CN1798786B - Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device - Google Patents

Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device Download PDF

Info

Publication number
CN1798786B
CN1798786B CN200480015573.6A CN200480015573A CN1798786B CN 1798786 B CN1798786 B CN 1798786B CN 200480015573 A CN200480015573 A CN 200480015573A CN 1798786 B CN1798786 B CN 1798786B
Authority
CN
China
Prior art keywords
liquid crystal
curable resin
crystal display
resin composition
weight parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN200480015573.6A
Other languages
Chinese (zh)
Other versions
CN1798786A (en
Inventor
谷川满
渡边贵志
尾山雄一
山本拓也
宇和川决
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2003162774A external-priority patent/JP2004361854A/en
Priority claimed from JP2003394614A external-priority patent/JP2005054164A/en
Priority claimed from JP2003394615A external-priority patent/JP4022194B2/en
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority claimed from PCT/JP2004/007811 external-priority patent/WO2004108790A1/en
Publication of CN1798786A publication Critical patent/CN1798786A/en
Application granted granted Critical
Publication of CN1798786B publication Critical patent/CN1798786B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

It is the object of the invention to provide a curable resin composition which causes no liquid crystal contamination, which are excellent in the adhesive property to a glass, and which causes no cell gap inequality in the case it is used as a sealant for a liquid crystal display element to produce a liquid crystal display element by a one drop fill process, a sealant for a liquid crystal displayelement, and a liquid crystal display element. The invention is a curable resin composition, which contains a curable resin to be cured by light and/or heat and a polymerization initiator, the curable resin being a crystalline (meth)acrylic acid-modified epoxy resin comprising a (meth)acrylic group and an epoxy group in one molecule.

