CN1798786A - 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 PDFInfo
- Publication number
- CN1798786A CN1798786A CN200480015573.6A CN200480015573A CN1798786A CN 1798786 A CN1798786 A CN 1798786A CN 200480015573 A CN200480015573 A CN 200480015573A CN 1798786 A CN1798786 A CN 1798786A
- Authority
- CN
- China
- Prior art keywords
- curable resin
- liquid crystal
- resin composition
- crystal display
- display device
- 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.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 327
- 239000011342 resin composition Substances 0.000 title claims abstract description 223
- 239000003566 sealing material Substances 0.000 title claims description 42
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- 239000011347 resin Substances 0.000 claims abstract description 154
- 238000000034 method Methods 0.000 claims abstract description 113
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011521 glass Substances 0.000 claims abstract description 36
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 124
- -1 (methyl) acryl Chemical group 0.000 claims description 114
- 238000007789 sealing Methods 0.000 claims description 109
- 150000001875 compounds Chemical class 0.000 claims description 72
- 239000007870 radical polymerization initiator Substances 0.000 claims description 65
- 125000000524 functional group Chemical group 0.000 claims description 63
- 239000000126 substance Substances 0.000 claims description 60
- 239000000758 substrate Substances 0.000 claims description 57
- 239000004593 Epoxy Substances 0.000 claims description 53
- 230000007704 transition Effects 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 49
- 238000006116 polymerization reaction Methods 0.000 claims description 47
- 239000007858 starting material Substances 0.000 claims description 38
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 36
- 230000000694 effects Effects 0.000 claims description 35
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- 239000001257 hydrogen Chemical group 0.000 claims description 33
- 229910052739 hydrogen Chemical group 0.000 claims description 33
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 28
- 238000010526 radical polymerization reaction Methods 0.000 claims description 25
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- 238000001029 thermal curing Methods 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
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- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- CCRIVCWOXSIYEP-UHFFFAOYSA-N methyl prop-2-enoate;hydrochloride Chemical compound Cl.COC(=O)C=C CCRIVCWOXSIYEP-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Liquid Crystal (AREA)
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 display element, 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
Technical field
The present invention relates to when being used for making the process of liquid crystal display device as sealing material for liquid crystal display device by liquid crystal drippage completion method (drop fill process) to the pollution of liquid crystal less, with the connectivity of substrate good and the not uneven curable resin composition in generation unit gap (cell gap), sealing material for liquid crystal display device and liquid crystal display device.
Background technology
In the past, liquid crystal display device such as liquid crystal display are made by the following method: make two transparency carriers that have an electrode every predetermined distance relatively to, use the sealing agent of forming by curable resin composition with sealing around it, and make sealant cures and form a unit, in the unit, inject liquid crystal from the liquid crystal injecting port that is located at wherein afterwards, then this liquid crystal injecting port is used sealing agent or sealing compound sealing.
That is, at first, on any substrate of two transparency carriers that have an electrode, form seal pattern by silk screen print method, use the Thermocurable sealing agent to be provided with liquid crystal injecting port in the described seal pattern, under 60-100 ℃, carry out prebake, make the solvent seasoning in the sealing agent.Then, make two substrate clampings partition (spacer) relatively to, and it is being aimed at the back applying, under 110-220 ℃, carried out hot pressing 10-90 minute, adjust near the gap of hermetic unit, in stove, heated 10-120 minute down then, make sealing agent carry out the fact and solidify (actually cure) at 110-220 ℃.Then, inject liquid crystal, use sealing compound encapsulated liquid crystals inlet at last, thereby make liquid crystal display device by liquid crystal injecting port.
But if according to this making method, then 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 the gap uneven, the sealing destroyed; The sealing and curing time is long; The prebake complex process; Because of solvent evaporates, the usable time of sealing agent shortens; Problem such as take a long time when injecting liquid crystal.Especially in large-scale liquid crystal display device in recent years, require a great deal of time when injecting liquid crystal, this has become very noticeable problem.
Be directed to this, studied and used the photocuring thermofixation also with the manufacture method type sealing agent, that be called as the liquid crystal display device that drips completion method.In the drippage completion method, at first on the substrate in two transparency carriers that have an electrode,, thereby form rectangular seal pattern (hermetic unit) by the agent of silk screen print method printing and sealing.Then, do not have under the solidified state liquid crystal carefully dripped at sealing agent and be 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, in the annealing of liquid crystal, carry out the fact and solidify, make liquid crystal display device by heating.If under reduced pressure carry out the applying of substrate, then 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, making in the method for liquid crystal indicator several problems that existence must overcome with the drippage completion method.
The 1st problem is the liquid crystal pollution problem.Owing to have the operation that uncured sealing agent directly contacts with liquid crystal, the pollution liquid crystal just becomes a very big problem so the sealing agent composition is eluted in the liquid crystal in the drippage completion method.When producing liquid crystal pollution, produce the orientation disorder of liquid crystal, cause even grade of irregular colour to show bad reason thereby become in the periphery branch of sealing agent.
For example; as the curable resin that was used as in the curable resin composition of sealing agent in the past; the for example part of bisphenol A type epoxy resin (methyl) acryl thing (patent documentation 1-5), (methyl) acrylate resin (patent documentation 6) etc. are disclosed; but these curable resins have demonstrated the character that is easy to affinity owing to having the polarity number close with liquid crystal material, so there is the tendency that is eluted in the liquid crystal.
In addition, the polymerization starter that is blended in the sealing agent as living radical generation agent also is a reason of polluting liquid crystal.Can use low-molecular-weight organic compound as the polymerization starter that is mixed in the sealing agent in the past, this polymerization starter is easy to be eluted in the liquid crystal, in addition, polymerization finishes the also remaining residue that comes from polymerization starter in back, so this residue thing is by being eluted to the reason that becomes liquid crystal pollution in the liquid crystal, the heating during perhaps by the liquid crystal reorientation becomes evolving gas and becomes the engaging force decline that causes between glass substrate 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 have a Photoepolymerizationinitiater initiater of (methyl) acryloxy and formed material and be supported on two liquid crystal apparatus between transparency carrier by the transparent polymer substance that polymerization forms.This liquid crystal apparatus is not owing to use low-molecular-weight polymerization starter, so the residue thing of the polymerization starter after polymerization finishes is difficult to be eluted in the 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 fully that the residue thing is eluted in the liquid crystal, still the unresolved polymerization starter that contacts with liquid crystal when uncured in drippage completion method etc. can be eluted in the liquid crystal, and the heating when perhaps the residue thing of the polymerization starter after the curing is because of the liquid crystal reorientation becomes the problem of evolving gas.
In addition, also be the reason of liquid crystal pollution as bonding auxiliary agent blended alkoxysilane compound containing trialkylsilyl group in molecular structure.With regard to sealing agent in the past, usually use γ-An Bingjisanjiayangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan, γ-Huan Yangbingyangbingjisanjiayangjiguiwan, 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, compare with the sealing agent that the resin combination by thermohardening type is in the past formed, a little less than the engaging force of glass substrate by the sealing agent that the resin combination of ultraviolet hardening is formed.In addition, in order to improve thermotolerance, the improvement of sealing agent is trended towards improving 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, method of known adding 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, the Resins, epoxy binder compositions that contains core shell particles (core-shell) is disclosed, the sandwich layer that described core shell particles is made up of the resin that by second-order transition temperature is 45 ℃ and be that the shell that 105 ℃ resin is formed is formed by second-order transition temperature.In the thermofixation of this Resins, epoxy reaction, the rubber constituent of core shell particles is because heating and swelling, and absorbs and improve the shock-resistance of resin combination from the impact of outside, peels off engaging force thereby improved.But, owing to be to be prerequisite in this method to make the swelling of core shell particles by heating, so to the resin combination of ultraviolet hardening (perhaps and composition with ultraviolet hardening and thermohardening type in, the material that carries out ultraviolet curing earlier) the improvement of connectivity may not have effect.
The 3rd problem is the uneven problem in gap.When making liquid crystal indicator with the drippage completion method, too high based on the solidified nature of photocuring sometimes with regard to sealing agent in the past, it is big that the linear expansion rate behind the photocuring becomes, and then understand problems such as the generation unit gap is inhomogeneous because of substrate is offset.
Thus, produced demand to the curable resin composition that can be used in sealing material for liquid crystal display device of the connectivity that solved liquid crystal pollution problem, sealing agent, the uneven problem in gap.
Patent documentation 1: the spy opens flat 6-160872 communique
Patent documentation 2: the spy opens flat 1-243029 communique
Patent documentation 3: the spy opens flat 7-13173 communique
Patent documentation 4: the spy opens flat 7-13174 communique
Patent documentation 5: the spy opens flat 7-13175 communique
Patent documentation 6: the spy opens flat 7-13174 communique
Patent documentation 7: the spy opens flat 5-264980 communique
Patent documentation 8: the spy opens flat 7-224144 communique
Summary of the invention
In view of the foregoing, the purpose of this invention is to provide when be used for by the drippage completion method when making the process of liquid crystal display device as sealing material for liquid crystal display device, pollution to liquid crystal is few, with the connectivity of substrate well and the not uneven curable resin composition in generation unit gap, sealing material for liquid crystal display device and liquid crystal display device.
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, even can obtain when as sealing material for liquid crystal display device, under uncured state, to contact the curable resin composition that also is difficult for polluting liquid crystal, so far finish the 1st, the 2nd and the 3rd the present invention with liquid crystal.Wherein, the 1st the present invention is the problem that has solved the liquid crystal pollution that is produced by curable resin, and the 2nd the invention solves the problem of the liquid crystal pollution that is produced by polymerization starter, and the 3rd the invention solves the problem of the liquid crystal pollution that is 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 a 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 Resins, epoxy and (methyl) vinylformic acid reaction formation (methyl) acrylic modified epoxy resin.
(methyl) acrylic modified epoxy resin is owing to have (methyl) acryl (acryl) and epoxy group(ing) in a part, so no matter use up or can make its curing with heat.Therefore, if the 1st curable resin composition of the present invention is used as sealing material for liquid crystal display device, then can adopt first irradiates light and temporary sealing after make it carry out true solidified mode by heating, go for adopting the manufacturing of the liquid crystal display device of drippage completion method.
(methyl) acrylic modified epoxy resin like this is owing to purity height, the foreign matter content of the crystallinity Resins, epoxy that is used as raw material are few, so may be difficult for polluting liquid crystal.Also have, so-called (methyl) vinylformic acid is meant vinylformic acid or methacrylic acid in the specification sheets of the present invention.In addition, so-called crystalline resin is meant and measures with differential scanning calorimeter that differential sharp-pointed fusing point peak clearly occurs when hot and the crystallization degree surpasses 10% resin in the specification sheets of the present invention, and so-called non-crystalline resin is meant to be measured differential with differential scanning calorimeter not occur sharp-pointed fusing point peak clearly and crystallization degree when hot be 10% or resin below it.
Above-mentioned (methyl) acrylic modified epoxy resin is preferably crystalline.Crystalline (methyl) acrylic modified epoxy resin is because the crystallinity height 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 ℃, need at high temperature heat when then mixing, can produce problems such as gelation.Be limited to 40 ℃ under preferred.If 40 ℃ of less thaies then can cause cohesive force to descend, the adaptation that curable resin composition of the present invention solidifies the cured article that forms is descended sometimes.
Above-mentioned (methyl) acrylic modified epoxy resin is preferably the resin that sulphur atom in the 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 then, if surpass 10, then wet fastness is poor sometimes.
Above-mentioned (methyl) acrylic modified epoxy resin, remove with the total atom number that sulphur atom and the preferred of Sauerstoffatom sum income value are limited to 0.08 down in the resin matrix, be limited to 0.14 on preferably.If less than 0.08, polarity step-down and be easy to pollute liquid crystal sometimes then, if surpass 0.14, then wet fastness is poor sometimes.
Above-mentioned (methyl) acrylic modified epoxy resin can be made by crystallinity Resins, epoxy and (methyl) vinylformic acid are reacted.
Have no particular limits as above-mentioned crystallinity Resins, epoxy, can enumerate for example bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, hydroquinone type Resins, epoxy, biphenyl type epoxy resin, toluylene type Resins, epoxy, sulfide type Resins, epoxy, ether type epoxy, naphthalene type Resins, epoxy and these derivative etc.
Be preferably 140 ℃ or below it as the fusing point of the crystallinity Resins, epoxy of above-mentioned raw materials.If surpass 140 ℃, then gelation can take place during modified-reaction sometimes.Be limited to 120 ℃ on preferred.In addition, be limited to 40 ℃ under preferred.If 40 ℃ of less thaies, then crystallinity descends sometimes.
Have no particular limits as the method that makes the reaction of above-mentioned crystallinity Resins, epoxy and (methyl) vinylformic acid, can use known method in the past.
When making the reaction of above-mentioned crystallinity Resins, epoxy and (methyl) vinylformic acid, the preferred basic catalyst that uses, have no particular limits as above-mentioned basic catalyst, can enumerate for example N, accelerine, triethylamine, triphenylphosphine, iron(ic) chloride, zinc chloride, vanadium chloride etc.
In addition, when making the reaction of above-mentioned crystallinity Resins, epoxy and (methyl) vinylformic acid, preferably in the presence of above-mentioned basic catalyst,, make the reaction of 1-0.5 equivalent (methyl) vinylformic acid with respect to 1 equivalent epoxy group(ing).
