the oxime ester compound which has the said polar group is 0.5 weight part, and a more preferable upper limit is 5 weight part.
本発明の液晶滴下工法用シール剤は、上記光ラジカル重合開始剤として、上記極性基を有するオキシムエステル化合物に加えて、その他の光ラジカル重合開始剤を含有してもよいが、光硬化性と液晶汚染を抑制する効果とを両立する観点から、その他の光ラジカル重合開始剤は含有しないことが好ましい。
The sealing agent for liquid crystal dropping method of the present invention may contain other photoradical polymerization initiator as the photoradical polymerization initiator in addition to the oxime ester compound having the polar group. From the viewpoint of achieving both the effect of suppressing liquid crystal contamination, it is preferable that no other radical photopolymerization initiator is contained.
本発明の液晶滴下工法用シール剤は、増感剤を含有することが好ましい。
本発明の液晶滴下工法用シール剤は、上記増感剤を含有することにより、高感度でより光硬化性に優れる液晶滴下工法用シール剤を得ることができる。 The sealing agent for liquid crystal dropping method of the present invention preferably contains a sensitizer.
By containing the above sensitizer, the liquid crystal dropping method sealing agent of the present invention can provide a liquid crystal dropping method sealing agent with high sensitivity and more excellent photocurability.
本発明の液晶滴下工法用シール剤は、上記増感剤を含有することにより、高感度でより光硬化性に優れる液晶滴下工法用シール剤を得ることができる。 The sealing agent for liquid crystal dropping method of the present invention preferably contains a sensitizer.
By containing the above sensitizer, the liquid crystal dropping method sealing agent of the present invention can provide a liquid crystal dropping method sealing agent with high sensitivity and more excellent photocurability.
上記増感剤は、紫外・可視領域に充分な光吸収帯を有すること好ましいことから、ベンゾフェノン骨格、アントラセン骨格、アントラキノン骨格、クマリン骨格、チオキサントン骨格、及び、フタロシアニン骨格からなる群より選択される少なくとも一種の骨格を有する化合物を含有することが好ましく、アントラセン骨格、アントラキノン骨格、及び、チオキサントン骨格からなる群より選択される少なくとも一種の骨格を有する化合物を含有することがより好ましい。
Since the sensitizer preferably has a sufficient light absorption band in the ultraviolet / visible region, at least selected from the group consisting of a benzophenone skeleton, an anthracene skeleton, an anthraquinone skeleton, a coumarin skeleton, a thioxanthone skeleton, and a phthalocyanine skeleton. It is preferable to contain a compound having one kind of skeleton, and it is more preferred to contain a compound having at least one kind of skeleton selected from the group consisting of an anthracene skeleton, an anthraquinone skeleton, and a thioxanthone skeleton.
上記ベンゾフェノン骨格を有する化合物としては、例えば、ベンゾフェノン、２，４－ジクロロベンゾフェノン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン等が挙げられる。
上記アントラセン骨格を有する化合物としては、例えば、９，１０－ジブトキシアントラセン、９，１０－ジプロキシアントラキノン、９，１０－エトキシアントラキノン等が挙げられる。
上記アントラキノン骨格を有する化合物としては、例えば、２－エチルアントラキノン、１－メチルアントラキノン、１，４－ジヒドロキシアントラキノン、２－（２－ヒドロキシエトキシ）－アントラキノン等が挙げられる。
上記クマリン骨格を有する化合物としては、例えば、７－ジエチルアミノ－４－メチルクマリン等が挙げられる。
上記チオキサントン骨格を有する化合物としては、例えば、２，４－ジエチルチオキサントン、２－クロロチオキサントン、４－イソプロピルチオキサントン、１－クロロ－４－プロピルチオキサントン等が挙げられる。
上記フタロシアニン骨格を有する化合物としては、例えば、フタロシアニン等が挙げられる。
これらの増感剤のなかでも、得られる液晶滴下工法用シール剤が遮光部の硬化性に特に優れるものとなることから、４，４’－ビス（ジメチルアミノ）ベンゾフェノン及び４，４’－ビス（ジエチルアミノ）ベンゾフェノンの少なくともいずれかが好ましい。 Examples of the compound having a benzophenone skeleton include benzophenone, 2,4-dichlorobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.
Examples of the compound having an anthracene skeleton include 9,10-dibutoxyanthracene, 9,10-diproxyanthraquinone, and 9,10-ethoxyanthraquinone.
Examples of the compound having an anthraquinone skeleton include 2-ethylanthraquinone, 1-methylanthraquinone, 1,4-dihydroxyanthraquinone, 2- (2-hydroxyethoxy) -anthraquinone and the like.
Examples of the compound having a coumarin skeleton include 7-diethylamino-4-methylcoumarin.
Examples of the compound having a thioxanthone skeleton include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and the like.
Examples of the compound having a phthalocyanine skeleton include phthalocyanine.
Among these sensitizers, the resulting sealant for liquid crystal dropping method is particularly excellent in light-curing part curability, so that 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis At least one of (diethylamino) benzophenone is preferred.
上記アントラセン骨格を有する化合物としては、例えば、９，１０－ジブトキシアントラセン、９，１０－ジプロキシアントラキノン、９，１０－エトキシアントラキノン等が挙げられる。
上記アントラキノン骨格を有する化合物としては、例えば、２－エチルアントラキノン、１－メチルアントラキノン、１，４－ジヒドロキシアントラキノン、２－（２－ヒドロキシエトキシ）－アントラキノン等が挙げられる。
上記クマリン骨格を有する化合物としては、例えば、７－ジエチルアミノ－４－メチルクマリン等が挙げられる。
上記チオキサントン骨格を有する化合物としては、例えば、２，４－ジエチルチオキサントン、２－クロロチオキサントン、４－イソプロピルチオキサントン、１－クロロ－４－プロピルチオキサントン等が挙げられる。
上記フタロシアニン骨格を有する化合物としては、例えば、フタロシアニン等が挙げられる。
これらの増感剤のなかでも、得られる液晶滴下工法用シール剤が遮光部の硬化性に特に優れるものとなることから、４，４’－ビス（ジメチルアミノ）ベンゾフェノン及び４，４’－ビス（ジエチルアミノ）ベンゾフェノンの少なくともいずれかが好ましい。 Examples of the compound having a benzophenone skeleton include benzophenone, 2,4-dichlorobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.
Examples of the compound having an anthracene skeleton include 9,10-dibutoxyanthracene, 9,10-diproxyanthraquinone, and 9,10-ethoxyanthraquinone.
Examples of the compound having an anthraquinone skeleton include 2-ethylanthraquinone, 1-methylanthraquinone, 1,4-dihydroxyanthraquinone, 2- (2-hydroxyethoxy) -anthraquinone and the like.