Description

Curable resin composition, sealing material for liquid crystal display device and liquid crystal display device
Technical field
The present invention relates to when as sealing material for liquid crystal display device and for by liquid crystal, drip completion method (drop fill process) while manufacturing the process of liquid crystal display device to the pollution of liquid crystal less, with the connectivity of substrate good and generation unit gap (cell gap) inhomogeneous curable resin composition, sealing material for liquid crystal display device and liquid crystal display device not.
Background technology
In the past, the liquid crystal display device such as liquid crystal display are made by the following method: make two transparency carriers with electrode every predetermined distance relatively to, use the sealing agent formed by curable resin composition by sealing around it, and make sealant cures and form a unit, inject liquid crystal from the liquid crystal injecting port be located at wherein in unit afterwards, then this liquid crystal injecting port is used to sealing agent or sealing compound sealing.
That is, at first, on any substrate of two transparency carriers with electrode, form seal pattern by silk screen print method, in described seal pattern, use the Thermocurable sealing agent to be provided with liquid crystal injecting port, carry out prebake under 60-100 ℃, make the solvent seasoning in sealing agent.Then, make two substrate clampings partition (spacer) relatively to, and laminating after it is aimed at, carry out hot pressing 10-90 minute under 110-220 ℃, adjust near the gap of hermetic unit, then heat 10-120 minute in stove, make sealing agent carry out the fact and solidify (actually cure) under 110-220 ℃.Then, by liquid crystal injecting port, inject liquid crystal, finally use sealing compound encapsulated liquid crystals inlet, thereby make liquid crystal display device.
But if, according to this making method, there are the following problems: degradation under the adaptation of, sealing agent uneven by thermal distortion occurrence positions dislocation, gap and substrate; Residual solvent produces bubble because of thermal expansion, cause gap uneven, seal destroyed; The sealing and curing time is long; The prebake complex process; Because of solvent evaporates, the usable time of sealing agent shortens; The problem such as take a long time while injecting liquid crystal.Especially in large-scale liquid crystal display device in recent years, while injecting liquid crystal, require a great deal of time, this has become very noticeable problem.
Be directed to this, studied and used the photocuring thermofixation also by the type sealing agent, manufacture method that be called as the liquid crystal display device that drips completion method.The drippage completion method in, at first two with a substrate in the transparency carrier of electrode on, by the agent of silk screen print method printing and sealing, thereby form rectangular seal pattern (hermetic unit).Then, at sealing agent, do not have under curing state liquid crystal is carefully dripped and is coated on the whole framework face of transparency carrier through dropping, another transparency carrier of lamination immediately afterwards, and solidify to the hermetic unit irradiation ultraviolet radiation temporarily.Then, carry out the fact by heating and solidify in the annealing of liquid crystal, make liquid crystal display device.If under reduced pressure carry out the laminating of substrate, can be with very high efficiency system liquid making crystal display element.This drippage completion method is expected to become the manufacture method of main liquid crystal indicator from now on.
But, in by the drippage completion method, manufacturing the method for liquid crystal indicator, several problems that existence must overcome.
The 1st problem is the liquid crystal pollution problem.In the drippage completion method, due to the operation that has uncured sealing agent and directly contact with liquid crystal, so the sealing agent composition is eluted in liquid crystal, the pollution liquid crystal just becomes a very large problem.While producing liquid crystal pollution, produce the orientation disorder of liquid crystal in the periphery branch of sealing agent, thereby become, cause even grade of irregular colour to show bad reason.
For example; as be used as the curable resin in the curable resin composition of sealing agent in the past; part (methyl) acryl compound (patent documentation 1-5) such as bisphenol A type epoxy resin, (methyl) acrylate resin (patent documentation 6) etc. are disclosed; but these curable resins have demonstrated owing to having the polarity number close with liquid crystal material the character that is easy to affinity, so exist, be eluted to the tendency in liquid crystal.
In addition, the polymerization starter be blended in sealing agent as living radical generation agent is also the reason of polluting liquid crystal.Can use low-molecular-weight organic compound as the polymerization starter be mixed in sealing agent in the past, this polymerization starter is easy to be eluted in liquid crystal, in addition, polymerization finishes the rear also remaining residue that comes from polymerization starter, so this residue thing is by being eluted in liquid crystal the reason that becomes liquid crystal pollution, or the heating during by the liquid crystal reorientation becomes evolving gas and becomes the engaging force caused between glass substrate and descend and produce the reason in gap.
Be directed to this, in patent documentation 7, disclose the transparent polymer substance that contains optical polymerism composition and there is the Photoepolymerizationinitiater initiater of (methyl) acryloxy and formed the transparent polymer substance that material forms by polymerization and be supported on two liquid crystal apparatus between transparency carrier.This liquid crystal apparatus is owing to not using low-molecular-weight polymerization starter, so the residue thing of the polymerization starter after polymerization finishes is difficult to be eluted in liquid crystal, thereby the bad problems of demonstration such as the disorderly and irregular colour of this generation liquid crystal aligning is even have been improved in a way.But, except can not preventing that the residue thing is eluted in liquid crystal fully, not yet solve when uncured in drippage completion method etc. during the polymerization starter contacted with liquid crystal can be eluted in liquid crystal, or the heating of the residue thing of the polymerization starter after curing during because of the liquid crystal reorientation becomes the problem of evolving gas.
In addition, the alkoxysilane compound containing trialkylsilyl group in molecular structure mixed as bonding auxiliary agent is also the reason of liquid crystal pollution.With regard to sealing agent in the past, usually use γ-aminopropyltrimethoxysilane, γ mercaptopropyitrimethoxy silane, γ-glycidoxypropyltrimethoxy silane, γ-alkoxysilane compound containing trialkylsilyl group in molecular structure such as isocyanato-propyl trimethoxy silicane are as bonding auxiliary agent, but these alkoxysilane compound containing trialkylsilyl group in molecular structure also have the character that is easy to wash-out in liquid crystal.
The 2nd problem is the problem of the connectivity of sealing agent.Usually, the sealing agent be comprised of the resin combination of ultraviolet hardening is compared with the sealing agent that the resin combination by thermohardening type in the past forms, a little less than the engaging force of glass substrate.In addition, in order to improve thermotolerance, the improvement of sealing agent is trended towards improving to the direction of resin glass temperature, but when the second-order transition temperature of resin uprises, just lower with the connectivity of glass substrate.As the method for improving with the connectivity of glass substrate, known method that adds silane coupling agent etc., but not only connectivity is improved the effect deficiency, silane coupling agent also can be in liquid crystal wash-out and cause the pollution of liquid crystal.
In patent documentation 8, disclose the epoxy resin binder compositions that contains core shell particles (core-shell), the shell that the sandwich layer that described core shell particles is comprised of the resin that is 45 ℃ by second-order transition temperature and the resin that is 105 ℃ by second-order transition temperature form forms.In the thermofixation of this epoxy resin reaction, the swelling due to heating of the rubber constituent of core shell particles, and absorb and improve the shock-resistance of resin combination from outside impact, peel off engaging force thereby improved.But, because in the method being take that to make the swelling of core shell particles by heating be prerequisite, so to the resin combination of ultraviolet hardening (or and composition with ultraviolet hardening and thermohardening type in, the material that first carries out ultraviolet curing) the improvement of connectivity may there is no effect.
The 3rd problem is the inhomogeneous problem in gap.While by the drippage completion method, making liquid crystal indicator, just the solidified nature based on photocuring is too high sometimes for sealing agent in the past, and it is large that the linear expansion rate after photocuring becomes, and then understands the problems such as the generation unit gap is inhomogeneous because substrate is offset.
Thus, produced the demand of the curable resin composition that can be used in sealing material for liquid crystal display device to having solved the inhomogeneous problem of liquid crystal pollution problem, the connectivity of sealing agent, gap.
Patent documentation 1: Unexamined Patent 6-160872 communique
Patent documentation 2: Unexamined Patent 1-243029 communique
Patent documentation 3: Unexamined Patent 7-13173 communique
Patent documentation 4: Unexamined Patent 7-13174 communique
Patent documentation 5: Unexamined Patent 7-13175 communique
Patent documentation 6: Unexamined Patent 7-13174 communique
Patent documentation 7: Unexamined Patent 5-264980 communique
Patent documentation 8: Unexamined Patent 7-224144 communique
Summary of the invention
In view of the foregoing, the purpose of this invention is to provide when as sealing material for liquid crystal display device for by the drippage completion method while manufacturing the process of liquid crystal display device, pollution to liquid crystal is few, with the connectivity of substrate inhomogeneous curable resin composition, sealing material for liquid crystal display device and the liquid crystal display device in generation unit gap well and not.
The present inventors have carried out wholwe-hearted research to the problem of liquid crystal pollution, found that by selecting specific curable resin, polymerization starter and bonding auxiliary agent, contact even can obtain the curable resin composition that also is difficult for polluting liquid crystal with liquid crystal when as sealing material for liquid crystal display device under uncured state, so far completed the 1st, the 2nd and the 3rd the present invention.Wherein, the 1st the present invention is the problem that has solved the liquid crystal pollution produced by curable resin, and the 2nd the invention solves the problem of the liquid crystal pollution produced by polymerization starter, and the 3rd the invention solves the problem of the liquid crystal pollution produced by bonding auxiliary agent.Therefore, 1-3 of the present invention can distinguish enforcement independently, but, when the several enforcement of combination, can obtain better effect.
The 1st the present invention is curable resin composition, it is to contain the curable resin that is cured and the curable resin composition of polymerization starter under the effect of light and/or heat, and above-mentioned curable resin is by making crystallinity epoxy resin and the reaction of (methyl) vinylformic acid form (methyl) acrylic modified epoxy resin.
(methyl) acrylic modified epoxy resin is owing to having (methyl) acryl (acryl) and epoxy group(ing) in a part, so no matter use up or can make it solidify by heat.Therefore, if the 1st curable resin composition of the present invention is used as to sealing material for liquid crystal display device, can adopt and first irradiate light and by heating, make it carry out true curing mode after temporary sealing, go for adopting the manufacture of the liquid crystal display device of drippage completion method.
(methyl) acrylic modified epoxy resin like this is because the purity of the crystallinity epoxy resin as raw material is high, foreign matter content is few, so may be difficult for polluting liquid crystal.Also have, in specification sheets of the present invention, so-called (methyl) vinylformic acid refers to vinylformic acid or methacrylic acid.In addition, in specification sheets of the present invention, so-called crystalline resin refers to that measuring differential with differential scanning calorimeter occurs that sharp-pointed fusing point peak clearly and crystallization degree surpass 10% resin when hot, and so-called non-crystalline resin refers to that measuring differential with differential scanning calorimeter does not occur that sharp-pointed fusing point peak clearly and crystallization degree are 10% or resin below it when hot.
Above-mentioned (methyl) acrylic modified epoxy resin is preferably crystalline.Crystalline (methyl) acrylic modified epoxy resin, because crystallinity is high, so intermolecular interaction is strong, thereby also may be difficult for polluting liquid crystal even uncured resin contacts with liquid crystal.
The fusing point of above-mentioned (methyl) acrylic modified epoxy resin is preferably 80 ℃ or below it.If surpass 80 ℃, while mixing, need at high temperature be heated, can produce the problems such as gelation.Be limited to 40 ℃ under preferred.If 40 ℃ of less thaies, can cause cohesive force to descend, the adaptation that curable resin composition of the present invention solidifies the cured article formed is descended sometimes.
Above-mentioned (methyl) acrylic modified epoxy resin is preferably the resin that sulphur atom in resin matrix and Sauerstoffatom add up to 5-10.If less than 5, the polarity step-down of molecule and be easy to pollute liquid crystal sometimes, if surpass 10, wet fastness is poor sometimes.
Above-mentioned (methyl) acrylic modified epoxy resin, be limited to 0.08 with the total atom number except under sulphur atom in resin matrix and Sauerstoffatom sum income value preferred, be limited to 0.14 on preferred.If less than 0.08, polarity step-down and be easy to pollute liquid crystal sometimes, if surpass 0.14, wet fastness is poor sometimes.
Above-mentioned (methyl) acrylic modified epoxy resin can react to manufacture by making crystallinity epoxy resin and (methyl) vinylformic acid.
Have no particular limits as above-mentioned crystallinity epoxy resin, can enumerate such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, Stilbene-based epoxy resin, sulfide type epoxy resin, ether type epoxy, naphthalene type epoxy resin and these derivative etc.
Be preferably 140 ℃ or below it as the fusing point of the crystallinity epoxy resin of above-mentioned raw materials.If surpass 140 ℃, gelation can occur during modified-reaction sometimes.Be limited to 120 ℃ on preferred.In addition, under preferred, be limited to 40 ℃.If 40 ℃ of less thaies, crystallinity descends sometimes.
Have no particular limits as the method that makes above-mentioned crystallinity epoxy resin and the reaction of (methyl) vinylformic acid, can use known method in the past.
When making above-mentioned crystallinity epoxy resin and the reaction of (methyl) vinylformic acid, preferably use basic catalyst, have no particular limits as above-mentioned basic catalyst, can enumerate such as DMA, triethylamine, triphenylphosphine, iron(ic) chloride, zinc chloride, vanadium chloride etc.
In addition, when making above-mentioned crystallinity epoxy resin and the reaction of (methyl) vinylformic acid, preferably, under the existence of above-mentioned basic catalyst, with respect to 1 equivalent epoxy group(ing), make the reaction of 1-0.5 equivalent (methyl) vinylformic acid.
In the 1st curable resin composition of the present invention, under the combined amount of above-mentioned (methyl) acrylic modified epoxy resin preferred, be limited to 10 % by weight, be limited to 50 % by weight on preferred.If less than 10 % by weight, make its adaptation of solidifying the cured article formed descend sometimes, if surpass 50 % by weight, crystallization can occur in composition.
In curable resin composition of the present invention, except above-mentioned (methyl) acrylic modified epoxy resin, also can contain other curable resin.
As such curable resin, can enumerate such as (methyl) acrylate, ethene derivatives, styrene derivatives, epoxy resin etc.Wherein, from promptly reacting and the good viewpoint of connectivity, what be applicable to is (methyl) acrylate, epoxy resin, oxetane resin.
Above-mentioned curable resin preferably has hydrogen bond functional group in molecule.Thus, can improve the associativity between curable resin, even also be difficult to pollute crystal while contacting with crystal.Above-mentioned curable resin preferably has two or its above addition reactivity functional group in molecule, more preferably has more than two below four.Thus, the remaining quantity of the unreacted resin after solidifying can be reduced, unreacted resin stain liquid crystal can be prevented.
As above-mentioned (methyl) acrylate, can enumerate such as the urethane with urethane bond (methyl) acrylate, by the compound with glycidyl and derivative epoxy (methyl) acrylate, the polyvalent alcohol that contains three above OH bases in a part or the polyester polyol of (methyl) vinylformic acid and (methyl) vinylformic acid derivative (methyl) acrylate etc. under the state that retains an above OH base.
As above-mentioned urethane (methyl) acrylate, can enumerate such as the vulcabond such as isophorone diisocyanate and vinylformic acid or Hydroxyethyl acrylate etc. can with derivative of the reactive compounds of isocyanic ester addition reaction etc.These derivatives also can carry out chain extension with caprolactone and polyvalent alcohol etc.In addition, as commercially available prod, can enumerate such as U-122P, U-340P, U-4HA, U-1084A (all Shi Xinzhong village chemistry society systems), KRM7595, KRM7610, KRM7619 (being all ダ イ セ Le UCB society system) etc.
As above-mentioned epoxy (methyl) acrylate, can enumerate such as by the epoxy resin such as bisphenol A type epoxy resin or propylene glycol diglycidylether and derivative epoxy (methyl) acrylate of (methyl) vinylformic acid etc.In addition, as commercially available prod, can enumerate such as EA-1020, EA-6320, EA-5520 (all Shi Xinzhong village chemistry society systems), epoxy ester 70PA, epoxy ester 3002A (being all chemistry society of common prosperity society system) etc.
As the polyvalent alcohol that contains three above OH bases in a part or polyester polyol and (methyl) vinylformic acid derivative (methyl) acrylate under the state that retains an above OH base, can enumerate for example methyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, IBOMA, HEMA, glycidyl methacrylate, polyethylene glycol dimethacrylate, 1, the 4-butylene glycol dimethacrylate, 1, the 6-hexanediol dimethacrylate, Viscoat 295, pentaerythritol triacrylate, the glycerine dimethacrylate, 2-hydroxyl-3-acryloxy propyl methyl acid esters etc.
Have no particular limits as above-mentioned epoxy resin, can enumerate such as (methyl) acrylic modified epoxy resin, urethane modification (methyl) acryl epoxy resin etc.
As above-mentioned (methyl) acrylic modified epoxy resin, can enumerate (methyl) acryloyl such as the part such as phenolic resin varnish type epoxy resin, bisphenol-type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, three (hydroxyphenyl) alkyl type epoxy resin, four (hydroxyphenyl) alkyl type epoxy resin, ring type aliphatic epoxy resin compound etc.Wherein, part (methyl) the acryloyl compound of preferred phenolic resin varnish type epoxy resin.This is because, by using phenolic resin varnish type epoxy resin as base resin, compare with the bisphenol-type epoxy resin of straight chain shape, can further improve the stability in storage of sealing agent of the present invention etc.
The raw material epoxy resin of above-mentioned (methyl) acrylic modified epoxy resin, for example, as phenolic varnish type, can enumerate phenol phenolic varnish type, cresols phenolic varnish type, biphenyl phenolic varnish type, triphenol phenolic varnish type, Dicyclopentadiene (DCPD) phenolic varnish type etc., as bisphenol type, can enumerate bisphenol A-type, Bisphenol F type, 2,2 '-diallyl bisphenol type, A Hydrogenated Bisphenol A type, polyoxypropylene bisphenol A-type ring type aliphatic epoxy resin etc.These can use separately, also can more than two kinds and use.
Commercially available prod as above-mentioned epoxy resin, as above-mentioned bisphenol A type epoxy resin, can enumerate for example エ ピ コ-ト 828, エ ピ コ-ト 834, エ ピ コ-ト 1001, エ ピ コ-ト 1004 (being all japan epoxy resin society system), エ ピ Network ロ Application 850, エ ピ Network ロ Application 860, エ ピ Network ロ Application 4055 (be all large Japanese ink chemical industry society system) etc., as above-mentioned bisphenol f type epoxy resin, can enumerate for example エ ピ コ-ト 807 (japan epoxy resin society system), エ ピ Network ロ Application 830 (Japanese ink chemical industry society system greatly) etc., as phenol novolak type epoxy resin, can enumerate for example エ ピ Network ロ Application N-740, N-770, N-775 (Japanese ink chemical industry society system greatly), エ ピ コ-ト 152, 154 (japan epoxy resin society systems) etc., as above-mentioned cresols phenolic varnish type, can enumerate for example エ ピ Network ロ Application N-660, N-665, N-670, N-673, N-680, N-695, N-665-EXP, N-672-EXP (Japanese ink chemical industry society system greatly) etc.
In addition, as above-mentioned ring type aliphatic epoxy resin, can enumerate such as セ ロ キ サ イ De 2021, セ ロ キ サ イ De 2080, セ ロ キ サ イ De 3000 (being all ダ イ セ Le UBC society system) etc., the material of changing as part (methyl) acryloyl (acryl) of above-mentioned epoxy resin, can enumerate for example by making epoxy resin and (methyl) vinylformic acid react the material obtained by ordinary method under the existence of basic catalyst.
Can, by combined amount and (methyl) acrylic acid combined amount of the above-mentioned epoxy resin of appropriate change, obtain the epoxy resin of desirable acryloyl rate.Specifically, carboxylic acid is limited to 0.1 equivalent with respect under 1 equivalent epoxy group(ing) preferred, is limited to 0.5 equivalent on preferred, is limited to 0.2 equivalent under preferred, is limited to 0.4 equivalent on preferred.
As above-mentioned urethane modification (methyl) acryl epoxy resin, can enumerate the resin for example obtained by following method: make the above isocyanate reaction of polyvalent alcohol and two senses, then make it the method for reacting with (methyl) acryl (acryl) monomer and the Racemic glycidol of hydroxyl again; Under the condition without polyvalent alcohol; making to have (methyl) acryl monomer of hydroxyl or the method for the isocyanate reaction more than Racemic glycidol and two senses etc., can be also the method that Racemic glycidol is reacted with (methyl) acrylate monomer that contains isocyanate group in addition.
Specifically, for example, at first make 1mol TriMethylolPropane(TMP) and 3mol isophorone diisocyanate be reacted under the tin series catalysts.Hydroxyethyl acrylate by making to be retained in isocyanate group in the compound obtained and acryl monomer as hydroxyl and react and obtain resin as the Racemic glycidol of the epoxy compounds of hydroxyl.
Be not particularly limited as above-mentioned polyvalent alcohol, can enumerate such as ethylene glycol, glycerine, Sorbitol Powder, TriMethylolPropane(TMP), (gathering) propylene glycol etc.
As above-mentioned isocyanic ester, so long as above just being not particularly limited of two senses, can enumerate for example isophorone diisocyanate, 2, the 4-inferior cresyl vulcabond, 2, the 6-inferior cresyl vulcabond, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, ditane-4, 4 '-vulcabond (MDI), hydrogenation MDI, polycondensation MDI, 1, the 5-naphthalene diisocyanate, norbornene alkyl diisocyanate, the tolidine vulcabond, eylylene diisocyanate (XDI), hydrogenation XDI, lysinediisocyanate, triphenylmethane triisocyanate, three (isocyano phenyl) thiophosphatephosphorothioate, tetramethylxylene diisocyanate, 1, 6, 10-undecane triisocyanate etc.
(methyl) acrylate monomer as above-mentioned hydroxyl is not particularly limited, and can enumerate one (methyl) acrylate of dibasic alcohol such as ethylene glycol, propylene glycol, 1,3-PD, 1,3 butylene glycol, BDO, polyoxyethylene glycol; One (methyl) acrylate, two (methyl) acrylate of the trivalent alcohols such as trimethylolethane, TriMethylolPropane(TMP), glycerine; The epoxy acrylates such as bisphenol A modified epoxy acrylate etc.These can use separately, also can more than two kinds, be used in combination.
The 2nd the present invention is curable resin composition, it is to contain the curable resin that is cured and the curable resin composition of polymerization starter under the effect of light and/or heat, and above-mentioned polymerization starter is in a part, to contain to irradiate light and/or be dissociated into the radical polymerization initiating radical of two living radical kinds and the radical polymerization initiator of hydrogen bond functional group when hot.
In above-mentioned radical polymerization initiator, liberty base polymerization initiating radical refers to and irradiates light and/or be dissociated into two living radical kinds when hot and the functional group of causing Raolical polymerizable.Wherein, the radical polymerization initiator with the radical polymerization initiating radical that is dissociated into two living radical kinds under the effect of light goes for dripping completion method, so preferably.As such radical polymerization initiating radical, can enumerate such as carbonyl, containing sulfenyl, azo-group, containing organic peroxide-based etc., but what wherein be applicable to is to have with the group of the structure of following general formula (1)-(6) expression etc.
[Chemical formula 1]
In above-mentioned general formula (1)-(6), R 1, R 2and R 3mean independently of one another alkoxyl group, (methyl) acryl, phenyl that alkyl, hydrogen atom, hydroxyl, carbonatoms that carbonatoms is 1-6 are 1-6, R 4, R 5, R 6and R 7mean alkoxyl group, (methyl) acryl that alkyl, hydrogen atom, hydroxyl, carbonatoms that cyano group, carbonatoms are 1-6 are 1-6, can there is alkyl that carbonatoms is 1-6 or the aromatic nucleus of halogen radical,
[Chemical formula 2]
Expression can have alkyl that carbonatoms is 1-6 or the aromatic nucleus of halogen radical.Wherein, the group that more preferably there is the structure of the above-mentioned general formula of use (1)-(4) expression that the photodissociation weak by specific absorption is the living radical kind, from the aspect of living radical production rate, further preferably there is the group of the structure meaned with above-mentioned general formula (1).
As above-mentioned hydrogen bond functional group, so long as there is the functional group of hydrogen bond or residue etc., just have no particular limits, can enumerate for example OH base, NH 2base, NHR base (R means aromatic series or aliphatic hydrocarbon and these derivative), COOH base, CONH 2base, NHOH base and there is group of the residues such as NHCO key, NH key, CONHCO key, NH-NH key etc. in molecule.
Above-mentioned radical polymerization initiator is owing to having such hydrogen bond functional group, even the 2nd uncured curable resin composition of the present invention contacts with liquid crystal, radical polymerization initiator also is difficult to elute, and is difficult for producing liquid crystal pollution.
Above-mentioned radical polymerization initiator preferably contains above-mentioned hydrogen bond functional group more than two in a part.In addition, two living radical kinds that the radical polymerization initiating radical dissociated produce by irradiating light and/or heat, preferably all have at least one hydrogen bond functional group.That is, above-mentioned hydrogen bond functional group in molecule, preferably be configured to by irradiate light and/or heat while the radical polymerization initiating radical being dissociated produce two living radical kinds any one living radical kind all there is at least one hydrogen bond functional group.Thus, all living radical kinds of generation, even contact with liquid crystal because above-mentioned polymerization starter rests in curable resin composition, so the composition of polymerization starter is difficult to be eluted in liquid crystal, be difficult for producing liquid crystal pollution.
Above-mentioned radical polymerization initiator also preferably has plural reactive functional groups in a part.By there is such reactive functional groups in molecule, above-mentioned radical polymerization initiator itself forms multipolymer with curable resin and is fixed, so polymerization finishes the residue thing of post polymerization initiator, can not be eluted in liquid crystal yet, in addition, heated also during the liquid crystal reorientation and can not become evolving gas.
As above-mentioned reactive functional groups; so long as can just have no particular limits with the functional group that curable resin described later is combined by polyreaction, can enumerate the ether such as the ring-type such as epoxy group(ing) and oxetanyl, (methyl) acryl, styryl etc.What wherein, be applicable to is (methyl) acryl or epoxy group(ing).
In the plural reactive functional groups of above-mentioned radical polymerization initiator, preferably at least one is (methyl) acryl, and preferably at least one is the ring-type ether.