In the 1st curable resin composition of the present invention, the preferred of the combined amount of above-mentioned (methyl) acrylic modified epoxy resin is limited to 10 weight % down, is limited to 50 weight % on preferably.If less than 10 weight % then make the adaptation of the cured article that its curing forms descend sometimes, if surpass 50 weight %, then crystallization can take place in composition.
In the 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, for example can enumerate (methyl) acrylate, ethene derivatives, styrene derivatives, Resins, epoxy etc.Wherein, from promptly reacting the viewpoint good with connectivity, what be fit to is (methyl) acrylate, Resins, epoxy, oxetane resin.
Above-mentioned curable resin preferably has hydrogen bond functional group at intramolecularly.Thus, can improve the associativity between the curable resin, even also be difficult to pollute crystal when contacting with crystal.Above-mentioned curable resin preferably has the above addition reactivity of two or its functional group at intramolecularly, more preferably has more than two below four.Thus, the remaining quantity of the unreacted resin after the curing can be reduced, unreacted resin stain liquid crystal can be prevented.
As above-mentioned (methyl) acrylate can enumerate urethane (methyl) acrylate that for example has urethane bond, by the compound with glycidyl and (methyl) vinylformic acid deutero-epoxy (methyl) acrylate, by polyvalent alcohol that contains three above OH bases in a part or polyester polyols pure and mild (methyl) vinylformic acid deutero-(methyl) acrylate etc. under the state that keeps an above OH base.
As above-mentioned urethane (methyl) acrylate, can enumerate for example 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 the commercially available prod, can enumerate for example U-122P, U-340P, U-4HA, U-1084A (all being Xin Zhong village chemistry society system), KRM7595, KRM7610, KRM7619 (all being ダ イ セ Le UCB society system) etc.
As above-mentioned epoxy (methyl) acrylate, can enumerate for example by Resins, epoxy such as bisphenol A type epoxy resin or propylene glycol diglycidylether and (methyl) vinylformic acid deutero-epoxy (methyl) acrylate etc.In addition, as the commercially available prod, can enumerate for example EA-1020, EA-6320, EA-5520 (all being Xin Zhong village chemistry society system), epoxy ester 70PA, epoxy ester 3002A (all being chemistry society of common prosperity society system) etc.
As keeping deutero-(methyl) acrylate under the state of an above OH base by polyvalent alcohol that contains three above OH bases in a part or polyester polyols pure and mild (methyl) vinylformic acid, can enumerate for example methyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, IBOMA, methacrylic acid 2-hydroxyl ethyl ester, 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 Resins, epoxy, for example can enumerate (methyl) acrylic modified epoxy resin, urethane modification (methyl) acryl Resins, epoxy etc.
As above-mentioned (methyl) acrylic modified epoxy resin, for example can enumerate part (methyl) propylene acylates such as phenolic resin varnish type epoxy resin, bisphenol-type epoxy resin, biphenyl type epoxy resin, naphthalene type Resins, epoxy, three (hydroxyphenyl) alkyl type Resins, epoxy, four (hydroxyphenyl) alkyl type Resins, epoxy, ring type aliphatic epoxy resin etc.Wherein, part (methyl) the propylene acylate of preferred phenolic resin varnish type epoxy resin.This is because by using phenolic resin varnish type epoxy resin as base resin, compare with straight catenate bisphenol-type epoxy resin, 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 Resins, epoxy, 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 (all being japan epoxy resin society system), エ ピ Network ロ Application 850, エ ピ Network ロ Application 860, エ ピ Network ロ Application 4055 (all be big 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 (big Japanese ink chemical industry society system) etc., as phenol novolak type epoxy resin, can enumerate for example エ ピ Network ロ Application N-740, N-770, N-775 (big Japanese ink chemical industry society system), 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 (big Japanese ink chemical industry society system) etc.
In addition, as above-mentioned ring type aliphatic epoxy resin, can enumerate for example セ ロ キ サ イ De 2021, セ ロ キ サ イ De 2080, セ ロ キ サ イ De 3000 (all being ダ イ セ Le UBC society system) etc., as the material that part (methyl) acryloyl (acryl) of above-mentioned Resins, epoxy is changed, can enumerate for example by making Resins, epoxy and (methyl) vinylformic acid in the presence of basic catalyst, react the material of acquisition with ordinary method.
Can obtain the Resins, epoxy of desirable propylene acidylate rate by combined amount and (methyl) acrylic acid combined amount of the above-mentioned Resins, epoxy of appropriate change.Specifically, carboxylic acid is limited to 0.1 equivalent down with respect to the preferred of 1 equivalent epoxy group(ing), is limited to 0.5 equivalent on preferably, is limited to 0.2 equivalent under preferred, is limited to 0.4 equivalent on preferred.
As above-mentioned urethane modification (methyl) acryl Resins, epoxy, for example can enumerate the resin that obtains with following method: make the above isocyanate reaction of polyvalent alcohol and two senses, make it then again and (methyl) acryl (acryl) monomer of hydroxyl and the method for Racemic glycidol reaction; Under condition without polyvalent alcohol; making the method for the above isocyanate reaction of (methyl) acryl monomer with hydroxyl or Racemic glycidol and two senses etc., also can be the method that makes Racemic glycidol and (methyl) acrylate monomer reaction that contains isocyanate group in addition.
Specifically, for example, 1mol TriMethylolPropane(TMP) and 3mol isophorone diisocyanate are reacted under the tin series catalysts.By making the isocyanate group that is retained in the compound that obtains and obtaining resin as the Hydroxyethyl acrylate of the acryl monomer of hydroxyl and as the Racemic glycidol reaction of the epoxy compounds of hydroxyl.
Be not particularly limited as above-mentioned polyvalent alcohol, can enumerate for example 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 for example ethylene glycol, propylene glycol, 1, ammediol, 1,3 butylene glycol, 1, one (methyl) acrylate of dibasic alcohol such as 4-butyleneglycol, polyoxyethylene glycol; One (methyl) acrylate, two (methyl) acrylate of trivalent alcohols such as trimethylolethane, TriMethylolPropane(TMP), glycerine; Epoxy acrylates such as bisphenol A modified epoxy acrylate etc.These can use separately, also can be used in combination more than two kinds.
The 2nd the present invention is a 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 to contain irradiates 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 a part.
In the above-mentioned radical polymerization initiator, so-called radical polymerization initiating radical is meant irradiates light and/or is 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 preferred.As such radical polymerization initiating radical, for example can enumerate carbonyl, contain sulfenyl, azo-group, contain organic peroxide-based etc., but what wherein be fit to is the group etc. with structure of representing with following general formula (1)-(6).
[Chemical formula 1]
In above-mentioned general formula (1)-(6), R
1, R
2And R
3Represent that independently of one another carbonatoms is that alkyl, hydrogen atom, hydroxyl, the carbonatoms of 1-6 is alkoxyl group, (methyl) acryl, the phenyl of 1-6, R
4, R
5, R
6And R
7Expression cyano group, carbonatoms be alkyl, hydrogen atom, hydroxyl, the carbonatoms of 1-6 be 1-6 alkoxyl group, (methyl) acryl, can to have carbonatoms be the alkyl of 1-6 or the aromatic nucleus of halogen radical,
[Chemical formula 2]
It is the alkyl of 1-6 or the aromatic nucleus of halogen radical that expression can have carbonatoms.Wherein, more preferably have by the more weak photodissociation of specific absorption is the group of structure of the above-mentioned general formula of usefulness (1)-(4) expression of living radical kind, from the aspect of living radical production rate, further preferably has group with the structure of above-mentioned general formula (1) expression.
As above-mentioned hydrogen bond functional group, just have no particular limits so long as have the functional group of hydrogen bond or residue etc., can enumerate for example OH base, NH
2Base, NHR basic (R represents aromatic series or aliphatic hydrocarbon and these derivative), COOH base, CONH
2Base, NHOH is basic and have the group etc. of residues such as NHCO key, NH key, CONHCO key, NH-NH key at intramolecularly.
Above-mentioned radical polymerization initiator is owing to have 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 wash-out and goes out, 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 by irradiates light and/or heat dissociate the radical polymerization initiating radical to produce preferably all have at least one hydrogen bond functional group.That is any one living radical kind all had at least one hydrogen bond functional group when, above-mentioned hydrogen bond functional group preferably was configured to the radical polymerization initiating radical be dissociated produce two living radical kinds by irradiates light and/or heat in molecule.Thus, all living radical kinds of generation even contact because above-mentioned polymerization starter rests in the curable resin composition with liquid crystal, so the composition of polymerization starter is difficult to be eluted in the liquid crystal, are difficult for producing liquid crystal pollution.
Above-mentioned radical polymerization initiator also preferably has plural reactive functional groups in a part.By in molecule, having such reactive functional groups, above-mentioned radical polymerization initiator itself forms multipolymer with curable resin and is fixed, can not be eluted in the liquid crystal so polymerization finishes the residue thing of post polymerization initiator yet, in addition, heat 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 curable resin bonded described later functional group, can enumerate for example ring-type such as epoxy group(ing) and oxetanyl ether, (methyl) acryl, styryl etc. by polyreaction.What wherein, be fit 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 irradiates light and/or hot two the living radical kinds that produce of dissociating.That is any one living radical kind all had at least one reactive functional groups when, above-mentioned reactive functional groups preferably was configured to the radical polymerization initiating radical be dissociated produce two living radical kinds by irradiates light and/or heat in molecule.Thus, all living radical kinds of generation all form multipolymer with curable resin and are fixed, and also can not be eluted in the liquid crystal so polymerization finishes the residue thing of post polymerization initiator, in addition, heat also during the liquid crystal reorientation 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, then the radical polymerization initiator composition is eluted in the liquid crystal sometimes, is easy to make the orientation disorder of liquid crystal.Be limited to 3000 on preferred.If surpass 3000, then 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
-1If not enough 200M
-1Cm
-1, during then as sealing material for liquid crystal display device, if illumination wavelength is not that the following high-energy line of 350nm just can not fully solidify sometimes, liquid crystal and alignment films can be because of shining such high-energy line variation.If surpass 10,000 M
-1Cm
-1, then when the sealing material for liquid crystal display device, during the about 350nm of illumination wavelength ultraviolet sometimes only the surface at first solidify, inside can not fully be solidified.300-3000M more preferably
-1Cm
-1
In addition, in this specification sheets, above-mentioned so-called molar absorptivity is meant by the ε (M for the acetonitrile solution that contains above-mentioned radical polymerization initiator ラ Application バ-ト ベ-Le formula definition shown in the following formula (7)
-1Cm
-1) value.
[mathematical expression 1]
Log(I
o/I)＝εcd (7)
In addition, in the above-mentioned formula (7), I represents transmission light intensity, I
oThe transmission light intensity of expression acetonitrile neat solvent, c represents volumetric molar concentration (M), d represents the thickness (cm) of solution layer, Log (I
o/ I) expression 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, then 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, to have the method that the alcohol derivate of above-mentioned radical polymerization initiating radical and hydroxyl more than two is implemented (methyl) acroleic acid esterification at intramolecularly; Make the method that has an epoxy reaction of the compound that above-mentioned radical polymerization initiating radical and hydroxyl more than two or amino compound and intramolecularly have two above epoxy group(ing) at intramolecularly; Make an epoxy reaction that has the compound that above-mentioned radical polymerization initiating radical and hydroxyl more than two or amino compound and intramolecularly have two above epoxy group(ing) at intramolecularly, make remaining epoxy group(ing) and (methyl) vinylformic acid again or have (methyl) acrylate monomer of active hydrogen base or method that styrene monomer etc. reacts; Make after intramolecularly has above-mentioned radical polymerization initiating radical and hydroxyl more than two or amino compound and cyclic ester compound or has the reactions such as carboxylic acid cpd of hydroxyl, make the method for above-mentioned hydroxyl (methyl) acroleic acid esterification again; By having at intramolecularly after above-mentioned radical polymerization initiating radical and hydroxyl more than two or the amino compound and the synthetic urethane derivatives of two functional isocyanate derivatives, make the method for another isocyanic ester and reactions such as (methyl) vinylformic acid, Racemic glycidol, (methyl) acrylate monomer, styrene monomer etc. again with hydroxyl.
As the above-mentioned compound that has two above epoxy group(ing) at intramolecularly, can enumerate for example difunctional epoxy resin compound.
Have no particular limits as above-mentioned difunctional epoxy resin compound, for example can enumerate bisphenol type epoxy compound, bisphenol f type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, with these hydrogenant Resins, epoxy, phenolic resin varnish type epoxy resin, urethane modified epoxy, with epoxidised nitrogen-containing epoxy thermosets such as m-xylene diamines, contain the rubber modified epoxy resin of polyhutadiene or paracril (NBR) etc.These difunctional epoxy resin compounds can be solid state, also can be liquid.
Have no particular limits as above-mentioned (methyl) acrylate monomer, can enumerate for example ethylene glycol, propylene glycol, 1, ammediol, 1,3 butylene glycol, 1, one (methyl) acrylate of dibasic alcohol such as 4-butyleneglycol, polyoxyethylene glycol with hydroxyl; One (methyl) acrylate of trivalent alcohols such as trimethylolethane, TriMethylolPropane(TMP), glycerine, two (methyl) acrylate etc.These can use separately, also can be used in combination more than two kinds.
As above-mentioned two functional isocyanate derivatives, can enumerate for example 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.
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 in the 2nd curable resin composition of the present invention, and preferred upper limit is 15 weight parts.If less than 0.1 weight part then can not make the 2nd curable resin composition of the present invention fully solidify sometimes, if surpass 15 weight parts, then 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, just have no particular limits so long as under the effect of light and/or heat, produce the compound of free radical.