Examples of the compound having a coumarin skeleton include 7-diethylamino-4-methylcoumarin.
Examples of the compound having a thioxanthone skeleton include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and the like.
Examples of the compound having a phthalocyanine skeleton include phthalocyanine.
Among these sensitizers, the resulting sealant for liquid crystal dropping method is particularly excellent in light-curing part curability, so that 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis At least one of (diethylamino) benzophenone is preferred.
上記増感剤の含有量は、上記光重合開始剤１００重量部に対して、好ましい下限が２重量部、好ましい上限が５０重量部である。上記増感剤の含有量が２重量部未満であると、得られる液晶滴下工法用シール剤の光硬化性をより向上させる効果が充分に発揮されないことがある。上記増感剤の含有量が５０重量部を超えると、液晶汚染が発生することがある。上記増感剤の含有量のより好ましい下限は５重量部、より好ましい上限は４０重量部である。
The content of the sensitizer is such that a preferred lower limit is 2 parts by weight and a preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the photopolymerization initiator. If the content of the sensitizer is less than 2 parts by weight, the effect of further improving the photocurability of the obtained liquid crystal dropping method sealing agent may not be sufficiently exhibited. When the content of the sensitizer exceeds 50 parts by weight, liquid crystal contamination may occur. The minimum with more preferable content of the said sensitizer is 5 weight part, and a more preferable upper limit is 40 weight part.
本発明の液晶滴下工法用シール剤は、熱ラジカル重合開始剤を含有してもよい。
上記熱ラジカル重合開始剤としては、例えば、アゾ化合物、有機過酸化物等からなるものが挙げられる。なかでも、高分子アゾ化合物からなる開始剤（以下、「高分子アゾ開始剤」ともいう）が好ましい。
なお、本明細書において高分子アゾ化合物とは、アゾ基を有し、熱によってラジカルを生成する、数平均分子量が３００以上の化合物を意味する。 The sealing agent for liquid crystal dropping method of the present invention may contain a thermal radical polymerization initiator.
As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
In the present specification, the polymer azo compound means a compound having an azo group and generating a radical by heat and having a number average molecular weight of 300 or more.
上記熱ラジカル重合開始剤としては、例えば、アゾ化合物、有機過酸化物等からなるものが挙げられる。なかでも、高分子アゾ化合物からなる開始剤（以下、「高分子アゾ開始剤」ともいう）が好ましい。
なお、本明細書において高分子アゾ化合物とは、アゾ基を有し、熱によってラジカルを生成する、数平均分子量が３００以上の化合物を意味する。 The sealing agent for liquid crystal dropping method of the present invention may contain a thermal radical polymerization initiator.
As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
In the present specification, the polymer azo compound means a compound having an azo group and generating a radical by heat and having a number average molecular weight of 300 or more.
上記高分子アゾ開始剤の数平均分子量の好ましい下限は１０００、好ましい上限は３０万である。上記高分子アゾ開始剤の数平均分子量が１０００未満であると、高分子アゾ開始剤が液晶に悪影響を与えることがある。上記高分子アゾ開始剤の数平均分子量が３０万を超えると、硬化性樹脂への混合が困難になることがある。上記高分子アゾ開始剤の数平均分子量のより好ましい下限は５０００、より好ましい上限は１０万であり、更に好ましい下限は１万、更に好ましい上限は９万である。
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Ｓｈｏｄｅｘ ＬＦ－８０４（昭和電工社製）等が挙げられる。 The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo initiator is less than 1000, the polymer 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 be difficult. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Ｓｈｏｄｅｘ ＬＦ－８０４（昭和電工社製）等が挙げられる。 The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo initiator is less than 1000, the polymer 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 be difficult. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
上記高分子アゾ開始剤としては、例えば、アゾ基を介してポリアルキレンオキサイドやポリジメチルシロキサン等のユニットが複数結合した構造を有するものが挙げられる。
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。このような高分子アゾ開始剤としては、例えば、４，４’－アゾビス（４－シアノペンタン酸）とポリアルキレングリコールの重縮合物や、４，４’－アゾビス（４－シアノペンタン酸）と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられ、具体的には例えば、ＶＰＥ－０２０１、ＶＰＥ－０４０１、ＶＰＥ－０６０１、ＶＰＳ－０５０１、ＶＰＳ－１００１（いずれも和光純薬工業社製）等が挙げられる。
また、高分子ではないアゾ化合物の例としてはＶ－６５、Ｖ－５０１（いずれも和光純薬工業社製）等が挙げられる。 Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable. Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
Examples of azo compounds that are not a polymer include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。このような高分子アゾ開始剤としては、例えば、４，４’－アゾビス（４－シアノペンタン酸）とポリアルキレングリコールの重縮合物や、４，４’－アゾビス（４－シアノペンタン酸）と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられ、具体的には例えば、ＶＰＥ－０２０１、ＶＰＥ－０４０１、ＶＰＥ－０６０１、ＶＰＳ－０５０１、ＶＰＳ－１００１（いずれも和光純薬工業社製）等が挙げられる。
また、高分子ではないアゾ化合物の例としてはＶ－６５、Ｖ－５０１（いずれも和光純薬工業社製）等が挙げられる。 Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable. Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
Examples of azo compounds that are not a polymer include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
上記有機過酸化物としては、例えば、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、パーオキシエステル、ジアシルパーオキサイド、パーオキシジカーボネート等が挙げられる。
Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
上記熱ラジカル重合開始剤の含有量は、硬化性樹脂１００重量部に対して、好ましい下限が０．０５重量部、好ましい上限が１０重量部である。上記熱ラジカル重合開始剤の含有量が０．０５重量部未満であると、得られる液晶滴下工法用シール剤の熱硬化反応が充分に進行しないことがある。上記熱ラジカル重合開始剤の含有量が１０重量部を超えると、得られる液晶滴下工法用シール剤が液晶汚染を引き起こすことがある。上記熱ラジカル重合開始剤の含有量のより好ましい下限は０．１重量部、より好ましい上限は５重量部である。
The content of the thermal radical polymerization initiator is preferably 0.05 parts by weight and preferably 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, the thermosetting reaction of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed. When content of the said thermal radical polymerization initiator exceeds 10 weight part, the sealing compound for liquid crystal dropping methods obtained may cause liquid crystal contamination. The minimum with more preferable content of the said thermal radical polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
本発明の液晶滴下工法用シール剤は、熱硬化剤を含有してもよい。
上記熱硬化剤としては、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。 The sealing agent for liquid crystal dropping method of the present invention may contain a thermosetting agent.
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
上記熱硬化剤としては、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。 The sealing agent for liquid crystal dropping method of the present invention may contain a thermosetting agent.