In addition, the radical polymerization initiating radical preferably all has at least one reactive functional groups by irradiation light and/or hot two the living radical kinds that produce of dissociating.That is, above-mentioned reactive functional groups in molecule, preferably be configured to by irradiate light and/or heat while the radical polymerization initiating radical being dissociated produce two living radical kinds any one living radical kind all there is at least one reactive functional groups.Thus, all living radical kinds of generation all form multipolymer with curable resin and are fixed, so polymerization finishes the residue thing of post polymerization initiator, also can not be eluted in liquid crystal, in addition, during the liquid crystal reorientation, are heated also and can not become evolving gas.
The number-average molecular weight of above-mentioned radical polymerization initiator preferably is limited to 300 down.If less than 300, the radical polymerization initiator composition is eluted in liquid crystal sometimes, is easy to make the orientation disorder of liquid crystal.Be limited to 3000 on preferred.If surpass 3000, the viscosity adjustment of the 2nd curable resin composition of the present invention sometimes becomes difficult.
The molar absorptivity under 350nm that above-mentioned radical polymerization initiator is preferably measured in acetonitrile is 200-1 ten thousand M -1cm -1.If not enough 200M -1cm -1, during as sealing material for liquid crystal display device, if illumination wavelength is not that the following high-energy line of 350nm sometimes just can not be fully curing, liquid crystal and alignment films can be because irradiating such high-energy line variation.If surpass 10,000 M -1cm -1, when the sealing material for liquid crystal display device, during the about 350nm of illumination wavelength ultraviolet, only surface is at first curing sometimes, and inside can not be fully curing.300-3000M more preferably -1cm -1.
In addition, in this specification sheets, above-mentioned so-called molar absorptivity refers to by the ε (M for ラ Application バ-ト ベ for the acetonitrile solution that contains above-mentioned radical polymerization initiator-Le formula definition shown in following formula (7) -1cm -1) value.
[mathematical expression 1]
Log(I o/I)＝εcd (7)
In addition, in above-mentioned formula (7), I means transmission light intensity, I omean the transmission light intensity of acetonitrile neat solvent, c means volumetric molar concentration (M), and d means the thickness (cm) of solution layer, Log (I o/ I) mean absorbancy.
The molar absorptivity under 430nm that above-mentioned radical polymerization initiator is preferably measured in acetonitrile is 100M -1cm -1or below it.If surpass 100M -1cm -1, can under the effect of the light of visible region wavelength, produce living radical, the operability non-constant that becomes.Manufacture method as above-mentioned radical polymerization initiator has no particular limits, can use known method in the past, for example can enumerate and to use (methyl) vinylformic acid or (methyl) acrylate chloride, implement the method for (methyl) acroleic acid esterification to there is the alcohol derivate of above-mentioned radical polymerization initiating radical and hydroxyl more than two in molecule; Make to have the method for an epoxy reaction of the compound that there are two above epoxy group(ing) in above-mentioned radical polymerization initiating radical and hydroxyl more than two or amino compound and molecule in molecule; Make to have in molecule in above-mentioned radical polymerization initiating radical and hydroxyl more than two or amino compound and molecule and there is an epoxy reaction of the compound of two above epoxy group(ing), then make remaining epoxy group(ing) and (methyl) vinylformic acid or there is (methyl) acrylate monomer of active hydrogen base or method that styrene monomer etc. reacts; After making to have above-mentioned radical polymerization initiating radical and hydroxyl more than two or amino compound and cyclic ester compound or there is the reactions such as carboxylic acid cpd of hydroxyl in molecule, then make the method for above-mentioned hydroxyl (methyl) acroleic acid esterification; By there is above-mentioned radical polymerization initiating radical and hydroxyl more than two or amino compound and the synthetic urethane derivatives of two functional isocyanate derivatives in molecule after, then the method that another isocyanic ester is reacted with (methyl) vinylformic acid, Racemic glycidol, (methyl) acrylate monomer with hydroxyl, styrene monomer etc. etc.
As the above-mentioned compound that there are two above epoxy group(ing) in molecule, can enumerate for example difunctional epoxy resin compound.
Have no particular limits as above-mentioned difunctional epoxy resin compound, can enumerate such as bisphenol type epoxy compound, bisphenol f type epoxy resin, dihydroxyphenyl propane D type epoxy resin, by the epoxy resin of these hydrogenations, phenolic resin varnish type epoxy resin, urethane modified epoxy, by the epoxidised nitrogen-containing epoxy thermosets such as m-xylene diamine, the rubber modified epoxy resin etc. that contains polyhutadiene or paracril (NBR).These difunctional epoxy resin compounds can be solid state, can be also liquid.
Have no particular limits as above-mentioned (methyl) acrylate monomer with hydroxyl, can enumerate one (methyl) acrylate of dibasic alcohol such as ethylene glycol, propylene glycol, 1,3-PD, 1,3 butylene glycol, BDO, polyoxyethylene glycol; One (methyl) acrylate of the trivalent alcohols such as trimethylolethane, TriMethylolPropane(TMP), glycerine, two (methyl) acrylate etc.These can use separately, also can more than two kinds, be used in combination.
As above-mentioned two functional isocyanate derivatives, can enumerate such as diphenylmethanediisocyanate (MDI), toluene support vulcabond (TDI), xylylene vulcabond (XDI), isophorone diisocyanate (IPDI), naphthalene diisocyanate (NDI), tolidine vulcabond (TPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), trimethyl hexamethylene diisocyanate (TMHDI) etc.
In the 2nd curable resin composition of the present invention, the preferred lower limit of the combined amount of above-mentioned radical polymerization initiator is 0.1 weight part with respect to curable resin 100 weight parts, and preferred upper limit is 15 weight parts.If less than 0.1 weight part, can not make the 2nd curable resin composition of the present invention fully curing sometimes, if surpass 15 weight parts, stability in storage descends sometimes.Be limited to 1 weight part under preferred, be limited to 7 weight parts on preferred.
Curable resin composition of the present invention can also contain other radical polymerization initiator except above-mentioned radical polymerization initiator.As the radical polymerization initiator of such other, so long as produce the compound of free radical under the effect of light and/or heat, just have no particular limits.
As the above-mentioned radical polymerization initiator that produces free radical under hot effect, can enumerate superoxide such as lauroyl peroxide, benzoyl peroxide, cumyl superoxide; The azo-compounds such as Diisopropyl azodicarboxylate etc.
As the above-mentioned radical polymerization initiator that produces free radical under the effect of light, can enumerate such as acetophenone compound, benzophenone cpd, bitter almond oil camphor compound, benzoin ether compound, acylphosphine oxide compound, thioxanthone compound etc.Particularly, can enumerate for example benzophenone, 2,2-diethoxy acetophenone, benzil, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexylphenylketone, thioxanthone etc.These other radical polymerization initiator can be used separately, also can more than two kinds, be used in combination.
In curable resin composition of the present invention, above-mentioned other the preferred lower limit of content of radical polymerization initiator is 0.1 weight part with respect to above-mentioned curable resin 100 weight parts, and preferred upper limit is 10 weight parts.If less than 0.1 weight part, sometimes can not solidify insufficient, if surpass 10 weight parts, likely because of the residual liquid crystal that pollutes of radical polymerization initiator.Be limited to 1 weight part under preferred, be limited to 5 weight parts on preferred.
The 3rd the present invention is curable resin composition, it is the curable resin composition that contains the curable resin, polymerization starter and the bonding auxiliary agent that are cured under the effect of light and/or heat, and above-mentioned bonding auxiliary agent is that molecular weight is the alkoxysilane compound containing trialkylsilyl group in molecular structure more than 500 and/or molecular weight is more than 200 and hydrogen bond functional group value is 2 * 10 -3-7 * 10 -3the alkoxysilane compound containing trialkylsilyl group in molecular structure of mol/g.
In addition, above-mentioned so-called alkoxysilane compound containing trialkylsilyl group in molecular structure is the compound meaned with following general formula (8).
[chemical formula 3]
-Si(OR 1) nR 2 (3-n) (8)
In formula (8), R 1, R 2independent separately, as structure, can enumerate alkyl, hydrogen, but more preferably methyl, ethyl, propyl group.In addition, n is the integer of 1-3.
Contain the 3rd curable resin composition of the present invention that the molecular weight in such alkoxysilane compound containing trialkylsilyl group in molecular structure is the alkoxysilane compound containing trialkylsilyl group in molecular structure more than 500, even manufacture the process of liquid crystal display device for drip completion method by liquid crystal as sealing material for liquid crystal display device, also can not produce liquid crystal pollution because of bonding auxiliary agent.
As such molecular weight, be that alkoxysilane compound containing trialkylsilyl group in molecular structure more than 500 has no particular limits, can enumerate for example three (3-trimethoxy-silylpropyl) chlorinated isocyanurates, N-triethoxysilylpropyltetrasulfide quinine urethane, (ten three fluoro-1,1,2,2,-tetrahydrochysene octyl group) triethoxyl silane, (ten seven fluoro-1,1,2,2,-tetrahydrochysene decyl) triethoxyl silane, two [(3-methyl dimethoxy oxygen base silyl) propyl group] poly(propylene oxide), two (pentanedioic acid (ペ Application タ Application ジ オ ネ-ト)) titanium-O, two (the oxoethyl)-aminopropyltriethoxywerene werene of O-etc.These alkoxysilane compound containing trialkylsilyl group in molecular structure, also can be synthetic by the organoalkoxysilane with reactive base and/or polymerizability base such as also using the commercially available products such as チ Star ソ society system, waste river chemistry society's system (" コ Application Port セ ラ Application E202 ").
In addition, to contain molecular weight in alkoxysilane compound containing trialkylsilyl group in molecular structure be more than 200 and hydrogen bond functional group value is 2 * 10 -3-7 * 10 -3the 3rd curable resin composition of the present invention of the alkoxysilane compound containing trialkylsilyl group in molecular structure of mol/g, can not produce liquid crystal pollution because of bonding auxiliary agent even manufacture the process of liquid crystal display device for drip completion method by liquid crystal as sealing material for liquid crystal display device yet.
In addition, above-mentioned hydrogen bond functional group value can be calculated by following formula (9).
[mathematical expression 2]
Quantity/the molecular weight of the hydrogen bond functional group in hydrogen bond functional group value (mol/g)=a part
(9)
As the hydrogen bond functional group in above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure, so long as except-NH 2the functional group with hydrogen bond beyond base or residue etc. just have no particular limits, can enumerate such as-OH base ,-the SH base ,-NHR base (R means aromatic hydrocarbons or aliphatic hydrocarbon or these derivative) ,-the COOH base ,-functional group such as NHOH base and molecular memory-the NHCO-base ,-the NH-base ,-CONHCO-,-residues such as NH-NH-.
As this molecular weight, be more than 200 and hydrogen bond functional group value is 2 * 10 -3-7 * 10 -3the alkoxysilane compound containing trialkylsilyl group in molecular structure of mol/g has no particular limits, and can enumerate for example N-3-acryloxy (ア Network リ ロ キ シ)-2-hydroxypropyl)-APTES, 3-(N-allyl amino) propyl trimethoxy silicane, two (2-hydroxyethyl)-APTESs, two [3-(triethoxysilyl) propyl group] urea, two (trimethoxy-silylpropyl) amine, two [3-(trimethoxy-silylpropyl)] quadrol, 3-(2,4-dinitrophenyl amino) propyl-triethoxysilicane, N-(hydroxyethyl)-N-methylamino propyl trimethoxy silicane, 2-hydroxyl-4-(3-triethoxy propoxy-) diphenylketone, 3-sulfydryl propyl trimethoxy silicane, O-(methacryloxyethyl)-N-(triethoxysilylpropyltetrasulfide) urethane, N-(3-methacryloxy-2-hydroxypropyl)-APTES, N-phenyl amino propyl trimethoxy silicane, N-1-styroyl-N '-triethoxysilylpropyltetrasulfide urea, O-(alkynes propoxy-)-N-(triethoxysilylpropyltetrasulfide) urethane, (3-triethoxysilylpropyltetrasulfide)-tertiary butyl carbamate, N-(3-triethoxysilylpropyltetrasulfide)-4-maloyl group amine, (S)-N-triethoxysilylpropyltetrasulfide-O-aminocarbamic acid in Meng ester, 3-(triethoxysilylpropyltetrasulfide)-p-nitrobenzamide, N-(triethoxysilylpropyltetrasulfide)-O-polyethylene oxide urethane, N-triethoxysilylpropyltetrasulfide quinine urethane, N-triethoxysilylpropyltetrasulfide quinine (キ ニ Application) urethane, N-[5-(trimethoxysilyl)-2-azepine-1-oxo-amyl group] hexanolactam, O-(vinyloxy group ethyl)-N-(triethoxysilylpropyltetrasulfide) urethane etc.These molecular weight are more than 200 and hydrogen bond functional group value is 2 * 10 -3-7 * 10 -3the alkoxysilane compound containing trialkylsilyl group in molecular structure of mol/g is such as also using the commercially available products such as チ Star ソ society system.In addition, these alkoxysilane compound containing trialkylsilyl group in molecular structure also can be by having NH 2the commercially available organoalkoxysilanes of base, NCO base, acryl, epoxy group(ing) isoreactivity functional group etc. are synthetic.Can enumerate for example equivalent reactant of 3-TSL 8330 and カ レ Application ズ MOI (clear and electrician society system), the equivalent reactant of 3-TSL 8330 and エ ピ コ-ト 828 (japan epoxy resin society system), the equivalent reactant of 3-TSL 8330 and 3-acryloxy propyl trimethoxy silicane, the equivalent reactant of 3-isocyanic ester propyl-triethoxysilicane and vinylformic acid-2-hydroxyl ethyl ester resin, the equivalent reactant of 3-isocyanic ester propyl-triethoxysilicane and 3-sulfydryl propyl trimethoxy silicane, the equivalent reactant of 3-isocyanic ester propyl-triethoxysilicane and 3-glycidoxypropyltrime,hoxysilane, the equivalent reactant of 3-glycidoxypropyltrime,hoxysilane and vinylformic acid-2-hydroxyl ethyl ester resin, the equivalent reactant of 3-glycidoxypropyltrime,hoxysilane and 3-sulfydryl propyl trimethoxy silicane etc.
Above-mentioned molecular weight is the alkoxysilane compound containing trialkylsilyl group in molecular structure more than 500 and molecular weight is more than 200 and hydrogen bond functional group value is 2 * 10 -3-7 * 10 -3the alkoxysilane compound containing trialkylsilyl group in molecular structure of mol/g can be used separately, also can be used in combination.
Above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure preferably has at least more than one polymerizability functional group and/or reactive functional groups.Thus, when the 3rd curable resin composition of the present invention is solidified, above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure embeds in cured article, so can not be eluted in liquid crystal after solidifying.
As above-mentioned polymerizability functional group, reactive functional groups, so long as just have no particular limits with the polymerizability functional group of free-radical polymerised, cationically polymerizable, anionoid polymerization or the reactive functional groups of reactive with active hydrogen.
As above-mentioned polymerizability functional group, can enumerate such as acryl, methacryloyl, epoxy group(ing), vinyl etc.As the reactive functional groups with above-mentioned reactive with active hydrogen, can enumerate such as isocyanate group, acryl, methacryloyl, epoxy group(ing) etc.Wherein, from solidifying together with common sealant cures composition and more being difficult to the aspect of dissolving with respect to liquid crystal, what be applicable to is to be selected from least one of epoxy group(ing), acryl and methacryloyl.
In the 3rd curable resin composition of the present invention, the preferred lower limit of the combined amount of above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure is 0.1 weight part with respect to curable resin 100 weight parts, and preferred upper limit is 20 weight parts.If less than 0.1 weight part, can not bring into play the function of bonding strength and water tolerance sometimes fully, if surpass 20 weight parts, likely damage the fundamental property as curable resin composition such as solidified nature.
The present inventors have carried out wholwe-hearted research to the problem of the connectivity of sealing agent, mix the resin particle with specific core shell structure in the curable resin composition that to found that by the second-order transition temperature to solidifying the after fixing thing be particular value, even using up while being cured, also can obtain the effect of significantly improving with the connectivity of substrate, so far complete the 4th the present invention.
The 4th the present invention is curable resin composition, it is to contain the curable resin be cured under the effect of light and/or heat, the curable resin composition of polymerization starter and resin particle, above-mentioned resin particle has the shell formed by have the core particle that caoutchouc elasticity and second-order transition temperature form for resin below-10 ℃ and the resin that is 50-150 ℃ by the second-order transition temperature formed on the surface of above-mentioned core particle, cured article is 5 ℃/minute of heat-up rates, the second-order transition temperature of measuring with dynamic viscoelastic method of masurement (DMA method) under the condition of frequency 10Hz is 120 ℃ or more than it.
Above-mentioned resin particle has the shell formed by have the core particle that caoutchouc elasticity and second-order transition temperature form for resin below-10 ℃ and the resin that is 50-150 ℃ by the second-order transition temperature formed on the surface of above-mentioned core particle.
In addition, in this specification sheets, unless be particularly limited, second-order transition temperature refers to the temperature of measuring under the condition of 10 ℃/minute of heat-up rates by common DSC method.
Have caoutchouc elasticity and second-order transition temperature and have no particular limits for the resin below-10 ℃ as above-mentioned, what be applicable to is the polymkeric substance of (methyl) acryl monomer for example.
As above-mentioned (methyl) acryl monomer, can enumerate such as ethyl propenoate, propyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-EHA, β-dimethyl-aminoethylmethacrylate, butyl methacrylate etc.These (methyl) acryl monomer polymerizations separately, also can copolymerization more than two kinds.
The resin that is 50-150 ℃ as above-mentioned second-order transition temperature has no particular limits, and can enumerate such as by polymerizations such as isopropyl methacrylate, Tert-butyl Methacrylate, cyclohexyl methacrylate, methacrylic acid phenylester, methyl methacrylate, vinylbenzene, 4-chloro-styrene, 2-ethyl styrene, vinyl cyanide, vinylchlorid and the polymkeric substance obtained.These monomers can be used separately, also can more than two kinds, be used in combination.
The particle diameter of above-mentioned resin particle can suitably be selected according to the application target of the 4th curable resin composition of the present invention, when when the sealing material for liquid crystal display device, is limited to 0.01 μ m under preferred, is limited to 5 μ m on preferred.If in this scope, resin particle is enough large with respect to the surface-area of above-mentioned curable resin, can effectively show the swelling effect of sandwich layer, the gap operating between the substrate in the time of can guaranteeing in addition as sealing material for liquid crystal display device.
Have no particular limits as the method for manufacturing above-mentioned resin particle, can enumerate following methods: only use the monomer that forms core to form core particle with emulsion polymerization, then add the monomer that forms shell to carry out polymerization and form shell on the surface of core particle.
In the 4th curable resin composition of the present invention, the preferred lower limit of the combined amount of above-mentioned resin particle is 15 weight parts with respect to above-mentioned curable resin 100 weight parts, and preferred upper limit is 50 weight parts.If less than 15 weight parts, sometimes can not obtain sufficient connectivity and improve effect, if surpass 50 weight parts, the thickening degree can surpass required degree sometimes.Be limited to 20 weight parts on preferred.
The second-order transition temperature that the cured article of the 4th curable resin composition of the present invention is measured with dynamic viscoelastic method of masurement (DMA method) under the condition of 5 ℃/minute of heat-up rates, frequency 10Hz is 120 ℃ or more than it.If 120 ℃ of less thaies, even add above-mentioned resin particle, can not obtain the effect of improving with the glass substrate connectivity.The upper limit of second-order transition temperature has no particular limits, but is limited to 180 ℃ on preferred.If surpass 180 ℃, sometimes can not obtain fully connectivity.Be limited to 150 ℃ on preferred.
In addition, wherein cured article refers to solidify the cured article formed under the effect of light and/or heat.
The 4th curable resin composition of the present invention is preferably 150N/cm in junction of glass substrate, bonding strength while making it curing 2above.If not enough 150N/cm 2, the insufficient strength of the liquid crystal indicator sometimes obtained is abundant.
When in addition, above-mentioned bonding strength is peeled off two glass substrates after for example can being engaged two glass substrates and it is solidified by use curable resin composition of the present invention, required tensile strength is obtained.
The present inventors' problem inhomogeneous to gap carried out wholwe-hearted research, found that if use the curable resin composition that shows specific average linear expansion rate that contains inorganic particles, can be not inhomogeneous because of the substrate generation unit gap that misplaces, so far completed the 5th and the 6th the present invention.
The 5th the present invention is curable resin composition, it is to contain the curable resin composition that the curable resin, polymerization starter and the median size that are cured are 1 μ m or the inorganic particulate below it under the effect of light and/or heat, the temperature of low 40 ℃ of ratio second-order transition temperature of cured article when curing has only occurred under the effect of light to the average linear expansion rate α between the temperature than low 10 ℃ of second-order transition temperature 1be 1 * 10 -4-5 * 10 -4/ ℃, and, than the temperature of high 10 ℃ of second-order transition temperature, arrive than the average linear expansion rate α between the temperature of high 40 ℃ of second-order transition temperature 2be 2 * 10 -4-1 * 10 -3/ ℃.
The 6th the present invention is curable resin composition, it is to contain the curable resin composition that the curable resin, polymerization starter and the median size that are cured are 1 μ m or the inorganic particulate below it under the effect of light and/or heat, it is characterized in that, the temperature of low 40 ℃ of ratio second-order transition temperature of cured article when curing has occurred under the effect of light and heat to the average linear expansion rate α between the temperature than low 10 ℃ of second-order transition temperature 1be 5 * 10 -5-1 * 10 -4/ ℃, and, than the temperature of high 10 ℃ of second-order transition temperature, arrive than the average linear expansion rate α between the temperature of high 40 ℃ of second-order transition temperature 2be 1 * 10 -4-3 * 10 -4/ ℃.
As for the 5th and the curable resin of the 6th curable resin composition of the present invention, applicable is the resin that has ring-type ether and free-radical polymerised functional group in a part.The the 5th and the 6th curable resin composition of the present invention can have light solidified and Thermocurable simultaneously thus, when at least one of sealing agent, sealing compound and the upper and lower conductive material of the manufacture with acting on the liquid crystal indicator that adopts the drippage completion method, carry out fact by heating after can it being solidified temporarily by rayed curing.
As for the above-mentioned the 5th and the ring-type ether of the curable resin of the 6th curable resin composition of the present invention have no particular limits, what be applicable to is for example epoxy group(ing) or oxetanyl.In addition, as the free-radical polymerised functional group in above-mentioned reaction resin, have no particular limits, what be applicable to is (methyl) acryl for example.
For the above-mentioned the 5th and the total functional group's equivalent preferred lower limit of ring-type ether and free-radical polymerised functional group of the curable resin of the 6th curable resin composition of the present invention be 2.5mmol/g, be limited to 5.5mmol/g on preferred.If not enough 2.5mmol/g, thermotolerance and wet fastness are poor sometimes, if surpass 5.5mmol/g, the adaptation to substrate etc. is inadequate sometimes.
For the above-mentioned the 5th and functional group's equivalent preferred lower limit of the free-radical polymerised functional group of the curable resin of the 6th curable resin composition of the present invention be 2.0mmol/g, be limited to 5.0mmol/g on preferred.If not enough 2.0mmol/g, thermotolerance and wet fastness are poor sometimes, if surpass 5.0mmol/g, the adaptation to substrate etc. is inadequate sometimes.
For the above-mentioned the 5th and the free-radical polymerised functional group equivalent of the curable resin of the 6th curable resin composition of the present invention divided by the value preferred lower limit of ring-type ether equivalent gained, be 1, preferred upper limit is 9.If less than 1, photoreactivity descends sometimes, even the backward sealing agent in adjusting play irradiates light, not only interim initial cure can not occur, and increases to the wash-out of liquid crystal, if surpass 9, sometimes with regard to the aspect of connectivity and water vapour permeability, becomes not enough.
From reducing and the intermiscibility of liquid crystal, the viewpoint of decontamination; for the above-mentioned the 5th and the curable resin of the 6th curable resin composition of the present invention preferably there is the resin of hydroxyl and/or urethane bond; in addition, at least one molecular skeleton that preferably there is part (methyl) the acryloyl compound of the biphenyl backbone of being selected from, naphthalene skeleton, bis-phenol skeleton, phenolic resin varnish type epoxy resin with regard to improving stable on heating viewpoint.
For the above-mentioned the 5th and the curable resin of the 6th curable resin composition of the present invention more preferably to have atomicity be the ring texture below 24.Wherein so-called atomicity refers to the summation of the atomicities such as carbon in the molecule that forms above-mentioned ring texture, hydrogen, oxygen.If atomicity surpasses 24, sometimes can not meet coefficient of linear expansion described later, or poor heat resistance.
For the above-mentioned the 5th and the equivalent preferred lower limit of the ring texture of the curable resin of the 6th curable resin composition of the present invention be 1.5mmol/g, be limited to 6.0mmol/g on preferred.If not enough 1.5mmol/g, coefficient of linear expansion becomes large sometimes, can not meet scope described later, if surpass 6.0mmol/g, the adaptation to substrate etc. is abundant not sometimes.
As the atom that forms above-mentioned ring texture, have no particular limits, but preferably skeleton structure is carbon atom, such ring texture is aromatic series preferably.
As having no particular limits of above-mentioned aromatic series, can enumerate such as benzene, indenes, naphthalene, tetralin, anthracene, phenanthrene etc.
For the above-mentioned the 5th and the number-average molecular weight preferred lower limit of the curable resin of the 6th curable resin composition of the present invention be 300, preferred upper limit is 550.If less than 300, make the orientation disorder of liquid crystal sometimes to the liquid crystal wash-out, if surpass 550, sometimes due to thickness, the modulation of sealing agent, sealing compound or upper and lower conductive material becomes difficult.
Above-mentioned inorganic particles has and prevents the 5th and the cure shrinkage of the 6th curable resin composition of the present invention, realizes the effect of following coefficient of linear expansion.
Have no particular limits as above-mentioned inorganic particles, can enumerate such as the material formed by silicon-dioxide, diatomite, aluminum oxide, zinc oxide, ferric oxide, magnesium oxide, stannic oxide, titanium oxide, magnesium hydroxide, aluminium hydroxide, magnesiumcarbonate, barium sulfate, gypsum, Calucium Silicate powder, talcum, granulated glass sphere, sericite activated clay, bentonite, aluminium nitride, silicon nitride, montmorillonite, kaolin, malthacite, potassium titanate, zeolite, sepiolite, calcium carbonate, calcium oxide, magnesium oxide, ferrite, rhombohedral iron ore, aluminum borate etc.What wherein, be applicable to is silicon-dioxide, aluminum oxide.
Shape as above-mentioned inorganic particles is not particularly limited, and can enumerate spherical, needle-like, the regular shape or irregularly shaped such as tabular.