As the above-mentioned radical polymerization initiator that under the effect of heat, produces free radical, can enumerate for example superoxide such as lauroyl peroxide, benzoyl peroxide, cumyl superoxide; Azo-compounds such as Diisopropyl azodicarboxylate etc.
As the above-mentioned radical polymerization initiator that under the effect of light, produces free radical, can enumerate for example 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 use separately, also can be used in combination more than two kinds.
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 in the curable resin composition of the present invention, and preferred upper limit is 10 weight parts.If less than 0.1 weight part, then can not solidify sometimes insufficient, if surpass 10 weight parts, then might be 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 a 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 with following general formula (8) expression.
[chemical formula 3]
-Si(OR
1)
nR
2 (3-n) (8)
In the 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.
The molecular weight that contains in such alkoxysilane compound containing trialkylsilyl group in molecular structure is the 3rd curable resin composition of the present invention of the alkoxysilane compound containing trialkylsilyl group in molecular structure more than 500, even be used for also can not producing liquid crystal pollution because of bonding auxiliary agent by the process of liquid crystal drippage completion method manufacturing liquid crystal display device as sealing material for liquid crystal display device.
As such molecular weight is 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, (13 fluoro-1,1,2,2,-tetrahydrochysene octyl group) triethoxyl silane, (17 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 Application ジ オ ネ-ト)) titanium-O, two (the oxoethyl)-aminopropyltriethoxywerene werene of O-etc.These alkoxysilane compound containing trialkylsilyl group in molecular structure for example also can use チ Star ソ society system, waste river chemistry society system commercially available products such as (" コ Application Port セ ラ Application E202 "), also can be synthetic by the organoalkoxysilane with reactive base and/or polymerizability base.
In addition, to contain molecular weight in the 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 is even be used for also can not producing liquid crystal pollution because of bonding auxiliary agent by the process of liquid crystal drippage completion method manufacturing liquid crystal display device as sealing material for liquid crystal display device.
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 the above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure, so long as except-NH
2Functional group with hydrogen bond or residue etc. beyond the base just have no particular limits, for example can enumerate-the OH base ,-the SH base ,-NHR base (R represents 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 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 has no particular limits, can enumerate for example N-3-acryloxy (ア Network リ ロ キ シ)-2-hydroxypropyl)-the 3-aminopropyltriethoxywerene werene, 3-(N-allyl amino) propyl trimethoxy silicane, two (2-hydroxyethyl)-3-aminopropyltriethoxywerene werene, 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)-3-aminopropyltriethoxywerene werene, 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 for example also can use 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, basic, the acryl of NCO, 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 use 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, above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure embedded in the cured article when the 3rd curable resin composition of the present invention was solidified, so can not be eluted in the 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 for example acryl, methacryloyl, epoxy group(ing), vinyl etc.As with the reactive functional groups of above-mentioned reactive with active hydrogen, can enumerate for example isocyanate group, acryl, methacryloyl, epoxy group(ing) etc.Wherein, from solidifying with common sealant cures composition and being difficult to the dissolved aspect more with respect to liquid crystal, what be fit to is be selected from epoxy group(ing), acryl and methacryloyl at least a.
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 in the 3rd curable resin composition of the present invention, and preferred upper limit is 20 weight parts.If less than 0.1 weight part then can not be brought into play bonding strength and water-proof function sometimes fully,, then might damage the fundamental property as curable resin composition such as solidified nature if surpass 20 weight parts.
Present inventors have carried out wholwe-hearted research to the problem of the connectivity of sealing agent, found that by being to mix resin particle in the curable resin composition of particular value to the second-order transition temperature of solidifying the after fixing thing with specific core shell structure, even using up when being cured, also can obtain the effect significantly improved with the connectivity of substrate, so far finish the 4th the present invention.
The 4th the present invention is a curable resin composition, it is to contain the curable resin that is cured under the effect of light and/or heat, the curable resin composition of polymerization starter and resin particle, above-mentioned resin particle has by having core particle that caoutchouc elasticity and second-order transition temperature form for resin below-10 ℃ and being the shell that 50-150 ℃ resin is formed by the second-order transition temperature that forms on the surface of above-mentioned core particle, and 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 by having core particle that caoutchouc elasticity and second-order transition temperature form for resin below-10 ℃ and being the shell that 50-150 ℃ resin is formed by the second-order transition temperature that forms on the surface of above-mentioned core particle.
In addition, in this specification sheets, unless special the qualification, second-order transition temperature refers to the temperature measured with common DSC method under the condition of 10 ℃/minute of heat-up rates.
Have caoutchouc elasticity and second-order transition temperature and have no particular limits for the resin below-10 ℃ as above-mentioned, what be fit to is the polymkeric substance of (methyl) acryl monomer for example.
As above-mentioned (methyl) acryl monomer, can enumerate for example ethyl propenoate, propyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-EHA, Jia Jibingxisuanyizhi, butyl methacrylate etc.These (methyl) acryl monomer polymerizations separately also can copolymerization more than two kinds.
As above-mentioned second-order transition temperature is that 50-150 ℃ resin has no particular limits, and for example can enumerate polymerizations such as isopropyl methacrylate, methacrylic tert-butyl acrylate, cyclohexyl methacrylate, methacrylic acid phenylester, methyl methacrylate, vinylbenzene, 4-chloro-styrene, 2-ethyl styrene, vinyl cyanide, vinylchlorid and the polymkeric substance that obtains.These monomers can use separately, also can be used in combination more than two kinds.
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, preferably is limited to 0.01 μ m down, is limited to 5 μ m on preferably.If in this scope, then resin particle is enough big with respect to the surface-area of above-mentioned curable resin, can show the swelling effect of sandwich layer effectively, the gap operating between the substrate in the time of can guaranteeing as sealing material for liquid crystal display device in addition.
Have no particular limits as the method for making above-mentioned resin particle, can enumerate following method: only use the monomer that constitutes core to form core particle, add the monomer that constitutes shell then and carry out polymerization and on the surface of core particle, form shell with emulsion polymerization.
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 in the 4th curable resin composition of the present invention, and preferred upper limit is 50 weight parts.If less than 15 weight parts then can not obtain sufficient connectivity sometimes and improve effect, if surpass 50 weight parts, then 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 then 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 ℃, then can not obtain connectivity fully sometimes.Be limited to 150 ℃ on preferred.
In addition, wherein cured article refers to solidify the cured article that forms under the effect of light and/or heat.
The 4th curable resin composition of the present invention is 150N/cm in junction of glass substrate, bonding strength when it is solidified preferably
2More than.If not enough 150N/cm
2, then the insufficient strength of the liquid crystal indicator that obtains sometimes is abundant.
Required tensile strength is obtained when peeling off two glass substrates after in addition, above-mentioned bonding strength for example can be engaged two glass substrates and it is solidified by use curable resin composition of the present invention.
Present inventors have carried out wholwe-hearted research to the uneven problem in gap, found that if use the curable resin composition that contains the specific average linear expansion rate of showing of inorganic particles, then can be not inhomogeneous because of the substrate generation unit gap that misplaces, so far finished the 5th and the 6th the present invention.
The 5th the present invention is a curable resin composition, it is to contain that the curable resin, polymerization starter and the median size that are cured are the curable resin composition of 1 μ m or the inorganic particulate below it under the effect of light and/or heat, and the temperature that the ratio second-order transition temperature of the cured article when only having taken place to solidify under the effect of light is low 40 ℃ is to than the average linear expansion rate α between the temperature of low 10 ℃ of second-order transition temperature
1Be 1 * 10
-4-5 * 10
-4/ ℃, and the temperature higher 10 ℃ than second-order transition temperature arrives than the average linear expansion rate α between the high 40 ℃ temperature of second-order transition temperature
2Be 2 * 10
-4-1 * 10
-3/ ℃.
The 6th the present invention is a curable resin composition, it is to contain that the curable resin, polymerization starter and the median size that are cured are the curable resin composition of 1 μ m or the inorganic particulate below it under the effect of light and/or heat, it is characterized in that the temperature that the ratio second-order transition temperature of the cured article when having taken place to solidify is low 40 ℃ arrives than the average linear expansion rate α between the temperature of low 10 ℃ of second-order transition temperature under the effect of light and heat
1Be 5 * 10
-5-1 * 10
-4/ ℃, and the temperature higher 10 ℃ than second-order transition temperature arrives than the average linear expansion rate α between the high 40 ℃ temperature of second-order transition temperature
2Be 1 * 10
-4-3 * 10
-4/ ℃.
As the curable resin that is used for the 5th and the 6th curable resin composition of the present invention, suitable 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, with the sealing agent of the manufacturing that acts on the liquid crystal indicator that adopts the drippage completion method, sealing compound with up and down during at least one of conductive material, can make its interim back of solidifying carry out fact curing by rayed by heating.
As be used 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 fit to is for example epoxy group(ing) or oxetanyl.In addition, have no particular limits as the free-radical polymerised functional group in the above-mentioned reaction resin, what be fit to is (methyl) acryl for example.
Be used 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, then thermotolerance and wet fastness are poor sometimes, if surpass 5.5mmol/g, then the adaptation to substrate etc. is not enough sometimes.
Be used 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, then thermotolerance and wet fastness are poor sometimes, if surpass 5.0mmol/g, then the adaptation to substrate etc. is not enough sometimes.
Be used 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 be 1 divided by the value preferred lower limit of ring-type ether equivalent gained, preferred upper limit is 9.If less than 1, then photoreactivity descends sometimes, though behind the adjusting play to the sealing agent irradiates light, not only interim initial cure can not take place, and increase to the wash-out of liquid crystal, if surpass 9, then become not enough with regard to the aspect of connectivity and water vapour permeability sometimes.
From reducing and the intermiscibility of liquid crystal, the viewpoint of decontamination; be used for the above-mentioned the 5th and the curable resin of the 6th curable resin composition of the present invention preferably have the resin of hydroxyl and/or urethane bond; in addition, just improve at least a molecular skeleton that stable on heating viewpoint preferably has part (methyl) the propylene acylate of the biphenyl backbone of being selected from, naphthalene skeleton, bis-phenol skeleton, phenolic resin varnish type epoxy resin.
Be used 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 ring texture below 24.Wherein so-called atomicity is meant the summation of atomicities such as carbon in the molecule that constitutes above-mentioned ring texture, hydrogen, oxygen.If atomicity surpasses 24, then can not satisfy coefficient of linear expansion described later, perhaps poor heat resistance sometimes.
Be used 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, then coefficient of linear expansion becomes big sometimes, can not satisfy scope described later, if surpass 6.0mmol/g, then the adaptation to substrate etc. is abundant inadequately sometimes.
Have no particular limits as the atom that constitutes above-mentioned ring texture, but preferred skeleton structure is a carbon atom that such ring texture is aromatic series preferably.
As having no particular limits of above-mentioned aromatic series, can enumerate for example benzene, indenes, naphthalene, tetralin, anthracene, phenanthrene etc.
Be used 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 then makes the orientation disorder of liquid crystal sometimes to the liquid crystal wash-out, if surpass 550, then sometimes because thickness, sealing agent, sealing compound or the modulation of the conductive material difficulty that becomes up and down.
Above-mentioned inorganic particles has the cure shrinkage that prevents the 5th and 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 the material of for example forming 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, lime carbonate, calcium oxide, magnesium oxide, ferrite, rhombohedral iron ore, aluminum borate etc.What wherein, be fit to is silicon-dioxide, aluminum oxide.
Shape as above-mentioned inorganic particles is not particularly limited, and can enumerate sphere, needle-like, regular shape or irregularly shaped such as tabular.
Above-mentioned inorganic particles also can at least aly carry out surface treatment with what be selected from imidazoles silane compound, epoxy silane compounds and amino silane compounds, contains imidazoles skeleton and alkoxysilyl in the above-claimed cpd across the spacer structure combining.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 then photo-thermal curing resin combination of the present invention being solidified the cured article that forms under the effect of light and/or heat becomes uneven, the low precision of cell gap.Preferred be limited to 0.01 μ m down, be limited to 0.1 μ m on preferably.If less than 0.01 μ m, then thixotropy uprises sometimes, can produce condensation product.
The preferred lower limit of the content of above-mentioned inorganic particulate is 10 weight parts with respect to curable resin 100 weight parts in the 5th and the 6th curable resin composition of the present invention, 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, the cured article when only making it to solidify by irradiates light than second-order transition temperature also low 40 ℃ temperature to than the second-order transition temperature average linear expansion rate α between low 10 ℃ the temperature also
1Be 1 * 10
-4-5 * 10
-4/ ℃, and the temperature also higher 10 ℃ than second-order transition temperature arrives than the average linear expansion rate α between the also high 40 ℃ temperature of second-order transition temperature
2Be 2 * 10
-4-1 * 10
-3/ ℃.If average linear expansion rate α
1Less than 1 * 10
-4/ ℃, perhaps average linear expansion rate α
2Less than 2 * 10
-4/ ℃, then as the sealing agent of making liquid crystal indicator by the drippage completion method, sealing compound with up and down during conductive material, carry out fact curing even solidify the back temporarily by heating, also become insufficient, can not obtain enough connectivities with the driving fit of substrate etc. by rayed.If average linear expansion rate α
1Surpass 5 * 10
-4/ ℃, perhaps average linear expansion rate α
2Surpass 1 * 10
-3/ ℃, inhomogeneous when then solidifying because of substrate dislocation generation unit gap temporarily.