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
上記有機酸ヒドラジドとしては、例えば、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジド、アジピン酸ジヒドラジド、マロン酸ジヒドラジド等が挙げられる。
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、ＳＤＨ、ＡＤＨ（いずれも大塚化学社製）、アミキュアＶＤＨ、アミキュアＶＤＨ－Ｊ、アミキュアＵＤＨ、アミキュアＵＤＨ－Ｊ（いずれも味の素ファインテクノ社製）等が挙げられる。 Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of commercially available organic acid hydrazides include, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、ＳＤＨ、ＡＤＨ（いずれも大塚化学社製）、アミキュアＶＤＨ、アミキュアＶＤＨ－Ｊ、アミキュアＵＤＨ、アミキュアＵＤＨ－Ｊ（いずれも味の素ファインテクノ社製）等が挙げられる。 Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of commercially available organic acid hydrazides include, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.
上記熱硬化剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が１重量部、好ましい上限が５０重量部である。上記熱硬化剤の含有量が１重量部未満であると、得られる液晶滴下工法用シール剤を充分に熱硬化させることができないことがある。上記熱硬化剤の含有量が５０重量部を超えると、得られる液晶滴下工法用シール剤の粘度が高くなり、塗布性が悪くなることがある。上記熱硬化剤の含有量のより好ましい上限は３０重量部である。
The content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit. When the content of the thermosetting agent is less than 1 part by weight, the resulting sealing agent for liquid crystal dropping method may not be sufficiently cured. When content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability | paintability may worsen. The upper limit with more preferable content of the said thermosetting agent is 30 weight part.
本発明の液晶滴下工法用シール剤は、粘度の向上、応力分散効果による接着性の改善、線膨張率の改善、硬化物の耐湿性の更なる向上等を目的として充填剤を含有することが好ましい。
The sealing agent for liquid crystal dropping method of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesiveness due to the stress dispersion effect, improving the coefficient of linear expansion, and further improving the moisture resistance of the cured product. preferable.
上記充填剤としては、例えば、タルク、石綿、シリカ、珪藻土、スメクタイト、ベントナイト、炭酸カルシウム、炭酸マグネシウム、アルミナ、モンモリロナイト、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、水酸化マグネシウム、水酸化アルミニウム、ガラスビーズ、窒化珪素、硫酸バリウム、石膏、珪酸カルシウム、セリサイト、活性白土、窒化アルミニウム等の無機充填剤や、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等の有機充填剤が挙げられる。これらの充填剤は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。
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, water Inorganic fillers such as aluminum oxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned. These fillers may be used alone or in combination of two or more.
本発明の液晶滴下工法用シール剤全体１００重量部中における上記充填剤の含有量の好ましい下限は１０重量部、好ましい上限は７０重量部である。上記充填剤の含有量が１０重量部未満であると、接着性の改善等の効果が充分に発揮されないことがある。上記充填剤の含有量が７０重量部を超えると、得られる液晶滴下工法用シール剤が、粘度が高すぎて塗布性に劣るものとなることがある。上記充填剤の含有量のより好ましい下限は２０重量部、より好ましい上限は６０重量部である。
The minimum with preferable content of the said filler in 100 weight part of whole sealing compound for liquid crystal dropping methods of this invention is 10 weight part, and a preferable upper limit is 70 weight part. When the content of the filler is less than 10 parts by weight, effects such as improvement of adhesiveness may not be sufficiently exhibited. When content of the said filler exceeds 70 weight part, the sealing compound for liquid crystal dropping methods obtained may have a viscosity too high, and may become inferior to applicability | paintability. The minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
本発明の液晶滴下工法用シール剤は、シランカップリング剤を含有することが好ましい。上記シランカップリング剤は、主にシール剤と基板等とを良好に接着するための接着助剤としての役割を有する。
The sealing agent for liquid crystal dropping method of the present invention preferably contains a silane coupling agent. The silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
上記シランカップリング剤としては、基板等との接着性を向上させる効果に優れ、硬化性樹脂と化学結合することにより液晶中への硬化性樹脂の流出を抑制することができることから、例えば、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－イソシアネートプロピルトリメトキシシラン等が好適に用いられる。これらのシランカップリング剤は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。
As said silane coupling agent, since it is excellent in the effect which improves adhesiveness with a board | substrate etc. and it can suppress the outflow of curable resin in a liquid crystal by chemically bonding with curable resin, it is 3 for example. -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These silane coupling agents may be used alone or in combination of two or more.
本発明の液晶滴下工法用シール剤１００重量部中における上記シランカップリング剤の含有量の好ましい下限は０．１重量部、好ましい上限は１０重量部である。上記シランカップリング剤の含有量が０．１重量部未満であると、接着性を向上させる等の効果が充分に発揮されないことがある。上記シランカップリング剤の含有量が１０重量部を超えると、得られる液晶滴下工法用シール剤が液晶汚染を引き起こすことがある。上記シランカップリング剤の含有量のより好ましい下限は０．３重量部、より好ましい上限は５重量部である。
The minimum with preferable content of the said silane coupling agent in 100 weight part of sealing agents for liquid crystal dropping methods of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part. When the content of the silane coupling agent is less than 0.1 parts by weight, effects such as improvement of adhesiveness may not be sufficiently exhibited. When content of the said silane coupling agent exceeds 10 weight part, the sealing compound for liquid crystal dropping methods obtained may cause liquid-crystal contamination. The minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.
本発明の液晶滴下工法用シール剤は、遮光剤を含有してもよい。上記遮光剤を含有することにより、本発明の液晶滴下工法用シール剤は、遮光シール剤として好適に用いることができる。
The sealing agent for liquid crystal dropping method of the present invention may contain a light shielding agent. By containing the said light shielding agent, the sealing compound for liquid crystal dropping methods of this invention can be used suitably as a light shielding sealing agent.
上記遮光剤としては、例えば、酸化鉄、チタンブラック、アニリンブラック、シアニンブラック、フラーレン、カーボンブラック、樹脂被覆型カーボンブラック等が挙げられる。なかでも、絶縁性が高いことから、チタンブラックが好ましい。
Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferred because of its high insulating properties.
上記チタンブラックは、表面処理されていないものでも充分な効果を発揮するが、表面がカップリング剤等の有機成分で処理されているものや、酸化ケイ素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化ジルコニウム、酸化マグネシウム等の無機成分で被覆されているもの等、表面処理されたチタンブラックを用いることもできる。なかでも、有機成分で処理されているものは、より絶縁性を向上できる点で好ましい。
また、遮光剤として上記チタンブラックを含有する本発明の液晶滴下工法用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 The above-mentioned 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, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display device manufactured using the sealing agent for liquid crystal dropping method of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has a high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
また、遮光剤として上記チタンブラックを含有する本発明の液晶滴下工法用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 The above-mentioned 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, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display device manufactured using the sealing agent for liquid crystal dropping method of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has a high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
上記チタンブラックのうち市販されているものとしては、例えば、１２Ｓ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ－Ｎ、１４Ｍ－Ｃ（いずれも三菱マテリアル社製）、ティラックＤ（赤穂化成社製）等が挙げられる。
Examples of commercially available titanium black include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like. Can be mentioned.