Above-mentioned inorganic particles also can carry out surface treatment by least one that is selected from imidazoles silane compound, epoxy silane compounds and amino silane compounds, contains the structure that imidazoles skeleton and alkoxysilyl combine across spacer in above-claimed cpd.By carrying out such surface treatment, can improve the avidity of above-mentioned inorganic particulate and above-mentioned reaction resin, can improve these as silane coupling agent role, engaging force and storage stability simultaneously.
Be limited to 1 μ m on the median size of above-mentioned inorganic particles.If surpass 1 μ m, the surface of photo-thermal curing resin combination of the present invention being solidified under the effect of light and/or heat to the cured article formed becomes uneven, the low precision of cell gap.Be limited to 0.01 μ m under preferred, be limited to 0.1 μ m on preferred.If less than 0.01 μ m, thixotropy uprises sometimes, can produce condensation product.
In the 5th and the 6th curable resin composition of the present invention, the preferred lower limit of the content of above-mentioned inorganic particulate is 10 weight parts with respect to curable resin 100 weight parts, and preferred upper limit is 50 weight parts.Be limited to 15 weight parts under preferred, be limited to 35 weight parts on preferred.
The 5th curable resin composition of the present invention, only the cured article when irradiating light and make it to solidify than second-order transition temperature also the temperature of low 40 ℃ to than the second-order transition temperature average linear expansion rate α between the temperature of low 10 ℃ also 1be 1 * 10 -4-5 * 10 -4/ ℃, and, than second-order transition temperature also the temperature of high 10 ℃ to than the second-order transition temperature average linear expansion rate α between the temperature of high 40 ℃ also 2be 2 * 10 -4-1 * 10 -3/ ℃.If average linear expansion rate α 1less than 1 * 10 -4/ ℃, or average linear expansion rate α 2less than 2 * 10 -4/ ℃, when the sealing agent as manufactured liquid crystal indicator by the drippage completion method, sealing compound and upper and lower conductive material, solidify even carry out the fact by heating after solidifying by rayed temporarily, with the closely sealed of substrate etc., also become insufficient, can not obtain enough connectivities.If average linear expansion rate α 1surpass 5 * 10 -4/ ℃, or average linear expansion rate α 2surpass 1 * 10 -3/ ℃, inhomogeneous because of substrate dislocation generation unit gap while solidifying temporarily.
The 6th curable resin composition of the present invention, the cured article while making it to solidify under the effect of light and heat arrives the average linear expansion rate α between the temperature of also hanging down 10 ℃ than second-order transition temperature in the temperature of also hanging down 40 ℃ than second-order transition temperature 1be 5 * 10 -5-1 * 10 -4/ ℃, and, than second-order transition temperature also the temperature of high 10 ℃ to than the second-order transition temperature average linear expansion rate α between the temperature of high 40 ℃ also 2be 1 * 10 -4-3 * 10 -4/ ℃.If average linear expansion rate α 1less than 5 * 10 -5/ ℃, or average linear expansion rate α 2less than 1 * 10 -4/ ℃, when the sealing agent as manufactured liquid crystal indicator by the drippage completion method, sealing compound and upper and lower conductive material, solidify even carry out the fact by heating after solidifying by rayed temporarily, with the closely sealed of substrate etc., also become insufficient, can not obtain enough connectivities.If average linear expansion rate α 1surpass 1 * 10 -4/ ℃, or average linear expansion rate α 2surpass 3 * 10 -4/ ℃, thermotolerance and the cold cycling characteristic of the liquid crystal indicator obtained are poor.
1-3 described above curable resin of the present invention has mainly solved the liquid crystal pollution problem, and the 4th curable resin of the present invention has mainly solved the connectivity problem, and 5-6 curable resin composition of the present invention has mainly solved the problem of cell gap.These can independently be implemented, but by being used in combination in not hindering the scope of purpose separately, the sealing material for liquid crystal display device used while going for manufacturing liquid crystal indicator by the drippage completion method.
1-6 curable resin composition of the present invention also can contain solidifying agent.Have no particular limits as above-mentioned solidifying agent, can enumerate such as amine compound, polyphenol based compound, anhydride compound etc.
Above-mentioned so-called amine compound refers to the compound that has more than one 1-3 level amino in molecule, can enumerate aromatic amines such as mphenylenediamine, diaminodiphenyl-methane; The imidazolium compoundss such as glyoxal ethyline, 1,2 dimethylimidazole, 1-1-cyanoethyl-2-methylimidazole; The imidazolinium compoundss such as glyoxal ethyline quinoline; The dihydrazide compound such as sebacic dihydrazide, isophthalic dihydrazide; Dyhard RU 100 etc.In addition, also can use the commercially available amine additives classes such as ア ミ キ ユ ア PN-23, ア ミ キ ユ ア MY-24 by monosodium glutamate Off ア イ Application テ Network ノ society.
As above-mentioned polyhydric phenols, can enumerate polyphenolic substances such as the エ ピ キ ユ ア 170 commercially available by japan epoxy resin society, エ ピ キ ユ ア YL6065; The phenolic varnish type resol such as エ ピ キ ユ ア MP402FPI etc.
As above-mentioned acid anhydrides, can enumerate such as エ ピ キ ユ ア YH306, the YH307 etc. commercially available by japan epoxy resin society.
These solidifying agent can be used separately, also can more than two kinds, be used in combination.Wherein, the good viewpoint of curability at low temperatures, useful life when mixing with curable resin, more suitably solid amine compound.In above-mentioned solid amine compound, from the viewpoint of the storage stability of solidification compound, more preferably fusing point is more than 100 ℃.
In 1-6 curable resin composition of the present invention, the preferred lower limit of content of above-mentioned solidifying agent is 0.1 weight part with respect to above-mentioned curable resin 100 weight parts, and preferred upper limit is 100 weight parts.If less than 0.1 weight part, sometimes solidify insufficient, if surpass 100 weight parts, the storage stability of curable resin composition variation likely.Be limited to 1 weight part under preferred, be limited to 50 weight parts on preferred.
1-6 curable resin composition of the present invention also can contain weighting agents such as adjusting thixotropic thixotropic agent, gap adjusting agent, defoamer, the flat agent of painting, polymerization retarder, filler etc. in addition as required.
As the method for manufacturing 1-6 curable resin composition of the present invention, have no particular limits, can enumerate such as by above-mentioned curable resin, polymerization starter and the various additives that mix as required etc. by known method was mixed method in the past etc.At this moment, also can make for the impurity of deionizing it contact with layer silicate mineral plasma adsorptive solid.
In addition, while manufacturing 1-6 curable resin composition of the present invention, preferably will form the operation of being used strainer to be filtered after the composition mixing of curable resin composition.
Usually, because the affinity of curable resin and solidifying agent or filler is not necessarily high, so, if only by common method, each composition is mixed, solidifying agent and filler just can not be scattered in resin fully, its part can form condensation product by cohesion.Even produce such condensation product, while by method in the past, manufacturing sealing material for liquid crystal display device, can pass through hot pressing process adjustment unit gap, so also can exert an influence hardly.But, while by the drippage completion method, manufacturing liquid crystal display device, because the cell gap based on hot pressing is not adjusted operation, so, while containing the large condensation product of particle diameter in sealing material for liquid crystal display device, can have influence on the cell gap of the liquid crystal display device of acquisition.
After mixing by the composition that will form curable resin composition, use strainer to be filtered, really can remove the larger condensation product of particle diameter ratio that affects cell gap, so it is bad can not produce the cell gap caused by above-mentioned condensation product.
The manufacture method that has after the composition that will form curable resin composition mixes the curable resin composition of the operation of using strainer to be filtered is also one of the present invention.
As above-mentioned strainer, so long as the cell gap that can remove at least to the Object LC display element brings the condensation product of the particle diameter of effect just to have no particular limits.Preferably can remove the condensation product of the above particle diameter of cell gap twice with Object LC display element, also preferably can remove the condensation product of the above particle diameter of cell gap with Object LC display element.Wherein, in the situation of the element formed on the transparency carriers such as circuit and the liquid crystal display device of the some or all of relevant structure of hermetic unit, the width of hermetic unit is equivalent to the size of this element in the degree of actual cell gap, so more preferably can remove the condensation product with this above particle diameter of hermetic unit width narrowed down.
As such strainer, the collection efficiency that for example can enumerate the particle to having the above particle diameter of Object LC display element substrate spacing (cell gap) is the strainer more than 70%; Flow through flow 2L/min, pressure 4.6N/cm 2air the time air flowing resistance value be 10mmH 2the strainer that O is above etc.
In addition, curable resin composition is because viscosity is high, so preferably pressurize to curable resin composition when above-mentioned filtration.Therefore, as above-mentioned strainer, even preferably pressurization also can be born.As such strainer, applicable waits with pottery the strainer formed by metals such as stainless steels.
In addition, in above-mentioned filter progress, temperature during filtration is more low more preferred, in order to suppress curing reaction, but for the viscosity of the above-mentioned curable resin composition of reduce to improve filtration efficiency, so preferably can not cause the above-mentioned curable resin composition of heating in curing scope.The temperature preferred lower limit of above-mentioned curable resin composition during above-mentioned filtration is 25 ℃, and preferred upper limit is 70 ℃.If outside this scope, filtration efficiency variation sometimes, heat-up time is elongated owing to filtering simultaneously, the viscosity rise of filtrate, the viscosity rise degree of sealing agent becomes large while sometimes preserving or while using.More preferably be limited to down 30 ℃, be limited to 60 ℃ on more preferably.
In addition, with regard to the constituent of curable resin composition, particularly solidifying agent, preferably select to suppress near the composition of the viscosity rise of above-mentioned curable resin composition normal temperature.
State in the use before strainer carries out filter progress, the composition that preferably will form in advance curable resin composition mixes fully.If undercompounding, the quantitative change of the composition of sometimes removing with strainer is many, can not obtain the sealing material for liquid crystal display device with the performance that meets standard.
Method as above-mentioned mixing has no particular limits, and can enumerate the method such as the use planetary-type mixer adopted and three roller mixing machines etc. all the time.
In curable resin composition of the present invention, the content with particle of the above particle diameter of Object LC display element substrate spacing is preferably below 30 % by weight.
When 1-6 curable resin composition of the present invention is manufactured liquid crystal display device as sealing material for liquid crystal display device for dripped completion method by liquid crystal, few to the pollution of liquid crystal, good with the connectivity of substrate, and also the generation unit gap is not inhomogeneous.
The sealing material for liquid crystal display device that uses curable resin composition of the present invention to form is also one of the present invention.
The used for liquid crystal display element sealing compound (endsealant) that uses curable resin composition of the present invention to form is also one of the present invention.
In addition, in liquid crystal display device, usually for make on two transparency carriers relatively to electrode between upper and lower conducting, and use upper and lower conductive material.Above-mentioned upper and lower conductive material forms by making curable resin composition contain electrically conductive microparticle.
The upper and lower conductive material of the used for liquid crystal display element that contains curable resin composition of the present invention and electrically conductive microparticle is also one of the present invention.
Have no particular limits as above-mentioned electrically conductive microparticle, can enumerate for example metal particle; The particulate (hereinafter referred to as the metal deposition particulate) formed at the enterprising row metal plating of reisn base material particulate; The particulate (hereinafter referred to as covering metal plating particulate) formed with coverings such as resins after the enterprising row metal plating of reisn base material particulate; And there is protruding particulate etc. on these metal particles, metal deposition particulate, covering metal plating microparticle surfaces.Wherein, from uniformly dispersed resin combination and aspect that electroconductibility is good, preferably implemented metal deposition particulate or the covering metal plating particulate of golden plating or copper plating.
Above-mentioned electrically conductive microparticle is 0.2 weight part with respect to the combined amount preferred lower limit of above-mentioned curable resin composition 100 weight parts, and preferred upper limit is 5 weight parts.
Have no particular limits as the method for manufacturing the upper and lower conductive material of used for liquid crystal display element of the present invention, can enumerate such as combined amount is according to the rules mixed with the planetary whipping appts of vacuum etc. after mixing by above-mentioned curable resin composition, above-mentioned electrically conductive microparticle etc. method etc.
As the method for using at least one the manufacture liquid crystal display device in sealing material for liquid crystal display device of the present invention, used for liquid crystal display element sealing compound of the present invention and the upper and lower conductive material of used for liquid crystal display element of the present invention, have no particular limits, for example, can be with following method manufacture.On a substrate of two transparency carriers with electrode such as ito thin film, sealing material for liquid crystal display device of the present invention is formed to rectangular seal pattern by silk screen printing, divider coating etc.In addition, on another transparency carrier, liquid crystal display device of the present invention is formed on the electrode of regulation to upper and lower conducting pattern with divider coating etc. by upper and lower conductive material.Also have, also can in sealing agent, contain electrically conductive microparticle and replace upper and lower conductive material to use, make its upper and lower conducting.Then, at sealing agent under uncured state, by liquid crystal carefully drip be coated in the transparency carrier framework whole upper, another transparency carrier of stack under uncured state in upper and lower conductive material immediately, and it is solidified to hermetic unit and upper and lower conductive material part irradiation ultraviolet radiation.When sealing material for liquid crystal display device of the present invention and the upper and lower conductive material of used for liquid crystal display element of the present invention have Thermocurable, then be heating and curing in the baking oven of 100-200 ℃ and within 1 hour, make it fully curing, thereby make liquid crystal display device.
Using the liquid crystal display device of at least one formation in sealing material for liquid crystal display device of the present invention, used for liquid crystal display element sealing compound of the present invention and the upper and lower conductive material of used for liquid crystal display element of the present invention is also one of the present invention.
In addition, the present inventors have carried out wholwe-hearted research to the liquid crystal display device by drippage completion method manufacture, found that in the situation that alignment films contact with sealing agent and are easy to cause that liquid crystal material pollutes, and are easy to produce the image demonstration bad.Therefore, in liquid crystal display device, by forming alignment films and the discontiguous structure of sealing agent, can effectively prevent from showing bad.
Following liquid crystal display device is also one of the present invention, to at least a portion on a surface, be formed with a pair of transparency carrier of alignment films, middle across near the sealing agent around forming its periphery, certain interval that is separated by is oppositely arranged, make simultaneously the described surface that is formed with alignment films relatively to, and enclose liquid crystal material is arranged in the space formed by described transparency carrier and sealing agent, wherein said alignment films does not contact mutually with described sealing agent.
The accompanying drawing explanation
Fig. 1 means the local amplification profile of an example of liquid crystal display device of the present invention.
Fig. 2 means the horizontal sectional drawing of an example of liquid crystal display device of the present invention.
Fig. 3 means the local amplification profile of an example of liquid crystal display device in the past.
In figure,
10,30 liquid crystal display device
11,31 transparency carriers
12,32 sealing agents
13,33 alignment films
14,34 liquid crystal materials
Embodiment
Fig. 1 is the local amplification profile that means in analog an example of liquid crystal display device of the present invention,
Fig. 2 means the horizontal sectional drawing of an example of liquid crystal display device of the present invention.
As shown in fig. 1, the structure of liquid crystal display device 10 of the present invention is engaged across sealing agent 12 in the middle of being formed with in its surface two transparency carriers 11 of alignment films 13 so that alignment films 13 relatively to.
In addition, though not shown, between transparency carrier 11 and alignment films 13, for example, be formed with the transparency electrode that indium oxide film (ITO film) by doped tin etc. forms.
Such transparency electrode can be with formation such as known vacuum vapour deposition, gunite, pyrosol method, pickling processes on the surface of above-mentioned transparency carrier.
In addition, as shown in Figure 2, in liquid crystal display device 10 of the present invention, sealing agent 12 forms near the periphery of transparency carrier 11, and alignment films 13 is formed in the zone surrounded by sealing agent 12 on surface of transparency carrier 11, and with sealing agent 12, does not contact.
In liquid crystal display device 10 of the present invention, sealing agent 12 is with 13 of alignment films otherwise contact and get final product, but these preferably are separated by more than 5 μ m.If less than 5 μ m, can not prevent from showing bad sometimes.
In addition, liquid crystal display device of the present invention is not limited to the structure shown in Fig. 1 and Fig. 2 especially, for example, can be to be provided with the structure as the needed known any member in the past of liquid crystal display device such as partition, TFT element, color filter yet.
Have no particular limits as the transparency carrier that forms liquid crystal display device of the present invention, can enumerate such as glass, resin etc. and be used as the known material of liquid crystal display device all the time.In addition, as size and the thickness of above-mentioned transparency carrier, have no particular limits, the size that can contrast the Object LC display element suitably determines.
In addition, as above-mentioned alignment films, have no particular limits, can use all the time the alignment films for liquid crystal display device, but from thermotolerance, chemical resistant properties with the good aspects such as connectivity of transparency carrier are considered, usually use polyimide.
The liquid crystal display device of the present invention of this structure can be used for example following methods manufacture.
At first, on the position of the regulation of two faces of the transparent glass substrate with two electrodes such as ito thin films, use flexographic printing, intaglio printing, ink jet printing, silk screen printing and spin-coating method etc. to form the rectangular alignment films formed by polyimide etc.Now, manage not form alignment films on the coating position of sealing agent.
Then, carry out the orientation process such as friction treatment on above-mentioned alignment films after, near the periphery of above-mentioned transparency carrier, silk screen printing for sealing agent, divider coating etc. are formed to the seal pattern of the shape of surrounding above-mentioned alignment films on the position do not contacted with alignment films.
Then, at sealing agent, under uncured state, liquid crystal is carefully dripped on whole that is coated in the transparency carrier framework, another transparency carrier that superposes immediately, solidify it to the hermetic unit irradiation ultraviolet radiation.When above-mentioned sealing agent has Thermocurable, can be heating and curing in the baking oven of 80-200 ℃ again and within 0.5-2 hour, make it fully curing, thereby manufacture liquid crystal display device of the present invention.
In liquid crystal display device of the present invention, because the alignment films formed on transparency carrier does not contact with sealing agent, near around the sealing agent that the most easily produces the formation that liquid crystal material pollutes liquid crystal material be difficult to contaminated, so can obtain high-quality demonstration image.
The effect of invention
According to the present invention, can provide when as sealing material for liquid crystal display device when by the drippage completion method, manufacturing the process of liquid crystal display device, to the pollution of liquid crystal less, with the connectivity of substrate inhomogeneous curable resin composition, sealing material for liquid crystal display device and the liquid crystal display device in generation unit gap well and not.
Embodiment
Below by embodiment, the present invention is described in further detail, but the present invention is not limited in these embodiment.
(embodiment 1)
Make (new day money chemistry society system: the YSLV-80XY of the crystallinity epoxy resin shown in following general formula (10); 78 ℃ of fusing points) 1000 weight parts, p methoxy phenol 2 weight parts as polymerization retarder, triethylamine 2 weight parts as catalysts, vinylformic acid 200 weight parts; react 5 hours 90 ℃ of lower stirring and refluxing when carrying air, obtain amorphism (methyl) acrylic modified epoxy resin (50% part propylene acylate).
[chemical formula 4]
In formula, G means glycidyl.
Add TriMethylolPropane(TMP) 134 weight parts, the BHT0.2 weight part as polymerization starter, dibutyl tin laurate 0.01 weight part as catalysts, isophorone diisocyanate 666 weight parts, under the condition of 60 ℃ of lower stirring and refluxing, reaction is 2 hours.Then, add vinylformic acid 2-hydroxyl ethyl ester 25.5 weight parts and Racemic glycidol 111 weight parts, when carrying air, 90 ℃ of lower stirring and refluxing, make it to react 2 hours.By the quartz that is filled with 10 weight parts and kaolinic natural bonding product (ホ Off マ Application ミ ネ ラ Le society system; シ リ チ Application V85) cylinder filters resulting resin 100 weight parts; with the ionic impurity in the absorption reaction thing, thereby obtain urethane modification part propylene acylate.
Using (methyl) acrylic modified epoxy resin 40 weight parts of obtaining, urethane modification part propylene acylate 20 weight parts, as hydrazides type solidifying agent (the monosodium glutamate Off ア イ Application テ Network ノ society system of latent energy solidifying agent; ア ミ キ ユ ア VDH) 15 weight parts, as 2 of Photoepolymerizationinitiater initiater; 2-diethoxy acetophenone 1 weight part, silicon oxide particle (median size is 1.5 μ m) 23 weight parts, γ-glycidoxypropyltrimethoxy silane 1 weight part; use three roller mixing machines fully to mix until form uniform liquid, thereby obtained curable resin composition.
The curable resin composition obtained is made to liquid crystal indicator as sealing material for liquid crystal display device.
That is, on a substrate of two transparency carriers with transparency electrode, with divider, be coated with sealing agent, thereby draw a rectangular frame.Then, by liquid crystal (チ Star ソ society system, it is JC-5004LA) thin that to drip whole of being coated in the transparency carrier framework upper, another transparency carrier that superposes immediately, to hermetic unit with high voltage mercury lamp with 100mW/cm 2intensity irradiation ultraviolet radiation 30 seconds.Then, make liquid crystal annealing 1 hour under 120 ℃, make its thermofixation, thereby obtain liquid crystal indicator.
(embodiment 2)
Make crystallinity epoxy resin (new day money chemistry society system: the YSLV-80DE meaned with following general formula (11); 79 ℃ of fusing points) 1000 weight parts, as p methoxy phenol 2 weight parts of polymerization retarder, as triethylamine 2 weight parts, vinylformic acid 200 weight parts of catalysts, when carrying air, 90 ℃ of lower stirring and refluxing, make it to react 5 hours, obtain crystallinity (methyl) acrylic modified epoxy resin (50% part propylene acylate).
Except replace amorphism (methyl) acrylic modified epoxy resin (50% part propylene acylate) with this crystallinity (methyl) acrylic modified epoxy resin (50% part propylene acylate); adopt the method identical with embodiment 1 to modulate curable resin composition, and it has been made to liquid crystal indicator as sealing agent.
[chemical formula 5]
In formula, G means glycidyl.
(comparative example 1)
Will be by the urethane acrylate meaned with following general formula (12) (chemistry society of common prosperity society system, AH-600) curable resin composition that 35 weight parts, vinylformic acid 2-hydroxyl butyl ester 15 weight parts, vinylformic acid isobornyl (イ ソ ボ ニ Le) ester 50 weight parts, benzophenone 3 weight parts form mixes, form uniform liquid, thereby obtain the sealing agent of light-cured type, use it to make liquid crystal indicator.
[chemical formula 6]
In formula, R 1mean the alkyl chain that carbonatoms is 5.
(comparative example 2)
Will be by bisphenol A type epoxy resin (the japan epoxy resin society system meaned with following general formula (13), エ ピ コ-ト 828US) 50 weight parts, hydrazides class solidifying agent (the industrial society of Japanese hydrazine system, NDH) curable resin composition that 25 weight parts form is used three roller mixing machines fully to mix until form uniform liquid, thereby the acquisition sealing agent, used it to make liquid crystal indicator.
[chemical formula 7]
For the liquid crystal indicator of being made by embodiment 1,2 and comparative example 1,2, before and after placing 500 hours under 60 ℃, 95%RH, the color ununiformity that the sealing peripheral part occurs in liquid crystal that detected by an unaided eye, estimated the liquid crystal pollution performance based on following four-stage: ◎ (do not have fully color inhomogeneous); Zero (having observed slight color inhomogeneous); △ (having observed some colors inhomogeneous); * (color is inhomogeneous quite clear).In addition, wherein for each part, with 5 samples, estimated.
The results are shown in table 1.
The color ununiformity is estimated
Embodiment 1 ○
Embodiment 2 ◎
Comparative example 1 ×
Comparative example 2 ×
(embodiment 3)
To use with the curable resin composition that embodiment 1 obtains in the same manner three roller mixing machines fully to mix until form uniform liquid, then with respect to curable resin composition 100 weight parts, mixing is as the metal deposition particulate that carries out golden plating (the ponding chemical industry society system of electrically conductive microparticle, ミ Network ロ パ-Le AU-206) 2 weight parts, mix with the planetary whipping appts of vacuum, thereby make the upper and lower conductive material of used for liquid crystal display element.
Except the conductive material up and down that utilize to obtain on transparency carrier through divider be coated on lead up and down on current electrode form upper and lower conducting with pattern, make in the same manner liquid crystal indicator with embodiment 1.
The liquid crystal indicator that obtains is placed 500 hours under 60 ℃, 95%RH environment, and now its conduction is good.
(embodiment 4)
(1) manufacture of radical polymerization initiator
Add 1-[4-(2-hydroxyl-oxethyl)-phenyl in reaction flask]-50 moles of 2-hydroxy-2-methyl-1-propane-1-ketone (Ciba Specialty Chemicals Inc. society system), make its heating for dissolving under the dry air atmosphere.