The 6th curable resin composition of the present invention, the cured article when under the effect of light and heat, making it to solidify than the temperature of also low 40 ℃ of second-order transition temperature to than the second-order transition temperature average linear expansion rate α between low 10 ℃ the temperature also
1Be 5 * 10
-5-1 * 10
-4/ ℃, and the temperature also higher 10 ℃ than second-order transition temperature arrives than the average linear expansion rate α between the also high 40 ℃ temperature of second-order transition temperature
2Be 1 * 10
-4-3 * 10
-4/ ℃.If average linear expansion rate α
1Less than 5 * 10
-5/ ℃, perhaps average linear expansion rate α
2Less than 1 * 10
-4/ ℃, then as the sealing agent of making liquid crystal indicator by the drippage completion method, sealing compound with up and down during conductive material, carry out fact curing even solidify the back temporarily by heating, also become insufficient, can not obtain enough connectivities with the driving fit of substrate etc. by rayed.If average linear expansion rate α
1Surpass 1 * 10
-4/ ℃, perhaps average linear expansion rate α
2Surpass 3 * 10
-4/ ℃, then the thermotolerance of the liquid crystal indicator of Huo Deing and cold cycling characteristic are poor.
More than Shuo Ming 1-3 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, employed sealing material for liquid crystal display device when going for making 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 for example amine compound, polyphenol based compound, anhydride compound etc.
Above-mentioned so-called amine compound is meant the compound that has more than one 1-3 level amino in molecule, can enumerate for example aromatic amine such as mphenylenediamine, diaminodiphenyl-methane; Imidazolium compoundss such as glyoxal ethyline, 1,2 dimethylimidazole, 1-1-cyanoethyl-2-methylimidazole; Imidazolinium compoundss such as glyoxal ethyline quinoline; Dihydrazide compound such as sebacic dihydrazide, isophthalic dihydrazide; Dyhard RU 100 etc.In addition, also can use commercially available amine affixture 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 for example by polyphenolic substances such as the commercially available エ ピ キ ユ ア 170 of japan epoxy resin society, エ ピ キ ユ ア YL6065; Phenolic varnish type resol such as エ ピ キ ユ ア MP402FPI etc.
As above-mentioned acid anhydrides, can enumerate for example by japan epoxy resin society commercially available エ ピ キ ユ ア YH306, YH307 etc.
These solidifying agent can use separately, also can be used in combination more than two kinds.Wherein, the good viewpoint of curability at low temperatures, useful life when mixing with curable resin, what be more suitable for is the solid amine compound.In the above-mentioned solid amine compound, from the viewpoint of the storage stability of solidification compound, more preferably fusing point is more than 100 ℃.
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 in the 1-6 curable resin composition of the present invention, and preferred upper limit is 100 weight parts.If less than 0.1 weight part then solidifies insufficiently sometimes, if surpass 100 weight parts, then the storage stability of curable resin composition might variation.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 the thixotropic thixotropic agent of adjustment in addition as required, the gap is adjusted agent, defoamer, is coated with weighting agents such as flat agent, polymerization retarder, filler etc.
Have no particular limits as the method for making 1-6 curable resin composition of the present invention, for example can enumerate with above-mentioned curable resin, polymerization starter and as required various additives of blended etc. with known method blended method in the past etc.At this moment, it is contacted with layer silicate mineral plasma adsorptive solid.
In addition, when making 1-6 curable resin composition of the present invention, after mixing, the composition that preferably will constitute curable resin composition use strainer to carry out filtering operation.
Usually, because the affinity of curable resin and solidifying agent or filler is not necessarily high, so if only with common method each composition is mixed, solidifying agent and filler just can not be scattered in the resin fully, its part can form condensation product by cohesion.Even produce such condensation product, when making sealing material for liquid crystal display device, can pass through hot pressing process adjustment unit gap, so also can exert an influence hardly with method in the past.But, when making liquid crystal display device by the drippage completion method, owing to do not adjust operation, so when in sealing material for liquid crystal display device, containing the big condensation product of particle diameter, can have influence on the cell gap of the liquid crystal display device of acquisition based on hot pressed cell gap.
Mix the back by the composition that will constitute curable resin composition and use strainer to filter, can remove the bigger condensation product of particle diameter ratio that influences cell gap really, so it is bad can not produce the cell gap that is caused by above-mentioned condensation product.
Having the manufacture method of using strainer to carry out the curable resin composition of filtering operation after the composition that will constitute curable resin composition mixes also is one of the present invention.
As above-mentioned strainer, bring the condensation product of the particle diameter of effect just to have no particular limits at least the cell gap of target liquid crystal display device so long as can remove.Preferably can remove the condensation product of the above particle diameter of cell gap twice, also preferably can remove the condensation product of the above particle diameter of cell gap with target liquid crystal display device with target liquid crystal display device.Wherein, under the situation of the element that forms 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 the cell gap of reality, so more preferably can remove the condensation product with this above particle diameter of hermetic unit width that narrows down.
As such strainer, for example can enumerate the collection efficiency with particle of distance (cell gap) above particle diameter between target liquid crystal display device substrate is 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 owing to the viscosity height, so preferably pressurize to curable resin composition when above-mentioned filtration.Therefore, as above-mentioned strainer, even preferred pressurization also can be born.As such strainer, the suitable strainer of forming by metals such as stainless steel and pottery etc.
In addition, in above-mentioned filtration operation, the temperature during filtration is low more preferred more, so that suppress curing reaction, but for the viscosity that as far as possible reduces above-mentioned curable resin composition to improve filtration efficiency, so preferably can not cause the above-mentioned curable resin composition of solidified scope internal heating.The temperature preferred lower limit of the 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 then, simultaneously since when filtering heat-up time elongated, the viscosity of filtrate rises, the viscosity rising degree of sealing agent becomes big when preserving sometimes or when using.More preferably be limited to 30 ℃ down, be limited to 60 ℃ on more preferably.
In addition, with regard to the constituent of curable resin composition, particularly solidifying agent, the preferred selection can be suppressed the composition that near the viscosity of above-mentioned curable resin composition normal temperature rises.
State strainer in the use and filter before the operation, the composition that preferably will constitute curable resin composition in advance mixes fully.If undercompounding, then the quantitative change of the composition of removing with strainer sometimes is many, the sealing material for liquid crystal display device that can not obtain to have the performance that meets standard.
Have no particular limits as above-mentioned blended method, for example can enumerate the method for the use planetary-type mixer of employing and three roller mixing machines etc. all the time.
In the curable resin composition of the present invention, the content with particle of the above particle diameter of distance between target liquid crystal display device substrate is preferably below the 30 weight %.
When 1-6 curable resin composition of the present invention is used for by liquid crystal drippage completion method manufacturing liquid crystal display device as sealing material for liquid crystal display device, 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 also is 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 also is one of the present invention.
In addition, in liquid crystal display device, usually for make on two transparency carriers relatively to electrode between conducting up and down, and use conductive material up and down.Above-mentioned conductive material up and down constitutes by making curable resin composition contain electrically conductive microparticle.
The used for liquid crystal display element that contains curable resin composition of the present invention and electrically conductive microparticle up and down conductive material also is one of the present invention.
Have no particular limits as above-mentioned electrically conductive microparticle, can enumerate for example metal particle; Particulate (hereinafter referred to as the metal deposition particulate) in the enterprising row metal plating formation of reisn base material particulate; The particulate that behind the enterprising row metal plating of reisn base material particulate, forms (hereinafter referred to as covering the metal deposition particulate) with coverings such as resins; And at these metal particles, metal deposition particulate, cover on the metal deposition microparticle surfaces lobed particulate etc.Wherein, from uniformly dispersed resin combination and aspect that electroconductibility is good, preferably implemented the metal deposition particulate of golden plating or copper plating or covered the metal deposition particulate.
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.
As make used for liquid crystal display element of the present invention up and down the method for conductive material have no particular limits, can enumerate and for example combined amount according to the rules such as above-mentioned curable resin composition, above-mentioned electrically conductive microparticle be mixed the back and carry out blended method etc. with the planetary whipping appts of vacuum etc.
Method as at least one the manufacturing liquid crystal display device in the conductive material about use 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 used for liquid crystal display element of the present invention has no particular limits, for example, can be with following method manufacturing.Have two of ito thin films etc. on the substrate of transparency carrier of electrode, sealing material for liquid crystal display device of the present invention is formed 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 conducting pattern up and down by conductive material up and down with divider coating etc. on the electrode of regulation.Also have, also can in sealing agent, contain electrically conductive microparticle and replace conductive material use up and down, make its conducting up and down.Then, under the uncured state of sealing agent, liquid crystal is carefully dripped on whole that is coated in the transparency carrier framework, another transparency carrier of stack under the uncured state of conductive material up and down immediately, and to hermetic unit and up and down conductive material part irradiation ultraviolet radiation make its curing.When conductive material had Thermocurable about sealing material for liquid crystal display device of the present invention and the used for liquid crystal display element of the present invention, being heating and curing in 100-200 ℃ baking oven made its completely solidified in 1 hour again, thereby made liquid crystal display device.
Use sealing material for liquid crystal display device of the present invention, used for liquid crystal display element sealing compound of the present invention and used for liquid crystal display element of the present invention up and down the liquid crystal display device of at least one formation in the conductive material also be one of the present invention.
In addition, present inventors have carried out wholwe-hearted research to the liquid crystal display device by drippage completion method manufacturing, found that under alignment films and the situation that sealing agent contact to be easy to cause the liquid crystal material pollution, and it is bad to be easy to produce pictorial display.Therefore, in liquid crystal display device,, can prevent to show bad effectively by forming alignment films and the discontiguous structure of sealing agent.
Following liquid crystal display device also is 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 centering near the sealing agent that forms 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 enclosing in the space that is formed by described transparency carrier and sealing agent has liquid crystal material, and wherein said alignment films does not contact mutually with described sealing agent.
Description of drawings
Fig. 1 is the local amplification profile of an example of expression liquid crystal display device of the present invention.
Fig. 2 is the horizontal sectional drawing of an example of expression liquid crystal display device of the present invention.
Fig. 3 represents the local amplification profile of an example of liquid crystal display device in the past.
Among the 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 of an example of simulation ground expression liquid crystal display device of the present invention,
Fig. 2 is the horizontal sectional drawing of an example of expression 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 to engage across sealing agent 12 in the middle of being formed with two transparency carriers 11 of alignment films 13 in its surface 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. is formed.
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 around near the periphery of transparency carrier 11, alignment films 13 be formed at transparency carrier 11 the surface by in sealing agent 12 area surrounded, and do not contact with sealing agent 12.
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 the 5 μ m.If less than 5 μ m then can not prevent to show 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 constitutes liquid crystal display device of the present invention, can enumerate for example glass, resin etc. all the time as the known material of liquid crystal display device.In addition, have no particular limits, can contrast the suitably decision of size of target liquid crystal display device as the size and the thickness of above-mentioned transparency carrier.
In addition, have no particular limits, can use the alignment films that all the time is used for liquid crystal display device, but consider, use polyimide usually from thermotolerance, chemical resistant properties with to the good aspects such as connectivity of transparency carrier as above-mentioned alignment films.
The liquid crystal display device of the present invention of this structure can be used for example following method manufacturing.
At first, on the position of the regulation of two faces of the transparent glass substrate that has two electrodes such as ito thin film, use flexographic printing, intaglio printing, ink jet printing, silk screen printing and spin-coating method etc. to form the rectangular alignment films of forming by polyimide etc.At this moment, manage on the coating position of sealing agent, not form alignment films.
Then, after carrying out orientation process such as friction treatment on the above-mentioned alignment films, near the periphery of above-mentioned transparency carrier, with on the alignment films position contacting sealing agent is not being surrounded the seal pattern of the shape of above-mentioned alignment films with formation such as silk screen printing, divider coatings.
Then, under the uncured state of sealing agent liquid crystal is carefully dripped on whole that is coated in the transparency carrier framework, another transparency carrier that superposes immediately makes its curing to the hermetic unit irradiation ultraviolet radiation.When above-mentioned sealing agent has Thermocurable, can in 80-200 ℃ baking oven, be heating and curing again and make its completely solidified in 0.5-2 hour, thereby make liquid crystal display device of the present invention.
In the liquid crystal display device of the present invention because the alignment films that forms on transparency carrier do not contact with sealing agent, near around the sealing agent of the formation that the easiest generation liquid crystal material pollutes liquid crystal material be difficult to contaminated, so can obtain high-quality display image.
The effect of invention
According to the present invention, can provide when being used for making the process of liquid crystal display device as sealing material for liquid crystal display device by the drippage completion method, to the pollution of liquid crystal less, with the connectivity of substrate well and the not uneven curable resin composition in generation unit gap, sealing material for liquid crystal display device and liquid crystal display device.
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 Resins, epoxy shown in the following general formula (10); 78 ℃ of fusing points) 1000 weight parts, p methoxy phenol 2 weight parts, triethylamine 2 weight parts, vinylformic acid 200 weight parts as catalysts as polymerization retarder; when carrying air, reacted 5 hours, obtain amorphism (methyl) acrylic modified epoxy resin (50% part propylene acylate) 90 ℃ of following stirring and refluxing.
[chemical formula 4]
In the formula, G represents 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, reaction is 2 hours under the condition of 60 ℃ of following stirring and refluxing.Then, add vinylformic acid 2-hydroxyl ethyl ester 25.5 weight parts and Racemic glycidol 111 weight parts, when carrying air, make it to react 2 hours 90 ℃ of following stirring and refluxing.With 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 (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-Huan Yangbingyangbingjisanjiayangjiguiwan 1 weight part; use three roller mixing machine thorough mixing up to the formation uniform liquid, thereby obtained curable resin composition.
The curable resin composition that obtains is made liquid crystal indicator as sealing material for liquid crystal display device.
That is, on a substrate of two transparency carriers that have transparency electrode, be coated with sealing agent, thereby draw a rectangular frame with divider.Then, (another transparency carrier that superposes immediately uses high voltage mercury lamp with 100mW/cm to hermetic unit for チ Star ソ society system, JC-5004LA) thin dripping on whole that is coated in the transparency carrier framework with liquid crystal
2Intensity irradiation ultraviolet radiation 30 seconds.Then, under 120 ℃, make liquid crystal annealing 1 hour, make its thermofixation, thereby obtain liquid crystal indicator.
(embodiment 2)
Make crystallinity Resins, epoxy (new day money chemistry society system: YSLV-80DE with following general formula (11) expression; 79 ℃ of fusing points) 1000 weight parts, as p methoxy phenol 2 weight parts of polymerization retarder, when carrying air, make it to react 5 hours 90 ℃ of following stirring and refluxing as triethylamine 2 weight parts, vinylformic acid 200 weight parts of catalysts, 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 to modulate curable resin composition, and it has been made liquid crystal indicator as sealing agent with embodiment 1.
[chemical formula 5]
In the formula, G represents glycidyl.
(comparative example 1)
Will be by urethane acrylate (chemistry society of common prosperity society system with following general formula (12) expression, AH-600) curable resin composition of 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 composition mixes, form uniform liquid, thereby obtain the sealing agent of light-cured type, use it to make liquid crystal indicator.
[chemical formula 6]
In the formula, R
1The expression carbonatoms is 5 alkyl chain.
(comparative example 2)
Will be by bisphenol A type epoxy resin (japan epoxy resin society system with following general formula (13) expression, エ ピ コ-ト 828US) 50 weight parts, hydrazides class solidifying agent (the industrial society of Japanese hydrazine system, NDH) curable resin composition of 25 weight parts composition uses three roller mixing machine thorough mixing up to forming uniform liquid, thereby the acquisition sealing agent uses it to make liquid crystal indicator.
[chemical formula 7]
For the liquid crystal indicator of making by embodiment 1,2 and comparative example 1,2, before and after under 60 ℃, 95%RH, placing 500 hours, the color ununiformity that the sealing peripheral part takes place in liquid crystal that detected by an unaided eye is estimated the liquid crystal pollution performance based on following four-stage: ◎ (do not have fully color inhomogeneous); Zero (it is inhomogeneous to have observed slight color); △ (it is inhomogeneous to have observed some colors); * (color is inhomogeneous quite clear).In addition, wherein all use 5 samples to estimate for each part.
The results are shown in the table 1.
| The color ununiformity is estimated | |
| Embodiment 1 | ○ |
| Embodiment 2 | ◎ |
| Comparative example 1 | × |
| Comparative example 2 | × |
(embodiment 3)
To use three roller mixing machine thorough mixing up to forming uniform liquid with the curable resin composition that embodiment 1 obtains in the same manner, 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 used for liquid crystal display element conductive material up and down.
Except the conductive material up and down that utilize to obtain on the transparency carrier through divider be coated on conducting up and down form on electrode conducting up and down with pattern, make liquid crystal indicator in the same manner with embodiment 1.
The liquid crystal indicator that obtains was placed 500 hours under 60 ℃, 95%RH environment, and this moment, its conduction was good.
(embodiment 4)
(1) manufacturing of radical polymerization initiator
In reaction flask, add 1-[4-(2-hydroxyl-oxethyl)-phenyl]-50 moles of 2-hydroxy-2-methyl-1-propane-1-ketone (Ciba Specialty Chemicals Inc. society system), under the dry air atmosphere, make its heating for dissolving.
To wherein dripping 100 moles of 0.05 mole of dibutyl tin laurate and 2-methacryloxy ethylidene isocyanic ester (clear and electrician society system) at leisure, drip and finish afterwards again 90 ℃ of reactions down, up to confirm not have remaining isocyanate group with infrared absorption spectrum analysis, then, make with extra care, obtain radical polymerization initiator A with following formula (14) expression.
[chemical formula 8]
(2) modulation of curable resin composition
Radical polymerization initiator A with the acquisition of 3 weight parts; part propylene acidylate Resins, epoxy (ダ イ セ Le ユ-シ-PVC-society's system as curable resin; UVAC1561) 40 weight parts; acrylate modified Resins, epoxy (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-Huan Yangbingyangbingjisanjiayangjiguiwan 1 weight part as coupler; use the paint roller thorough mixing up to the formation uniform liquid, thereby obtained curable resin composition.
(3) making of liquid crystal display device
Make particulate (ponding chemical industry society system at interval, 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, be coated on divider on the substrate of two glass substrates that have the alignment films of having finished friction treatment and a transparency electrode.
Then with liquid crystal (チ Star ソ society system, JC-5004LA) thin drippage is coated in the sealing agent framework of the glass substrate that has transparency electrode on whole, superposeing immediately, another has the glass substrate of transparency electrode, partly uses high voltage mercury lamp with 100mW/cm to sealing agent
2Irradiation ultraviolet radiation 30 seconds.
Heated 1 hour down at 120 ℃ then, make its thermofixation, thereby obtain liquid crystal display device.
(embodiment 5)
In reaction flask, add 1-[4-(2-hydroxyl-oxethyl)-phenyl]-50 moles in 2-hydroxy-2-methyl-1-propane-1-ketone, under the dry air atmosphere, make its heating for dissolving.
Be no more than in temperature of reaction under 90 ℃ the condition, to wherein dripping 50 moles of 0.05 mole of dibutyl tin laurate and 2-methacryloxy ethylidene isocyanic ester at leisure, drip and finish afterwards again 90 ℃ of reactions down, up to confirm not have remaining isocyanate group with infrared absorption spectrum analysis, then, make with extra care, obtain intermediate a with following formula (15) expression.
[chemical formula 9]
The intermediate a of 50 moles of acquisitions is added in the reaction flask, under the dry air atmosphere, make its heating for dissolving.Be no more than in temperature of reaction under 90 ℃ the condition to wherein dripping 0.05 mole of dibutyl tin laurate and 2 at leisure, 2,4-and 2,4,4-trimethyl hexamethylene diisocyanate (デ グ サ society system, TMHDI) 50 moles, be no more than under 90 ℃ the condition dropwise addition of acrylic acid 2-hydroxyl ethyl ester at leisure in temperature of reaction again after drip finishing, 90 ℃ of reactions down, up to confirm not have remaining isocyanate group with infrared absorption spectrum analysis, make with extra care then, obtain radical polymerization initiator B with following formula (16) expression.
[Chemical formula 1 0]
In the above-mentioned general formula (16), A represents 2,2,4-and 2,4,4-tri-methyl hexamethylene.
Except using radical polymerization initiator B to replace the 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 that makes among 100 moles of embodiment 5 is added in the reaction flask, under the dry air atmosphere, make its heating for dissolving.Be no more than in temperature of reaction under 90 ℃ the condition to wherein dripping 0.1 mole of dibutyl tin laurate and 2 at leisure, 2,4-and 2,4,50 moles of 4-trimethyl hexamethylene diisocyanates drip and finish afterwards 90 ℃ of reactions down, up to confirm not have remaining isocyanate group with infrared absorption spectrum analysis, make with extra care then, obtain radical polymerization initiator C with following formula (17) expression.
[Chemical formula 1 1]
In the above-mentioned general formula (17), A represents 2,2,4-and 2,4,4-tri-methyl hexamethylene.
Except using radical polymerization initiator C to replace the radical polymerization initiator A, use the method modulation curable resin composition identical with embodiment 4, make liquid crystal display device.
(embodiment 7)
In reaction flask, add 1-[4-(2-hydroxyl-oxethyl)-phenyl]-50 moles in 2-hydroxy-2-methyl-1-propane-1-ketone, under the dry air atmosphere, make its heating for dissolving.Be no more than in temperature of reaction under 90 ℃ the condition to wherein dripping 0.05 mole of dibutyl tin laurate and 3-pseudoallyl-α at leisure, 50 moles of α-Er Jiajibianji isocyanic ester, drip and finish afterwards again 90 ℃ of reactions down, up to confirm not have remaining isocyanate group with infrared absorption spectrum analysis, then, make with extra care, obtain intermediate b with following formula (18) expression.
[Chemical formula 1 2]
The intermediate b of 50 moles of acquisitions is added in the reaction flask, under the dry air atmosphere, make its heating for dissolving.Be no more than in temperature of reaction under 90 ℃ the condition to wherein dripping 0.05 mole of dibutyl tin laurate and 2 at leisure, 2,4-and 2,4,50 moles of 4-trimethyl hexamethylene diisocyanates drip Racemic glycidol after drip finishing again at leisure under temperature of reaction is no more than 90 ℃ condition, 90 ℃ of reactions down, up to confirm not have remaining isocyanate group with infrared absorption spectrum analysis, make with extra care then, obtain radical polymerization initiator D with following formula (19) expression.
[Chemical formula 1 3]
Except using radical polymerization initiator D to replace the 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) to replace the 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) to replace the radical polymerization initiator A, use the method modulation curable resin composition identical with embodiment 4, make liquid crystal display device.
In order to radical polymerization initiator, curable resin composition and the liquid crystal display device of following method evaluation by embodiment 4-7 and comparative example 3,4 acquisitions.
The results are shown in the 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 120 ℃ baking oven 1 hour, 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 liquid (to pacify the electric society of rattan system as electrode with electrode, the LE-21 type), measure liquid crystal resistivity down at 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 behind the sealing agent/when 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 120 ℃ baking oven 1 hour, return to room temperature (25 ℃) and afterwards lcd segment is put on the aluminium sheet, measure and measure the peak temperature with 10 ℃/minute heat-up rate.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 variation of N-I point (℃)=(N-I of liquid crystal point when not adding sealing agent)-(the N-I point of liquid crystal behind the adding sealing agent)
(connectivity evaluation)
Make particulate (ponding chemical industry society system at interval, 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, another slide glass of stack makes the sealing agent expansion and makes thickness even on it, uses high voltage mercury lamp with 100mW/cm
2Irradiation ultraviolet radiation 30 seconds.Heated 1 hour down at 120 ℃ then, obtain the conjugation test sheet.This test film is measured bonding strength with tonometer.
(display panels evaluation (evaluation of color ununiformity))
For the liquid crystal display device that obtains, with the naked eye just made the back and near the liquid crystal aligning race conditio the sealing agent after 1000 hours of service test under the condition of 65 ℃ of 95%RH according to following standard evaluation.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 three roller mixing machine thorough mixing up to forming uniform liquid with the curable resin composition that embodiment 4 obtains in the same manner, 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 used for liquid crystal display element conductive material up and down.
Except on transparency carrier, with the conductive material up and down that obtains through divider be coated on conducting up and down form on electrode conducting up and down with pattern beyond, make liquid crystal display device in the same manner with embodiment 4.
The liquid crystal indicator that obtains was placed 500 hours under 60 ℃, 95%RH environment, and this moment, conduction was good.
(embodiment 9)
(synthesizing of compound (1))
In the there-necked flask that has dropping funnel, mechanical stirrer, hydrogen chloride gas collector, add diphenyl sulfide (phenyl sulfide) (10mol), aluminum chloride (10mol), dithiocarbonic anhydride (2L), stir down at 0 ℃.Be no more than at reaction soln under 10 ℃ the condition and in this reaction soln, drip isobutyryl chloride (10mol) at leisure, drip and at room temperature stirred again 24 hours after finishing.Add frozen water in this reaction soln, stopped reaction is used the chloroform extraction organic layer, with ion-exchange water washing organic layer, uses anhydrous magnesium sulfate drying then.This solution is under reduced pressure concentrated and makes with extra care, obtain to be shown in the compound (1) of the structure in the following formula (20).
[Chemical formula 1 4]
(synthesizing of compound (2))
In the there-necked flask that has dropping funnel, mechanical stirrer, hydrogen chloride gas collector, add compound (1) (5mol), aluminum chloride (5mol), dithiocarbonic anhydride (1L), stir down at 0 ℃.Be no more than at reaction soln under 10 ℃ the condition and in this reaction soln, drip Benzoyl chloride (5mol) at leisure, drip and at room temperature stirred again 24 hours after finishing.Add frozen water in this reaction soln, stopped reaction is used the chloroform extraction organic layer, with ion-exchange water washing organic layer, uses anhydrous magnesium sulfate drying then.This solution is under reduced pressure concentrated and makes with extra care, obtain to be shown in the compound (2) of the structure in the following formula (21).
[Chemical formula 1 5]
(radical polymerization initiator A's is synthetic)
Add in the flask under nitrogen compound (2) (2mol), methyl-sulphoxide (2L), add the methanol solution (potassium hydroxide: 2mol/ ethanol: 100mL), at room temperature stir of potassium hydroxide again.In this solution, add Paraformaldehyde 96 (aldehyde unit 2mol), at room temperature stirred 5 hours.In this solution, add hydrochloric acid and neutralize, use the ethyl acetate extraction organic layer,, use anhydrous magnesium sulfate drying then with ion-exchange water washing organic layer.This solution is under reduced pressure concentrated and makes with extra care, obtain to be shown in the radical polymerization initiator A of the structure in the following formula (22).