上記チタンブラックの比表面積の好ましい下限は１３ｍ２／ｇ、好ましい上限は３０ｍ２／ｇであり、より好ましい下限は１５ｍ２／ｇ、より好ましい上限は２５ｍ２／ｇである。
また、上記チタンブラックの体積抵抗の好ましい下限は０．５Ω・ｃｍ、好ましい上限は３Ω・ｃｍであり、より好ましい下限は１Ω・ｃｍ、より好ましい上限は２．５Ω・ｃｍである。 The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
また、上記チタンブラックの体積抵抗の好ましい下限は０．５Ω・ｃｍ、好ましい上限は３Ω・ｃｍであり、より好ましい下限は１Ω・ｃｍ、より好ましい上限は２．５Ω・ｃｍである。 The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
上記遮光剤の一次粒子径は、液晶表示素子の基板間の距離以下であれば特に限定されないが、好ましい下限は１ｎｍ、好ましい上限は５μｍである。上記遮光剤の一次粒子径が１ｎｍ未満であると、得られる液晶滴下工法用シール剤の粘度やチクソトロピーが大きく増大してしまい、作業性が悪くなることがある。上記遮光剤の一次粒子径が５μｍを超えると、得られる液晶滴下工法用シール剤の基板への塗布性が悪くなることがある。上記遮光剤の一次粒子径のより好ましい下限は５ｎｍ、より好ましい上限は２００ｎｍ、更に好ましい下限は１０ｎｍ、更に好ましい上限は１００ｎｍである。
なお、上記遮光剤の一次粒子径は、ＮＩＣＯＭＰ ３８０ＺＬＳ（ＰＡＲＴＩＣＬＥ ＳＩＺＩＮＧ ＳＹＳＴＥＭＳ社製）を用いて、上記遮光剤を溶媒（水、有機溶媒等）に分散させて測定することができる。 The primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, 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 liquid crystal dropping method sealing agent are greatly increased, and workability may be deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
なお、上記遮光剤の一次粒子径は、ＮＩＣＯＭＰ ３８０ＺＬＳ（ＰＡＲＴＩＣＬＥ ＳＩＺＩＮＧ ＳＹＳＴＥＭＳ社製）を用いて、上記遮光剤を溶媒（水、有機溶媒等）に分散させて測定することができる。 The primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, 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 liquid crystal dropping method sealing agent are greatly increased, and workability may be deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
本発明の液晶滴下工法用シール剤１００重量部中における上記遮光剤の含有量の好ましい下限は５重量部、好ましい上限は８０重量部である。上記遮光剤の含有量が５重量部未満であると、充分な遮光性が得られないことがある。上記遮光剤の含有量が８０重量部を超えると、得られる液晶滴下工法用シール剤の基板に対する密着性や硬化後の強度が低下したり、描画性が低下したりすることがある。上記遮光剤の含有量のより好ましい下限は１０重量部、より好ましい上限は７０重量部であり、更に好ましい下限は３０重量部、更に好ましい上限は６０重量部である。
The preferable lower limit of the content of the light shielding agent in 100 parts by weight of the sealing agent for liquid crystal dropping method 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 obtained sealing agent for liquid crystal dropping method to the substrate and the strength after curing may be lowered, or the drawing property may be lowered. The more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
本発明の液晶滴下工法用シール剤を製造する方法としては、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、３本ロール等の混合機を用いて、硬化性樹脂と、光ラジカル重合開始剤と、必要に応じて添加するシランカップリング剤等の添加剤とを混合する方法等が挙げられる。
As a method for producing the sealing agent for liquid crystal dropping method of the present invention, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light Examples thereof include a method of mixing a radical polymerization initiator and an additive such as a silane coupling agent added as necessary.
本発明の液晶滴下工法用シール剤に、導電性微粒子を配合することにより、上下導通材料を製造することができる。このような本発明の液晶滴下工法用シール剤と導電性微粒子とを含有する上下導通材料もまた、本発明の１つである。
A vertical conduction material can be produced by blending conductive fine particles with the sealant for the liquid crystal dropping method of the present invention. Such a vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
上記導電性微粒子としては、金属ボール、樹脂微粒子の表面に導電金属層を形成したもの等を用いることができる。なかでも、樹脂微粒子の表面に導電金属層を形成したものは、樹脂微粒子の優れた弾性により、透明基板等を損傷することなく導電接続が可能であることから好適である。
As the conductive fine particles, a metal ball, a resin fine particle formed with a conductive metal layer on the surface, or the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
本発明の液晶滴下工法用シール剤又は本発明の上下導通材料を用いてなる液晶表示素子もまた、本発明の１つである。
The liquid crystal display element using the sealing agent for liquid crystal dropping method of the present invention or the vertical conduction material of the present invention is also one aspect of the present invention.
本発明の液晶表示素子を製造する方法としては、例えば、ＩＴＯ薄膜等の電極付きのガラス基板やポリエチレンテレフタレート基板等の２枚の透明基板の一方に、本発明の液晶滴下工法用シール剤等をスクリーン印刷、ディスペンサー塗布等により長方形状のシールパターンを形成する工程、本発明の液晶滴下工法用シール剤等が未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下塗布し、すぐに別の基板を重ね合わせる工程、及び、本発明の液晶滴下工法用シール剤等のシールパターン部分に紫外線等の光を照射してシール剤を仮硬化させる工程、及び、仮硬化させたシール剤を加熱して本硬化させる工程を有する方法等が挙げられる。
As a method for producing the liquid crystal display element of the present invention, for example, the sealing agent for the liquid crystal dropping method of the present invention is applied to one of two transparent substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate. The process of forming a rectangular seal pattern by screen printing, dispenser application, etc., the liquid crystal drop method sealing agent of the present invention is uncured, and liquid crystal microdrops are dropped on the entire surface of the transparent substrate and applied immediately. A step of superimposing another substrate on the substrate, a step of irradiating the seal pattern portion of the sealant for the liquid crystal dropping method of the present invention with light such as ultraviolet rays, and the step of pre-curing the sealant, and a pre-cured sealant The method etc. which have the process of heating this and making it harden | cure are mentioned.