Drip at leisure wherein 100 moles of 0.05 mole of dibutyl tin laurate and 2-methacryloxy ethylidene isocyanic ester (clear and electrician society system), drip and finish reaction under 90 ℃ more afterwards, until confirm not have remaining isocyanate group with infrared absorption spectrum analysis, then, made with extra care, obtained the radical polymerization initiator A meaned by following formula (14).
[chemical formula 8]
(2) modulation of curable resin composition
The radical polymerization initiator A that 3 weight parts are obtained, part propylene acidylate epoxy resin (ダ イ セ Le ユ-シ-PVC-society's system as curable resin, UVAC1561) 40 weight parts, Acrylate Modified Epoxy resin (ダ イ セ Le ユ-シ-PVC-society's system, EB3700) 20 weight parts, spherical silicon dioxide (ア De マ テ Star Network ス society system as weighting agent, SO-C1) 15 weight parts, Off ジ キ ユ ア-FXR-1030 (Fuji changes into industrial society system) 15 weight parts as the epoxy thermosetting agent, γ-glycidoxypropyltrimethoxy silane 1 weight part as coupler, use paint roller fully to mix until form uniform liquid, thereby obtained curable resin composition.
(3) making of liquid crystal display device
Make interval particulate (ponding chemical industry society system, ミ Network ロ パ-Le SP-2055) 1 weight part is scattered in curable resin composition 100 weight parts of acquisition, as sealing material for liquid crystal display device, with divider, be coated on a substrate of two glass substrates with the alignment films that has completed friction treatment and transparency electrode.
Then by liquid crystal (チ Star ソ society system, JC-5004LA) thin drippage is coated on in the sealing agent framework of the glass substrate of transparency electrode whole, another glass substrate with transparency electrode that superposes immediately, partly use high voltage mercury lamp with 100mW/cm to sealing agent 2irradiation ultraviolet radiation 30 seconds.
Then heat 1 hour under 120 ℃, make its thermofixation, thereby obtain liquid crystal display device.
(embodiment 5)
Add 1-[4-(2-hydroxyl-oxethyl)-phenyl in reaction flask]-2-hydroxy-2-methyl-1-propane-50 moles of 1-ketone, make its heating for dissolving under the dry air atmosphere.
In temperature of reaction, be no more than under the condition of 90 ℃, drip at leisure wherein 50 moles of 0.05 mole of dibutyl tin laurate and 2-methacryloxy ethylidene isocyanic ester, drip and finish reaction under 90 ℃ more afterwards, until confirm not have remaining isocyanate group with infrared absorption spectrum analysis, then, made with extra care, obtained the intermediate a meaned by following formula (15).
[chemical formula 9]
Figure A20048001557300401
The intermediate a of 50 moles of acquisitions is added in reaction flask, make its heating for dissolving under the dry air atmosphere.Be no more than in temperature of reaction under the condition of 90 ℃ and drip at leisure wherein 0.05 mole of dibutyl tin laurate and 2,2,4-and 2,4,4-trimethyl hexamethylene diisocyanate (デ グ サ society system, TMHDI) 50 moles, under being no more than the condition of 90 ℃, temperature of reaction drips at leisure vinylformic acid 2-hydroxyl ethyl ester again after drip finishing, reaction under 90 ℃, until confirm not have remaining isocyanate group with infrared absorption spectrum analysis, then made with extra care, obtained the radical polymerization initiator B meaned by following formula (16).
[Chemical formula 1 0]
In above-mentioned general formula (16), A means 2,2,4-and 2,4,4-tri-methyl hexamethylene.
Except using radical polymerization initiator B replacement radical polymerization initiator A, use the method modulation curable resin composition identical with embodiment 4, make liquid crystal display device.
(embodiment 6)
The intermediate a made in 100 moles of embodiment 5 is added in reaction flask, make its heating for dissolving under the dry air atmosphere.Be no more than in temperature of reaction under the condition of 90 ℃ and drip at leisure wherein 0.1 mole of dibutyl tin laurate and 2,2,4-and 2,4,50 moles of 4-trimethyl hexamethylene diisocyanates, drip and finish reaction under 90 ℃ afterwards, until confirm not have remaining isocyanate group with infrared absorption spectrum analysis, then made with extra care, obtained the radical polymerization initiator C meaned by following formula (17).
[Chemical formula 1 1]
In above-mentioned general formula (17), A means 2,2,4-and 2,4,4-tri-methyl hexamethylene.
Except using radical polymerization initiator C replacement radical polymerization initiator A, use the method modulation curable resin composition identical with embodiment 4, make liquid crystal display device.
(embodiment 7)
Add 1-[4-(2-hydroxyl-oxethyl)-phenyl in reaction flask]-2-hydroxy-2-methyl-1-propane-50 moles of 1-ketone, make its heating for dissolving under the dry air atmosphere.Be no more than in temperature of reaction under the condition of 90 ℃ and drip at leisure wherein 0.05 mole of dibutyl tin laurate and 3-pseudoallyl-α, 50 moles of α-dimethylbenzyl isocyanic ester, drip and finish reaction under 90 ℃ more afterwards, until confirm not have remaining isocyanate group with infrared absorption spectrum analysis, then, made with extra care, obtained the intermediate b meaned by following formula (18).
[Chemical formula 1 2]
Figure A20048001557300412
The intermediate b of 50 moles of acquisitions is added in reaction flask, make its heating for dissolving under the dry air atmosphere.Be no more than in temperature of reaction under the condition of 90 ℃ and drip at leisure wherein 0.05 mole of dibutyl tin laurate and 2,2,4-and 2,50 moles of 4,4-trimethyl hexamethylene diisocyanates drip at leisure Racemic glycidol after drip finishing again under temperature of reaction is no more than the condition of 90 ℃, reaction under 90 ℃, until confirm not have remaining isocyanate group with infrared absorption spectrum analysis, then made with extra care, obtain the radical polymerization initiator D meaned by following formula (19).
[Chemical formula 1 3]
Figure A20048001557300421
Except using radical polymerization initiator D replacement radical polymerization initiator A, use the method modulation curable resin composition identical with embodiment 4, make liquid crystal display device.
(comparative example 3)
Except using " ダ ロ キ ユ ア 1173 " (Ciba Specialty Chemicals Inc. system) replacement radical polymerization initiator A, use the method modulation curable resin composition identical with embodiment 4, make liquid crystal display device.
(comparative example 4)
Except using " イ Le ガ キ ユ ア 184 " (Ciba Specialty Chemicals Inc. system) replacement radical polymerization initiator A, use the method modulation curable resin composition identical with embodiment 4, make liquid crystal display device.
The radical polymerization initiator, curable resin composition and the liquid crystal display device that with the following methods evaluation, by embodiment 4-7 and comparative example 3,4, are obtained.
The results are shown in table 2.
(measurement of liquid crystal resistivity conservation rate)
To ampoule (internal diameter: add curable resin composition 0.5g 10.0mm), add liquid crystal 0.5g.This bottle put into to the baking oven 1 hour of 120 ℃, return to room temperature (25 ℃) afterwards to lcd segment, use liquid crystal resistivity test device (East Asia electric wave industry society system, the SM-8210 type), use (the peace electric society of the rattan system of electrode for liquid as electrode, the LE-21 type), in the lower liquid crystal resistivity of measuring of standard temperature moisture condition (20 ℃, 65%RH).In addition, liquid crystal resistivity conservation rate is obtained by following formula.
[mathematical expression 3]
Liquid crystal resistivity conservation rate (%)=(the use liquid crystal resistivity that adds use liquid crystal resistivity after sealing agent/while not adding sealing agent) * 100
(measurement that nematic-isotropic liquid point of inversion (N-I point) changes)
To ampoule (internal diameter: add curable resin composition 0.5g 10.0mm), add liquid crystal 0.5g.This bottle put into to the baking oven 1 hour of 120 ℃, returned to room temperature (25 ℃) and afterwards lcd segment is put on aluminium sheet, with the heat-up rate of 10 ℃/minute, measured and measure the peak temperature.In addition, use MDSC (TA Insturumenes society system) as apparatus for thermal analysis.Nematic-isotropic liquid point of inversion changes to be obtained by following formula.
[mathematical expression 4]
The N-I point change (℃)=(N-I of liquid crystal point while not adding sealing agent)-(the N-I point that adds liquid crystal after sealing agent)
(connectivity evaluation)
Make interval particulate (ponding chemical industry society system, ミ Network ロ パ-Le SP-2055) 1 weight part is scattered in curable resin composition 100 weight parts, be placed on the slide glass center, on it, another slide glass of stack makes sealing agent launch and make even thickness, uses high voltage mercury lamp with 100mW/cm 2irradiation ultraviolet radiation 30 seconds.Then heat 1 hour under 120 ℃, obtain the conjugation test sheet.This test film is measured to bonding strength with tonometer.
(display panels evaluation (evaluation of color ununiformity))
For the liquid crystal display device obtained, near service test liquid crystal aligning race conditio sealing agent after 1000 hours after with the naked eye just having made according to following standard evaluation and under the condition of 65 ℃ of 95%RH.Also have, sample number is 6.
◎: do not have color inhomogeneous fully
Zero: have slight color inhomogeneous
△: have some colors inhomogeneous
*: color is inhomogeneous quite clear
[table 2]
Liquid crystal resistivity conservation rate (%) The variation of N-I point (℃) Connectivity is estimated (N/cm 2) Display panels is estimated
Embodiment 4 80.2 -2.03 470 ◎
Embodiment 5 88.3 -1.81 510 ◎
Embodiment 6 84.8 -2.43 392 ◎
Embodiment 7 76.4 -2.53 451 ◎
Comparative example 3 7.8 -4.29 363 △
Comparative example 4 4.2 -5.13 314 ×
(embodiment 8)
To use with the curable resin composition that embodiment 4 obtains in the same manner three roller mixing machines fully to mix until form uniform liquid, then with respect to curable resin composition 100 weight parts, mixing is as the metal deposition particulate that carries out golden plating (the ponding chemical industry society system of electrically conductive microparticle, ミ Network ロ パ-Le AU-206) 2 weight parts, mix with the planetary whipping appts of vacuum, thereby make the upper and lower conductive material of used for liquid crystal display element.
Except on transparency carrier, by the conductive material up and down that obtains through divider be coated on lead up and down on current electrode form upper and lower conducting with pattern beyond, make in the same manner liquid crystal display device with embodiment 4.
The liquid crystal indicator that obtains is placed 500 hours under 60 ℃, 95%RH environment, and now conduction is good.
(embodiment 9)
(synthesizing of compound (1))
To add in the there-necked flask with dropping funnel, mechanical stirrer, hydrogen chloride gas collector diphenyl sulfide (phenyl sulfide) (10mol), aluminum chloride (10mol), dithiocarbonic anhydride (2L), under 0 ℃, stir.Drip at leisure isobutyryl chloride (10mol) in this reaction soln under reaction soln is no more than the condition of 10 ℃, drips after finishing and at room temperature stir again 24 hours.Add frozen water in this reaction soln, stopped reaction, use the chloroform extraction organic layer, with ion-exchange water washing organic layer, then uses anhydrous magnesium sulfate drying.This solution is under reduced pressure concentrated and made with extra care, obtain the compound (1) that is shown in the structure in following formula (20).
[Chemical formula 1 4]
Figure A20048001557300451
(synthesizing of compound (2))
To add in the there-necked flask with dropping funnel, mechanical stirrer, hydrogen chloride gas collector compound (1) (5mol), aluminum chloride (5mol), dithiocarbonic anhydride (1L), under 0 ℃, stir.Drip at leisure Benzoyl chloride (5mol) in this reaction soln under reaction soln is no more than the condition of 10 ℃, drips after finishing and at room temperature stir again 24 hours.Add frozen water in this reaction soln, stopped reaction, use the chloroform extraction organic layer, with ion-exchange water washing organic layer, then uses anhydrous magnesium sulfate drying.This solution is under reduced pressure concentrated and made with extra care, obtain the compound (2) that is shown in the structure in following formula (21).
[Chemical formula 1 5]
Figure A20048001557300452
(radical polymerization initiator A's is synthetic)
To add in the flask under nitrogen compound (2) (2mol), methyl-sulphoxide (2L), then add the methanol solution (potassium hydroxide: 2mol/ ethanol: 100mL), at room temperature stir of potassium hydroxide.Add paraformaldehyde (aldehyde unit 2mol) in this solution, at room temperature stir 5 hours.In this solution, add hydrochloric acid to be neutralized, use the ethyl acetate extraction organic layer, with ion-exchange water washing organic layer, then use anhydrous magnesium sulfate drying.This solution is under reduced pressure concentrated and made with extra care, obtain the radical polymerization initiator A that is shown in the structure in following formula (22).
[Chemical formula 1 6]
By 2 weight part radical polymerization initiator A, part acrylic acid esterification epoxy resin (ダ イ セ Le ユ-シ-PVC-society's system, UVAC1561) 40 weight parts, bisphenol A epoxy acrylate resin (ダ イ セ Le ユ-シ-PVC-society's system, EB3700) 20 weight parts mix, being heated 70 ℃ dissolves radical polymerization initiator A, then stirred with planetary whipping appts, obtained mixture.
Mix spherical silicon dioxide (the ア De マ テ Star Network ス society system as weighting agent in this mixture; SO-C1) 15 weight parts, epoxy thermosetting agent (the chemical society in large tomb system, ADH) 5 weight parts, coupler (chemistry society of SHIN-ETSU HANTOTAI system; KBM403) 1 weight part; stirred with planetary whipping appts, then with three ceramic rollers, make its dispersion and obtain curable resin composition.
Make interval particulate (ponding chemical industry society system, ミ Network ロ パ-Le SP-2055) 1 weight part is scattered in curable resin composition 100 weight parts of acquisition, as sealing material for liquid crystal display device, on a substrate of two glass substrates with the alignment films that has completed friction treatment and transparency electrode, with divider, be coated with.
Then by liquid crystal (チ Star ソ society system, JC-5004LA) thin dripping is coated in in the sealing agent framework of the glass substrate of transparency electrode whole, another glass substrate with transparency electrode that superposes immediately, partly use high voltage mercury lamp with the strainer of holding back the following light of 350nm with 50mW/cm to sealing agent 2irradiate 20 seconds, it is solidified, thereby obtain liquid crystal display device.
(embodiment 10)
(radical polymerization initiator B's is synthetic)
To the compound (2) that adds embodiment 9 records in reaction flask (1mol), make its heating for dissolving under the dry air atmosphere.Drip at leisure wherein 1 mole of 0.001 mole of dibutyl tin laurate and 2-methacryloxy ethylidene isocyanic ester (clear and electrician society system), drip and finish reaction under 90 ℃ more afterwards, until confirm not have remaining isocyanate group with infrared absorption spectrum analysis under 90 ℃, then, made with extra care, obtained the radical polymerization initiator B that is shown in the structure in following formula (23).
[Chemical formula 1 7]
Except the radical polymerization initiator A that uses radical polymerization initiator B replacement embodiment 9, use the method modulation curable resin composition identical with embodiment 9
Then, use the curable resin composition and the embodiment 9 that obtain to obtain in the same manner liquid crystal display device.
(embodiment 11)
(radical polymerization initiator C's is synthetic)
To the compound (2) that adds embodiment 9 records in reaction flask (1mol), make its heating for dissolving under the dry air atmosphere.Be no more than in temperature of reaction under the condition of 90 ℃ and drip at leisure wherein 0.001 mole of dibutyl tin laurate and 2,2,4-and 2,4,4-trimethyl hexamethylene diisocyanate (デ グ サ society system, 0.5mol), under being no more than the condition of 90 ℃, temperature of reaction drips at leisure vinylformic acid 2-hydroxyl ethyl ester (0.5mol) again after drip finishing, reaction under 90 ℃, until confirm not have remaining isocyanate group with infrared absorption spectrum analysis, then made with extra care, obtained the radical polymerization initiator C that is shown in the structure in following formula (24).
[Chemical formula 1 8]
Figure A20048001557300472
Wherein, in formula (24), A means 2,2,4-and 2,4,4-tri-methyl hexamethylene.
Except the radical polymerization initiator A that uses radical polymerization initiator C replacement embodiment 9, with embodiment 9, obtain in the same manner curable resin composition.
Then, use the curable resin composition and the embodiment 9 that obtain to obtain in the same manner liquid crystal display device.
(embodiment 12)
(radical polymerization initiator D's is synthetic)
Add 2-carboxylic ylmethoxy thioxane-9-ketone (1mol) in reaction flask, make its heating for dissolving under the dry air atmosphere.Drip at leisure wherein 1 mole of 0.001 mole of dibutyl tin laurate and 2-methacryloxy ethylidene isocyanic ester (clear and electrician society system), drip and finish reaction under 90 ℃ more afterwards, until confirm not have remaining isocyanate group with infrared absorption spectrum analysis under 90 ℃, then made with extra care, obtained the radical polymerization initiator D that is shown in the structure in following formula (25).
[Chemical formula 1 9]
Figure A20048001557300481
Except the radical polymerization initiator A that uses radical polymerization initiator D replacement embodiment 9, with embodiment 9, obtain in the same manner curable resin composition.
Then, use the curable resin composition and the embodiment 9 that obtain to obtain in the same manner liquid crystal display device.
(comparative example 5)
Except the radical polymerization initiator A that uses イ Le ガ キ ユ ア 2959 (long Lai Chanyeshe system) replacement embodiment 9, with embodiment 9, obtain in the same manner curable resin composition.
Then, use the curable resin composition and the embodiment 9 that obtain to obtain in the same manner liquid crystal display device.
(comparative example 6)
Except the radical polymerization initiator A that uses イ Le ガ キ ユ ア 651 (long Lai Chanyeshe system) replacement embodiment 9, with embodiment 9, obtain in the same manner curable resin composition.
Then, use the curable resin composition and the embodiment 9 that obtain to obtain in the same manner liquid crystal display device.
The radical polymerization initiator, curable resin composition and the liquid crystal display device that with the following methods evaluation, by embodiment 9-12 and comparative example 5,6, are obtained, the results are shown in following table 3 separately.
(measurement of molar absorptivity)
The use ultraviolet light absorption is acetonitrile (colleague's chemistry society system) modulation radical polymerization initiator solution for spectrum, and sample solution concentration is 1.0 * 10 -4m, put into the quartzy unit of optical length 1cm and use spectrophotometer (UV-2450, society of Shimadzu Seisakusho Ltd. system) to carry out the measurement of absorbancy.Molar absorptivity is the value of the absorbancy with measuring divided by thickness (cm) gained of the volumetric molar concentration (M) of solution and unit.
(measurement of liquid crystal resistivity conservation rate)
To ampoule (ample bottle) (internal diameter: add curable resin composition 0.5g 10.0mm), add liquid crystal 0.5g.This bottle put into to the baking oven 1 hour of 120 ℃, return to room temperature (25 ℃) afterwards, lcd segment is used to liquid crystal resistivity test device (KEITHLEY Instruments society system, 6517A), as electrode, use liquid electrode (the peace electric society of rattan system, the LE-21 type), in the lower measurement of standard temperature moisture condition (20 ℃, 65%RH) liquid crystal resistivity, thereby obtain liquid crystal resistivity conservation rate.
(nematic-isotropic liquid point of inversion (N-I point) measure of the change)
To ampoule (internal diameter: add curable resin composition 0.5g 10.0mm), add liquid crystal 0.5g.This bottle put into to the baking oven 1 hour of 120 ℃, return to room temperature (25 ℃) afterwards, lcd segment is put on aluminium sheet, measured and measured the peak temperature with 10 ℃ of/minute heat-up rates, thereby obtained nematic-isotropic liquid point of inversion and nematic-isotropic liquid point of inversion variation.In addition, use MDSC (TA Insturumenes society system) as apparatus for thermal analysis.
(conversion rate measurement of acryl)
Make interval particulate (ponding chemical industry society system, ミ Network ロ パ-Le SP-2055) 1 weight part is scattered in curable resin composition 100 weight parts of acquisition, be placed on glass (コ-ニ Application グ society system, 1737) center, another glass of stack (コ-ニ Application グ society system on it, 1737) curable resin composition launched and make even thickness, thereby making test film.
To the test film of making, use high voltage mercury lamp with the strainer of holding back the following light of 350nm with 50mW/cm 2irradiate 20 seconds.Then a glass on the stripping test sheet, used infrared spectrophotometer (EXCALIBUR FTS3000MX, BIO RAD society system) to be measured.By the peak area (815-800cm that solidifies front acryl measuring in addition -1) and solidify after the peak area (815-800cm of acryl -1) and reference peaks area (845-820cm -1) relatively calculate transformation efficiency.The transformation efficiency of acryl is calculated by following formula.
[mathematical expression 5]
The transformation efficiency of acryl={ 1-(peak area of the acryl after solidifying/reference peaks area) after solidifying/(peak area of the acryl before solidifying/reference peaks area) before solidifying } * 100
(connectivity evaluation)
Make interval particulate (ponding chemical industry society system, ミ Network ロ パ-Le SP-2055) 1 weight part is scattered in curable resin composition 100 weight parts, be placed on the slide glass center, on it, another slide glass of stack launches curable resin composition and makes even thickness, uses high voltage mercury lamp with the strainer of holding back the following light of 350nm with 50mW/cm 2irradiate 20 seconds.Then heat 1 hour under 120 ℃, obtain the conjugation test sheet.This test film is measured to bonding strength with tonometer.
(display panels evaluation (evaluation of color ununiformity))
For the liquid crystal display device obtained, with the naked eye according to following standard evaluation after just making and under the condition of 65 ℃ of 95%RH near service test liquid crystal aligning race conditio sealing agent after 1000 hours.Also have, sample number is 6.
◎: do not have color inhomogeneous fully
Zero: have slight color inhomogeneous
△: have some colors inhomogeneous
*: color is inhomogeneous quite clear
[table 3]
Molar absorptivity (M -1 ·cm -1) Liquid crystal resistivity conservation rate (%) The variation of N-I point (℃) Acryl transformation efficiency (%) Connectivity is estimated (N/cm 2) Display panels is estimated
Embodiment 9 1900 80 -1.6 95 450 ◎
Embodiment 10 1500 70 -1.8 95 420 ◎
Embodiment 11 1200 65 -1.4 95 410 ◎
Embodiment 12 1200 75 -1.8 90 480 ◎
Comparative example 5 50 40 -1.4 20 400 ×
Comparative example 6 150 5 -6.5 80 360 △
(embodiment 13)
To use with the curable resin composition that embodiment 9 obtains in the same manner three roller mixing machines fully to mix until form uniform liquid, then with respect to curable resin composition 100 weight parts, mixing is as the metal deposition particulate that carries out golden plating (the ponding chemical industry society system of electrically conductive microparticle, ミ Network ロ パ-Le AU-206) 2 weight parts, mix with the planetary whipping appts of vacuum, thereby make the upper and lower conductive material of used for liquid crystal display element.
Except the conductive material up and down that will obtain on transparency carrier through divider be coated on lead up and down on current electrode form upper and lower conducting with pattern, make in the same manner liquid crystal display device with embodiment 9.
Liquid crystal display device for obtaining, similarly carry out display panels evaluation (evaluation of color ununiformity), near the situation of the liquid crystal aligning disorder upper and lower conductive material that detects by an unaided eye, and result does not have color inhomogeneous fully.In addition, conduction is also good.
(embodiment 14)
Will be by (the ダ イ セ Le ユ-シ-PVC-society's system of the part acrylic acid esterification epoxy resin as curable resin, UVAC1561) 70 weight parts, bisphenol f type epoxy resin (large Japanese ink chemical industry society system, エ ピ Network ロ Application 830S) 30 weight parts, spherical silicon dioxide (ア De マ Off ア イ Application society system as weighting agent, SO-Cl) 20 weight parts, ア ミ キ ユ ア VDH (monosodium glutamate Off ア イ Application テ Network ノ society system) 40 weight parts as solidifying agent, the composition formed as イ Le ガ キ ユ ア 907 (Ciba Specialty Chemicals Inc. system) 3 weight parts of optical free radical polymerization starter mixes until form uniform liquid, thereby obtained curable resin composition stoste.
In curable resin composition stoste 100 weight parts that obtain, mix コ Application Port セ ラ Application E202 (the chemical society in waste river system, molecular-weight average 560), thus the modulation curable resin composition.
The curable resin composition obtained is made to liquid crystal indicator as sealing material for liquid crystal display device.
That is, on a substrate of two transparency carriers with transparency electrode, with divider, be coated with sealing agent, thereby draw a rectangular frame.Then, by liquid crystal (チ Star ソ society system, it is JC-5004LA) thin that to drip whole of being coated in the transparency carrier framework upper, another transparency carrier that superposes immediately, to hermetic unit with high voltage mercury lamp with 50mW/cm 2intensity irradiation ultraviolet radiation 120 seconds.Then make liquid crystal annealing 1 hour under 120 ℃, make the sealing material for liquid crystal display device thermofixation simultaneously, thereby obtain liquid crystal display device.
(embodiment 15)
Make 3-isocyanic ester Trimethoxy silane 1mol and エ ピ Network ロ Application EXA-7120 (Japanese ink chemical industry society system greatly) 1mol within 12 hours, make alkoxysilane compound containing trialkylsilyl group in molecular structure in 70 ℃ of reactions under tin catalyst exists.The molecular weight of this alkoxysilane compound containing trialkylsilyl group in molecular structure is approximately 655.
Alkoxysilane compound containing trialkylsilyl group in molecular structure 5 weight parts that obtain are mixed with curable resin composition stoste 100 weight parts of being made by embodiment 14, thus the modulation curable resin composition.
Except using the curable resin composition obtained, use the method identical with embodiment 14 to make liquid crystal display device.
(embodiment 16)
With respect to curable resin composition stoste 100 weight parts of being made by embodiment 14, mix N-1-styroyl-N '-triethoxysilylpropyltetrasulfide urea (molecular weight 349.5, hydrogen bond functional group value 5.72 * 10 -3mol/g) 5 weight parts, thereby modulation curable resin composition.
Except using the curable resin composition obtained, use the method identical with embodiment 14 to make liquid crystal display device.
(embodiment 17)
Make 3-TSL 8330 1mol and 3-acryloxy propyl trimethoxy silicane 1mol within 12 hours, make alkoxysilane compound containing trialkylsilyl group in molecular structure 70 ℃ of reactions.The molecular weight of this alkoxysilane compound containing trialkylsilyl group in molecular structure is approximately 413, and hydrogen bond functional group value is 2.42 * 10 -3mol/g.
Alkoxysilane compound containing trialkylsilyl group in molecular structure 5 weight parts that obtain are mixed with curable resin composition stoste 100 weight parts of being made by embodiment 14, thus the modulation curable resin composition.
Except using the curable resin composition obtained, use the method identical with embodiment 14 to make liquid crystal display device.
(embodiment 18)
Make 3-TSL 8330 1mol and 1mol カ レ Application ズ MOI reaction within 12 hours, make alkoxysilane compound containing trialkylsilyl group in molecular structure.The molecular weight of this alkoxysilane compound containing trialkylsilyl group in molecular structure is approximately 334, and hydrogen bond functional group value is 2.99 * 10 -3mol/g.
Alkoxysilane compound containing trialkylsilyl group in molecular structure 5 weight parts that obtain are mixed with curable resin composition stoste 100 weight parts of being made by embodiment 14, thus the modulation curable resin composition.
Except using the curable resin composition obtained, use the method identical with embodiment 14 to make liquid crystal display device.
(embodiment 19)
Make 3-isocyanic ester Trimethoxy silane 1mol and HEMA 1mol within 12 hours, make alkoxysilane compound containing trialkylsilyl group in molecular structure in 70 ℃ of reactions under tin catalyst exists.The molecular weight of this alkoxysilane compound containing trialkylsilyl group in molecular structure is approximately 271, and hydrogen bond functional group value is 3.69 * 10 -3mol/g.
Alkoxysilane compound containing trialkylsilyl group in molecular structure 5 weight parts that obtain are mixed with curable resin composition stoste 100 weight parts of being made by embodiment 14, thus the modulation curable resin composition.
Except using the curable resin composition obtained, use the method identical with embodiment 14 to make liquid crystal display device.
(comparative example 7)
Only using the stoste of the curable resin composition of being made by embodiment 14 (mixing コ Application Port ラ セ Application E202 curable resin composition before) as curable resin composition.
