CN103026292A - Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element - Google Patents

Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element Download PDF

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CN103026292A
CN103026292A CN2012800021670A CN201280002167A CN103026292A CN 103026292 A CN103026292 A CN 103026292A CN 2012800021670 A CN2012800021670 A CN 2012800021670A CN 201280002167 A CN201280002167 A CN 201280002167A CN 103026292 A CN103026292 A CN 103026292A
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liquid crystal
methyl
crystal display
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display element
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CN103026292B (en
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新井启己
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • 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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)

Abstract

The purpose of the present invention is to provide: a light-shielding sealing agent for a liquid crystal display element, which can exhibit excellent adhesion strength to a substrate even after being exposed to a high-temperature and high-humidity environment; and a top-to-bottom conductive material and a liquid crystal display element, each of which is produced using the light-shielding sealing agent for a liquid crystal display element. The present invention is a light-shielding sealing agent for a liquid crystal display element which is a light-shielding sealing agent for use in a liquid crystal dropping process, comprising a curable resin that contains a curable compound having an unsaturated double bond, a radical polymerization initiator and a light-shielding agent, wherein the curable resin has a hydrogen-binding functional group value of 0.5*10-3 to 3.0*10-3 mol/g and titanium black is contained as the light-shielding agent.

Description

Used for liquid crystal display element shading sealant, up and down conductive material and liquid crystal display cells
Technical field
Even the object of the present invention is to provide a kind of in being exposed to hot and humid environment after at also very excellent used for liquid crystal display element shading sealant aspect the bonding strength of substrate.In addition, the invention still further relates to up and down conductive material and the liquid crystal display cells that uses this used for liquid crystal display element shading sealant manufacturing.
Background technology
In the past, the liquid crystal display cells such as liquid crystal display are to utilize the following technique made that is known as the vacuum injection mode, namely, 2 transparency carriers with electrode are separated the interval of regulation and make them relative, to form the unit with the sealant encapsulation around it, in the unit, inject liquid crystal from being located at its a part of liquid crystal injecting port, this liquid crystal injecting port is sealed with sealant or sealing compound.
In the vacuum injection mode, at first,, under 60～100 ℃, carry out prebake conditions and make solvent seasoning in the sealant in 2 seal patterns that are provided with liquid crystal injecting port that used the Thermocurable sealant with arbitrary formation in the transparency carrier of electrode by serigraphy.Then, folder makes 2 plate bases relatively and aims at and fit across distance piece, under 110～220 ℃, carry out 10～90 minutes hot pressing, behind near the gap the adjustment sealing, in baking oven, 110～220 ℃ of lower heating 10～120 minutes sealant is formally solidified.Then, inject liquid crystal from liquid crystal injecting port, use at last sealing compound that liquid crystal injecting port is sealed, produce liquid crystal display cells.
But, in recent years, from shortening the productive temp time, using the optimized viewpoint of amount of liquid crystal to consider, the manufacture method of the liquid crystal display cells such as liquid crystal display becomes following the being known as mode under the liquid crystal drop of technique of dripping from above-mentioned vacuum injection mode just gradually, that is, used the heat-curing resin such as light-cured resins such as containing acryl resin and optical free radical polymerization initiator and epoxy resin and thermal curing agents, by light, heat and the sealant that consists of with the resin combination of curing type.
In the mode, at first, form seal pattern in 2 with a slice in the substrate of electrode under the liquid crystal drop.Then, under the uncured state of sealant, the tiny droplets of liquid crystal whole face in the frame of substrate is dripped, the other substrate of stack under vacuum returns to the curing (interim curing process) of the sealing irradiation ultraviolet radiation being carried out behind the normal pressure light-cured resin.Thereafter, liquid crystal display cells is made in heating and carry out the curing of heat-curing resin.
But in the modern times that the various mobile apparatus with liquid crystal panel such as mobile phone, portable game machine have been popularized, the miniaturization of device is the purpose of being pursued most.As the gimmick of miniaturization, can enumerate the narrow frame of liquid crystal display part, for example can carry out the operation of position configuration under black matrix with sealing.
But, because sealant in the past is transparent or milky, even therefore originally should suppress the black matrix of light leak, also can't block the light through sealant, thereby have the problem that reduces contrast.
Therefore, can consider to make it to have the method for light-proofness by in sealant, adding opacifier etc.For example, disclose in the patent documentation 1～3 and contained the black based material of titanium, carbon black based material or other light-proofness particulate as the sealant of light-proofness composition.Particularly, in the middle of these opacifiers, as opacifier contained in the sealant, the black based material of the titanium that preferred insulativity is high.
But, contain the black sealant of titanium and in a single day be exposed in the hot and humid environment, the problem that reduces significantly with regard to the bonding strength that has thereafter.
Patent documentation
Patent documentation 1: TOHKEMY 2006-099027 communique
Patent documentation 2: TOHKEMY 2005-292801 communique
Patent documentation 3: the international pamphlet that discloses No. 09/128470
Summary of the invention
Invent problem to be solved
The object of the invention is to, a kind of used for liquid crystal display element shading sealant is provided, though its in being exposed to hot and humid environment after, also very excellent aspect the bonding strength of substrate.In addition, the present invention also aims to, the up and down conductive material and the liquid crystal display cells that use this used for liquid crystal display element shading sealant manufacturing are provided.
Solve the required means of problem
The invention provides a kind of used for liquid crystal display element shading sealant, it is to contain: comprise the liquid crystal dripping process shading sealant of curable resin, radical polymerization initiator and the opacifier of the curing compound with unsaturated double-bond, the hydrogen bond functional group value of above-mentioned curable resin is 0.5 * 10 -3～3.0 * 10 -3Mol/g contains titanium black in above-mentioned opacifier.
Below the present invention is described in detail.
The inventor finds: in containing the black used for liquid crystal display element shading sealant of titanium, be 0.5 * 10 in the hydrogen bond functional group value of the curable resin that comprises the curing compound with unsaturated double-bond -3～3.0 * 10 -3In the situation of mol/g, can suppress the reduction of the bonding strength after the hot and humid processing, thereby finish the present invention.
It is black in opacifier that used for liquid crystal display element shading sealant of the present invention (below be also referred to as shading sealant of the present invention) contains titanium.
Titanium is black to be following material, that is, compare with the average transmittance to the light of wavelength 300～800nm, near the ultraviolet range, particularly the optical transmission rate to wavelength 370～450nm is higher.That is to say, above-mentioned titanium is black to be the light of the wavelength by covering fully the visible region and shading sealant of the present invention is given the opacifier of light-proofness, is the opacifier with character of the light generation transmission that makes near the wavelength the ultraviolet range on the other hand.Thereby, make the wavelength that the black transmissivity of above-mentioned titanium uprises (370～450nm) light comes the material of initiation reaction as optical free radical polymerization initiator described later, thereby can further increase the photo-curable of shading sealant of the present invention by using to utilize.In addition, on the other hand, as contained opacifier in the shading sealant of the present invention, the preferred high material of insulativity, as the high opacifier of insulativity, titanium is black also very suitable.