本発明によれば、光硬化性に優れ、かつ、液晶汚染を抑制することができる液晶滴下工法用シール剤を提供することができる。また、本発明によれば、該液晶滴下工法用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods which can be excellent in photocurability and can suppress liquid crystal contamination can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
硬化性樹脂として、ビスフェノールＡ型エポキシアクリレート（ダイセル・オルネクス社製、「ＥＢＥＣＲＹＬ３７００」、誘電率１４）４０重量部、及び、部分アクリル変性ビスフェノールＡ型エポキシ樹脂（ダイセル・オルネクス社製、「ＵＶＡＣＵＲＥ１５６１」、誘電率１３）２０重量部と、光ラジカル重合開始剤として、下記式（２）で表される化合物（ＡＤＥＫＡ社製、「ＮＣＩ－９３０」）１重量部と、熱硬化剤として、アジピン酸ジヒドラジド（大塚化学社製、「ＡＤＨ」）３重量部と、充填剤として、シリカ（アドマテックス社製、「アドマファインＳＯ－Ｃ２」）１５重量部、及び、タルク（日本タルク社製、「ナノエースＤ６００」）５重量部と、シランカップリング剤として、３－グリシドキシプロピルトリメトキシシラン（信越化学工業社製、「ＫＢＭ－４０３」）１重量部とを配合し、遊星式撹拌機（シンキー社製、「あわとり練太郎」）にて撹拌した後、セラミック３本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 Example 1
As curable resin, 40 parts by weight of bisphenol A type epoxy acrylate (manufactured by Daicel Ornex Co., Ltd., “EBECRYL 3700”, dielectric constant 14), and partially acrylic modified bisphenol A type epoxy resin (manufactured by Daicel Ornex Co., Ltd., “UVACURE 1561”) Dielectric constant 13) 20 parts by weight, 1 part by weight of a compound represented by the following formula (2) (produced by ADEKA, “NCI-930”) as a radical photopolymerization initiator, and adipic acid dihydrazide as a thermosetting agent 3 parts by weight (manufactured by Otsuka Chemical Co., Ltd., “ADH”), 15 parts by weight of silica (manufactured by Admatechs, “Admafine SO-C2”) as a filler, and talc (manufactured by Nippon Talc Co., Ltd., “Nanoace D600” ]) 5 parts by weight and 3-glycidoxypropyltrimethoxy as silane coupling agent 1 part by weight of silane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-403”) is mixed and stirred with a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Nertaro ”), then with a ceramic three roll It mixed uniformly and the sealing compound for liquid crystal dropping methods was obtained.
硬化性樹脂として、ビスフェノールＡ型エポキシアクリレート（ダイセル・オルネクス社製、「ＥＢＥＣＲＹＬ３７００」、誘電率１４）４０重量部、及び、部分アクリル変性ビスフェノールＡ型エポキシ樹脂（ダイセル・オルネクス社製、「ＵＶＡＣＵＲＥ１５６１」、誘電率１３）２０重量部と、光ラジカル重合開始剤として、下記式（２）で表される化合物（ＡＤＥＫＡ社製、「ＮＣＩ－９３０」）１重量部と、熱硬化剤として、アジピン酸ジヒドラジド（大塚化学社製、「ＡＤＨ」）３重量部と、充填剤として、シリカ（アドマテックス社製、「アドマファインＳＯ－Ｃ２」）１５重量部、及び、タルク（日本タルク社製、「ナノエースＤ６００」）５重量部と、シランカップリング剤として、３－グリシドキシプロピルトリメトキシシラン（信越化学工業社製、「ＫＢＭ－４０３」）１重量部とを配合し、遊星式撹拌機（シンキー社製、「あわとり練太郎」）にて撹拌した後、セラミック３本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 Example 1
As curable resin, 40 parts by weight of bisphenol A type epoxy acrylate (manufactured by Daicel Ornex Co., Ltd., “EBECRYL 3700”, dielectric constant 14), and partially acrylic modified bisphenol A type epoxy resin (manufactured by Daicel Ornex Co., Ltd., “UVACURE 1561”) Dielectric constant 13) 20 parts by weight, 1 part by weight of a compound represented by the following formula (2) (produced by ADEKA, “NCI-930”) as a radical photopolymerization initiator, and adipic acid dihydrazide as a thermosetting agent 3 parts by weight (manufactured by Otsuka Chemical Co., Ltd., “ADH”), 15 parts by weight of silica (manufactured by Admatechs, “Admafine SO-C2”) as a filler, and talc (manufactured by Nippon Talc Co., Ltd., “Nanoace D600” ]) 5 parts by weight and 3-glycidoxypropyltrimethoxy as silane coupling agent 1 part by weight of silane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-403”) is mixed and stirred with a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Nertaro ”), then with a ceramic three roll It mixed uniformly and the sealing compound for liquid crystal dropping methods was obtained.
（実施例２～１１、比較例１～５）
表１、２に記載された配合比に従い、各材料を、実施例１と同様にして、遊星式撹拌機（シンキー社製、「あわとり練太郎」）を用いて混合した後、更に３本ロールを用いて混合することにより実施例２～１１、比較例１～５の液晶滴下工法用シール剤を調製した。
なお、表１、２中に記載した、「式（３）で表される化合物」は、下記式（３）で表される化合物であり、「式（４）で表される化合物」は、下記式（４）で表される化合物である。 (Examples 2 to 11, Comparative Examples 1 to 5)
According to the blending ratios described in Tables 1 and 2, each material was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., “Awatori Netaro”) in the same manner as in Example 1, and then 3 more The sealing agents for the liquid crystal dropping method of Examples 2 to 11 and Comparative Examples 1 to 5 were prepared by mixing using a roll.
The “compound represented by the formula (3)” described in Tables 1 and 2 is a compound represented by the following formula (3), and the “compound represented by the formula (4)” It is a compound represented by following formula (4).
表１、２に記載された配合比に従い、各材料を、実施例１と同様にして、遊星式撹拌機（シンキー社製、「あわとり練太郎」）を用いて混合した後、更に３本ロールを用いて混合することにより実施例２～１１、比較例１～５の液晶滴下工法用シール剤を調製した。
なお、表１、２中に記載した、「式（３）で表される化合物」は、下記式（３）で表される化合物であり、「式（４）で表される化合物」は、下記式（４）で表される化合物である。 (Examples 2 to 11, Comparative Examples 1 to 5)
According to the blending ratios described in Tables 1 and 2, each material was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., “Awatori Netaro”) in the same manner as in Example 1, and then 3 more The sealing agents for the liquid crystal dropping method of Examples 2 to 11 and Comparative Examples 1 to 5 were prepared by mixing using a roll.
The “compound represented by the formula (3)” described in Tables 1 and 2 is a compound represented by the following formula (3), and the “compound represented by the formula (4)” It is a compound represented by following formula (4).
なお、表１、２中の部分アクリル変性フェノールノボラック型エポキシ樹脂は、以下の方法により調製した。
即ち、フェノールノボラック型エポキシ樹脂（ＤＩＣ社製、「Ｎ－７７０」）１９０ｇをトルエン５００ｍＬに溶解させ、この溶液にトリフェニルホスフィン０．１ｇを加え、均一な溶液とした。得られた溶液にアクリル酸３５ｇを還流撹拌下にて２時間かけて滴下した後、更に還流撹拌を６時間行った。トルエンを除去することによって、フェノールノボラック型エポキシ樹脂の５０モル％のエポキシ基がアクリル基に変性した部分アクリル変性フェノールノボラック型エポキシ樹脂（誘電率９）を得た。 In addition, the partial acrylic modified phenol novolac type epoxy resins in Tables 1 and 2 were prepared by the following method.
That is, 190 g of phenol novolac type epoxy resin (manufactured by DIC, “N-770”) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to this solution to obtain a uniform solution. After 35 g of acrylic acid was added dropwise to the obtained solution under reflux stirring over 2 hours, the mixture was further stirred under reflux for 6 hours. By removing toluene, a partially acrylic-modified phenol novolac epoxy resin (dielectric constant 9) in which 50 mol% of the epoxy group of the phenol novolac epoxy resin was modified to an acrylic group was obtained.
即ち、フェノールノボラック型エポキシ樹脂（ＤＩＣ社製、「Ｎ－７７０」）１９０ｇをトルエン５００ｍＬに溶解させ、この溶液にトリフェニルホスフィン０．１ｇを加え、均一な溶液とした。得られた溶液にアクリル酸３５ｇを還流撹拌下にて２時間かけて滴下した後、更に還流撹拌を６時間行った。トルエンを除去することによって、フェノールノボラック型エポキシ樹脂の５０モル％のエポキシ基がアクリル基に変性した部分アクリル変性フェノールノボラック型エポキシ樹脂（誘電率９）を得た。 In addition, the partial acrylic modified phenol novolac type epoxy resins in Tables 1 and 2 were prepared by the following method.
That is, 190 g of phenol novolac type epoxy resin (manufactured by DIC, “N-770”) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to this solution to obtain a uniform solution. After 35 g of acrylic acid was added dropwise to the obtained solution under reflux stirring over 2 hours, the mixture was further stirred under reflux for 6 hours. By removing toluene, a partially acrylic-modified phenol novolac epoxy resin (dielectric constant 9) in which 50 mol% of the epoxy group of the phenol novolac epoxy resin was modified to an acrylic group was obtained.
＜評価＞
実施例及び比較例で得られた各液晶滴下工法用シール剤について以下の評価を行った。結果を表１、２に示した。 <Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal dropping methods obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
実施例及び比較例で得られた各液晶滴下工法用シール剤について以下の評価を行った。結果を表１、２に示した。 <Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal dropping methods obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
（光硬化性）
実施例及び比較例で得られた各液晶滴下工法用シール剤をガラス基板上に約５μｍ塗布し、その基板に同サイズのガラス基板を重ね合わせ、次に、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の光を１０秒照射した。なお、照射装置とガラス基板との間に３８０ｎｍ以下の波長をカットする基板を挿入した。赤外分光装置（ＢＩＯＲＡＤ社製、「ＦＴＳ３０００」）を用い、アクリロイル基由来ピークの光照射前後での変化量を測定することで光硬化性の評価を行った。光照射後のアクリロイル基由来のピークの減少率が９３％以上であった場合を「◎」、８５％以上９３％未満であった場合を「○」、７５％以上８５％未満であった場合を「△」、７５％未満であった場合を「×」として光硬化性を評価した。 (Photo-curing)
About 5 μm of each liquid crystal dropping method sealing agent obtained in Examples and Comparative Examples was applied on a glass substrate, a glass substrate of the same size was superimposed on the substrate, and then 100 mW / cm 2 using a metal halide lamp. Was irradiated for 10 seconds. A substrate that cuts a wavelength of 380 nm or less was inserted between the irradiation device and the glass substrate. Photocurability was evaluated by measuring the amount of change in the acryloyl group-derived peak before and after light irradiation using an infrared spectroscope (BIORAD, “FTS3000”). When the rate of decrease in the peak derived from the acryloyl group after light irradiation is 93% or more, “「 ”, when it is 85% or more and less than 93%,“ ◯ ”, when it is 75% or more and less than 85% Was evaluated as “Δ”, and the case where it was less than 75% was evaluated as “×”.
実施例及び比較例で得られた各液晶滴下工法用シール剤をガラス基板上に約５μｍ塗布し、その基板に同サイズのガラス基板を重ね合わせ、次に、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の光を１０秒照射した。なお、照射装置とガラス基板との間に３８０ｎｍ以下の波長をカットする基板を挿入した。赤外分光装置（ＢＩＯＲＡＤ社製、「ＦＴＳ３０００」）を用い、アクリロイル基由来ピークの光照射前後での変化量を測定することで光硬化性の評価を行った。光照射後のアクリロイル基由来のピークの減少率が９３％以上であった場合を「◎」、８５％以上９３％未満であった場合を「○」、７５％以上８５％未満であった場合を「△」、７５％未満であった場合を「×」として光硬化性を評価した。 (Photo-curing)
About 5 μm of each liquid crystal dropping method sealing agent obtained in Examples and Comparative Examples was applied on a glass substrate, a glass substrate of the same size was superimposed on the substrate, and then 100 mW / cm 2 using a metal halide lamp. Was irradiated for 10 seconds. A substrate that cuts a wavelength of 380 nm or less was inserted between the irradiation device and the glass substrate. Photocurability was evaluated by measuring the amount of change in the acryloyl group-derived peak before and after light irradiation using an infrared spectroscope (BIORAD, “FTS3000”). When the rate of decrease in the peak derived from the acryloyl group after light irradiation is 93% or more, “「 ”, when it is 85% or more and less than 93%,“ ◯ ”, when it is 75% or more and less than 85% Was evaluated as “Δ”, and the case where it was less than 75% was evaluated as “×”.
（液晶汚染性）
実施例及び比較例で得られた各液晶滴下工法用シール剤１００重量部にスペーサ微粒子（積水化学工業社製、「ミクロパールＳＩ－Ｈ０５０」）１重量部を分散させ、２枚のラビング済み配向膜及び透明電極付き基板の一方にシール剤の線幅が１ｍｍになるようにディスペンサーで塗布した。続いて液晶（チッソ社製、「ＪＣ－５００４ＬＡ」）の微小滴を透明電極付き基板のシール剤の枠内全面に滴下塗布し、すぐにもう一方の透明電極付き基板を貼り合わせ、シール剤部分にメタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線を３０秒照射してシール剤を硬化させ、更に、１２０℃で１時間加熱して液晶表示素子を得た。
得られた液晶表示素子について、作製直後、シール剤付近の液晶配向乱れを光学顕微鏡観察によって確認した。液晶配向乱れは表示部の色むらより判断しており、色むらの程度に応じて、色むらが全くなかった場合を「◎」、色むらが微かにあった場合を「○」、色むらが少しあった場合を「△」、色むらがかなりあった場合を「×」として液晶汚染性を評価した。
なお、評価が「◎」、「○」の液晶表示素子は実用に全く問題のないレベルであり、「△」は液晶表示素子の表示設計によって問題になる可能性があるレベルであり、「×」は実用に耐えないレベルである。 (Liquid crystal contamination)
1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of each liquid crystal dropping method sealant obtained in the examples and comparative examples, and two rubbed orientations are obtained. It applied with a dispenser so that the line width of a sealing agent might be set to 1 mm to one of a film | membrane and a board | substrate with a transparent electrode. Subsequently, liquid crystal (Chisso, “JC-5004LA”) microdrops are applied to the entire surface of the sealant frame of the substrate with the transparent electrode, and the other substrate with the transparent electrode is immediately bonded to the sealant part. A metal halide lamp was used to irradiate 100 mW / cm 2 of ultraviolet rays for 30 seconds to cure the sealant, and further heated at 120 ° C. for 1 hour to obtain a liquid crystal display element.
About the obtained liquid crystal display element, immediately after preparation, liquid crystal alignment disorder near the sealant was confirmed by observation with an optical microscope. The liquid crystal alignment disorder is judged from the color unevenness of the display part. Depending on the degree of the color unevenness, “◎” indicates that there is no color unevenness, “○” indicates that the color unevenness is slight, and “color unevenness”. The liquid crystal contamination property was evaluated as “△” when there was a slight amount of color, and “X” when there was considerable color unevenness.
In addition, the liquid crystal display elements with the evaluations “◎” and “O” are at a level where there is no problem in practical use, and “Δ” is a level at which the display design of the liquid crystal display element may cause a problem. "Is a level that can not be put into practical use.
実施例及び比較例で得られた各液晶滴下工法用シール剤１００重量部にスペーサ微粒子（積水化学工業社製、「ミクロパールＳＩ－Ｈ０５０」）１重量部を分散させ、２枚のラビング済み配向膜及び透明電極付き基板の一方にシール剤の線幅が１ｍｍになるようにディスペンサーで塗布した。続いて液晶（チッソ社製、「ＪＣ－５００４ＬＡ」）の微小滴を透明電極付き基板のシール剤の枠内全面に滴下塗布し、すぐにもう一方の透明電極付き基板を貼り合わせ、シール剤部分にメタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線を３０秒照射してシール剤を硬化させ、更に、１２０℃で１時間加熱して液晶表示素子を得た。
得られた液晶表示素子について、作製直後、シール剤付近の液晶配向乱れを光学顕微鏡観察によって確認した。液晶配向乱れは表示部の色むらより判断しており、色むらの程度に応じて、色むらが全くなかった場合を「◎」、色むらが微かにあった場合を「○」、色むらが少しあった場合を「△」、色むらがかなりあった場合を「×」として液晶汚染性を評価した。
なお、評価が「◎」、「○」の液晶表示素子は実用に全く問題のないレベルであり、「△」は液晶表示素子の表示設計によって問題になる可能性があるレベルであり、「×」は実用に耐えないレベルである。 (Liquid crystal contamination)
1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of each liquid crystal dropping method sealant obtained in the examples and comparative examples, and two rubbed orientations are obtained. It applied with a dispenser so that the line width of a sealing agent might be set to 1 mm to one of a film | membrane and a board | substrate with a transparent electrode. Subsequently, liquid crystal (Chisso, “JC-5004LA”) microdrops are applied to the entire surface of the sealant frame of the substrate with the transparent electrode, and the other substrate with the transparent electrode is immediately bonded to the sealant part. A metal halide lamp was used to irradiate 100 mW / cm 2 of ultraviolet rays for 30 seconds to cure the sealant, and further heated at 120 ° C. for 1 hour to obtain a liquid crystal display element.
About the obtained liquid crystal display element, immediately after preparation, liquid crystal alignment disorder near the sealant was confirmed by observation with an optical microscope. The liquid crystal alignment disorder is judged from the color unevenness of the display part. Depending on the degree of the color unevenness, “◎” indicates that there is no color unevenness, “○” indicates that the color unevenness is slight, and “color unevenness”. The liquid crystal contamination property was evaluated as “△” when there was a slight amount of color, and “X” when there was considerable color unevenness.
In addition, the liquid crystal display elements with the evaluations “◎” and “O” are at a level where there is no problem in practical use, and “Δ” is a level at which the display design of the liquid crystal display element may cause a problem. "Is a level that can not be put into practical use.
本発明によれば、光硬化性に優れ、かつ、液晶汚染を抑制することができる液晶滴下工法用シール剤を提供することができる。また、本発明によれば、該液晶滴下工法用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods which can be excellent in photocurability and can suppress liquid crystal contamination can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods can be provided.
Claims (10)
- 硬化性樹脂と光ラジカル重合開始剤とを含有する液晶滴下工法用シール剤であって、
前記硬化性樹脂は、誘電率が１０以上であり、
前記光ラジカル重合開始剤は、極性基を有するオキシムエステル化合物である
ことを特徴とする液晶滴下工法用シール剤。 A liquid crystal dropping method sealing agent containing a curable resin and a radical photopolymerization initiator,
The curable resin has a dielectric constant of 10 or more,
The said radical photopolymerization initiator is an oxime ester compound which has a polar group, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. - 硬化性樹脂は、（メタ）アクリロイル基を有する化合物を含有することを特徴とする請求項１記載の液晶滴下工法用シール剤。 The sealing agent for liquid crystal dropping method according to claim 1, wherein the curable resin contains a compound having a (meth) acryloyl group.
- （メタ）アクリロイル基を有する化合物としてエポキシ（メタ）アクリレート及び／又は部分（メタ）アクリル変性エポキシ樹脂を含有することを特徴とする請求項２記載の液晶滴下工法用シール剤。 The epoxy compound (meth) acrylate and / or a partial (meth) acryl-modified epoxy resin as a compound having a (meth) acryloyl group is contained.
- （メタ）アクリロイル基を有する化合物としてエポキシ（メタ）アクリレートを含有することを特徴とする請求項３記載の液晶滴下工法用シール剤。 The epoxy compound (meth) acrylate is contained as a compound having a (meth) acryloyl group, The sealing agent for liquid crystal dropping method according to claim 3.
- 極性基を有するオキシムエステル化合物の極性基は、－ＯＨ基、－ＣＯＯＨ基、－ＳＨ基、－ＣＯＮＨ２基、及び、－ＮＨ２基からなる群より選択される少なくとも一種であることを特徴とする請求項１、２、３又は４記載の液晶滴下工法用シール剤。 The polar group of the oxime ester compound having a polar group is at least one selected from the group consisting of —OH group, —COOH group, —SH group, —CONH 2 group, and —NH 2 group. The sealing agent for liquid crystal dropping methods according to claim 1, 2, 3, or 4.
- 極性基を有するオキシムエステル化合物は、下記式（１）で表される化合物であることを特徴とする請求項５記載の液晶滴下工法用シール剤。
- 増感剤を含有することを特徴とする請求項１、２、３、４、５又は６記載の液晶滴下工法用シール剤。 A sensitizer is contained, The sealing agent for liquid crystal dropping methods according to claim 1, 2, 3, 4, 5 or 6.
- 遮光剤を含有することを特徴とする請求項１、２、３、４、５、６又は７記載の液晶滴下工法用シール剤。 The light-shielding agent is contained, The sealing agent for liquid crystal dropping methods of Claim 1, 2, 3, 4, 5, 6 or 7 characterized by the above-mentioned.
- 請求項１、２、３、４、５、６、７又は８記載の液晶滴下工法用シール剤と導電性微粒子とを含有することを特徴とする上下導通材料。 A vertical conduction material comprising the sealing agent for a liquid crystal dropping method according to claim 1, 2, 3, 4, 5, 6, 7 or 8, and conductive fine particles.
- 請求項１、２、３、４、５、６、７若しくは８記載の液晶滴下工法用シール剤又は請求項９記載の上下導通材料を用いてなることを特徴とする液晶表示素子。 A liquid crystal display element comprising the sealing agent for liquid crystal dropping method according to claim 1, 2, 3, 4, 5, 6, 7 or 8, or the vertical conduction material according to claim 9.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020167007211A KR20160137944A (en) | 2014-03-31 | 2015-03-27 | Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element |
| CN201580003348.9A CN105849632A (en) | 2014-03-31 | 2015-03-27 | Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element |
| JP2015518702A JP6408983B2 (en) | 2014-03-31 | 2015-03-27 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
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|---|---|---|---|
| JP2014074800 | 2014-03-31 | ||
| JP2014-074800 | 2014-03-31 |
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| WO2015152030A1 true WO2015152030A1 (en) | 2015-10-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2015/059565 WO2015152030A1 (en) | 2014-03-31 | 2015-03-27 | Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6408983B2 (en) |
| KR (1) | KR20160137944A (en) |
| CN (1) | CN105849632A (en) |
| TW (1) | TW201546151A (en) |
| WO (1) | WO2015152030A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017061255A1 (en) * | 2015-10-09 | 2017-04-13 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
| WO2017130786A1 (en) * | 2016-01-26 | 2017-08-03 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
| JP2017142316A (en) * | 2016-02-09 | 2017-08-17 | 三菱電機株式会社 | Method for manufacturing liquid crystal panel |
| WO2021177316A1 (en) * | 2020-03-03 | 2021-09-10 | 積水化学工業株式会社 | Curable resin composition, sealing agent for display elements, sealing agent for liquid crystal display elements, vertically conductive material, display element, adhesive for electronic components, and electronic component |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013146748A1 (en) * | 2012-03-30 | 2013-10-03 | 積水化学工業株式会社 | Sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
| JP5337294B1 (en) * | 2012-12-03 | 2013-11-06 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
| JP5337318B1 (en) * | 2012-11-22 | 2013-11-06 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
| JP2013228716A (en) * | 2012-03-30 | 2013-11-07 | Sekisui Chem Co Ltd | Sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
| JP5340503B1 (en) * | 2012-05-16 | 2013-11-13 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
| WO2014136667A1 (en) * | 2013-03-06 | 2014-09-12 | 積水化学工業株式会社 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3583326B2 (en) | 1999-11-01 | 2004-11-04 | 協立化学産業株式会社 | Sealant for dripping method of LCD panel |
| WO2002092718A1 (en) | 2001-05-16 | 2002-11-21 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| JP5778038B2 (en) | 2010-06-28 | 2015-09-16 | 株式会社Adeka | Curable resin composition |
| JP5238909B2 (en) * | 2011-04-05 | 2013-07-17 | 積水化学工業株式会社 | Light-shielding sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
-
2015
- 2015-03-27 CN CN201580003348.9A patent/CN105849632A/en active Pending
- 2015-03-27 KR KR1020167007211A patent/KR20160137944A/en not_active Application Discontinuation
- 2015-03-27 JP JP2015518702A patent/JP6408983B2/en active Active
- 2015-03-27 WO PCT/JP2015/059565 patent/WO2015152030A1/en active Application Filing
- 2015-03-30 TW TW104110216A patent/TW201546151A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013146748A1 (en) * | 2012-03-30 | 2013-10-03 | 積水化学工業株式会社 | Sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
| JP2013228716A (en) * | 2012-03-30 | 2013-11-07 | Sekisui Chem Co Ltd | Sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
| JP5340503B1 (en) * | 2012-05-16 | 2013-11-13 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
| JP5337318B1 (en) * | 2012-11-22 | 2013-11-06 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
| JP5337294B1 (en) * | 2012-12-03 | 2013-11-06 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
| WO2014136667A1 (en) * | 2013-03-06 | 2014-09-12 | 積水化学工業株式会社 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6126756B1 (en) * | 2015-10-09 | 2017-05-10 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| WO2017061255A1 (en) * | 2015-10-09 | 2017-04-13 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
| CN107250904A (en) * | 2015-10-09 | 2017-10-13 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, up and down conductive material and liquid crystal display cells |
| TWI707945B (en) * | 2015-10-09 | 2020-10-21 | 日商積水化學工業股份有限公司 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN107710060B (en) * | 2016-01-26 | 2021-11-12 | 积水化学工业株式会社 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| WO2017130786A1 (en) * | 2016-01-26 | 2017-08-03 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
| CN107710060A (en) * | 2016-01-26 | 2018-02-16 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells |
| JPWO2017130786A1 (en) * | 2016-01-26 | 2018-11-15 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| JP7048314B2 (en) | 2016-01-26 | 2022-04-05 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| JP2017142316A (en) * | 2016-02-09 | 2017-08-17 | 三菱電機株式会社 | Method for manufacturing liquid crystal panel |
| JPWO2021177316A1 (en) * | 2020-03-03 | 2021-09-10 | ||
| WO2021177316A1 (en) * | 2020-03-03 | 2021-09-10 | 積水化学工業株式会社 | Curable resin composition, sealing agent for display elements, sealing agent for liquid crystal display elements, vertically conductive material, display element, adhesive for electronic components, and electronic component |
| JP7084550B2 (en) | 2020-03-03 | 2022-06-14 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2015152030A1 (en) | 2017-04-13 |
| TW201546151A (en) | 2015-12-16 |
| JP6408983B2 (en) | 2018-10-17 |
| KR20160137944A (en) | 2016-12-02 |
| CN105849632A (en) | 2016-08-10 |
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