Except using the curable resin composition obtained, use the method identical with embodiment 14 to make liquid crystal display device.
(comparative example 8)
3-glycidoxypropyltrime,hoxysilane 3 weight parts are mixed with curable resin composition stoste 100 weight parts of being made by embodiment 14, thus the modulation curable resin composition.
Except using the curable resin composition obtained, use the method identical with embodiment 14 to make liquid crystal display device.
(comparative example 9)
3-methacryloxypropyl trimethoxy silane 3 weight parts are mixed with curable resin composition stoste 100 weight parts of being made by embodiment 14, thus the modulation curable resin composition.
Except using the curable resin composition obtained, use the method identical with embodiment 14 to make liquid crystal display device.
(evaluation)
The color ununiformity of connectivity, moisture-proof connectivity and the liquid crystal display device of the curable resin composition obtained by embodiment 14-19 and comparative example 7-9 with the following methods evaluation.
(1) connectivity evaluation
The polymkeric substance hollow bead that is 5 μ m by median size (ponding chemical industry society system, ミ Network ロ パ-Le SP) 3 weight parts are scattered in curable resin composition 100 weight parts with planetary whipping appts, form uniform liquid, it is placed on to the slide glass center on a small quantity, on it, another slide glass of stack is launched, then with 100mW/cm 2intensity irradiation ultraviolet radiation 30 seconds.
Then heat 1 hour under 100 ℃, obtain the conjugation test sheet.To the test film obtained, use self-registering instrument (society of Shimadzu Seisakusho Ltd. system) to measure bonding strength.
(2) the moisture-proof connectivity is estimated
To preserve 24 hours in 120 ℃, 2 atmospheric saturated steams with the identical joint fastener of making in connectivity is estimated, and then use self-registering instrument (society of Shimadzu Seisakusho Ltd. system) to measure bonding strength.
(3) the color ununiformity is estimated
The color produced in liquid crystal for the used for liquid crystal display element visual inspection hermetic unit periphery obtained is inhomogeneous, according to following standard, is estimated.
◎: do not have color inhomogeneous fully
Zero: almost do not have color inhomogeneous
△: have a small amount of color inhomogeneous
*: color is inhomogeneous quite a lot of
[table 4]
Connectivity (N/cm 2) Moisture-proof connectivity (N/cm 2) The color ununiformity is estimated
Embodiment 14 392 343 ◎
Embodiment 15 451 392 ◎
Embodiment 16 353 304 ◎
Embodiment 17 363 314 ◎
Embodiment 18 402 343 ◎
Embodiment 19 441 392 ◎
Comparative example 7 216 20 ◎
Comparative example 8 392 314 ×
Comparative example 9 343 294 ×
(embodiment 20)
To use with the curable resin composition that embodiment 14 obtains in the same manner three roller mixing machines fully to mix until form uniform liquid, then with respect to curable resin composition 100 weight parts, mixing is as the metal deposition particulate that carries out golden plating (the ponding chemical industry society system of electrically conductive microparticle, ミ Network ロ パ-Le AU-206) 2 weight parts, mix with the planetary whipping appts of vacuum, thereby make the upper and lower conductive material of used for liquid crystal display element.
Except the conductive material up and down that will obtain on transparency carrier with the divider coating lead up and down on current electrode form upper and lower conducting with pattern, make in the same manner liquid crystal display device with embodiment 14.
The conduction of the liquid crystal display device obtained is good.
(embodiment 21)
(1) making of curable resin composition
Will be as bisphenol-a epoxy acrylate (the ダ イ セ Le UCB society system of the resin with free-radical polymerised functional group, EB3700) (japan epoxy resin society system: エ ピ コ-ト 828) (Ciba SpecialtyChemicals Inc. system: IR-651) 2 weight parts mix for 10 weight parts, optical free radical polymerization starter for 60 weight parts, bisphenol A type epoxy resin, and be heated 70 ℃ the optical free radical polymerization starter is dissolved, then with planetary whipping appts, stir the acquisition mixture.
To (Nippon Zeon Co., Ltd. (ゼ the is Application society) system: F-351) 10 weight parts, spherical silicon dioxide (ア De マ Off ア イ Application society system of mixed core shell structure particulate in this mixture; SO-C1) 16 weight parts, thermal curing agents (the chemical society in large tomb system, ADH) 2 weight parts; carry out mix and blend with planetary whipping appts; then make its dispersion with three ceramic rollers, obtain curable resin composition.
(2) measurement of the second-order transition temperature of cured article
Be the rectangular laminar of 5 * 35 * 0.35mm by the curable resin composition of acquisition coating, irradiate the ultraviolet ray 30 seconds of 100mW intensity to it, and then within 60 minutes, make it solidify 120 ℃ of lower thermal treatments, obtain to measure and use test film.
Obtain spring rate E ' and tan δ with dynamic viscoelastic measuring apparatus (DMA) in the temperature range of 20 ℃-180 ℃, measured the second-order transition temperature of the cured article of curable resin composition by this value, result is 50 ℃.
(3) conjugation test
With respect to curable resin composition 100 weight parts that obtain, staple glass fibre partition 5 weight parts that mix 5 μ m, the material of mixing is slightly dropped in to alkali-free glass substrate (コ-ニ Application グ society system: #1737) above, adhere to the same glass substrate according to crosswise thereon.The ultraviolet ray of irradiation 100mW intensity 30 seconds, and then within 60 minutes, make it solidify 120 ℃ of lower thermal treatments, obtain to measure and use test film.
Each glass substrate is fixed on the chuck distributed up and down, obtains tensile strength under the condition that is 5mm/sec at draw speed, and it is defined as to bonding strength.Bonding strength is 180N/cm 2.
(comparative example 10)
Will be as bisphenol-a epoxy acrylate (the ダ イ セ Le UCB society system of the resin with free-radical polymerised functional group, EB3700) (japan epoxy resin society system: エ ピ コ-ト 828) (Ciba Specialty Chemicals Inc. system: IR-651) 2 weight parts mix for 10 weight parts, optical free radical polymerization starter for 60 weight parts, bisphenol A type epoxy resin, and be heated 70 ℃ the optical free radical polymerization starter is dissolved, then with planetary whipping appts, carry out mix and blend acquisition mixture.Mix spherical silicon dioxide (ア De マ Off ア イ Application society system in this mixture; SO-C1) 26 weight parts, thermal curing agents (the chemical society in large tomb system, ADH) 2 weight parts; carry out mix and blend with planetary whipping appts; then make its dispersion with three ceramic rollers, obtain curable resin composition.
For the curable resin composition obtained, use the method identical with embodiment 21 to measure second-order transition temperature and the bonding strength of cured article, second-order transition temperature is 150 ℃ as a result, bonding strength is 80N/cm 2.
(comparative example 11)
Will be as propylene oxide addition bisphenol-a epoxy acrylate (chemistry society of the common prosperity society system: 3002A) 60 weight parts, bisphenol A type epoxy resin (japan epoxy resin society system: エ ピ コ-ト 828) 10 weight parts, optical free radical polymerization starter (CibaSpecialty Chemicals Inc. system: IR-651) 2 weight parts mixing of the resin with free-radical polymerised functional group, and be heated 70 ℃ the optical free radical polymerization starter is dissolved, then with planetary whipping appts, stir the acquisition mixture.To (the Japanese ゼ オ Application society system: F-351) 10 weight parts, spherical silicon dioxide (ア De マ Off ア イ Application society system of mixed core shell structure particulate in this mixture; SO-C1) 16 weight parts, thermal curing agents (the chemical society in large tomb system, ADH) 2 weight parts; carry out mix and blend with planetary whipping appts; then make its dispersion with three ceramic rollers, obtain curable resin composition.
For the curable resin composition obtained, use the method identical with embodiment 21 to measure second-order transition temperature and the bonding strength of cured article, second-order transition temperature is 100 ℃ as a result, bonding strength is 90N/cm 2.
(embodiment 22)
To use with the curable resin composition that embodiment 21 obtains in the same manner three roller mixing machines fully to mix until form uniform liquid, then with respect to curable resin composition 100 weight parts, mixing is as the metal deposition particulate that carries out golden plating (the ponding chemical industry society system of electrically conductive microparticle, ミ Network ロ パ-Le AU-206) 2 weight parts, mix with the planetary whipping appts of vacuum, thereby make the upper and lower conductive material of used for liquid crystal display element.
On a substrate of two transparency carriers with transparency electrode, the curable resin composition that will be obtained by embodiment 21 is coated with divider as sealing agent, thereby draws a rectangular frame.In addition, on another transparency carrier, the conductive material up and down obtained is coated on and leads up and down the upper and lower conducting pattern of formation on current electrode with divider.Then, by liquid crystal (チ Star ソ society system, it is JC-5004LA) thin that to drip whole of being coated in the transparency carrier framework that is coated with sealing agent upper, another transparency carrier that superposes immediately, partly use high voltage mercury lamp with 100mW/cm to hermetic unit and upper and lower conductive material 2intensity irradiation ultraviolet radiation 30 seconds.Then, make liquid crystal annealing 1 hour under 120 ℃, make its thermofixation, thereby obtain liquid crystal indicator.
The conduction of the liquid crystal indicator obtained is good.
(embodiment 23)
(A) acrylic acid modified phenol phenolic resin varnish is synthetic
Make liquid phase phenol novolak type epoxy resin (the ダ ウ ケ ミ カ Le D.E.N.431 processed of society) 1000 weight parts, as p methoxy phenol 2 weight parts of polymerization retarder, as triethylamine 2 weight parts, vinylformic acid 200 weight parts of catalysts, when carrying air, 90 ℃ of lower stirring and refluxing, make it to react 5 hours.By the quartz that is filled with 10 weight parts and kaolinic natural bonding product (ホ Off マ Application ミ ネ ラ Le society system; シ リ チ Application V85) cylinder filters resulting resin 100 weight parts; with the ionic impurity in the absorption reaction thing, thereby obtain acrylic acid modified phenol phenolic resin varnish (50% part propylene acylate).
(B) urethane modification part propylene acylate is synthetic
Add TriMethylolPropane(TMP) 134 weight parts, the BHT0.2 weight part as polymerization starter, dibutyl tin laurate 0.01 weight part as catalysts, isophorone diisocyanate 666 weight parts, 60 ℃ of lower stirring and refluxing, make it to react 2 hours.Then, add vinylformic acid 2-hydroxyl ethyl ester 25.5 weight parts and Racemic glycidol 111 weight parts, when carrying air, 90 ℃ of lower stirring and refluxing, make it to react 2 hours.By the quartz that is filled with 10 weight parts and kaolinic natural bonding product (ホ Off マ Application ミ ネ ラ Le society system; シ リ チ Application V85) cylinder filters resulting resin 100 weight parts; with the ionic impurity in the absorption reaction thing, thereby obtain urethane modification part propylene acylate.
Acrylic acid modified phenol phenolic resin varnish 40 weight parts that will obtain in (A), (B) urethane modification part propylene acylate 20 weight parts that obtain in, hydrazides type solidifying agent (monosodium glutamate Off ア イ Application テ Network ノ society system as the hot-setter of hiding, ア ミ キ ユ ア VDH) 15 weight parts, as 2 of Photoepolymerizationinitiater initiater, 2-diethoxy acetophenone 1 weight part, silicon oxide particle (median size is 0.5 μ m) 23 weight parts, the curable resin composition that γ-glycidoxypropyltrimethoxy silane 1 weight part forms is used three roller mixing machines fully to mix until form uniform liquid, thereby acquisition sealing agent.
On a substrate of two transparency carriers with transparency electrode, the sealing agent obtained with the divider coating, thus draw a rectangular frame.Then, by liquid crystal (チ Star ソ society system, it is JC-5004LA) thin that to drip whole of being coated in the transparency carrier framework upper, another transparency carrier that superposes immediately, to hermetic unit with high voltage mercury lamp with 100mW/cm 2irradiation ultraviolet radiation 30 seconds.Then, make liquid crystal annealing 1 hour under 120 ℃, make its thermofixation, thereby make liquid crystal indicator.
(embodiment 24)
(C) acrylic acid modified propylene oxide bisphenol A epoxide resin is synthetic
Make liquid phase polyoxy alkylidene bisphenol A diglycidyl ether (the Xu electricity Hua Gongyeshe system, EP4000S) 1440 weight parts, as p methoxy phenol 2 weight parts of polymerization retarder, as triethylamine 2 weight parts, vinylformic acid 200 weight parts of catalysts, when carrying air, 90 ℃ of lower stirring and refluxing, make it to react 5 hours.By the quartz that is filled with 10 weight parts and kaolinic natural bonding product (ホ Off マ Application ミ ネ ラ Le society system; シ リ チ Application V85) cylinder filters resulting resin 100 weight parts; with the ionic impurity in the absorption reaction thing, thereby obtain acrylic acid modified propylene oxide bisphenol A epoxide resin (50% part propylene acylate).
Except using acrylic acid modified propylene oxide bisphenol A epoxide resin 20 weight parts that obtained by (C) to replace urethane modification part propylene acylate 20 weight parts that obtained by embodiment 23 (B); use hydrazides type solidifying agent (the industrial society of Japanese hydrazine system; NDH) 15 weight parts replace hydrazides type solidifying agent (monosodium glutamate Off ア イ Application テ Network ノ society system; ア ミ キ ユ ア VDH) beyond 15 weight parts; obtain in the same manner sealing agent with embodiment 23, use it to make liquid crystal indicator.
(comparative example 12)
Will be by urethane acrylate (chemistry society of common prosperity society system, AH-600) curable resin composition that 35 weight parts, vinylformic acid-2-hydroxy butyl ester 15 weight parts, isobornyl acrylate 50 weight parts, benzophenone 3 weight parts form mixes, form uniform liquid, thereby obtain the sealing agent of light-cured type, use it to make liquid crystal indicator.
(comparative example 13)
Will be by bisphenol A type epoxy resin (japan epoxy resin society system, エ ピ コ-ト 828US) 50 weight parts, hydrazides class solidifying agent (the industrial society of Japanese hydrazine system, NDH) curable resin composition that 25 weight parts form is used three roller mixing machines fully to mix until form uniform liquid, thereby the acquisition sealing agent, used it to make liquid crystal indicator.
For the sealing agent of being made by embodiment 23,24 and comparative example 12,13, with after following method evaluation photocuring and the average linear expansion rate after photo-thermal curing and solidify after volume resistance value, specific inductivity, the tensile elasticity rate under 100kHz, in addition, for the following method evaluation color ununiformity for liquid crystal indicator obtained.
(after photocuring and photo-thermal curing after average linear expansion rate)
Evenly be coated with thinly sealing agent on the fluorinated ethylene propylene substrate, then at 3000mJ/cm 2condition under carry out ultraviolet curing, thereby make size, be the photocuring sample of 15mm * 4mm, thick 0.6mm.In addition, evenly be coated with thinly sealing agent on the fluorinated ethylene propylene substrate, then at 3000mJ/cm 2condition under carry out ultraviolet curing, then thermofixation 1 hour under the condition of 120 ℃, be the photo-thermal curing sample of 15mm * 4mm, thick 0.6mm thereby make size.
Use Seiko electronic industry society's system " EXSTAR6000TMA/SS ", temperature in the early stage: 35 ℃, the heating end temp: 150 ℃, heat-up rate: 5 ℃/min, measure the photocuring sample of making and the average linear expansion rate of photo-thermal curing sample under the measuring condition of hold-time: 0min.
Cured article by the value obtained when only solidifying under the effect of light and the cured article while solidifying under the effect of light and heat are calculated from the temperature than low 40 ℃ of second-order transition temperature to the average linear expansion rate α the temperature than low 10 ℃ of second-order transition temperature 1, with from the temperature than high 10 ℃ of second-order transition temperature to the average linear expansion rate α the temperature than high 40 ℃ of second-order transition temperature 2.
(the volume resistance value after solidifying)
Evenly be coated with thinly sealing agent on the chromium evaporation surface of chromium evaporation glass substrate, then carry out ultraviolet curing, form the ultraviolet curing thing that size is 3mm for 85mm * 85mm, thickness, place chromium evaporation glass substrate thereon and make chromium evaporation surface be positioned at ultraviolet curing thing one side, applying load, add thermo-compressed 1 hour on the hot-plate of 120 ℃, thereby make test sample.Measure the area (S (cm of sealing agent in this sample 2)), by constant voltage generating apparatus (ケ Application ウ Star De society system, PA 36-2A modulates direct supply) apply constant voltage (V (V)) between the chromium evaporation surface of opposed chromium evaporation glass substrate, measure mobile electric current (A (A)) in film with amperometer (ア De バ Application テ ス ト society system, R 644C digital multimeter).When the mould by sealing agent is made as T (cm), by following formula, obtain volume specific resistance (Ω .cm).
[mathematical expression 6]
Volume specific resistance (Ω cm)=(V * S)/(A * T)
Wherein, applying voltage is direct current 500V, and conduction time is 1 minute.
(specific inductivity after solidifying under 100kHz)
Evenly be coated with thinly sealing agent on glass substrate, then be cured, thereby make the test sample that size is 3mm for 60mm * 60mm, thickness.Method according to ASTM D150, by electrode contact process (gap method) not, with dielectric medium measure with electrode (Yokogawa HP society system, HP16451B), (ヒ ユ-レ Star ト パ Star カ-De society system, 4284A) measured the LCR meter under frequency 100kHz.
(tensile elasticity rate after solidifying)
Evenly be coated with thinly sealing agent on the fluorinated ethylene propylene substrate, then carry out ultraviolet curing, form the ultraviolet curing thing of big or small 50mm * 5mm, thick 0.5mm, then heat 1 hour under the condition of 120 ℃, thereby make test sample.
Use テ イ-エ イ イ Application ス Star Le メ Application ト society's system " RSA II ", long between clamping plate: 30mm, temperature condition: initial stage temperature: room temperature, heating end temp: 150 ℃, heat-up rate: 5 ℃/min, regulation obtains the interval of data, lower limit spring rate: 10Pa, lower limit power: 0.008N, survey frequency: 10Hz, distortion (E>108): 0.1%, quiet/power ratio: 0, upper limit extensibility: 50%, tensile figure: the tensile elasticity rate of measuring the test sample of making under 1 condition.
(evaluation of color ununiformity)
For the liquid crystal indicator obtained, at 60 ℃, 95%RH, before and after 500 hours, the color that produces in liquid crystal of detecting by an unaided eye is inhomogeneous, based on following level Four standard, is estimated: ◎ (do not have fully color inhomogeneous); Zero (have slight color inhomogeneous); △ (have some colors inhomogeneous); * (color is inhomogeneous quite a lot of).In addition, wherein for each part, with 5 samples, estimated.
[table 5]
(embodiment 25)
To use with the curable resin composition that embodiment 23 obtains in the same manner three roller mixing machines fully to mix until form uniform liquid, then with respect to curable resin composition 100 weight parts, mixing is as the metal deposition particulate that carries out golden plating (the ponding chemical industry society system of electrically conductive microparticle, ミ Network ロ パ-Le AU-206) 2 weight parts, mix with the planetary whipping appts of vacuum, thereby make the upper and lower conductive material of used for liquid crystal display element.
Form upper and lower conducting with pattern except the conductive material up and down that will obtain is coated on to lead up and down on current electrode with divider on transparency carrier, with embodiment 23, make in the same manner liquid crystal indicator.
Liquid crystal indicator for obtaining, similarly carry out the evaluation of color ununiformity, near the color ununiformity produced in liquid crystal the upper and lower conductive material that detects by an unaided eye, and result is the evaluation result more than zero.In addition, conduction is also good.
(embodiment 26)
Make liquid phase phenol novolak type epoxy resin (the ダ ウ ケ ミ カ Le D.E.N.431 processed of society) 1000 weight parts, as p methoxy phenol 2 weight parts of polymerization retarder, as triethylamine 2 weight parts, vinylformic acid 200 weight parts of catalysts, when carrying air, 90 ℃ of lower stirring and refluxing, make it to react 5 hours.By the quartz that is filled with 10 weight parts and kaolinic natural bonding product (ホ Off マ Application ミ ネ ラ Le society system; シ リ チ Application V85) cylinder filters resulting resin 100 weight parts; with the ionic impurity in the absorption reaction thing, thereby obtain acrylic acid modified phenol phenolic resin varnish (50% part propylene acylate).
Add TriMethylolPropane(TMP) 134 weight parts, the BHT0.2 weight part as polymerization starter, dibutyl tin laurate 0.01 weight part as catalysts, isophorone diisocyanate 666 weight parts, 60 ℃ of lower stirring and refluxing, make it to react 2 hours.Then, add vinylformic acid 2-hydroxyl ethyl ester 25.5 weight parts and Racemic glycidol 111 weight parts, when carrying air, 90 ℃ of lower stirring and refluxing, make it to react 2 hours.By the quartz that is filled with 10 weight parts and kaolinic natural bonding product (ホ Off マ Application ミ ネ ラ Le society system; シ リ チ Application V85) cylinder filters resulting resin 100 weight parts; with the ionic impurity in the absorption reaction thing, thereby obtain urethane modification part propylene acylate.
With respect to acrylic acid modified phenol phenolic resin varnish 40 weight parts that obtain, urethane modification part propylene acylate 20 weight parts; add hydrazides type solidifying agent (the monosodium glutamate Off ア イ Application テ Network ノ society system as the hot-setter of hiding; ア ミ キ ユ ア UDH; 160 ℃ of fusing points) 15 weight parts, as 2 of Photoepolymerizationinitiater initiater; 2-diethoxy acetophenone 1 weight part, silicon oxide particle (median size is 1.5 μ m) 23 weight parts, γ-glycidoxypropyltrimethoxy silane 1 weight part, used three roller mixing machines fully to mix the acquisition mixture.
Be used as ベ キ ボ ア (beki-pore) the 10 μ m (ニ チ ダ イ society system) of strainer at 40 ℃ of temperature, pressure 45N/cm in the mixture of acquisition 2condition under filtered, obtain curable resin composition.Using it as sealing material for liquid crystal display device.
On a substrate of two transparency carriers with transparency electrode, the sealing material for liquid crystal display device obtained with the divider coating, thus draw a rectangular frame.Then, by liquid crystal (チ Star ソ society system, it is JC-5004LA) thin that to drip whole of being coated in the transparency carrier framework upper, another transparency carrier that superposes immediately, to hermetic unit with high voltage mercury lamp with 100mW/cm 2irradiation ultraviolet radiation 30 seconds.Then, make liquid crystal annealing 1 hour under 120 ℃, make its thermofixation, thereby make liquid crystal display device.In addition, the cell gap of this liquid crystal display device is set as 5 μ m.
(comparative example 14)
Except being filtered without strainer, use the method identical with embodiment 26 to make curable resin composition, using it as sealing material for liquid crystal display device.In addition, use the sealing material for liquid crystal display device obtained, use the method identical with embodiment 26 to make liquid crystal display device.
(evaluation)
Sealing material for liquid crystal display device and liquid crystal display device for being made by embodiment 26 and comparative example 14, carry out the evaluation of inspection of foreign substance and cell gap by following method.
(1) inspection of foreign substance
Weighing sealing material for liquid crystal display device 2mL exactly on the SUS system of mesh 10 μ m sieve (φ 75-h20), according to the 1.2mL/min acetone that drips, used 16 times of magnifying glasses countings to remain in the number of the foreign matter on sieve by top.Carry out same operation under n=5, obtain its mean value.
(2) cell gap evaluation
Use 16 times of magnifying glasses with the naked eye to have or not bad in the detecting unit gap.
[table 6]
The quantity of foreign matter (individual) Have or not cell gap inhomogeneous
Embodiment 26 0 Nothing
Comparative example 14 115.6 Have
[0491](embodiment 27)
(1) acrylic acid modified phenol phenolic resin varnish is synthetic
Make liquid phase phenol novolak type epoxy resin (the ダ ウ ケ ミ カ Le D.E.N.431 processed of society) 1000 weight parts, as p methoxy phenol 2 weight parts of polymerization retarder, as triethylamine 2 weight parts, vinylformic acid 200 weight parts of catalysts, when carrying air, 90 ℃ of lower stirring and refluxing, make it to react 5 hours.By the quartz that is filled with 10 weight parts and kaolinic natural bonding product (ホ Off マ Application ミ ネ ラ Le society system; シ リ チ Application V85) cylinder filters resulting resin 100 weight parts; with the ionic impurity in the absorption reaction thing, thereby obtain acrylic acid modified phenol phenolic resin varnish (50% part propylene acylate).
(2) urethane modification part propylene acylate is synthetic
Add TriMethylolPropane(TMP) 134 weight parts, the BHT0.2 weight part as polymerization starter, dibutyl tin laurate 0.01 weight part as catalysts, isophorone diisocyanate 666 weight parts, 60 ℃ of lower stirring and refluxing, make it to react 2 hours.Then, add vinylformic acid 2-hydroxyl ethyl ester 25.5 weight parts and Racemic glycidol 111 weight parts, when carrying air, 90 ℃ of lower stirring and refluxing, make it to react 2 hours.By the quartz that is filled with 10 weight parts and kaolinic natural bonding product (ホ Off マ Application ミ ネ ラ Le society system; シ リ チ Application V85) cylinder filters resulting resin 100 weight parts; with the ionic impurity in the absorption reaction thing, thereby obtain urethane modification part propylene acylate.
(3) modulation of sealing agent
Will be by acrylic acid modified phenol phenolic resin varnish 40 weight parts that obtain, urethane modification part propylene acylate 20 weight parts, hydrazides type solidifying agent (monosodium glutamate Off ア イ Application テ Network ノ society system as the latent energy solidifying agent, ア ミ キ ユ ア VDH) 15 weight parts, as 2 of Photoepolymerizationinitiater initiater, 2-diethoxy acetophenone 1 weight part, silicon oxide particle (median size is 1.5 μ m) 23 weight parts, the curable resin composition that γ-glycidoxypropyltrimethoxy silane 1 weight part forms is used three roller mixing machines fully to mix until form uniform liquid, thereby acquisition sealing agent.
(4) manufacture of liquid crystal display device
On the position of the regulation on two transparency carrier surfaces with transparency electrode, with flexographic printing, form the rectangular alignment films formed by polyimide (produce chemical society system daily, サ Application エ バ-(SE-7492)).Then, the sealing agent obtained with divider coating draws a rectangular frame, and avoids contacting with the alignment films of a side transparency carrier.
Then, by liquid crystal (チ Star ソ society system, it is JC-5004LA) thin that to drip whole of being coated in the transparency carrier framework upper, the face that is formed with alignment films of another transparency carrier that superposes immediately, to sealing agent with high voltage mercury lamp with 100mW/cm 2irradiation ultraviolet radiation 30 seconds.Then, make liquid crystal annealing 1 hour under 120 ℃, make its thermofixation, thereby make liquid crystal display device.
The liquid crystal display device that detects by an unaided eye and obtain, the results verification sealing agent does not contact with alignment films.
(comparative example 15)
On surface except the transparency carrier with transparency electrode, form beyond the sealing agent contacted with alignment films, with embodiment 27, make in the same manner liquid crystal display device.
Color ununiformity as the liquid crystal display device for being made by embodiment 27 and comparative example 15 is estimated, near service test liquid crystal aligning race conditio sealing agent after 1000 hours after with the naked eye confirming just to have made and under 65 ℃, the condition of 95%RH.Also have, sample number is 10.
Its result, can confirm that the liquid crystal display device in embodiment 27 does not have color inhomogeneous fully, but the liquid crystal display device in comparative example 15 mainly has a small amount of color inhomogeneous at peripheral part.In addition, analyze the inhomogeneous part of color of the liquid crystal display device of being made by comparative example 15 with Tof-sims, result has been observed the composition of sealing agent.
Industrial utilizability
According to the present invention, can provide when as sealing material for liquid crystal display device when by the drippage completion method, manufacturing the process of liquid crystal display device, to the pollution of liquid crystal less, with the connectivity of glass inhomogeneous curable resin composition, sealing material for liquid crystal display device and the liquid crystal display device in generation unit gap well and not.