[Chemical formula 1 6]
With 2 weight part radical polymerization initiator A, part acrylic acid esterification Resins, epoxy (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, be heated 70 ℃ and make radical polymerization initiator A dissolving, stir with planetary whipping appts then, obtain mixture.
In this mixture, mix spherical silicon dioxide (ア De マ テ Star Network ス society system as weighting agent; SO-C1) 15 weight parts, epoxy thermosetting agent (the chemical society in big tomb system, ADH) 5 weight parts, coupler (chemistry society of SHIN-ETSU HANTOTAI system; KBM403) 1 weight part; stir with planetary whipping appts, make its dispersion and obtain curable resin composition with three ceramic rollers then.
Make particulate (ponding chemical industry society system at interval, 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 that have the alignment films of having finished friction treatment and a transparency electrode, be coated with divider.
Then with liquid crystal (チ Star ソ society system, JC-5004LA) thin dripping in the sealing agent framework that is coated in the glass substrate that has transparency electrode on whole, superposeing immediately, another has the glass substrate of transparency electrode, partly uses to sealing agent to have the high voltage mercury lamp of the strainer of holding back the following light of 350nm with 50mW/cm
2Shone 20 seconds, and made its curing, thereby obtain liquid crystal display device.
(embodiment 10)
(radical polymerization initiator B's is synthetic)
The compound (2) of adding embodiment 9 records (1mol) makes its heating for dissolving under the dry air atmosphere in reaction flask.To wherein dripping 1 mole of 0.001 mole of dibutyl tin laurate and 2-methacryloxy ethylidene isocyanic ester (clear and electrician society system) at leisure, drip and finish afterwards again 90 ℃ of reactions down, up under 90 ℃, confirming not have remaining isocyanate group with infrared absorption spectrum analysis, then, make with extra care, obtain to be shown in the radical polymerization initiator B of the structure in the following formula (23).
[Chemical formula 1 7]
Except using radical polymerization initiator B to replace the radical polymerization initiator A of 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 liquid crystal display device in the same manner.
(embodiment 11)
(radical polymerization initiator C's is synthetic)
The compound (2) of adding embodiment 9 records (1mol) makes its heating for dissolving under the dry air atmosphere in reaction flask.Be no more than in temperature of reaction under 90 ℃ the condition to wherein dripping 0.001 mole of dibutyl tin laurate and 2 at leisure, 2,4-and 2,4,4-trimethyl hexamethylene diisocyanate (デ グ サ society system, 0.5mol), be no more than under 90 ℃ the condition dropwise addition of acrylic acid 2-hydroxyl ethyl ester (0.5mol) at leisure in temperature of reaction again after drip finishing, 90 ℃ of reactions down, up to confirm not have remaining isocyanate group with infrared absorption spectrum analysis, make with extra care then, obtain to be shown in the radical polymerization initiator C of the structure in the following formula (24).
[Chemical formula 1 8]
Wherein, A represents 2,2,4-and 2,4,4-tri-methyl hexamethylene in the formula (24).
Except the radical polymerization initiator A that uses radical polymerization initiator C replacement embodiment 9, obtain curable resin composition in the same manner with embodiment 9.
Then, use the curable resin composition and the embodiment 9 that obtain to obtain liquid crystal display device in the same manner.
(embodiment 12)
(radical polymerization initiator D's is synthetic)
In reaction flask, add 2-carboxylic ylmethoxy thioxane-9-ketone (1mol), under the dry air atmosphere, make its heating for dissolving.To wherein dripping 1 mole of 0.001 mole of dibutyl tin laurate and 2-methacryloxy ethylidene isocyanic ester (clear and electrician society system) at leisure, drip and finish afterwards again 90 ℃ of reactions down, up under 90 ℃, confirming not have remaining isocyanate group with infrared absorption spectrum analysis, make with extra care then, obtain to be shown in the radical polymerization initiator D of the structure in the following formula (25).
[Chemical formula 1 9]
Except the radical polymerization initiator A that uses radical polymerization initiator D replacement embodiment 9, obtain curable resin composition in the same manner with embodiment 9.
Then, use the curable resin composition and the embodiment 9 that obtain to obtain liquid crystal display device in the same manner.
(comparative example 5)
Except the radical polymerization initiator A that uses イ Le ガ キ ユ ア 2959 (long Lai Chanyeshe systems) replacement embodiment 9, obtain curable resin composition in the same manner with embodiment 9.
Then, use the curable resin composition and the embodiment 9 that obtain to obtain liquid crystal display device in the same manner.
(comparative example 6)
Except the radical polymerization initiator A that uses イ Le ガ キ ユ ア 651 (long Lai Chanyeshe systems) replacement embodiment 9, obtain curable resin composition in the same manner with embodiment 9.
Then, use the curable resin composition and the embodiment 9 that obtain to obtain liquid crystal display device in the same manner.
The radical polymerization initiator, curable resin composition and the liquid crystal display device that obtain by embodiment 9-12 and comparative example 5,6 in order to following method evaluation, the results are shown in the following table 3 separately.
(measurement of molar absorptivity)
Use ultraviolet light absorption spectrum to modulate radical polymerization initiator solution with acetonitrile (colleague's chemistry society system), sample solution concentration is 1.0 * 10
-4M puts into the quartzy unit of optical length 1cm and uses spectrophotometer (UV-2450, society of Shimadzu Seisakusho Ltd. system) to carry out the measurement of absorbancy.Molar absorptivity is for using the absorbancy of measuring divided by the volumetric molar concentration (M) of solution and the value of unitary thickness (cm) gained.
(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 120 ℃ baking oven 1 hour, return to room temperature (25 ℃) afterwards, lcd segment is used liquid crystal resistivity test device (KEITHLEY Instruments society system, 6517A), use liquid electrode (the electric society of peace rattan system as electrode, the LE-21 type), measure liquid crystal resistivity down at standard temperature moisture condition (20 ℃, 65%RH), 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 120 ℃ baking oven 1 hour, return to room temperature (25 ℃) afterwards, lcd segment is put on the aluminium sheet, measured and measure the peak temperature, thereby obtain nematic-isotropic liquid point of inversion and nematic-isotropic liquid point of inversion variation with 10 ℃ of/minute heat-up rates.In addition, use MDSC (TA Insturumenes society system) as apparatus for thermal analysis.
(transformation efficiency of acryl is measured)
Make particulate (ponding chemical industry society system at interval, 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 is launched and make thickness even, thereby make test film.
To the test film of making, with having the high voltage mercury lamp of the strainer of holding back the following light of 350nm with 50mW/cm
2Shone 20 seconds.A glass on the stripping test sheet uses infrared spectrophotometer (EXCALIBUR FTS3000MX, BIO RAD society system) to measure then.Peak area (815-800cm by the acryl before the curing of 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-(the reference peaks area after the peak area/curing of the acryl after the curing)/(the reference peaks area before the peak area/curing of the acryl before solidifying) } * 100
(connectivity evaluation)
Make particulate (ponding chemical industry society system at interval, 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, another slide glass of stack makes the curable resin composition expansion and makes thickness even on it, with having the high voltage mercury lamp of the strainer of holding back the following light of 350nm with 50mW/cm
2Shone 20 seconds.Heated 1 hour down at 120 ℃ then, obtain the conjugation test sheet.This test film is measured bonding strength with tonometer.
(display panels evaluation (evaluation of color ununiformity))
For the liquid crystal display device that obtains, with the naked eye just making the back and near the liquid crystal aligning race conditio the sealing agent after 1000 hours of service test under the condition of 65 ℃ of 95%RH according to following standard evaluation.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 three roller mixing machine thorough mixing up to forming uniform liquid with the curable resin composition that embodiment 9 obtains in the same manner, 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 used for liquid crystal display element conductive material up and down.
Except the conductive material up and down that will obtain on the transparency carrier through divider be coated on up and down conducting form on electrode conducting up and down with pattern, make liquid crystal display device in the same manner with embodiment 9.
Liquid crystal display device for obtaining similarly carries out display panels evaluation (evaluation of color ununiformity), near the situation of the liquid crystal aligning disorder of conductive material up and down that detects by an unaided eye, and the result does not have color inhomogeneous fully.In addition, conduction is also good.
(embodiment 14)
Will be by part acrylic acid esterification Resins, epoxy (ダ イ セ Le ユ-シ-PVC-society's system as curable resin, UVAC1561) 70 weight parts, bisphenol f type epoxy resin (big 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 of forming as イ Le ガ キ ユ ア 907 (Ciba Specialty Chemicals Inc. system) 3 weight parts of optical free radical polymerization starter mixes up to the formation uniform liquid, thereby has 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 that obtains is made liquid crystal indicator as sealing material for liquid crystal display device.
That is, on a substrate of two transparency carriers that have a transparency electrode, be coated with sealing agent with divider, thereby draw a rectangular frame.Then, (another transparency carrier that superposes immediately uses high voltage mercury lamp with 50mW/cm to hermetic unit for チ Star ソ society system, JC-5004LA) thin dripping on whole that is coated in the transparency carrier framework with liquid crystal
2Intensity irradiation ultraviolet radiation 120 seconds.Under 120 ℃, make liquid crystal annealing 1 hour then, 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 (big Japanese ink chemical industry society system) 1mol in the presence of tin catalyst, make alkoxysilane compound containing trialkylsilyl group in molecular structure in 12 hours in 70 ℃ of reactions.The molecular weight of this alkoxysilane compound containing trialkylsilyl group in molecular structure is about 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 the curable resin composition that use to obtain, use the method identical to make liquid crystal display device with embodiment 14.
(embodiment 16)
With respect to curable resin composition stoste 100 weight parts of making 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 the curable resin composition that use to obtain, use the method identical to make liquid crystal display device with embodiment 14.
(embodiment 17)
Make 3-TSL 8330 1mol and 3-acryloxy propyl trimethoxy silicane 1mol make alkoxysilane compound containing trialkylsilyl group in molecular structure in 12 hours 70 ℃ of reactions.The molecular weight of this alkoxysilane compound containing trialkylsilyl group in molecular structure is about 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 the curable resin composition that use to obtain, use the method identical to make liquid crystal display device with embodiment 14.
(embodiment 18)
Make 3-TSL 8330 1mol and 1mol カ レ Application ズ MOI reaction make alkoxysilane compound containing trialkylsilyl group in molecular structure in 12 hours.The molecular weight of this alkoxysilane compound containing trialkylsilyl group in molecular structure is about 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 the curable resin composition that use to obtain, use the method identical to make liquid crystal display device with embodiment 14.
(embodiment 19)
Make 3-isocyanic ester Trimethoxy silane 1mol and methacrylic acid 2-hydroxyl ethyl ester 1mol in the presence of tin catalyst, make alkoxysilane compound containing trialkylsilyl group in molecular structure in 12 hours in 70 ℃ of reactions.The molecular weight of this alkoxysilane compound containing trialkylsilyl group in molecular structure is about 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 the curable resin composition that use to obtain, use the method identical to make liquid crystal display device with embodiment 14.
(comparative example 7)
Only the stoste of the curable resin composition of making by embodiment 14 (mix コ Application Port ラ セ Application E202 before curable resin composition) as curable resin composition.
Except the curable resin composition that use to obtain, use the method identical to make liquid crystal display device with embodiment 14.
(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 the curable resin composition that use to obtain, use the method identical to make liquid crystal display device with embodiment 14.
(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 the curable resin composition that use to obtain, use the method identical to make liquid crystal display device with embodiment 14.
(evaluation)
In order to the color ununiformity of following method evaluation by connectivity, moisture-proof connectivity and the liquid crystal display device of the curable resin composition of embodiment 14-19 and comparative example 7-9 acquisition.
(1) connectivity evaluation
With median size is polymkeric substance hollow bead (the ponding chemical industry society system of 5 μ m, 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 the slide glass center on a small quantity, another slide glass of stack launches on it, then with 100mW/cm
2Intensity irradiation ultraviolet radiation 30 seconds.
Heated 1 hour down at 100 ℃ then, obtain the conjugation test sheet.To the test film that obtains, use self-registering instrument (society of Shimadzu Seisakusho Ltd. system) to measure bonding strength.
(2) the moisture-proof connectivity is estimated
To in 120 ℃, 2 atmospheric saturated steams, preserve 24 hours with the identical joint fastener of in connectivity is estimated, making, and use self-registering instrument (society of Shimadzu Seisakusho Ltd. system) to measure bonding strength then.
(3) the color ununiformity is estimated
The color that produces in the liquid crystal for the used for liquid crystal display element visual inspection hermetic unit periphery that obtains is inhomogeneous, estimates according to following standard.
◎: 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 three roller mixing machine thorough mixing up to forming uniform liquid with the curable resin composition that embodiment 14 obtains in the same manner, 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 used for liquid crystal display element conductive material up and down.
Except the conductive material up and down that will obtain on the transparency carrier with divider coating and conducting up and down form on electrode conducting up and down with pattern, make liquid crystal display device in the same manner with embodiment 14.
The conduction of the liquid crystal display device that obtains 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 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 ℃ and make optical free radical polymerization starter dissolving, stir the acquisition mixture with planetary whipping appts then.
(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 big tomb system, ADH) 2 weight parts; with planetary whipping appts mixing stirring; make its dispersion with three ceramic rollers then, obtain curable resin composition.
(2) measurement of the second-order transition temperature of cured article
With the curable resin composition coating that obtains is the rectangular laminar of 5 * 35 * 0.35mm, to the ultraviolet ray of its irradiation 100mW intensity 30 seconds, and then makes its curing in 60 minutes 120 ℃ of following thermal treatments, obtains to measure and uses test film.
Obtain spring rate E ' and tan δ with dynamic viscoelastic measuring apparatus (DMA) in 20 ℃-180 ℃ temperature range, by this second-order transition temperature that is worth the cured article of measuring curable resin composition, the 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 blended material is slightly dropped in alkali-free glass substrate (コ-ニ Application グ society system: #1737), adhere to the same glass substrate according to crosswise thereon.The ultraviolet ray of irradiation 100mW intensity 30 seconds, and then made its curing in 60 minutes 120 ℃ of following thermal treatments, obtain to measure and use test film.
Each glass substrate is fixed on up and down on the chuck that distributes, is to obtain tensile strength under the condition of 5mm/sec at draw speed, and it is defined as 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 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 ℃ and make optical free radical polymerization starter dissolving, mix with planetary whipping appts then and stir the acquisition mixture.In this mixture, mix spherical silicon dioxide (ア De マ Off ア イ Application society system; SO-C1) 26 weight parts, thermal curing agents (the chemical society in big tomb system, ADH) 2 weight parts; with planetary whipping appts mixing stirring, make its dispersion with three ceramic rollers then, obtain curable resin composition.
For the curable resin composition that obtains, use the method identical to measure the second-order transition temperature and the bonding strength of cured article with embodiment 21, 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 resin with free-radical polymerised functional group, and be heated 70 ℃ and make optical free radical polymerization starter dissolving, stir the acquisition mixture with planetary whipping appts then.(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 big tomb system, ADH) 2 weight parts; with planetary whipping appts mixing stirring; make its dispersion with three ceramic rollers then, obtain curable resin composition.
For the curable resin composition that obtains, use the method identical to measure the second-order transition temperature and the bonding strength of cured article with embodiment 21, second-order transition temperature is 100 ℃ as a result, bonding strength is 90N/cm
2
(embodiment 22)
To use three roller mixing machine thorough mixing up to forming uniform liquid with the curable resin composition that embodiment 21 obtains in the same manner, 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 used for liquid crystal display element conductive material up and down.
On a substrate of two transparency carriers that have transparency electrode, will be coated with divider as sealing agent by the curable resin composition that embodiment 21 obtains, thereby draw a rectangular frame.In addition, on another transparency carrier, the conductive material up and down that obtains is coated on conducting up and down with forming conducting pattern up and down on the electrode with divider.Then, with liquid crystal (チ Star ソ society system, JC-5004LA) thin dripping on whole that is coated in the transparency carrier framework that is coated with sealing agent, another transparency carrier that superposes immediately, to hermetic unit and up and down conductive material partly use high voltage mercury lamp with 100mW/cm
2Intensity irradiation ultraviolet radiation 30 seconds.Then, under 120 ℃, make liquid crystal annealing 1 hour, make its thermofixation, thereby obtain liquid crystal indicator.
The conduction of the liquid crystal indicator that obtains is good.
(embodiment 23)
(A) acrylic acid modified phenol phenolic resin varnish is synthetic
Make liquid phase phenol novolak type epoxy resin (ダ ウ ケ ミ カ Le society system D.E.N.431) 1000 weight parts, as p methoxy phenol 2 weight parts of polymerization retarder, when carrying air, make it to react 5 hours 90 ℃ of following stirring and refluxing as triethylamine 2 weight parts, vinylformic acid 200 weight parts of catalysts.With 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, BHT0.2 weight part, dibutyl tin laurate 0.01 weight part, isophorone diisocyanate 666 weight parts, make it to react 2 hours 60 ℃ of following stirring and refluxing as catalysts as polymerization starter.Then, add vinylformic acid 2-hydroxyl ethyl ester 25.5 weight parts and Racemic glycidol 111 weight parts, when carrying air, make it to react 2 hours 90 ℃ of following stirring and refluxing.With 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.
Will be by acrylic acid modified phenol phenolic resin varnish 40 weight parts that 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-Huan Yangbingyangbingjisanjiayangjiguiwan 1 weight part is formed uses three roller mixing machine thorough mixing up to the formation uniform liquid, thereby obtains sealing agent.
On a substrate of two transparency carriers that have transparency electrode,, thereby draw a rectangular frame with the sealing agent of divider coating acquisition.Then, (another transparency carrier that superposes immediately uses high voltage mercury lamp with 100mW/cm to hermetic unit for チ Star ソ society system, JC-5004LA) thin dripping on whole that is coated in the transparency carrier framework with liquid crystal
2Irradiation ultraviolet radiation 30 seconds.Then, under 120 ℃, make liquid crystal annealing 1 hour, 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 Dianhuagongyeshe system, EP4000S) 1440 weight parts, as p methoxy phenol 2 weight parts of polymerization retarder, when carrying air, make it to react 5 hours 90 ℃ of following stirring and refluxing as triethylamine 2 weight parts, vinylformic acid 200 weight parts of catalysts.With 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 obtain by (C) to replace urethane modification part propylene acylate 20 weight parts that obtain 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 part; obtain sealing agent in the same manner 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 of 35 weight parts, vinylformic acid-2-hydroxy butyl ester 15 weight parts, isobornyl acrylate 50 weight parts, benzophenone 3 weight parts composition 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 of 25 weight parts composition uses three roller mixing machine thorough mixing up to forming uniform liquid, thereby the acquisition sealing agent uses it to make liquid crystal indicator.
For the sealing agent of making by embodiment 23,24 and comparative example 12,13, with following method estimate behind the photocuring and average linear expansion rate behind the photo-thermal curing and solidify after volume resistance value, specific inductivity, the tensile elasticity rate under the 100kHz, in addition, estimate the color ununiformity for the liquid crystal indicator that obtains with following method.
(behind the photocuring and photo-thermal curing after average linear expansion rate)
On the fluorinated ethylene propylene substrate, evenly be coated with sealing agent thinly, then at 3000mJ/cm
2Condition under carry out ultraviolet curing, be the photocuring sample of 15mm * 4mm, thick 0.6mm thereby make size.In addition, on the fluorinated ethylene propylene substrate, evenly be coated with sealing agent thinly, then at 3000mJ/cm
2Condition under carry out ultraviolet curing, thermofixation 1 hour under 120 ℃ condition again is 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, the measuring condition of hold-time: 0min is measured the photocuring sample of making and the average linear expansion rate of photo-thermal curing sample down.
By the value that obtains when only under the effect of light, solidifying cured article and the cured article when under the effect of light and heat, solidifying calculate from than the temperature of low 40 ℃ of second-order transition temperature to than the average linear expansion rate α the temperature of low 10 ℃ of second-order transition temperature
1, and from than the high 10 ℃ temperature of second-order transition temperature to than the average linear expansion rate α the high 40 ℃ temperature of second-order transition temperature
2
(the volume resistance value after the curing)
On the chromium evaporation surface of chromium evaporation glass substrate, evenly be coated with sealing agent thinly, carry out ultraviolet curing then, forming size is the ultraviolet curing thing of 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, on 120 ℃ hot-plate, add thermo-compressed 1 hour, thereby make test sample.Measure the area (S (cm of sealing agent in this sample
2)), with constant voltage generating apparatus (ケ Application ウ Star De society system, PA 36-2A modulates direct supply) between the chromium evaporation surface of opposed chromium evaporation glass substrate, apply constant voltage (V (V)), measure mobile electric current (A (A)) in the film with amperometer (ア De バ Application テ ス ト society system, R 644C digital multimeter).When the mould with sealing agent is made as T (cm), obtain volume specific resistance (Ω .cm) with following formula.
[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.
(solidifying the specific inductivity under the 100kHz of back)
Evenly being coated with sealing agent thinly on glass substrate, being cured then, is the test sample of 3mm thereby make size for 60mm * 60mm, thickness.According to the method for 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) measures under frequency 100kHz the LCR meter.
(tensile elasticity rate after the curing)
On the fluorinated ethylene propylene substrate, evenly be coated with sealing agent thinly, carry out ultraviolet curing then, form the ultraviolet curing thing of big or small 50mm * 5mm, thick 0.5mm, under 120 ℃ condition, heated 1 hour again, 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/the power ratio: 0, upper limit extensibility: 50%, tensile figure: the tensile elasticity rate of measuring the test sample of making under 1 the condition.
(evaluation of color ununiformity)
For the liquid crystal indicator that obtains, at 60 ℃, 95%RH, before and after 500 hours, the color that produces in liquid crystal of detecting by an unaided eye is inhomogeneous, estimates based on following level Four standard: ◎ (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 all use 5 samples to estimate for each part.
[table 5]
| Embodiment 23 | Embodiment 24 | Comparative example 12 | Comparative example 13 | ||
| Reactive resin compositions (weight part) | Acrylic acid modified phenol phenolic resin varnish | 40 | 40 | - | - |
| Urethane acrylate | - | - | 35 | - | |
| The partially modified propylene acylate of urethane | 20 | - | - | - | |
| Acrylic acid modified propylene oxide bisphenol A epoxide resin | - | 20 | - | - | |
| Vinylformic acid-2-hydroxy butyl ester | - | - | 15 | - | |
| Bisphenol A epoxide resin | - | - | - | 50 | |
| Isobornyl acrylate | - | - | 50 | - | |
| Hydrazides class solidifying agent (VDH) | 15 | - | - | - | |
| Hydrazides class solidifying agent (NDH) | - | 15 | - | 25 | |
| Silicon dioxide granule | 23 | 23 | - | - | |
| Estimate | Average linear expansion rate α behind the photocuring 1(/℃) | 2×10 -4 | 2×10 -4 | 9×10 -5 | - |
| Average linear expansion rate α behind the photocuring 2(/℃) | 8×10 -4 | 8×10 -4 | 4×10 -4 | - | |
| Average linear expansion rate α behind the photo-thermal curing 1(/℃) | 7×10 -5 | 8×10 -5 | 8×10 -5 | 3×10 -5 | |
| Average linear expansion rate α behind the photo-thermal curing 2(/℃) | 2×10 -4 | 3×10 -4 | 3×10 -4 | 1×10 -4 | |
| Volume resistance value (Ω .cm) | 1.5×10 13 | 2.1×10 13 | 1.2×10 13 | 3.0×10 13 | |
| Specific inductivity (100kHz) | 3.4 | 3.2 | 3.4 | 3.1 | |
| Tensile elasticity rate (MPa) | 2000 | 1000 | 2000 | 4000 | |
| The color ununiformity is estimated (initial stage) | ◎○◎○◎ | ◎○◎○◎ | ○○○○○ | ××××× | |
| The color ununiformity is estimated (after the moisture-proof evaluation) | ◎○◎○◎ | ◎○◎○◎ | ××××× | ××××× |
(embodiment 25)
To use three roller mixing machine thorough mixing up to forming uniform liquid with the curable resin composition that embodiment 23 obtains in the same manner, 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 used for liquid crystal display element conductive material up and down.
Except be coated on divider in the conductive material up and down that will obtain on the transparency carrier up and down conducting form on electrode conducting up and down with pattern, make liquid crystal indicator in the same manner with embodiment 23.
Liquid crystal indicator for obtaining similarly carries out the evaluation of color ununiformity, near the color ununiformity that produces in the liquid crystal conductive material about detecting by an unaided eye, and the result is the evaluation result more than zero.In addition, conduction is also good.
(embodiment 26)
Make liquid phase phenol novolak type epoxy resin (ダ ウ ケ ミ カ Le society system D.E.N.431) 1000 weight parts, as p methoxy phenol 2 weight parts of polymerization retarder, when carrying air, make it to react 5 hours 90 ℃ of following stirring and refluxing as triethylamine 2 weight parts, vinylformic acid 200 weight parts of catalysts.With 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, BHT0.2 weight part, dibutyl tin laurate 0.01 weight part, isophorone diisocyanate 666 weight parts, make it to react 2 hours 60 ℃ of following stirring and refluxing as catalysts as polymerization starter.Then, add vinylformic acid 2-hydroxyl ethyl ester 25.5 weight parts and Racemic glycidol 111 weight parts, when carrying air, make it to react 2 hours 90 ℃ of following stirring and refluxing.With 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 (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-Huan Yangbingyangbingjisanjiayangjiguiwan 1 weight part use three roller mixing machine thorough mixing to obtain mixture.
Use ベ キ ボ ア (beki-pore) 10 μ m (ニ チ ダ イ society system) as strainer at 40 ℃ of temperature, pressure 45N/cm in the mixture that obtains
2Condition under filter, obtain curable resin composition.It as sealing material for liquid crystal display device.
On a substrate of two transparency carriers that have transparency electrode,, thereby draw a rectangular frame with the sealing material for liquid crystal display device of divider coating acquisition.Then, (another transparency carrier that superposes immediately uses high voltage mercury lamp with 100mW/cm to hermetic unit for チ Star ソ society system, JC-5004LA) thin dripping on whole that is coated in the transparency carrier framework with liquid crystal
2Irradiation ultraviolet radiation 30 seconds.Then, under 120 ℃, make liquid crystal annealing 1 hour, make its thermofixation, thereby make liquid crystal display device.In addition, the cell gap of this liquid crystal display device is set at 5 μ m.
(comparative example 14)
Except filtering without strainer, use the method identical to make curable resin composition with embodiment 26, it as sealing material for liquid crystal display device.In addition, the sealing material for liquid crystal display device that use to obtain uses 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 with 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, uses 16 times of magnifying glasses to count the number that remains in the foreign matter on the sieve by top.Under n=5, carry out same operation, 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 | Do not have |
| Comparative example 14 | 115.6 | Have |
(embodiment 27)
(1) acrylic acid modified phenol phenolic resin varnish is synthetic
Make liquid phase phenol novolak type epoxy resin (ダ ウ ケ ミ カ Le society system D.E.N.431) 1000 weight parts, as p methoxy phenol 2 weight parts of polymerization retarder, when carrying air, make it to react 5 hours 90 ℃ of following stirring and refluxing as triethylamine 2 weight parts, vinylformic acid 200 weight parts of catalysts.With 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, BHT0.2 weight part, dibutyl tin laurate 0.01 weight part, isophorone diisocyanate 666 weight parts, make it to react 2 hours 60 ℃ of following stirring and refluxing as catalysts as polymerization starter.Then, add vinylformic acid 2-hydroxyl ethyl ester 25.5 weight parts and Racemic glycidol 111 weight parts, when carrying air, make it to react 2 hours 90 ℃ of following stirring and refluxing.With 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-Huan Yangbingyangbingjisanjiayangjiguiwan 1 weight part is formed uses three roller mixing machine thorough mixing up to the formation uniform liquid, thereby obtains sealing agent.
(4) manufacturing of liquid crystal display device
On the position of the regulation on two transparency carrier surfaces that have transparency electrode, form the rectangular alignment films of forming by polyimide (produce chemical society system daily, サ Application エ バ-(SE-7492)) with flexographic printing.Then, the sealing agent that obtains with the divider coating rectangular frame that draws, and avoid contacting with the alignment films of a side transparency carrier.
Then, (face that is formed with alignment films of another transparency carrier that superposes immediately uses high voltage mercury lamp with 100mW/cm to sealing agent for チ Star ソ society system, JC-5004LA) thin dripping on whole that is coated in the transparency carrier framework with liquid crystal
2Irradiation ultraviolet radiation 30 seconds.Then, under 120 ℃, make liquid crystal annealing 1 hour, 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)
Except on the surface of the transparency carrier that has transparency electrode, form with sealing agent that alignment films contacts beyond, make liquid crystal display device in the same manner with embodiment 27.
As estimating, with the naked eye confirm just to have made the back and near service test liquid crystal aligning race conditio the sealing agent after 1000 hours under 65 ℃, the condition of 95%RH for the color ununiformity of the liquid crystal display device of making by embodiment 27 and comparative example 15.Also have, sample number is 10.
Its result can confirm that the liquid crystal display device among the embodiment 27 does not have color inhomogeneous fully, but the liquid crystal display device in the comparative example 15 mainly has a spot of color inhomogeneous at peripheral part.In addition, with the color inhomogeneous part of Tof-sims analysis by the liquid crystal display device of comparative example 15 making, the result has observed the composition of sealing agent.
Industrial utilizability
According to the present invention, can provide when being used for making the process of liquid crystal display cells by the drippage completion method as sealing material for liquid crystal display device, to the pollution of liquid crystal less, with the zygosity of glass inhomogeneous hardening resin composition, sealing material for liquid crystal display device and the liquid crystal display cells in generation unit gap well and not.
Claims (34)
1. curable resin composition, it is to contain the curable resin composition that solidified curable resin and polymerization starter take place under the effect of light and/or heat, it is characterized in that described curable resin (methyl) acrylic modified epoxy resin for making crystallinity Resins, epoxy and (methyl) vinylformic acid react and form.
2. curable resin composition as claimed in claim 1 is characterized in that, (methyl) acrylic modified epoxy resin is crystalline.
3. curable resin composition as claimed in claim 1 or 2 is characterized in that, the fusing point of (methyl) acrylic modified epoxy resin is 80 ℃ or below it.
4. as claim 1,2 or 3 described curable resin compositions, it is characterized in that, (methyl) acrylic modified epoxy resin in its resin matrix sulphur atom and total number of Sauerstoffatom be 5-10.
5. as claim 1,2,3 or 4 described curable resin compositions, it is characterized in that, (methyl) acrylic modified epoxy resin, remove with the total atom number that the value of sulphur atom and the total number of Sauerstoffatom is 0.08-0.14 in the resin matrix.
6. curable resin composition, it is to contain the curable resin composition that solidified curable resin and polymerization starter take place under the effect of light and/or heat, it is characterized in that, described polymerization starter is, the radical polymerization initiator that contains radical polymerization initiating radical and hydrogen bond functional group in a part, described radical polymerization initiating radical are dissociated into two living radical kinds at irradiates light and/or when hot.
7. curable resin composition as claimed in claim 6 is characterized in that, under the condition of irradiates light and/or heat, two living radical kinds that produced through dissociating of radical polymerization initiating radical all have at least one hydrogen bond functional group.
8. as claim 6 or 7 described curable resin compositions, it is characterized in that radical polymerization initiator also has plural reactive functional groups in a part.
9. curable resin composition as claimed in claim 8, it is characterized in that, under the condition of irradiates light and/or heat, two living radical kinds that produced through dissociating of radical polymerization initiating radical all have at least one hydrogen bond functional group and at least one reactive functional groups.
10. as claim 6,7,8 or 9 described curable resin compositions, it is characterized in that the radical polymerization initiating radical has the structure with following general formula (1) expression,
[Chemical formula 1]
In the formula (1), R
1And R
2Expression hydrogen atom, hydroxyl, carbonatoms are the alkyl of 1-6, alkoxyl group or the phenyl that carbonatoms is 1-6, and
[Chemical formula 2]
It is the alkyl of 1-6 or the aromatic nucleus of halogen radical that expression can have carbonatoms.
11., it is characterized in that at least one is (methyl) acryl and/or ring-type ether in the reactive functional groups as each described curable resin composition in the claim 6 to 10.
12., it is characterized in that hydrogen bond functional group is urethane groups and/or hydroxyl as each described curable resin composition in the claim 6 to 11.
13., it is characterized in that the number-average molecular weight of radical polymerization initiator is more than 300 as each described curable resin composition in the claim 6 to 12.
14., it is characterized in that radical polymerization initiator is as each described curable resin composition in the claim 6 to 13, in acetonitrile, measure, the molar absorptivity under 350nm is 200-1 ten thousand M
-1Cm
-1Radical polymerization initiator.
15. curable resin composition as claimed in claim 14 is characterized in that, the molar absorptivity under 430nm radical polymerization initiator, that measure in acetonitrile is 100M
-1Cm
-1Or below it.
16. curable resin composition, it is to contain the curable resin composition that solidified curable resin, polymerization starter and bonding auxiliary agent take place under the effect of light and/or heat, it is characterized in that, described bonding auxiliary agent be molecular weight 500 or alkoxysilane compound containing trialkylsilyl group in molecular structure more than it and/or molecular weight be 200 or more than it and hydrogen bond functional group value be 2 * 10
-3-7 * 10
-3The alkoxysilane compound containing trialkylsilyl group in molecular structure of mol/g.
17. curable resin composition as claimed in claim 16 is characterized in that, alkoxysilane compound containing trialkylsilyl group in molecular structure has at least more than one polymerizability functional group and/or reactive functional groups.
18. curable resin composition as claimed in claim 17 is characterized in that, polymerizability functional group and/or reactive functional groups are to be selected from least a group of epoxy group(ing), acryl and methacryloyl.
19. curable resin composition, it is to contain under the effect of light and/or heat the solidified curable resin takes place, the curable resin composition of polymerization starter and resin particle, it is characterized in that, described resin particle has core particle and is formed on the lip-deep shell of described core particle, described core particle is formed for-10 ℃ or resin below it by having caoutchouc elasticity and second-order transition temperature, described shell is that 50-150 ℃ resin is formed by second-order transition temperature, and is 5 ℃/minute at heat-up rate, frequency is to be that the second-order transition temperature of the cured article measured of DMA method is 120 ℃ or more than it with the dynamic viscoelastic method of masurement under the condition of 10Hz.
20. curable resin composition as claimed in claim 19 is characterized in that, the median size of resin particle is 0.01-5 μ m.
21., it is characterized in that having caoutchouc elasticity and second-order transition temperature is the polymkeric substance of (methyl) acryl monomer for the following resin of-10 ℃ or its as claim 19 or 20 described curable resin compositions.
22., it is characterized in that bonding strength glass substrate is bonding and when making it to solidify is 150N/cm as claim 19,20 or 21 described curable resin compositions
2Or more than it.
23. curable resin composition, it is to contain that under the effect of light and/or heat solidified curable resin, polymerization starter and median size to take place be the curable resin composition of 1 μ m or the inorganic particulate below it, it is characterized in that the temperature that the ratio second-order transition temperature of the cured article when only having taken place to solidify is low 40 ℃ arrives than the average linear expansion rate α between the temperature of low 10 ℃ of second-order transition temperature under the effect of light
1Be 1 * 10
-4-5 * 10
-4/ ℃, and the temperature higher 10 ℃ than second-order transition temperature arrives than the average linear expansion rate α between the high 40 ℃ temperature of second-order transition temperature
2Be 2 * 10
-4-1 * 10
-3/ ℃.
24. curable resin composition, it is to contain that under the effect of light and/or heat solidified curable resin, polymerization starter and median size to take place be the curable resin composition of 1 μ m or the inorganic particulate below it, it is characterized in that the temperature that the ratio second-order transition temperature of the cured article when having taken place to solidify is low 40 ℃ arrives than the average linear expansion rate α between the temperature of low 10 ℃ of second-order transition temperature under the effect of light and heat
1Be 5 * 10
-5-1 * 10
-4/ ℃, and the temperature higher 10 ℃ than second-order transition temperature arrives than the average linear expansion rate α between the high 40 ℃ temperature of second-order transition temperature
2Be 1 * 10
-4-3 * 10
-4/ ℃.
25., it is characterized in that the combined amount of inorganic particles is the 10-20 weight part with respect to curable resin 100 weight parts as claim 23 or 24 described curable resin compositions.
26. a curable resin composition is characterized in that, the content of particle diameter above particle of distance between the substrate of target liquid crystal display device is 30 weight % or below it.
27. the manufacture method of a curable resin composition is characterized in that, has to use strainer to carry out filtering operation after the composition that will form curable resin composition mixes.
28. the manufacture method of curable resin composition as claimed in claim 27 is characterized in that, strainer is 70% or more than it for the collection efficiency of particle diameter above particle of distance between the substrate of target liquid crystal display device.
29. the manufacture method as claim 27 or 28 described curable resin compositions is characterized in that, the circulation flow is that 2L/ minute, pressure are 4.6N/cm
2Air the time, the air flowing resistance value of strainer is 10mmH
2O or more than it.
30. a sealing material for liquid crystal display device is characterized in that, is made up of each the described curable resin composition in the claim 1 to 26.
31. a used for liquid crystal display element sealing compound is characterized in that, is made up of each the described curable resin composition in the claim 1 to 26.
32. conductive material about the used for liquid crystal display element is characterized in that, contains each described curable resin composition and electrically conductive microparticle in the claim 1 to 26.
33. liquid crystal display device, it is characterized in that at least a formation about the described sealing material for liquid crystal display device of use claim 30, the described used for liquid crystal display element sealing compound of claim 31 and the described used for liquid crystal display element of claim 32 in the conductive material.
34. liquid crystal display device, wherein, to at least a portion on a surface, be formed with a pair of transparency carrier of alignment films, middle across centering near the sealing agent that forms its periphery, certain interval that is separated by is oppositely arranged, make simultaneously be formed with described alignment films the surface relatively to, and enclose in the space that forms by described transparency carrier and sealing agent liquid crystal material arranged, wherein, described alignment films does not contact mutually with described sealing agent.
Applications Claiming Priority (25)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003159909 | 2003-06-04 | ||
| JP159909/2003 | 2003-06-04 | ||
| JP2003159905 | 2003-06-04 | ||
| JP159905/2003 | 2003-06-04 | ||
| JP159906/2003 | 2003-06-04 | ||
| JP2003159906 | 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 | ||
| JP279299/2003 | 2003-07-24 | ||
| JP2003279299 | 2003-07-24 | ||
| JP284115/2003 | 2003-07-31 | ||
| JP2003284115 | 2003-07-31 | ||
| 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 |
| JP394614/2003 | 2003-11-25 | ||
| JP394618/2003 | 2003-11-25 | ||
| JP394615/2003 | 2003-11-25 | ||
| JP394619/2003 | 2003-11-25 | ||
| JP394616/2003 | 2003-11-25 | ||
| JP394617/2003 | 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 |
|---|---|---|---|
| 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 |
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1798786A true CN1798786A (en) | 2006-07-05 |
| CN1798786B CN1798786B (en) | 2013-05-15 |
Family
ID=36819188
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200480015573.6A Expired - Lifetime CN1798786B (en) | 2003-06-04 | 2004-06-04 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| CN2008102149439A Expired - Lifetime 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 Expired - Lifetime CN101367982B (en) | 2003-06-04 | 2004-06-04 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102149439A Expired - Lifetime 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 Expired - Lifetime 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) | CN1798786B (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1798786B (en) | 2013-05-15 |
| CN101369098A (en) | 2009-02-18 |
| CN101367982A (en) | 2009-02-18 |
| CN101367982B (en) | 2013-06-12 |
| CN101369098B (en) | 2012-01-04 |
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