With regard to above-mentioned titanium was black, the optical concentration of per 1 μ m (OD value) was preferably more than 3, more preferably more than 4.The light-proofness that above-mentioned titanium is black is more high better, though in the black OD value of above-mentioned titanium, there is not the preferred upper limit, be generally below 5.
Do not carry out the surface-treated material and can bring into play sufficient effect yet even above-mentioned titanium is black, yet also can use the surface was processed with organic principles such as coupling agents, or black with the covered titanium of the inorganic constituents such as monox, titanium dioxide, germanium oxide, aluminium oxide, zirconia, the magnesium oxide surface-treated titanium that carried out such as black.Wherein, consider from the aspect of further raising insulativity, the titanium of preferably processing with organic principle is black.
In addition, use the liquid crystal display cells of shading sealant of the present invention manufacturing because the shading sealant has sufficient light-proofness, therefore do not have spilling of light, have high-contrast, can realize having the liquid crystal display cells of excellent display quality of image.
Above-mentioned titanium is black to be not particularly limited, yet as concrete commercially available product, such as enumerating " 12S ", " 13M ", " 13M-C ", " 13R-N " (being Mitsubishi Materials company system), " TilackD " (red fringe changes into company's system) etc.
Be limited to 13m under the specific surface area that above-mentioned titanium is black preferred 2/ g is limited to 30m on preferred 2/ g is limited to 15m under preferred 2/ g is limited to 25m on preferred 2/ g.
The preferred lower of the specific insulation that above-mentioned titanium is black is limited to 0.5 Ω cm, is limited to 3 Ω cm on preferably, is limited to 1 Ω cm under preferred, is limited to 2.5 Ω cm on preferred.
In the shading sealant of the present invention, the primary particle size of above-mentioned opacifier is as long as for below the distance between the substrate of liquid crystal display cells, just be not particularly limited, yet preferably is limited to 1nm down, is limited to 5 μ m on preferably.If the primary particle size of above-mentioned opacifier is less than 1nm, then the viscosity of the shading sealant of gained or thixotropy will significantly increase, thereby have the situation of operability variation.If the primary particle size of above-mentioned opacifier surpasses 5 μ m, then can rewarding shading sealant the situation of coating variation on the substrate.Be limited to 5nm under the primary particle size of above-mentioned opacifier preferred, be limited to 200nm on preferred, further preferably be limited to 10nm down, further be limited to 100nm on preferably.
The content of the above-mentioned opacifier in the shading sealant of the present invention is not particularly limited, yet preferred lower is limited to 5 % by weight, is limited to 80 % by weight on preferably.If the content of above-mentioned opacifier less than 5 % by weight, then has the situation that can't obtain sufficient light-proofness.If the content of above-mentioned opacifier surpasses 80 % by weight, then can rewarding shading sealant and the adaptation of substrate or the strength decreased after the curing, the perhaps situation of illustrative reduction.Be limited to 10 % by weight under the content of above-mentioned opacifier preferred, be limited to 70 % by weight on preferred, further preferably be limited to 30 % by weight down, further be limited to 60 % by weight on preferably.
Shading sealant of the present invention contains curable resin.
Above-mentioned curable resin comprises the curing compound with unsaturated double-bond.Namely, shading sealant of the present invention is curing compound and the radical polymerization initiator described later that has unsaturated double-bond by containing, thereby utilize light and/or heat to come the shading sealant of initiation reaction, specifically, can make it to solidify by carrying out ultraviolet ray irradiation and/or heating.
The hydrogen bond functional group value of above-mentioned curable resin is 0.5 * 10 -3～3.0 * 10 -3Mol/g.If the hydrogen bond functional group of above-mentioned curable resin value is less than 0.5 * 10 -3Mol/g, then easily stripping in the liquid crystal of resinous principle produces liquid crystal pollution.If the hydrogen bond functional group of above-mentioned curable resin value surpasses 3.0 * 10 -3Mol/g, then the bonding strength after the hot and humid processing of the shading sealant of gained reduces significantly.Be limited to 0.7 * 10 under the hydrogen bond functional group value of above-mentioned curable resin preferred - 3Mol/g is limited to 2.5 * 10 on preferred -3Mol/g is limited to 2.0 * 10 under preferred -3Mol/g.
In addition, in this instructions the hydrogen bond functional group value of said curable resin in the situation that curable resin is made of the value of utilizing following formula to calculate a kind of compound.
The hydrogen bond functional group value of curable resin=(consisting of the hydrogen bond functional group number in 1 molecule of compound)/(consisting of the molecular weight of compound)
In addition, in the situation that above-mentioned curable resin is made of the potpourri of various kinds of resin, the hydrogen bond functional group value of curable resin is calculated as the hydrogen bond functional group value of per unit weight.For example, in the situation of above-mentioned curable resin by Compound C (the value γ mol/g of the hydrogen bond functional group) formation of the compd A (hydrogen bond functional group is worth α mol/g) of ag, the compd B of bg (the value β mol/g of hydrogen bond functional group), cg, the hydrogen bond functional group value of curable resin is expressed from the next.
The hydrogen bond functional group value of curable resin=(a * α+b * β+c * γ)/(a+b+c)
Above-mentioned so-called hydrogen bond functional group so long as have the functional group of hydrogen bond or residue etc., just is not particularly limited, for example can enumerate to have-the OH base ,-NH 2Base ,-NHR base (R represents aromatic series or aliphatic hydrocarbon and their derivant) ,-the COOH base ,-CONH 2Base ,-group of the functional groups such as NHOH base; Or in molecule, have-the NHCO-key ,-the NH-key ,-the CONHCO-key ,-group of the residues such as NH-NH-key etc.
As above-mentioned compound with hydrogen bond functional group, hydrogen bond functional group value both can be in the above-mentioned scope individually, also can also be by being adjusted in the above-mentioned scope mixing more than 2 kinds.That is, as long as the mean value of the hydrogen bond functional group value of employed compound with hydrogen bond functional group is in the above-mentioned scope.
Above-mentioned curing compound with unsaturated double-bond does not limit; have vinyl such as enumerating, the resin of allyl, cinnamoyl, cinnamylidene, dimaleoyl imino, (methyl) acryloxy etc.; wherein; consider from reactive aspect; the resin that preferably has (methyl) acryloxy more preferably has the resin of 2～3 (methyl) acryloxies in molecule.
In addition, said above-mentioned " (methyl) acryloxy " refers to " acryloxy or methacryloxy " in this instructions.
Above-mentioned resin with (methyl) acryloxy is not particularly limited, such as can enumerate ester compounds by compound with hydroxyl and the reaction of (methyl) acrylic acid get, by (methyl) acrylic acid and epoxy compound being reacted get complete (methyl) acrylic modified epoxy resin, by making (methyl) acrylic acid derivative with hydroxyl and urethanes (methyl) acrylate that isocyanate reaction gets etc.
In addition, said above-mentioned " (methyl) acrylic acid " refers to " acrylic or methacrylic acid " in this instructions, and above-mentioned what is called " (methyl) acrylate " refers to " acrylate or methacrylate ".In addition, said above-mentioned " fully (methyl) acrylic modified epoxy resin " is the compound that expression makes the whole epoxy radicals in the epoxy resin get with the reaction of (methyl) acrylic acid in this instructions.
It is above-mentioned by the compound with hydroxyl and the ester compounds that the reaction of (methyl) acrylic acid gets are not particularly limited, compound as simple function, for example can enumerate (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) n-stearyla crylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, methoxyl ethylene glycol (methyl) acrylate, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid ethyl carbitol ester, (methyl) acrylic acid phenoxy ethyl, phenoxy group diglycol (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, (methyl) acrylic acid 2,2, the 2-trifluoro ethyl ester, (methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester, (methyl) acrylic acid 1H, 1H, 5H-octafluoro pentyl ester, (methyl) acrylic acid imide ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid n-octyl, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, the different myristin of (methyl) acrylic acid, (methyl) acrylic acid 2-butoxyethyl, (methyl) acrylic acid 2-phenoxy ethyl, (methyl) acrylic acid dicyclopentenyl ester, (methyl) isodecyl acrylate, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid dimethylamino ethyl ester, 2-(methyl) acryloxy ethyl succinic acid, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy ethyl 2-hydroxypropyl phthalic ester, (methyl) glycidyl acrylate, 2-(methyl) acryloxy ethyl phosphonic acid ester etc.
In addition, compound as 2 officials energy, for example can enumerate 1,4-butylene glycol two (methyl) acrylate, 1,3-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, 2-normal-butyl-2-ethyl-1, ammediol two (methyl) acrylate, dipropyl glycol two (methyl) acrylate, 3 third glycol two (methyl) acrylate, polypropylene glycol (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diglycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, epoxypropane addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxirane modification isocyanuric acid two (methyl) acrylate, 2-hydroxyl-3-(methyl) acryloxy propyl group (methyl) acrylate, carbonic ester glycol two (methyl) acrylate, PTMEG two (methyl) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate, tristane dimethanol diacrylate etc.
In addition, as the above compound of 3 officials energy, for example can enumerate pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, epoxypropane addition trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, pentaerythrite four (methyl) acrylate, glycerine three (methyl) acrylate, epoxypropane addition glycerine three (methyl) acrylate, three (methyl) acryloxy ethyl phosphonic acid ester etc.
Complete (methyl) acrylic modified epoxy resin that the reaction of (methyl) acrylic acid above-mentioned by making and epoxy compound get is not particularly limited, such as can enumerate epoxy resin and (methyl) acrylic acid reacted in the presence of base catalyst according to well-established law and must resin etc.
Become for the synthesis of the above-mentioned fully epoxy compound of the raw material of (methyl) acrylic modified epoxy resin and be not particularly limited, for example can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2,2 '-diallyl bisphenol type epoxy resin, A Hydrogenated Bisphenol A type epoxy resin, epoxypropane addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether-type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol phenolic epoxy varnish, the bicyclopentadiene phenolic resin varnish type epoxy resin, the biphenyl phenolic resin varnish type epoxy resin, the naphthalene phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyols type epoxy resin, modified rubber type epoxy resin, glycidyl ester compounds etc.
As the commercially available resin in the middle of the above-mentioned bisphenol A type epoxy resin, such as enumerating Epikoat828EL, Epikoat1004 (all being Mitsubishi Chemical Ind's system), Epiclon850-S (DIC company system) etc.
As the commercially available resin in the middle of the above-mentioned bisphenol f type epoxy resin, such as enumerating Epikoat806, Epikoat4004 (all being Mitsubishi Chemical Ind's system) etc.
As the commercially available resin in the middle of the above-mentioned bisphenol-s epoxy resin, such as enumerating Epiclon EXA1514 (DIC company system) etc.
As above-mentioned 2, the commercially available resin in the middle of 2 '-diallyl bisphenol type epoxy resin is such as enumerating RE-810NM (Japanese chemical drug company system) etc.
As the commercially available resin in the middle of the above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as enumerating Epiclon EXA7015 (DIC company system) etc.
As the commercially available resin in the middle of the above-mentioned epoxypropane addition bisphenol A type epoxy resin, such as enumerating EP-4000S (ADEKA company system) etc.
As the commercially available resin in the middle of the above-mentioned resorcinol type epoxy resin, such as enumerating EX-201 (Nagasechemtex company system) etc.
As the commercially available resin in the middle of the above-mentioned biphenyl type epoxy resin, such as enumerating EpikoatYX-4000H (Mitsubishi Chemical Ind's system) etc.
As the commercially available resin in the middle of the above-mentioned thioether-type epoxy resin, such as enumerating YSLV-50TE (chemical company of Nippon Steel system) etc.
As the commercially available resin in the middle of the above-mentioned diphenyl ether type epoxy resin, such as enumerating YSLV-80DE (chemical company of Nippon Steel system) etc.
As the commercially available resin in the middle of the above-mentioned dicyclopentadiene-type epoxy resin, such as enumerating EP-4088S (ADEKA company system) etc.
As the commercially available resin in the middle of the above-mentioned naphthalene type epoxy resin, such as enumerating EpiclonHP4032, Epiclon EXA-4700 (all being DIC company system) etc.
As the commercially available resin in the middle of the above-mentioned phenol novolak type epoxy resin, such as enumerating Epiclon N-770 (DIC company system) etc.
As the commercially available resin in the middle of the above-mentioned o-cresol phenolic epoxy varnish, such as enumerating Epiclon N-670-EXP-S (DIC company system) etc.
As the commercially available resin in the middle of the above-mentioned bicyclopentadiene phenolic resin varnish type epoxy resin, such as enumerating Epiclon HP7200 (DIC company system) etc.
As the commercially available resin in the middle of the above-mentioned biphenyl phenolic resin varnish type epoxy resin, such as enumerating NC-3000P (Japanese chemical drug company system) etc.
As the commercially available resin in the middle of the above-mentioned naphthalene phenol novolak type epoxy resin, such as enumerating ESN-165S (chemical company of Nippon Steel system) etc.
As the commercially available resin in the middle of the above-mentioned glycidyl amine type epoxy resin, such as enumerating Epikoat630 (Mitsubishi Chemical Ind's system), Epiclon430 (DIC company system), TETRAD-X (gas chemical company of Mitsubishi system) etc.
As the commercially available resin in the middle of the abovementioned alkyl polyvalent alcohol type epoxy resin, such as enumerating ZX-1542 (chemical company of Nippon Steel system), Epiclon726 (DIC company system), Epolite80MFA (chemical company of common prosperity society system), Denacol EX-611 (Nagasechemtex company system) etc.
As the commercially available resin in the middle of the above-mentioned modified rubber type epoxy resin, such as enumerating YR-450, YR-207 (all being chemical company of Nippon Steel system), Epolead PB (Daicel company system) etc.
As the commercially available compound in the middle of the above-mentioned epihydric alcohol ester compound, such as enumerating Denacol EX-147 (Nagasechemtex company system) etc.
As other the commercially available resin in the middle of the above-mentioned epoxy resin, such as enumerating YDC-1312, YSLV-80XY, YSLV-90CR (all being chemical company of Nippon Steel system), XAC4151 (Asahi Kasei Corporation system), Epikoat1031, Epikoat1032 (all being Mitsubishi Chemical Ind's system), EXA-7120 (DIC company system), TEPIC (daily output chemical company system) etc.
For complete (methyl) acrylic modified epoxy resin that reaction gets for (methyl) acrylic acid above-mentioned by making and epoxy compound, specifically, for example can pass through resorcinol type epoxy resin (Nagasechemtex company system, " EX-201 ") 360 weight portions, p methoxy phenol 2 weight portions as polymerization inhibitor, triethylamine 2 weight portions as catalysts, and acrylic acid 210 weight portions when sending into air at 90 ℃ of lower return stirrings, make their reactions 5 hours, thereby can obtain complete acrylic acid modified resorcinol type epoxy resin.
As the commercially available resin in the middle of above-mentioned fully (methyl) acrylic modified epoxy resin, for example can enumerate EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (all being Daicel-Cytec company system), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all being Xin Zhong village chemical industrial company system), EpoxyEster M-600A, Epoxy Ester40EM, Epoxy Ester70PA, Epoxy Ester200PA, Epoxy Ester80MFA, Epoxy Ester3002M, Epoxy Ester3002A, Epoxy Ester1600A, Epoxy Ester3000M, Epoxy Ester3000A, Epoxy Ester200EA, EpoxyEster400EA (all being chemical company of common prosperity society system), Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all being Nagasechemtex company system) etc.
For by making for urethanes (methyl) acrylate that (methyl) acrylic acid derivative with hydroxyl and above-mentioned isocyanate reaction get, for example can be by the compound with 2 isocyanate group with respect to 1 equivalent, in the presence of the tin based compound of catalytic amount, make (methyl) acrylic acid derivative reaction with hydroxyl of 2 equivalents and obtain.
The isocyanates that becomes the raw material by making urethanes (methyl) acrylate that (methyl) acrylic acid derivative with hydroxyl and above-mentioned isocyanate reaction obtain is not particularly limited, for example can enumerate isophorone diisocyanate, 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-4,4 '-diisocyanate (MDI), hydrogenation MDI, polyethylene diphenylmethane MDI, 1, the 5-naphthalene diisocyanate, norbornene alkyl diisocyanate, the toluidine diisocyanate, Xylene Diisocyanate (XDI), hydrogenation XDI, lysinediisocyanate, triphenylmethane triisocyanate, tri o cresyl thiophosphate (isocyanate group phenyl) ester, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate etc.
In addition, as the isocyanates that becomes by the raw material that makes urethanes (methyl) acrylate that (methyl) acrylic acid derivative with hydroxyl and above-mentioned isocyanate reaction get, such as the chain elongation that also can use polyvalent alcohols such as utilizing ethylene glycol, glycerine, sorbierite, trimethylolpropane, (gathering) propylene glycol, carbonic ester glycol, PTMEG, polyester-diol, polycaprolactone glycol to obtain with the reaction of superfluous isocyanates isocyanate compound.
For becoming raw material by making urethanes (methyl) acrylate that (methyl) acrylic acid derivative with hydroxyl and above-mentioned isocyanate reaction get, (methyl) acrylic acid derivative with hydroxyl, be not particularly limited, for example can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, the commercially available product of (methyl) acrylic acid 2-hydroxyl butyl ester etc., ethylene glycol, propylene glycol, 1, ammediol, 1, the 3-butylene glycol, 1, the 4-butylene glycol, the list of the dibasic alcohol such as polyglycol (methyl) acrylate, trimethylolethane, trimethylolpropane, the list of the trihydroxy alcohols such as glycerine (methyl) acrylate or two (methyl) acrylate, epoxy (methyl) acrylate such as bisphenol type epoxy (methyl) acrylate etc.
For by making for urethanes (methyl) acrylate that (methyl) acrylic acid derivative with hydroxyl and above-mentioned isocyanate reaction get, can obtain by following operation specifically, namely, for example add trimethylolpropane 134 weight portions, BHT0.2 weight portion as polymerization inhibitor, dibutyl tin laurate 0.01 weight portion as catalysts, isophorone diisocyanate 666 weight portions, in 60 ℃ of lower return stirrings, make their reactions 2 hours, then add acrylic acid 2-hydroxy methacrylate 51 weight portions, when sending into air, at 90 ℃ of lower return stirrings, make their reactions 2 hours and get.
As the commercially available resin in the middle of above-mentioned urethanes (methyl) acrylate, for example can enumerate M-1100, M-1200, M-1210, M-1600 (all being East Asia Synesis Company system), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (all being Daicel-Cytec company system), Art-Resin UN-9000H, Art-Resin UN-9000A, Art-Resin UN-7100, Art-Resin UN-1255, Art-Resin UN-330, Art--Resin UN--3320HB, Art--Resin UN--1200TPK, Art--Resin SH-500B (all being industrial group's system on the root), 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 being Xin Zhong village chemical industrial company system), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I etc.
Above-mentioned curable resin can also contain other the resin such as resin with epoxy radicals except containing the curing compound with unsaturated double-bond.
Above-mentioned resin with epoxy radicals is not particularly limited, and becomes for the synthesis of the epoxy compound of the raw material of above-mentioned fully (methyl) acrylic modified epoxy resin or part (methyl) acrylic modified epoxy resin etc. such as enumerating.
In addition, said above-mentioned part (methyl) acrylic modified epoxy resin refers to have respectively the resin of epoxy radicals more than 1 and (methyl) acryloxy in this instructions in 1 molecule, and the epoxy radicals of a part that for example can be by making the resin with the epoxy radicals more than 2 obtains with the reaction of (methyl) acrylic acid.
Above-mentioned part (methyl) acrylic modified epoxy resin for example can obtain by epoxy resin and (methyl) acrylic acid are reacted in the presence of base catalyst according to well-established law.Specifically, for example phenol novolak type epoxy resin N-770 (DIC company system) 190g can be dissolved among the toluene 500mL, in this solution, add triphenylphosphine 0.1g, form uniform solution, in this solution behind the acrylic acid 35g that dripped with 2 hours under the return stirring, carry out again 6 hours return stirrings, then the epoxy radicals that obtains 50 % by mole by removing toluene is reacted the part acrylic acid modified phenol phenolic resin varnish type epoxy resin (in this situation, 50% part is by the propylene acidifying) that gets with (methyl) acrylic acid.
As the commercially available resin in the middle of above-mentioned part (methyl) acrylic modified epoxy resin, for example can enumerate UVACURE1561 (Daicel-Cytec company system).
In the middle of the above-mentioned resin with epoxy radicals, the resin (below be also referred to as the resin that only has epoxy radicals) that does not have (methyl) acryloxy as reactive functional groups and only have an epoxy radicals is owing to becoming the reason that causes liquid crystal pollution etc., therefore preferably do not cooperated, yet for the purpose that improves cementability, also can in the scope that liquid crystal pollution is not impacted, add.
For the content of the above-mentioned resin that only has an epoxy radicals, with respect to overall 100 weight portions of curable resin, be limited to 10 % by weight on preferred.If the content of the above-mentioned resin that only has an epoxy radicals surpasses 10 % by weight, then can rewarding used for liquid crystal display element shading sealant cause the situation of liquid crystal pollution.
In the situation that cooperates above-mentioned resin with (methyl) acryloxy and above-mentioned resin with epoxy radicals as above-mentioned curable resin, the ratio of preferred so that (methyl) acryloxy of above-mentioned curable resin and epoxy radicals with molar ratio computing reach 50: 50～95: 5 mode cooperates the resin with (methyl) acryloxy and the resin with epoxy radicals.If less than 50%, even then the free radical polymerization by radical polymerization initiator described later finishes, also can there be a lot of uncured epoxy resin compositions in the ratio of above-mentioned (methyl) acryloxy, thereby has the situation with liquid crystal pollution.If the ratio of above-mentioned (methyl) acryloxy surpasses 95%, then have the situation of the effect that can't obtain fully to improve bonding force.
Shading sealant of the present invention contains radical polymerization initiator.Liberty base polymerization initiator is to utilize the outside stimuluss such as ultraviolet ray irradiation, heating to produce the material of free radical, and used for liquid crystal display element shading sealant of the present invention contains the hot radical polymerization initiator that utilizes ultraviolet irradiation to produce the optical free radical polymerization initiator of free radical and/or utilize heating generation free radical.
Shading sealant of the present invention preferably contains the hot radical polymerization initiator.By making shading sealant of the present invention contain above-mentioned hot radical polymerization initiator, thereby in the liquid crystal display cells of made, even exist the position that does not shine light because deceiving matrix etc. to have hermetic unit, also can utilize heat that it is solidified reliably, the situation that therefore produces liquid crystal pollution becomes few.
The preferred lower limit of 10 hours half life temperatures of above-mentioned hot radical polymerization initiator is 50 ℃, and preferred upper limit is 90 ℃.If 10 hours half life temperatures of above-mentioned hot radical polymerization initiator are less than 50 ℃, the situation of bin stability variation that then can rewarding used for liquid crystal display element shading sealant.If 10 hours half life temperatures of above-mentioned hot radical polymerization initiator surpass 90 ℃, then in the curing of used for liquid crystal display element shading sealant of the present invention, need high temperature and long-time, the situation that exists the throughput rate of counter plate to impact.
In addition, said above-mentioned 10 hours half life temperatures refer in the presence of inactive gas in this instructions, and the concentration of hot radical polymerization initiator reaches the temperature of a half of the front concentration of reaction when carrying out 10 hours pyrolysis at a certain temperature.
Above-mentioned hot radical polymerization initiator is not particularly limited, and can enumerate azo-compound, organic peroxide etc.Wherein, be preferably the polymeric azo initiating agent that is consisted of by polymeric azo compound.
In addition, in this instructions said polymeric azo initiating agent refer to have azo group and generate free radical, molecular weight is the compound 300 or more, described free radical is the free radical that can make by heat above-mentioned curable resin curing.
In addition, because above-mentioned polymeric azo initiating agent usually also can decompose by irradiation and produce free radical, therefore also can be used as the optical free radical polymerization initiator and play a role.
The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiating agent is 1000, and preferred upper limit is 300,000.If the number-average molecular weight of above-mentioned polymeric azo initiating agent, then has the polymeric azo initiating agent less than 1000 liquid crystal is caused dysgenic situation.If the number-average molecular weight of above-mentioned polymeric azo initiating agent surpasses 300,000, then have the situation of the mixing difficult in the above-mentioned curable resin.The number-average molecular weight of above-mentioned polymeric azo initiating agent more preferably be limited to 5000 down, be limited to 100,000 on more preferably, further preferred lower limit is 10,000, further preferred upper limit is 90,000.
Above-mentioned polymeric azo initiating agent such as can enumerate have by azo group with the unit such as dimethyl silicone polymer or polyalkylene oxide in conjunction with a plurality of and the azo initiator of structure.
As with the unit such as polyalkylene oxide in conjunction with a plurality of and structure, the material that preferably has the polyethylene oxide structure.
As this kind polymeric azo initiating agent, for example can enumerate 4, the condensed polymer or 4 of 4 '-azo two (4-cyanopentanoic acid) and ployalkylene glycol, the condensed polymer of 4 '-azo two (4-cyanopentanoic acids) and the dimethyl silicone polymer with terminal amino group etc., specifically, such as enumerating VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all being and the pure pharmaceutical worker's industry of light company system) etc.
As above-mentioned polymeric azo initiating agent, can also use well in addition the polymeric azo compound of following general formula (I) expression of putting down in writing in TOHKEMY 2008-50572 communique, the TOHKEMY 2003-12784 communique.
In the formula (I), R 12, R 13, R 22And R 23The alkyl or the cyano group that represent independently of one another carbon number 1～10, a and b are 0～4 number independently of one another, A 11And A 12Macromolecular chain, Y 11And Y 12Be independently of one another-CO-O-,-O-CO-,-NH-CO-,-CO-NH-,-O-or-S-.
In the above-mentioned general formula (I), as with R 12, R 13, R 22And R 23The alkyl of the carbon number 1～10 of expression is such as enumerating methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, isobutyl, amyl group, isopentyl, tertiary pentyl, hexyl, cyclohexyl, cyclohexyl methyl, cyclohexyl ethyl, heptyl, different heptyl, uncle's heptyl, n-octyl, iso-octyl, uncle's octyl group, 2-ethylhexyl, n-nonyl, positive decyl etc.
In the above-mentioned general formula (I), with A 11And A 12The macromolecular chain of expression is not particularly limited, such as enumerating polyoxyethylene chain, polymethylene chain, polyether chain, polyester chain, polysiloxane chain, poly-(methyl) acrylate chains, polystyrene-vinyl acetate chain, polyamide chains, polyimide chain, polyurethane chain, polyureas chain, polypeptied chain etc.Wherein, preferred Y 11For-O-CO-, Y 12Be the compound of-CO-O-, since cheap and easy to manufacture especially, therefore more preferably with A 11And the macromolecular chain that A12 represents is polyether chain and polyester chain.
In the middle of the above-mentioned general formula (I), at A 11And A 12In the middle of the polymeric azo compound for polyether chain, easy, therefore more preferred with the compound molecular weight control good owing to dissolubility, polymerization initiator of following general formula (II) expression.
Figure BDA00002777154500151
In the formula (II), R 12, R 13, R 22, R 23, a and b be identical with above-mentioned general formula (I), R 11And R 21The alkyl that represents independently of one another carbon number 1～24, Z 11, Z 12, Z 21And Z 22The alkylidene that represents independently of one another carbon number 1～4, m, n, s and t are 0～1000 number independently of one another, and m+n sum, s+t sum are more than 2 independently of one another.
In the above-mentioned general formula (II), as with Z 11, Z 12, Z 21And Z 22The alkylidene of the carbon number 1～4 of expression for example can be enumerated methylene, 1,2-ethylidene, trimethylene, 1,2-propylidene, propylidene, isopropylidene, tetramethylene, butylidene, isobutylene, ethyl ethylidene, dimethyl ethylidene etc.
In addition, as with R 11And R 21The alkyl of the carbon number 1～24 of expression is such as enumerating methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, isobutyl, amyl group, isopentyl, tertiary pentyl, hexyl, cyclohexyl, cyclohexyl methyl, cyclohexyl ethyl, heptyl, different heptyl, uncle's heptyl, n-octyl, iso-octyl, uncle's octyl group, 2-ethylhexyl, n-nonyl, positive decyl, lauryl, stearyl, docosyl etc.Because reactive high, and preferably with R 11And R 21The alkyl of the carbon number 1～24 of expression is carbon number 1～4.
A with the polymeric azo compound of above-mentioned general formula (I) expression 11And A 12In the middle of the compound for polyester chain, the compound that represents with following general formula (III) is good owing to dissolubility, water tolerance is excellent, and is therefore preferred.
Figure BDA00002777154500161
In the formula (III), R 12, R 13, R 22, R 23, a and b be identical with above-mentioned general formula (I), Z 13And Z 23The alkylidene that represents independently of one another carbon number 1～18, R 31And R 41The alkyl that represents independently of one another hydrogen atom or carbon number 1～24, p and u are 1～1000 number independently of one another.
In the above-mentioned general formula (III), as with Z 13, Z 23The alkylidene of the carbon number 1～18 of expression, for example can enumerate methylene, 1,2-ethylidene, trimethylene, 1,2-propylidene, propylidene, isopropylidene, tetramethylene, butylidene, isobutylene, ethyl ethylidene, dimethyl ethylidene, pentamethylene, hexa-methylene, heptamethylene, eight methylene, 1,4-pentane two bases, decamethylene, 11 methylene, 1,4-undecane two bases, ten dimethylenes, 1,11-heptadecane two bases, 18 methylene etc.
In addition, as with R 31And R 41The alkyl of the carbon number 1～24 of expression for example can be enumerated as the R in the above-mentioned general formula (II) 11And R 21Illustrated alkyl.Because reactive high, and preferably with R 31And R 41The alkyl of the carbon number 1～24 of expression is carbon number 1～4.
In the above-mentioned general formula (III), since reactive high, and preferred p and u are 20～100.
Above-mentioned organic peroxide is not particularly limited, such as enumerating ketone peroxide, peroxy ketal, hydroperoxides, dialkyl peroxide, peroxyester, diacyl peroxide, peroxy dicarbonate etc.
The content of the above-mentioned hot radical polymerization initiator in the shading sealant of the present invention is not particularly limited, yet preferably is limited to down 0.1 weight portion with respect to above-mentioned curable resin 100 weight portions, is limited to 30 weight portions on preferred.If the content of above-mentioned hot radical polymerization initiator, then has the situation that the curing of the shading sealant of above-mentioned gained can not advance fully less than 0.1 weight portion.If the content of above-mentioned hot radical polymerization initiator surpasses 30 weight portions, then the viscosity of the used for liquid crystal display element shading sealant of gained uprises, thereby have coating operability etc. is caused dysgenic situation.Be limited to 0.5 weight portion under the content of above-mentioned hot radical polymerization initiator preferred, be limited to 10 weight portions on preferred.
Shading sealant of the present invention preferably contains the optical free radical polymerization initiator.Shading sealant of the present invention is owing to containing the black based material of titanium, therefore by containing above-mentioned optical free radical polymerization initiator, thereby can become the material that has light-proofness and photo-curable concurrently.
In addition, above-mentioned optical free radical polymerization initiator be preferably can be as previously mentioned the light of wavelength region may by irradiation 370～450nm and the optical free radical polymerization initiator of sensitization, also can be can be with less than the light of the wavelength of 370nm or surpass the light of wavelength of 450nm and the optical free radical polymerization initiator of sensitization.
This kind optical free radical polymerization initiator is not particularly limited, yet for example can enumerate IRGACURE127, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE1300, IRGACURE1700, IRGACURE1800, IRGACURE1870, IRGACURE2959, IRGACURE4265, IRGACUREOXE01, IRGACUREOXE02, CGI242, LUCIRIN TPO, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether (all being BASF Japan company system), ESACURE TPO (Lamberti company system), Speedcure TPO, Speedcure TPO-L (all being LAMBSON company system), MICURE TPO (MIWON company system), N-1414 (ADEKA company system), SOLVASLON BIPE, SOLVASLON BIBE, bisglyoxaline (dark fund changes into company's system), KAYACURE BP, KAYACURE DETX-S (all be Japanese flower pesticide company system), ESACURE KIP150 (Lamberti company system), S-121 (the Shinco skill is ground company's system), SEIKUOL BEE (Seiko chemical company system), KR-02 (Lightchemical company system) etc.
The content of above-mentioned optical free radical polymerization initiator is not particularly limited, yet with respect to above-mentioned curable resin 100 weight portions, preferred lower is limited to 0.1 weight portion, is limited to 10 weight portions on preferably.If, then having photopolymerization less than 0.1 weight portion, the content of above-mentioned optical free radical polymerization initiator can not advance fully or react the situation that became slow.If the content of above-mentioned optical free radical polymerization initiator surpasses 10 weight portions, then have the situation that operability reduces, reaction becomes inhomogeneous.Be limited to 1 weight portion under the content of optical free radical polymerization initiator preferred, be limited to 5 weight portions on preferred.
Contain at above-mentioned curable resin in the situation of above-mentioned resin with epoxy radicals, used for liquid crystal display element shading sealant of the present invention preferably also contains thermal curing agents.
Above-mentioned thermal curing agents is not particularly limited, such as enumerating organic acid hydrazides, imdazole derivatives, amines, polyhydric phenol based compound, acid anhydrides etc.Wherein, preferably use under the normal temperature organic acid hydrazides as solid.
Be not particularly limited for the organic acid hydrazides of solid under the above-mentioned normal temperature, such as enumerating sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic acid two hydrazides etc., as commercially available material, such as enumerating SDH (Japanese Finechem company system), Amicure VDH, Amicure VDH-J, Amicure UDH (all being aginomoto FINETECHNO company system), ADH (Da mound chemical company system) etc.
The content of above-mentioned thermal curing agents is not particularly limited, yet preferably lower for above-mentioned curable resin 100 weight portions is limited to 1 weight portion, is limited to 50 weight portions on preferably.If the content of above-mentioned thermal curing agents less than 1 weight portion, then can't obtain to contain the effect of thermal curing agents basically.If the content of above-mentioned thermal curing agents surpasses 50 weight portions, then the viscosity of the shading sealant of gained uprises, thereby has the situation of infringement coating etc.Be limited to 30 weight portions on the content of above-mentioned thermal curing agents preferred.
For improve viscosity, by means of the improvement of the improvement of the cementability of stress dispersion effect, linear expansivity, further improve the purposes such as moisture-proof of solidfied material, shading sealant of the present invention preferably contains filling agent.
Above-mentioned filling agent is not particularly limited, such as enumerating the inorganic fillers such as talcum, asbestos, silicon dioxide, zeyssatite, terre verte, bentonitic clay, calcium carbonate, magnesium carbonate, aluminium oxide, smectite, zinc paste, iron oxide, magnesium oxide, tin oxide, titanium dioxide, magnesium hydroxide, aluminium hydroxide, beaded glass, silicon nitride, barium sulphate, gypsum, calcium silicate, sericite atlapulgite, aluminium nitride; Or the organic filler such as polyester micropartical, polyurethane particulate, polyvinyl particulate, acrylic polymers particulate.
Shading sealant of the present invention preferably contains silane coupling agent.Above-mentioned silane coupling agent mainly has as being used for well effects of bonding bonding auxiliary agent such as sealant and substrates.
Above-mentioned silane coupling agent is not particularly limited, yet such as being fit to use gamma-amino propyl trimethoxy silicane, γ mercaptopropyitrimethoxy silane, γ-glycidoxypropyltrime,hoxysilane etc.
Shading sealant of the present invention can also contain as required and is useful on the reactive diluent of adjusting viscosity, adjusts the thixotropic polymer beads that becomes agent, be used for adjusting panel gap uniformly-spaced part, 3-rubigan-1 of shaking, the curing accelerators such as 1-dimethyl urea, defoamer, leveling agent, polymerization inhibitor, other adjuvant etc.
The method of making shading sealant of the present invention is not particularly limited, such as enumerating above-mentioned curable resin, above-mentioned radical polymerization initiator, above-mentioned opacifier and the utilizations such as adjuvant that cooperate the as required known method method of being mixed etc. in the past.
For the optical concentration (OD value) of the firming body that makes shading sealant cures of the present invention, be in the situation of 2～7 μ m at the thickness of firming body, be preferably more than 2.0.If the OD value of above-mentioned firming body is less than 2.0, then light-proofness is abundant not, produces spilling of light in the liquid crystal display cells of technique manufacturing is dripped in utilization, thereby has the situation that can't obtain high-contrast.The OD value of above-mentioned firming body is more preferably more than 2.5, more preferably more than 3.0.Although the OD value of above-mentioned firming body is more high better, if yet cooperate too much opacifier for the OD value that improves above-mentioned firming body, then the thickening because of sealant causes operability to reduce or the illustrative reduction, therefore in order to obtain the balance with the use level of opacifier, the OD value of above-mentioned firming body preferably on be limited to 5.
For shading sealant of the present invention, making by used for liquid crystal display element shading sealant of the present invention with 2 sheet glass substrates with the bonding adhesive test sheet that forms of crosswise, this adhesive test sheet is carried out the bonding strength of 24 hours pressure cooker testings when (121 ℃, 100%RH, 0.2MPa) is preferably 30kgf/cm 2Above.If the bonding strength when carrying out pressure cooker testing is less than 30kgf/cm 2, then can rewarding liquid crystal display cells become the situation of the element of the poor reliability under the hot and humid environment.
By in used for liquid crystal display element shading sealant of the present invention, cooperating electrically conductive microparticle, thereby can make up and down conductive material.In addition, the up and down conductive material that contains used for liquid crystal display element shading sealant of the present invention and electrically conductive microparticle also is one of the present invention.
Above-mentioned electrically conductive microparticle is not particularly limited, and can use Metal Ball, be formed with the material of conductive metal layer etc. on the surface of resin particle.Wherein, be formed with the material of conductive metal layer on the surface of resin particle because of the elasticity of the excellence of resin particle, just conduct electricity connection and can not damage transparency carrier etc., therefore preferred.
In addition, using used for liquid crystal display element shading sealant of the present invention and/or the up and down liquid crystal display cells of conductive material manufacturing of the present invention also is one of the present invention.
As the method for making liquid crystal display cells of the present invention, such as enumerating following method etc., that is, described method has: of the present invention used for liquid crystal display element shading sealant etc. formed the operation of rectangular seal pattern 2 of ito thin films etc. on a slice in the transparency carrier of electrode by serigraphy, divider coating etc.; The coating of under the uncured state such as used for liquid crystal display element shading sealant of the present invention, the tiny droplets of liquid crystal whole ground in the frame of transparency carrier being dripped, the operation of another sheet transparency carrier that superposes immediately; And the light such as the seal pattern part irradiation ultraviolet radiation of used for liquid crystal display element shading sealant of the present invention etc. made the interim operation of solidifying of sealant; And the sealant that will temporarily solidify heating and make its formal operation of solidifying.
The effect of invention
According to the present invention, though after can providing in being exposed to hot and humid environment at also very excellent used for liquid crystal display element shading sealant aspect the bonding strength of substrate.In addition, can also provide up and down conductive material and the liquid crystal display cells that uses this used for liquid crystal display element shading sealant manufacturing.
Description of drawings
Fig. 1 is shown schematically in to utilize under the liquid crystal drop mode to make the figure of the step of liquid crystal display cells in embodiment, the comparative example.
Embodiment
Below will enumerate embodiment mode of the present invention is described in detail, yet the present invention not only is defined in these embodiment.
(acrylic modified epoxy resin is synthetic fully)
Resorcinol type epoxy resin (Nagasechemtex company system, " EX-201 ") 120g is dissolved among the toluene 500mL, in this solution, adds triphenylphosphine 0.1g, make uniform solution.Behind the acrylic acid 70g that dripped with 2 hours under the return stirring, carry out again 8 hours return stirring in this solution.Then, by removing toluene, and obtain all epoxy radicals are modified as the complete acrylic acid modified resorcinol type epoxy resin (EX-201 modification product) of acryloyl group.
(synthesizing of part acrylic acid modified epoxy)
Phenol novolak type epoxy resin (DIC company system, " N-770 ") 190g is dissolved among the toluene 500mL, add triphenylphosphine 0.1g, make uniform solution, behind the acrylic acid 35g that dripped with 2 hours under the return stirring, carry out again 6 hours return stirring in the solution of gained.Then, obtain the epoxy radicals of 50mol% is modified as the part acrylic acid modified phenol phenolic resin varnish type epoxy resin (the partially modified product of N-770) of acryloxy by removing toluene.
(embodiment 1～17 and comparative example 1～9)
After cooperating each curable resin according to the match ratio of record in table 1～3, cooperate hot radical polymerization initiator and/or optical free radical polymerization initiator.Then, after hot radical polymerization initiator and/or optical free radical polymerization initiator dissolved fully, after using planetary stirring machine (Thinky company system " あ わ と り Practice is the youth too ") to stir, cooperate opacifier, thermal curing agents, filling agent and silane coupling agent, stir with planetary stirring machine again.By with three-roller type grinding machine equably disperse, thereby prepare the used for liquid crystal display element shading sealant of embodiment and comparative example thereafter.
Fig. 1 is shown schematically in to utilize under the liquid crystal drop mode to make the figure of the step of liquid crystal display cells in embodiment, the comparative example.As shown in Figure 1, utilize divider to be coated with the used for liquid crystal display element shading sealant of gained in the mode of depicting foursquare frame at the substrate that is formed with transparency electrode and alignment films.Next the coating of the tiny droplets of liquid crystal (Chisso company system " JC-5004LA ") whole ground in the frame of transparent substrates being dripped, the other substrate that is formed with transparency electrode and alignment films in a vacuum superposes, after removing vacuum, the housing sealing is used 30 seconds 100mW/cm of high-pressure mercury light irradiation 2Ultraviolet ray., 120 ℃ under carry out 1 hour liquid crystal annealing, make used for liquid crystal display element shading sealant heat curing and obtain liquid crystal display cells thereafter.
＜estimate
Used for liquid crystal display element shading sealant and the liquid crystal display cells that obtains in embodiment and the comparative example carried out following evaluation.The results are shown in table 1～3.
(bonding strength)
Glass substrate (20mm * 50mm * central portion 1.1mmt) is got the used for liquid crystal display element shading sealant of the gained of denier, thereon with form criss-cross mode superpose formed objects glass substrate and sealing material for liquid crystal display device is spread out.30 seconds 100mW/cm of irradiation under this state 2Ultraviolet ray after, under 120 ℃, carry out 1 hour the heating, obtain initial stage adhesive test sheet.In addition, the initial stage adhesive test sheet of gained carried out 24 hours pressure cooker testing (121 ℃, 100%RH, 0.2MPa), obtain adhesive test sheet after the hot and humid processing.The adhesive test sheet is measured bonding strength (kgf/cm after using tensiometer to the initial stage adhesive test sheet of gained and hot and humid processing 2).
(optical concentration (OD value))
Add silicon dioxide spacer spare (ponding chemical industrial company system, " Micropearl the SI ") 1g of diameter 5 μ m as distance piece in the used for liquid crystal display element shading sealant 100g of gained and carried out mix and blend.
With the adding of gained the used for liquid crystal display element shading sealant of distance piece be coated on the glass substrate of 20mm * 20mm, at the glass substrate of this substrate stack same size, imposed load, crushing makes even thickness to the diameter of distance piece.Then, use 30 seconds 100mW/cm of metal halide light irradiation 2Ultraviolet ray after, under 120 ℃, carry out 1 hour the heating, obtain the optical test sheet.Optical test sheet to gained uses X-rite360T (v) (X-rite company system) to determine optical concentration (OD value).
(display performance of liquid crystal display cells (irregular colour))
For the liquid crystal display cells of gained, the irregular colour that in the liquid crystal of used for liquid crystal display element shading sealant periphery, produces that utilized visualization.Consequently, to there be the average evaluation of irregular colour to be " ◎ " fully, the average evaluation that there is no irregular colour is " zero ", will exists slightly the average evaluation of irregular colour to be " △ ", will have the average evaluation of considerable irregular colour to be " * ".
As shown in table 1,2, the bonding strength of shading sealant behind high temperature and humidity test that obtains among the embodiment is 30kgf/cm 2Above, be in practical fully no problem level.In addition, optical concentration (OD value) is all very high, is more than 3.0, has enough light-proofnesss.With regard to irregular colour, be the degree that does not have fully, there is no or exist slightly, be in practical fully no problem level.
Utilizability on the industry
According to the present invention, though after can providing in being exposed to hot and humid environment at also very excellent used for liquid crystal display element shading sealant aspect the bonding strength of substrate.In addition, can also provide up and down conductive material and the liquid crystal display cells that uses this used for liquid crystal display element shading sealant manufacturing.

Claims (6)

1. a used for liquid crystal display element shading sealant is characterized in that, is to contain: comprise the liquid crystal dripping process shading sealant of curable resin, radical polymerization initiator and the opacifier of the curing compound with unsaturated double-bond,
The hydrogen bond functional group value of described curable resin is 0.5 * 10 -3～3.0 * 10 -3Mol/g,
Contain titanium black in described opacifier.
2. used for liquid crystal display element shading sealant according to claim 1 is characterized in that,
Curing compound with unsaturated double-bond has (methyl) acryloxy.
3. used for liquid crystal display element shading sealant according to claim 1 and 2 is characterized in that,
Radical polymerization initiator contains the hot radical polymerization initiator.
4. used for liquid crystal display element shading sealant according to claim 1 and 2 is characterized in that,
The optical free radical polymerization initiator that radical polymerization initiator contains the polymeric azo initiating agent and/or carries out sensitization with the light of the wavelength region may of 370～450nm.
5. conductive material about in the of a kind is characterized in that,
Contain each described used for liquid crystal display element shading sealant and electrically conductive microparticle in the claim 1～4.
6. a liquid crystal display cells is characterized in that,
Each described used for liquid crystal display element shading sealant and/or up and down conductive material claimed in claim 5 are made in the right to use requirement 1～4.
CN201280002167.0A 2011-04-05 2012-04-03 Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element Active CN103026292B (en)

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