Claims (6)

1. a liquid crystal drips the completion method sealing agent, described liquid crystal drippage completion method contains under the effect of light and/or heat curing curable resin occurs with sealing agent, polymerization starter and resin particle, described resin particle has core particle and is formed on the lip-deep shell of described core particle, described core particle forms for the resin below-10 ℃ by having caoutchouc elasticity and second-order transition temperature, the resin that described shell is 50-150 ℃ by second-order transition temperature forms, and it is 5 ℃/minute at heat-up rate, the second-order transition temperature that is the cured article of DMA method measurement with the dynamic viscoelastic method of masurement under the condition that frequency is 10Hz is more than 120 ℃, the median size of described resin particle is 0.01-0.3 μ m.
2. liquid crystal as claimed in claim 1 drips completion method sealing agent, the F-351 that described resin particle is Nippon Zeon Co., Ltd.'s system.
3. liquid crystal as claimed in claim 1 or 2 drippage completion method sealing agent, is characterized in that, has caoutchouc elasticity and second-order transition temperature and be resin below-10 ℃ and be the polymkeric substance that the polymerization through (methyl) acryl monomer obtains.
4. liquid crystal as claimed in claim 1 or 2 drippage completion method sealing agent, is characterized in that, bonding strength glass substrate is bonding and while making it curing is 150N/cm 2above.
5. the upper and lower conductive material of used for liquid crystal display element, is characterized in that, contains liquid crystal drippage completion method sealing agent and electrically conductive microparticle claimed in claim 1.
6. a liquid crystal display device, is characterized in that, right to use requires 1 described liquid crystal drippage completion method to form with sealing agent.
CN200480015573.6A 2003-06-04 2004-06-04 Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device Active CN1798786B (en)

Applications Claiming Priority (25)

Application Number Priority Date Filing Date Title
JP159909/2003 2003-06-04
JP159905/2003 2003-06-04
JP2003159905 2003-06-04
JP159906/2003 2003-06-04
JP2003159906 2003-06-04
JP2003159909 2003-06-04
JP162774/2003 2003-06-06
JP2003162774A JP2004361854A (en) 2003-06-06 2003-06-06 Liquid crystal display element
JP2003165410 2003-06-10
JP165410/2003 2003-06-10
JP270397/2003 2003-07-02
JP2003270397 2003-07-02
JP2003279299 2003-07-24
JP279299/2003 2003-07-24
JP284115/2003 2003-07-31
JP2003284115 2003-07-31
JP394617/2003 2003-11-25
JP394618/2003 2003-11-25
JP394616/2003 2003-11-25
JP394619/2003 2003-11-25
JP394614/2003 2003-11-25
JP2003394614A JP2005054164A (en) 2003-07-24 2003-11-25 Photo- and heat-curable resin composition, sealing agent for liquid crystal display element, opening-sealing agent for the liquid crystal display element, vertically-conducting material for the liquid crystal display element, and liquid crystal display device
JP394615/2003 2003-11-25
JP2003394615A JP4022194B2 (en) 2003-06-04 2003-11-25 Curable resin composition for liquid crystal display element, sealing agent for liquid crystal display element, sealing agent for liquid crystal display element, vertical conduction material for liquid crystal display element, and liquid crystal display device
PCT/JP2004/007811 WO2004108790A1 (en) 2003-06-04 2004-06-04 Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device

Related Child Applications (2)

Application Number Title Priority Date Filing Date
CN 200810214942 Division CN101367982B (en) 2003-06-04 2004-06-04 Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device
CN2008102149439A Division CN101369098B (en) 2003-06-04 2004-06-04 Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device

Publications (2)

Publication Number Publication Date
CN1798786A CN1798786A (en) 2006-07-05
CN1798786B true CN1798786B (en) 2013-05-15

Family

ID=36819188

Family Applications (3)

Application Number Title Priority Date Filing Date
CN2008102149439A Active CN101369098B (en) 2003-06-04 2004-06-04 Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device
CN 200810214942 Active CN101367982B (en) 2003-06-04 2004-06-04 Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device
CN200480015573.6A Active CN1798786B (en) 2003-06-04 2004-06-04 Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device

Family Applications Before (2)

Application Number Title Priority Date Filing Date
CN2008102149439A Active CN101369098B (en) 2003-06-04 2004-06-04 Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device
CN 200810214942 Active CN101367982B (en) 2003-06-04 2004-06-04 Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device

Country Status (1)

Country Link
CN (3) CN101369098B (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101463640B1 (en) * 2007-07-30 2014-11-19 아사히 가라스 가부시키가이샤 Curable resin composition, transparent laminate using the same, and method for producing the transparent laminate
WO2009038190A1 (en) * 2007-09-19 2009-03-26 Hitachi Chemical Company, Ltd. Adhesive composition and bonded body
JP5862021B2 (en) * 2010-03-05 2016-02-16 株式会社リコー Actinic ray curable ink composition, actinic ray curable inkjet ink composition and printing method thereof
WO2012050308A2 (en) * 2010-10-11 2012-04-19 Lg Electronics Inc. Vacuum insulation glass panel and refrigerator having the same
JP4762374B1 (en) * 2011-02-14 2011-08-31 積水化学工業株式会社 Photosensitive composition and printed wiring board
CN106978122A (en) * 2011-08-17 2017-07-25 积水化学工业株式会社 Sealing material for liquid crystal display device and liquid crystal display cells
JP5370706B1 (en) * 2012-12-14 2013-12-18 デクセリアルズ株式会社 Manufacturing method of image display device
CN104813224B (en) * 2013-05-31 2019-03-22 积水化学工业株式会社 Sealing material for liquid crystal display device, upper and lower conductive material, the manufacturing method of liquid crystal display element and sealing material for liquid crystal display device
KR101569129B1 (en) * 2014-01-21 2015-11-13 디아이씨 가부시끼가이샤 Liquid crystal display device
CN106662782B (en) * 2014-07-17 2019-07-26 日本化药株式会社 Liquid crystal sealing agent and the liquid crystal display for using it
CN105068328A (en) * 2015-09-22 2015-11-18 武汉华星光电技术有限公司 Method for manufacturing liquid-crystal display screen and liquid-crystal display screen
CN107250903B (en) * 2015-10-09 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
WO2018034223A1 (en) * 2016-08-17 2018-02-22 シャープ株式会社 Liquid crystal cell for scanning antenna, and method for manufacturing liquid crystal cell for scanning antenna
WO2018079427A1 (en) * 2016-10-28 2018-05-03 シャープ株式会社 Seal material composition, liquid crystal cell, and scanning antenna
JP7156946B2 (en) * 2017-07-14 2022-10-19 積水化学工業株式会社 Liquid crystal display element sealant, vertical conduction material, and liquid crystal display element
WO2021157377A1 (en) * 2020-02-06 2021-08-12 三井化学株式会社 Light- and heat-curable resin composition, liquid crystal sealing agent containing same, liquid crystal display panel, and manufacturing method therefor
CN114479456B (en) * 2021-12-28 2023-09-22 安徽国风新材料股份有限公司 High-strength low-dielectric polyimide film and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2446125A1 (en) * 2001-05-16 2002-11-21 Sekisui Chemical Co., Ltd. Curing resin composition and sealants and end-sealing materials for displays

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1040598A (en) * 1988-01-28 1990-03-21 中国科学院长春物理研究所 Red fluorescence transferring film
CN1051050A (en) * 1989-10-20 1991-05-01 天津市合成材料工业研究所 Preparation of insulation coating of high-voltage electric apparatus
JP3708770B2 (en) * 1999-12-24 2005-10-19 セイコーエプソン株式会社 Manufacturing method of liquid crystal device

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2446125A1 (en) * 2001-05-16 2002-11-21 Sekisui Chemical Co., Ltd. Curing resin composition and sealants and end-sealing materials for displays

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开平7-224144A 1995.08.22

Also Published As

Publication number Publication date
CN101367982B (en) 2013-06-12
CN101369098B (en) 2012-01-04
CN1798786A (en) 2006-07-05
CN101367982A (en) 2009-02-18
CN101369098A (en) 2009-02-18

Similar Documents

Publication Publication Date Title
CN1798786B (en) Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device
CN101176033B (en) Sealing material for liquid crystal dropping method, vertically conducting material, and liquid crystal display element
TWI509015B (en) A hardened resin composition, a sealant for a liquid crystal display element, and a liquid crystal display element
CN100404579C (en) One-pack-type resin composition curable with combination of light and heat and use of the same
CN102361947B (en) Adhesive protective film, screen panel, and portable electronic terminal
CN102516916B (en) Liquid crystal sealant composition
CN101416104B (en) Sealing material for liquid-crystal dropping process, vertical-conduction material, and liquid-crystal display element
CN102007447B (en) Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element
KR101084487B1 (en) Liquid crystal sealing material, process for production of liquid crystal display panels with the same, and liquid crystal display panels
CN103026292A (en) Light-shielding sealing agent for liquid crystal display element, top-to-bottom conductive material, and liquid crystal display element
CN104620166B (en) Liquid crystal indicator
CN105062400A (en) Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element
KR20130073610A (en) Black sealing agent composition for liquid crystal display materials
US20060240198A1 (en) Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device
CN105103044B (en) Liquid crystal indicator
CN106833442A (en) Sealant, liquid crystal panel, liquid crystal display and preparation method thereof
TW201600588A (en) Sealant for one-drop filling process, vertically conductive material, and liquid crystal display element
JP2005015757A (en) Light curable resin composition, sealing agent for liquid crystal display element, encapsulating agent for liquid crystal display element, vertical conduction material for liquid crystal display element, and liquid crystal display device
JP2005054164A (en) Photo- and heat-curable resin composition, sealing agent for liquid crystal display element, opening-sealing agent for the liquid crystal display element, vertically-conducting material for the liquid crystal display element, and liquid crystal display device
CN100398621C (en) Curing resin composition and sealants and end-sealing materials for displays
JP2005060651A (en) Curable resin composition, sealing agent for liquid crystal display element, mouth-sealing agent for liquid crystal display element, vertical conduction material for liquid crystal display element and liquid crystal display element
JP2005015758A (en) Curable resin composition, sealing agent for liquid crystal display element, encapsulating agent for liquid crystal display element, vertical conduction material for liquid crystal display element, and liquid crystal display element
JP2005258353A (en) Hardening resin composition for liquid crystal display element, sealing agent for liquid crystal dropping process, vertical conductive material and liquid crystal display element
CN109541855B (en) Liquid crystal cell and liquid crystal display device
JP2004361854A (en) Liquid crystal display element

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant