CN1867861A - Sealant for liquid crystal, liquid-crystal display made with the same, and process for produicng the display - Google Patents
Sealant for liquid crystal, liquid-crystal display made with the same, and process for produicng the display Download PDFInfo
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- CN1867861A CN1867861A CN 200480030310 CN200480030310A CN1867861A CN 1867861 A CN1867861 A CN 1867861A CN 200480030310 CN200480030310 CN 200480030310 CN 200480030310 A CN200480030310 A CN 200480030310A CN 1867861 A CN1867861 A CN 1867861A
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Abstract
A liquid crystal sealant comprising an epoxy resin represented by the following formula (1): (in the formula, n denotes an average polymerization degree and is a positive number of 0-5) as a resin component, a curing agent, a curing accelerator and an inorganic filler is excellent in screen printability as a liquid crystal sealant in making a liquid crystal display device and can provide excellent reliability in moisture resistance for the liquid crystal display device obtained).
Description
Technical field
The present invention relates to a kind of liquid crystal sealing agent, a kind of liquid crystal indicator and a kind of method that is used to make this display device that adopts this liquid crystal sealing agent.More specifically, the present invention relates to a kind of heat-setting liquid crystal sealing agent, it has good silk screen impressionability in the manufacture process of liquid crystal indicator, and the liquid crystal indicator with height moisture-proof reliability can be provided; The invention still further relates to a kind of liquid crystal indicator and a kind of method that is used to make this display device that adopts sealing agent manufacturing.
Background technology
In the process that adopts heat-setting liquid crystal sealing agent manufacturing liquid crystal indicator, base material up and down will be laminated to by following method together: this method comprises and adopts divider (dispenser) or such as the method for serigraphy liquid crystal sealing agent is applied on the base material, usually make coating precuring (solvent evaporates) by heating then, utilize alignment mark that base material is up and down highly precisely put together and hot sealing agent then afterwards.
Recently, when producing liquid crystal indicator, the size of base material becomes big and pitch time (tacttime) (time that step is required) shortens with further increase (mass) throughput rate in batch.And after pre-cure step, in the process of the glass baseplate up and down of lamination color filter substrate and array (array) base material, also requiring up and down, the alignment procedures of base material has high-speed and high precision.Along with the change of substrate sizes is big, particularly under the situation of the scarf of the LCDs of portable telephone, the spreading area of liquid crystal sealing agent will increase, and this requires to having big rotating torque on time, to increase pitch time.
In addition, when producing liquid crystal indicator, after the step of the glass baseplate up and down of lamination, aligning and precuring color filter substrate and array base material, also have a step, its base material up and down with lamination is transported in the subsequent process steps with the still uncured state of liquid crystal sealing agent.When carrying them, because the low adhesion of liquid crystal sealing agent, slippage each other or separation appear in the base material up and down of this lamination sometimes when the upper substrate of the base material up and down that clamps this lamination by vacuum (be called vacuum and clamp method).The base material weight that causes along with nearest substrate sizes increase increases, and it is serious day by day that this problem becomes.
And the increase along with present liquid crystal indicator precision, liquid-crystal composition response speed and framework (frame) contractility requires liquid crystal sealing agent to have high cohesive and moisture-proof reliability.If liquid crystal sealing agent does not have good moisture-proof reliability, then the water that contains in the air will infiltrate in the liquid crystal sealing agent, the liquid-crystal composition in the contaminating fluid crystal device, thus produce low-quality demonstration.
Liquid crystal sealing agent with good cohesive and moisture-proof reliability is for example disclosed in the patent documentation 1.But,, make that the operability of the aligning behind the base material lamination is insufficient because disclosed these liquid crystal sealing agents have high viscosity in the patent documentation 1 after precuring; Perhaps, their poor adhesion after precuring, therefore may make up and down base material slippage occurs in vacuum pinching conveying operations.
Therefore, being starved of exploitation has good cohesive and moisture-proof reliability, has high aligning operability and can not cause base material slippage or the liquid crystal sealing agent that separates in vacuum pinching conveying operations when lamination.
[patent documentation 1]: JA-A-11-15005
Summary of the invention
The invention provides a kind of heat-setting liquid crystal sealing agent, it can and distribute coating (dispensation coating) to be coated with by serigraphy, making in the process of liquid crystal indicator by it, lamination is the time that only need lack of the alignment procedures during base material up and down, and when adopting vacuum clamping method to carry the base material up and down that utilizes uncured liquid crystal sealing agent lamination by vacuum clamping and lifting upper substrate, the separation of base material up and down can not appear, in addition, this liquid crystal sealing agent has the water-fast moisture-proof of low-down liquid crystal pollution and height.
Of the present invention finishing is the result that the inventor furthers investigate in order to attempt to address the above problem.
That is to say, the present invention relates to a kind of liquid crystal sealing agent, it is characterized in that comprising epoxy resin by following formula (1) expression:
[formula 1]
(in the following formula, n represents average degree of polymerization, is 0～5 positive number), hardening agent, curing accelerator and inorganic filler.
In addition, the present invention relates to utilize the liquid crystal indicator of above-mentioned liquid crystal sealing agent sealing.
And, the present invention relates to a kind of method that is used to produce liquid crystal indicator, this liquid crystal indicator comprises and is positioned in the middle of the base material that contains color filter layer and the base material that contains the liquid crystal aligning layer on electrode layer and adopts the fixing liquid crystal material of liquid crystal sealing agent, the method is characterized in that to comprise by serigraphy this liquid crystal sealing agent is coated on the step of step on one of described base material, another base material of heat pressure adhesive and this liquid crystal material is poured into step in the gap between the described base material.
The invention effect
The epoxy resin by following formula (1) expression that is used for liquid crystal sealing agent of the present invention has following feature: have low viscosity in the glass transition temperature that keeps conventional epoxy resin.Therefore, the liquid crystal sealing agent that contains this epoxy resin has low resin viscosity and good cohesive removing when desolvating.Therefore, when the process middle level that produces liquid crystal indicator presses base material, the resin viscosity of liquid crystal sealing agent is low, pressure load during lamination is little, this just can shorten the time of alignment procedures, when the base material up and down that adopts uncured liquid crystal sealing agent lamination was carried on the top that promotes laminate substrate by vacuum clamping method, base material can not separate up and down, and was easy to form when compacting the space.In addition, can produce and have the significantly good water-fast moisture-proof and the liquid crystal indicator of very high strength.
The best mode that carries out an invention
Liquid crystal sealing agent of the present invention contains epoxy resin, hardening agent, curing accelerator and the inorganic filler by following formula (1) expression as necessary component.
What liquid crystal sealing agent of the present invention was used can be according to the method for routine by the epoxy resin of formula (1) expression, reacts down and makes by oreinol diphenol and chloropropylene oxide are existed at for example alkali metal hydroxide (such as, NaOH).If wherein n is the content height of 0 formula (1) compound, then viscosity is tending towards reducing, if but crystallization just takes place in its too high levels easily, so this epoxy resin preferably contains common 50-95wt%, and the wherein n of preferred 50-80wt% is 0 formula (1) compound.An example of this based epoxy resin is Nippon Kayaku Co., the RE-600NM that Ltd. produces.
Epoxy resin content in the liquid crystal sealing agent of the present invention is 5-60wt%, preferred 20-55wt%, more preferably 30-50wt%.
Liquid crystal sealing agent of the present invention also can contain the epoxy resin except that the epoxy resin of formula (1), and its content should not influence the operability and the physical property of this liquid crystal sealing agent.Epoxy resin except that formula (1) epoxy resin is not subjected to concrete restriction, and the example is the epoxy resin of bisphenol A-type; The epoxy resin of Bisphenol F type; Polyfunctional epoxy resin, this resin is the product of the glycidyl ether of polyphenolic substance, this polyphenolic substance is bisphenol S, 4 for example, 4-diphenyl phenol, 2,2,6,6-tetramethyl-4,4-diphenyl phenol, 2,2-methylene-two (4-methyl-6-tert butyl phenol), trihydroxy benzene methylmethane, 1,2,3,-thrihydroxy-benzene, have the diisopropylidene skeleton phenol, have fluorene skeleton as 1, the phenol of 1-two-4-hydroxy phenyl fluorenes and phenol aldehyde modified (phenolated) polybutadiene; Novolac resin, this resin is by various phenol such as phenol, cresols, ethyl-phenol, butylphenol, octyl phenol, bisphenol-A, Bisphenol F, bisphenol S and naphthols preparation as raw material; Phenol novolac resin (phenol novolak) with xylylene skeleton; Phenol novolac resin with bicyclopentadiene skeleton; Various novolac resins are as the glycidyl ether product of the phenol novolac resin that contains fluorene skeleton; Cycloaliphatic epoxy resin with aliphatic skeleton such as cyclohexane; Heterocyclic ring epoxy resins with heterocycle such as isocyanide urea ring or hydantoins ring; The diglycidyl product of brominated phenol such as bromo bisphenol-A, bromo Bisphenol F, bromo bisphenol S, bromophenol novolac resin and bromo cresols novolac resin; With common production and the epoxy resin that is purchased, as N, N-diglycidyl-ortho-aminotoluene, N, N-diglycidylaniline, phenylglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Pehanorm triglycidyl group ether, polypropylene glycol diglycidyl ether, (3,4-3, the 4-epoxide ring) hexyl methyl cyclohexane carboxylic-acid ester and hexahydrophthalic anhydride diglycidyl ester.Use these epoxy resin with the operability that do not influence prepared liquid crystal sealing agent and the content of physical property.The potpourri that these epoxy resin can be used as two or more uses.
In the liquid crystal sealing agent of the present invention, preferably unite the epoxy resin that adopts bisphenol A type epoxy resin and formula (1).By the coupling bisphenol A type epoxy resin, the liquid crystal sealing agent that the epoxy resin of formula (1) produces has the physical property of the viscosity that is suitable for serigraphy and good cured article, as the moisture-proof reliability.The example of available bisphenol A type epoxy resin comprises the RE-310S that Nippon Kayaku Co.Ltd. makes.The epoxy resin of formula (1) expression and the weight ratio of bisphenol A type epoxy resin are 20: 80～40: 60 (weight portion), more preferably 25: 75～35: 65 (weight portion).
Novolac resin is used as the hardening agent of liquid crystal sealing agent of the present invention usually.Example as novolac resin, can mention the novolac resin that obtains as raw material with various phenol, this phenol is bisphenol-A for example, tetrabromobisphenol A, Bisphenol F, bisphenol S, 4,4-diphenyl phenol, 2,2,6,6-tetramethyl-4,4-diphenyl phenol, 2,2-methylene-two (4-methyl-6-tert butyl phenol), the trihydroxy benzene methylmethane, 1,2,3,-thrihydroxy-benzene, phenol with diisopropylidene skeleton, has fluorene skeleton as 1, the phenol of 1-two-4-hydroxy phenyl fluorenes, polyphenolic substance such as phenol aldehyde modified polybutadiene, phenol, cresols, ethyl-phenol, butylphenol, octyl phenol, bisphenol-A, allyl phenol, the bromo bisphenol-A, Bisphenol F, bisphenol S and naphthols; Phenolic novolac (phenolic novolak), for example have the xylylene skeleton the phenol novolac resin, have the phenol novolac resin of bicyclopentadiene skeleton and have the phenol novolac resin of fluorene skeleton; And by making various phenol such as phenol, cresols, ethyl-phenol, butylphenol, octyl phenol, bisphenol-A, bromo bisphenol-A, Bisphenol F, bisphenol S be connected the phenolic novolac that one of crosslinked group (inferior aralkyl) by following formula (2)～(4) expressions obtains with naphthols:
[formula 2]
(in the following formula, R
1Expression hydrogen atom, the alkyl that contains 1～4 carbon atom, allyl or halogen atom; M represents 1～4 integer, and when m be 2 or when bigger, R
1Can be identical or different),
[formula 3]
(in the following formula, R
2And R
3Represent hydrogen atom independently of one another, contain alkyl, allyl or the halogen atom of 1～4 carbon atom; N and p represent 1～4 integer, and when n or p be 2 or when bigger, R
2And R
3Separately can be identical or different),
[formula 4]
(in the following formula, R
4Expression hydrogen atom, the alkyl that contains 1～8 carbon atom, allyl, halogen atom or hydroxyl; Q represents 1～5 integer, and when q be 2 or when bigger, R
4Can be identical or different).
Preferably use various phenol such as phenol, cresols, ethyl-phenol, butylphenol, octyl phenol, bisphenol-A, chavicol, Bisphenol F, the novolac resin that bisphenol S and naphthols obtain as raw material, phenol novolac resin with xylylene skeleton, phenol novolac resin with bicyclopentadiene skeleton, phenol novolac resin with fluorene skeleton, and by making various phenol such as phenol, cresols, ethyl-phenol, butylphenol, octyl phenol, bisphenol-A, the bromo bisphenol-A, Bisphenol F, bisphenol S is connected the phenolic novolac that obtains with naphthols with one of crosslinked group (inferior aralkyl) of being represented by following formula (5)～(7):
[formula 5]
(in the following formula, R
1' expression hydrogen atom or contain the alkyl of 1～4 carbon atom; M represents 1～4 integer, and when m be 2 or when bigger, R
1' can be identical or different)
[formula 6]
(in the following formula, R
2' and R
3' represent hydrogen atom independently of one another or contain the alkyl of 1～4 carbon atom; N and p represent 1～4 integer, and when n or p be 2 or when bigger, R
2' and R
3' separately can be identical or different),
[formula 7]
(in the following formula, R
4' expression hydrogen atom, the alkyl that contains 1～8 carbon atom or hydroxyl; Q represents 1～5 integer, and when q be 2 or when bigger, R
4' can be identical or different).
The novolac resin that obtains as raw material with various phenol such as phenol, cresols, octyl phenol, bisphenol-A, Bisphenol F, bisphenol S and naphthols more preferably is with by making various phenol be connected the phenolic novolac that obtains as phenol, cresols, octyl phenol, bisphenol-A, Bisphenol F, bisphenol S and naphthols with one of crosslinked group shown in following formula (5)～(7) (inferior aralkyl).
Particularly preferably be the novolac resin that obtains as raw material with monohydric phenol, for example phenol novolac resin that obtains as raw material with phenol and the cresols novolac resin that obtains as raw material with cresols; With make various phenol be connected the phenolic novolac that obtains with one of crosslinked group shown in following formula (8)～(12) (inferior aralkyl) as phenol, cresols and bisphenol-A:
[formula 8]
[formula 9]
[formula 10]
[formula 11]
[formula 12]
Preferred novolac resin used in this invention is with the phenolic novolac of monohydric phenol as feedstock production, and it is represented by following general formula (13):
[formula 13]
(in the following formula, R represents hydrogen, low alkyl group, lower alkoxy or halogen; M represents 1～3 integer, and when m was 2 or 3, R can be identical or different, n represent 0 or positive integer).
In following formula (2)～(13), this alkyl that contains 1～4 carbon atom comprises for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl and the tert-butyl group.This alkyl that contains 1～8 carbon atom comprises for example methyl, ethyl, n-pro-pyl, isopropyl, amyl group, hexyl and octyl group.This low alkyl group is the alkyl that contains 1～8 carbon atom, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl and the tert-butyl group are preferably the alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl and the tert-butyl group that contain 1～4 carbon atom.This lower alkoxy is alkoxy such as methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy and the tert-butoxy that contains 1～8 carbon atom, is preferably the alkoxy that contains 1～4 carbon atom such as methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy.Halogen comprises for example bromine, chlorine and fluorine.In formula (13), positive integer n is preferred 1～15, more preferably 1～10.
These novolac resins can use separately separately, and perhaps the potpourri as two or more uses.According to the epoxide equivalent of the epoxy resin in the liquid crystal sealing agent, in the hydroxyl equivalent in the novolac resin, the amount that is used for novolac resin of the present invention is 0.2～1.4 chemical equivalent, preferred 0.3～1.1 chemical equivalent, more preferably 0.4～0.9 chemical equivalent.
The compound that to be suitable for the hardening agent that comprises phenolic novolac used in this invention be following formula (13).Because n=1 or higher component produce high resin viscosity in the formula (13), therefore the component (compound) that preferably has n=0 with two rings, and the amount of this component in novolac resin (remainder is n=1 or higher component) is about 20～80wt% usually, preferred about 25～70wt%, more preferably from about 30～50wt%.
In the reaction of phenolic novolac and epoxy resin, (for example have three or more the phenol novolac resin hardening agent that encircle, the compound of n=1 in the following formula (13)) when solidifying, forms three-dimensional crosslinking structure, and the phenol novolac resin with two rings (for example, the compound of n=0 in the formula (13)) crosslinked with the line style form, therefore given flexiblely for rigid structure, improved cohesive glass baseplate.
In addition, owing to be applicable to that phenolic novolac of the present invention has low resin viscosity, therefore can provide good silk screen impressionability, base material is easy to lamination up and down in producing the liquid crystal indicator process, and the formation in space becomes easier.
As the curing accelerator that the present invention adopts, can mention for example imidazoles, imidazoles and polybasic carboxylic acid such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), 1,2, the salt that 4-benzenetricarboxylic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid form; Acid amides, the salt that for example dicyandiamide, and acid amides and phenol, above-mentioned polybasic carboxylic acid or phosphinic acids form; The diaza compound, for example 1,8-diaza-dicyclo (5.4.0) undecylene-7, and diaza compound and phenol, above-mentioned polybasic carboxylic acid or phosphinic acids, phosphine such as triphenylphosphine and tetraphenylphosphoniphenolate tetraphenyl borate salts, phenol are as 2,4, the salt and the amine adduct of 6-three aminomethyl phenol.
As imidazoles, can mention for example glyoxal ethyline, the 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-glyoxal ethyline, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl imidazole, 2,4-diamido-6 (2 '-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamido-6 (2 '-undecyl imidazole (1 ')) ethyl-s-triazine, 2,4-diamido-6 (2 '-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, 2, the adduct of 4-diamido-6 (2 '-methylimidazole (1 ')) ethyl-s-triazine and isocyanuric acid, the 2:3 adduct of glyoxal ethyline and isocyanuric acid, the adduct of 2-phenylimidazole and isocyanuric acid, 2-phenyl-3,5-hydroxymethyl-imidazole, 2-phenyl-4-methylol-5-methylimidazole, with 1-cyanoethyl-2-phenyl-3,5-dicyan ethoxyl methyl imidazoles.
In these curing accelerators, preferably for example 2, the adduct of 4-diamido-6 (2 '-methylimidazole (1 ')) ethyl-s-triazine and isocyanuric acid, the 2:3 adduct of glyoxal ethyline and isocyanuric acid, the adduct of 2-phenylimidazole and isocyanuric acid, imidazoles and polybasic carboxylic acid such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), 1,2, the salt of 4-benzenetricarboxylic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid, and amine adduct.
In 100 parts by weight of epoxy resin in the liquid crystal sealing agent, the addition of curing accelerator is 1～25 weight portion, preferred 2～20 weight portions, more preferably 3～15 weight portions.
Preferably use these curing accelerators, because they have the advantage of for example improving operability (prolonging time storage period) with the form of potential (latent) curing accelerator.Potential curing accelerator is that those at room temperature are curing accelerator solid-state and that only participate in to react as curing accelerator heating for dissolving after, it for example comprise by these curing accelerator micro-capsules are sealed the microcapsule-type curing accelerator that makes, insoluble,practically solid dispersing curing accelerator (for example imidazoles) and amine adduct in solvent or epoxy resin.High response when single component (one-pack) storage stability when mixing with epoxy resin and heating especially preferably adopts amine adduct as curing accelerator.
In these curing accelerators, the mean grain size that the potential curing accelerator of solid dispersing is measured according to laser method is about 6 μ m or littler, preferred about 4 μ m or littler, more preferably from about 3 μ m or littler.If adopt the potential curing accelerator of mean grain size greater than 6 μ m, then be difficult to carry out the divider coating, and also inhomogeneous except the shape after the coating, the shape of the seal (seal) after the base material lamination is also inhomogeneous.Adopting under the situation of mean grain size greater than the liquid crystal sealing agent of the curing accelerator of 6 μ m, owing to can identify filler in the part of sealing, it is inhomogeneous and coarse that the curing of sealant becomes, and be easy to ooze out.Mean grain size to potential curing accelerator does not have special lower limit, adopts those of about 1.5～2.5 μ m of lower limit usually.
The inorganic filler that the present invention adopts comprises, for example metal oxide such as aluminium oxide, silicon dioxide, talcum, clay, barium titanate, titanium dioxide, cobalt oxide, magnesium oxide, nickel oxide, iron oxide, zinc paste and zirconia, carbonate such as lime carbonate and magnesium carbonate, sulfate such as barium sulphate and calcium sulphate, metal hydroxides such as aluminium hydroxide and magnesium hydroxide, silicate such as calcium silicate, alumina silicate and zirconium silicate, wherein preferred aluminium oxide and silicon dioxide.These inorganic fillers can be used separately separately, also can two or more potpourri use.
The mean grain size of the inorganic filler that the present invention is used is preferably 10～2000 nanometers.If the mean grain size of inorganic filler is greater than 2000nm, because the specific surface area of inorganic filler is little, so in producing the process of liquid crystal indicator at lamination up and down during the hot pressing after the base material, the inorganic filler of liquid crystal sealing agent and resin Composition are separated from one another easily and oozing out of inorganic filler take place.Therefore, solidify bond strength afterwards and moisture absorption adhesive strength deteriorates afterwards.If the mean grain size of inorganic filler is less than 10nm, the specific surface area of inorganic filler increases excessive, so the viscosity of liquid crystal sealing agent is too high, forms space, unit (cell gap) and just becomes difficult.
The content of the inorganic filler that is used for liquid crystal sealing agent of the present invention in whole liquid crystal sealing agents is 5～45wt% and more preferably 15～35wt%.If the content of inorganic filler is less than 5wt%, then the viscosity of liquid crystal sealing agent is low, because in the hot pressing stage of producing liquid crystal indicator, have small amount of filler to ooze out.If content surpasses 45wt%, because the too high levels of filler then is difficult to the space that filler is broken and can not form liquid crystal indicator.
As inorganic filler of the present invention, preferably adopt the silicon dioxide of amorphous alumina and/or pulverizing, more preferably unite the silicon dioxide that uses amorphous alumina and pulverizing.The present invention can with amorphous alumina be noncrystal aluminium oxide, it does not have specific crystal mechanism, is shaped as amorphously, granularity is about 0.01～5 μ m.The mean grain size of the preferred amorphous alumina that the present invention is used is 0.01～2 μ m.The silicon dioxide of the pulverizing that the present invention uses prepares by making pulverizing such as crystalline silica, fused silica, so has squarely, and granularity is about 0.01～5 μ m.The mean grain size of the silicon dioxide of the preferred pulverizing that the present invention is used is 0.01～2 μ m.
The content of the amorphous alumina in the liquid crystal sealing agent and/or the silicon dioxide of pulverizing is 5～45wt%, more preferably 15～35wt%.If the content of inorganic filler is less than 5wt%, then because the content of filler is low, and liquid crystal sealing agent will have low viscosity, and in screen printing process during the shape of seal regular meeting confusing.If the content of inorganic filler surpasses 45wt%, because filer content is too high, liquid crystal sealing agent prints by the screen cloth of silk screen plate with regard to being difficult to, and this causes flaw in printing (blurring) often.In addition, under the situation of silicon dioxide that adopts amorphous alumina and/or pulverizing as inorganic filler, a preferred implementation of liquid crystal sealing agent of the present invention is: the content by the epoxy resin of formula (1) expression is 5～30wt% in liquid crystal sealing agent, and the content of inorganic filler is 5～45wt% in liquid crystal sealing agent.
Liquid crystal sealing agent of the present invention can add organic filler, as long as this adding can not influence the feature of liquid crystal sealing agent.Organic filler comprises, for example polymer beads of core-shell type and gum filler.These fillers can use separately separately or use as two or more potpourri.The mean grain size of organic filler is no more than 3 μ m, preferably is no more than 2 μ m.If the mean grain size of organic filler surpasses 3 μ m, just be difficult to form the space, unit.In the weight of inorganic filler, the addition of organic filler is for being no more than 50wt%, if surpass 50wt%, then viscosity is excessive, is difficult to form the space, unit.
If necessary, can add coupling agent in the liquid crystal sealing agent of the present invention.The example of coupling agent is silane coupling agent such as 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy methyl dimethoxysilane, 3-epoxypropoxy methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-(2-amino-ethyl) 3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-aminopropyl methyltrimethoxy silane, the 3-aminopropyltriethoxywerene werene, 3-sulfydryl propyl trimethoxy silicane, vinyltrimethoxy silane, N-(2-(vinyl benzyl amino) ethyl) 3-TSL 8330 hydrochloride, the 3-methacryloxypropyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, with the 3-r-chloropropyl trimethoxyl silane; Titanium base coupling agent is as (N-ethylamino ethylamino) isopropyl titanate, isopropyl triisostearoyltitanate, two (dioctylphyrophosphoric acid) titanium oxyacetate, two (dioctyl phosphite) tetraisopropyl titanates and new alkoxy three (right-N-(β-aminoethyl) aminophenyl) titanate esters; With zirconium base or aluminium base coupling agent; as zirconium-acetyl-pyruvate, zirconium-methacrylate, zirconium-propionate, new alkoxy zirconium ester (zirconate), new alkoxy three new capryl zirconates, new alkoxy three (dodecane acyl group) benzenesulfonyl zirconate, new alkoxy three (ethylene amino-ethyl) zirconate, new alkoxy three (m-aminophenyl base) zirconate, ammonium zirconium carbonate, aluminium-acetyl-pyruvate, aluminium-methacrylate and aluminium-propionate.Preferred siloxane coupling agent, more preferably amino silicane coupling agent.By using coupling agent, the liquid crystal sealing agent that obtains has good moisture-proof reliability, and the loss of the bond strength after the moisture absorption is less.
When adding coupling agent, its content in liquid crystal sealing agent is about 0.1～15wt%.
Sealant viscosity when liquid crystal sealing agent of the present invention can contain solvent with the minimizing coating, thus the operability that on base material, is coated with improved.The solvent that is fit to comprises, for example alcohols solvent, ether solvent, acetate esters solvent and dibasic acid dimethyl ester solvent.They can use separately separately or use as two or more potpourri according to optional amount.
The example of alcohols solvent is alkylol such as ethanol and isopropyl alcohol and alkoxyl alcohol such as 3-methyl-3-methoxybutanol, 3-methyl-3-ethoxy butanols, 3-methyl-3-positive propoxy butanols, 3-methyl-3-isopropoxy butanols, 3-methyl-3-n-butoxy butanols, 3-methyl-3-isobutoxy butanols, 3-methyl-3-sec-butoxy butanols and 3-methyl-3-tert-butoxy butanols.
The example of ether solvent is monohydroxy alcohol ether solvent, alkylene glycol monoalkyl ethers kind solvent, aklylene glycol dialkyl ether kind solvent, two aklylene glycol alkyl ether solvents and Sanya alkylene glycol alkyl ether kind solvent.
The example of monohydroxy alcohol ether solvent is 3-methyl-3-methoxybutanol methyl ether, 3-methyl-3-ethoxy butanols ether, 3-methyl-3-n-butoxy butanols ether, 3-methyl-3-isobutoxy butanols propyl ether, 3-methyl-3-sec-butoxy butanols-isopropyl ether and 3-methyl-3-tert-butoxy butanols-n-butyl ether.
The example of alkylene glycol monoalkyl ethers kind solvent is propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol one propyl ether, propylene glycol one isopropyl ether, propylene glycol one n-butyl ether, propylene glycol one isobutyl ether, propylene glycol one secondary butyl ether, propylene glycol one uncle's butyl ether, glycol monomethyl ether, ethylene glycol monoethyl ether, propyl cellosolve, ethylene glycol one isopropyl ether, ethylene glycol one n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol one secondary butyl ether and ethylene glycol one uncle's butyl ether.
The example of aklylene glycol dialkyl ether kind solvent is Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol diisopropyl ether, propylene glycol di-n-butyl ether, propylene glycol diisobutyl ether, propylene glycol di-secondary butyl ether, propylene glycol two uncle's butyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, ethylene glycol bisthioglycolate isopropyl ether, ethylene glycol bisthioglycolate n-butyl ether, ethylene glycol bisthioglycolate isobutyl ether, ethylene glycol di-secondary butyl ether and ethylene glycol bisthioglycolate uncle butyl ether.
The example of two aklylene glycol alkyl ether solvents is dipropylene glycol methyl ethers, the dipropylene glycol ether, the dipropylene glycol dipropyl ether, the dipropylene glycol diisopropyl ether, the dipropylene glycol di-n-butyl ether, the dipropylene glycol diisobutyl ether, dipropylene glycol di-secondary butyl ether, dipropylene glycol two uncle's butyl ether, diglycol dimethyl ether (diethylene glycol dimethyl ether), the diglycol diethyl ether, the diglycol dipropyl ether, the diglycol diisopropyl ether, the diglycol di-n-butyl ether, the diglycol diisobutyl ether, diglycol di-secondary butyl ether, with diglycol two uncle's butyl ether.
The example of Sanya alkylene glycol alkyl ether kind solvent is the tripropylene glycol dimethyl ether, the tripropylene glycol diethyl ether, the tripropylene glycol dipropyl ether, the tripropylene glycol diisopropyl ether, the tripropylene glycol di-n-butyl ether, the tripropylene glycol diisobutyl ether, tripropylene glycol di-secondary butyl ether, tripropylene glycol two uncle's butyl ether, the triethylene glycol dimethyl ether, the triethylene glycol diethyl ether, the triethylene glycol dipropyl ether, the triethylene glycol diisopropyl ether, the triethylene glycol di-n-butyl ether, the triethylene glycol diisobutyl ether, triethylene glycol di-secondary butyl ether, with triethylene glycol two uncle's butyl ether.
The example of acetate esters solvent is alkylene glycol monoalkyl ethers acetic acid esters, for example methyl glycol acetate, ethoxyethyl acetate(EA), the propyl cellosolve acetic acid esters, ethylene glycol one isopropyl ether acetic acid esters, ethylene glycol one n-butyl ether acetic acid esters, ethylene glycol one secondary butyl ether acetic acid esters, the ethylene glycol monoisobutyl ether acetic acid esters, ethylene glycol one uncle's butyl ether acetic acid esters, propylene glycol monomethyl ether acetic acid esters, ethoxy propyl acetate, propylene glycol one isopropyl ether acetic acid esters, propylene glycol one propyl ether acetic acid esters, propylene glycol one n-butyl ether acetic acid esters, propylene glycol one secondary butyl ether acetic acid esters, with propylene glycol one isobutyl ether acetic acid esters, propylene glycol one uncle's butyl ether acetic acid esters, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-ethoxy butylacetic acid ester, 3-methyl-3-propoxyl group butylacetic acid ester, 3-methyl-3-isopropoxy butylacetic acid ester, 3-methyl-3-n-butoxy ethylhexoate, 3-methyl-3-isobutoxy butylacetic acid ester, 3-methyl-3-sec-butoxy butylacetic acid ester, with 3-methyl-3-tert-butoxy butylacetic acid ester, diacetate glycol ester, diglycol diacetate, the oxalic acid triethyleneglycol ester, propylene glycol diacetate, oxalic acid dipropylene glycol ester, oxalic acid tripropylene glycol ester, and butyl acetate.
Dibasic acid dimethyl ester comprises, for example CH
3OCO-(CH
2-)
n-COOCH
3The ester of (n=2～4) expression.The example of this type of ester is dimethyl glutarate, dimethyl adipate and dimethyl succinate.They can two or more potpourri use.As they potpourris of three kinds, for example RHODIASOLVE RPDE (Rhodia Nikka Co.Ltd. manufacturing) can be commercially available.
Among the present invention, dibasic acid dimethyl ester can use together in conjunction with other solvent.Preferably the solvent with the dibasic acid dimethyl ester coupling comprises, for example butyl cellosolve.
About the amount of solvent, as long as being adjusted to the viscosity of liquid crystal sealing agent, they are suitable for can adopting optional amount by method coatings such as divider coating or serigraphys, wherein said viscosity is for example 25 ℃ of following about 20～40Pas.Use solvent in the following manner: make the content of nonvolatile matter in liquid crystal sealing agent be generally 70wt% or higher, preferred 85～95wt%, more preferably 90～95wt%.Using solvent-laden liquid crystal sealing agent to make in the process of liquid crystal indicator, after the liquid crystal sealing agent coating, when heating precuring, make solvent evaporates by drying, and then base material about the lamination.
Make after the solvent evaporates by drying, the viscosity of liquid crystal sealing agent is preferably 500～50000Pas, more preferably 800～10000Pas, the measurement of the beasurement base dynamic viscoelastic of viscosity (30 ℃).
Producing in the process of liquid crystal indicator with liquid crystal sealing agent of the present invention, liquid crystal sealing agent will be screen-printed on the base material that contains color filter layer under the air that flows downward usually continuously.In order to prevent that liquid crystal sealing agent thickens in the production stage under the air that flows downward, preferably adopt the solvent of higher boiling, low-steam pressure.Particularly, boiling point is 200 ℃ or higher under the preferred 1013.25hPa, and 20 ℃ of following vapour pressures are 20Pa or those lower solvents.Preferred solvent for example is butyl cellosolve, dibasic acid dimethyl ester and triglyme.Dibasic acid dimethyl ester comprises, for example dimethyl glutarate, dimethyl succinate and dimethyl adipate.These compounds can two or more potpourri use.These compounds can be purchased, and concrete commercial obtainable compound comprises RPDE (Rhodia Nikka Co.Ltd. manufacturing), and it is the mixed solvent of dimethyl glutarate, dimethyl succinate and dimethyl adipate.The amount of these solvents in liquid crystal sealing agent is about 1～50wt%, preferred 3～30wt%.
Liquid crystal sealing agent of the present invention can following method prepare: make above-mentioned epoxy resin, hardening agent and solvent (if necessary) dissolving by mixing under stirring and heating, again to wherein adding inorganic filler and other filler (if necessary), make the potpourri fine dispersion with known mixing arrangement such as bowl mill, sand mill or three-roller, further add the curing accelerator of specified rate and if necessary then, add coupling agent, defoamer, levelling agent etc., mix afterwards.
In liquid crystal indicator of the present invention, have a pair of base material of giving fixed electrode that forms thereon and be disposed opposite to each other with given gap, their edge seals with liquid crystal sealing agent of the present invention, and the gap inner sealing liquid crystal in the middle of two base materials.There is not concrete restriction for liquid crystal to be sealed.Liquid crystal indicator is meant a kind of liquid crystal panel, and it comprises a pair of base material, sealing liquid crystal in the middle of the base material, and also base material is equipped with polarizing plate, driving circuit, signal input cable, backlight etc.Here, the constituting of the base material that described base material is made by glass, quartz, plastics, silicon or other analog, and also at least one base material is a printing opacity.Display device can use-case such as following mode produce.At first, in liquid crystal sealing agent of the present invention, add interval base (spacer) (gap control material) such as glass fibre.This interval base comprises, for example glass fibre, silicon dioxide bead and polymer beads.Its diameter is selected according to the space, unit of liquid crystal indicator to be made, and is generally 0.5～10 μ m.In liquid crystal sealing agent of the present invention is 100 weight portions, and the consumption of this interval base is about 0.1～4 weight portion, preferred about 0.5～2 weight portion, more preferably from about 0.9～1.5 weight portion.With divider or other analog, be applied on the base material in a pair of base material wherein adding the liquid crystal sealing agent of base at interval, heating (for example then, heated 10 minutes down at 90 ℃) so that solvent evaporation, this base material on the other side of lamination subsequently, remove the space by hot pressing, solidify 1～2 hour down to obtain display device at 120 ℃～160 ℃ afterwards.
In addition, (wherein liquid crystal material is at the base material that contains color filter layer and contain between the base material of the liquid crystal aligning layer on the electrode layer in order to produce the liquid crystal indicator that comprises liquid crystal material, and fix) by liquid crystal sealing agent, can liquid crystal sealing agent be applied on one of described base material by serigraphy, another base material of heat pressure adhesive thereon then, and liquid crystal material is poured in the gap in the middle of two base materials.Heat pressure adhesive can be implemented by sheeter or multi-daylight press under normal pressure or decompression.
For continuously and carry out the serigraphy of liquid crystal sealing agent long-term and stably, the liquid crystal sealing agent of preferred employing physical property η 2＜60 (Pas) and η 2/ η 1＜1.5 (wherein, η 1 implements the preceding liquid crystal sealing agent viscosity of serigraphy, and η 2 is the liquid crystal sealing agent viscosity after implementing to print continuously).Viscosity is measured by E type viscosity meter.
During the serigraphy liquid crystal sealing agent, liquid crystal sealing agent is cast on the plates for screen printing, and owing to production is carried out in dirt pocket usually, therefore liquid crystal sealing agent is exposed in the air that flows downward, the contained solvent little by little surface of liquid crystal sealing agent volatilizees away, and the viscosity of sealant is increased.When the viscosity of liquid crystal sealing agent increases to 60Pas or when higher, often go wrong, the shape deterioration of Yin Shua seal (spot, attenuation, thicken, rupture) for example, the fracture that seal takes place is because the screen cloth of plates for screen printing stops up, and the surface of liquid crystal sealing agent becomes too hard in temporary baking step, causes the poor adhesion with relative base material.When the viscosities il after the continuous printing 2 surpasses printing when initial during 1.5 times of viscosities il 1, if do not change the serigraphy condition such as the print speed printing speed of initial setting, spot, attenuation and fracture take place in regular meeting in the time of then.In order to change printing condition during the printing continuously, must stop to produce and checking printing condition, these steps cause the reduction of production efficiency, and are therefore not preferred.
The present invention can illustrate in greater detail by the following examples, and this embodiment may not be interpreted as any limitation of the invention.
Embodiment 1
Epoxy resin (RE-600NM with 100g formula (1) expression, Nippon Kayaku Co.Ltd. makes, it comprises the compound of n=0 in the formula (1) of 65～80wt%) and comprise the phenol novolac resin (PN-152 of the compound of 30～50wt% with dicyclo as the 30g of hardening agent, Nippon Kayaku Co.Ltd. manufacturing) heating for dissolving is in the 10gRHODIASOLVE RPDE (contain 57～63wt% dimethyl glutarate, 21～27wt% dimethyl succinate, 12～20wt% dimethyl adipate, Rhodia Nikka Co. makes) as solvent.In the resin solution of gained, by the 60g mean grain size of mixing as inorganic filler with sand mill is ball-aluminium oxide (the NANOTEC ALUMINA SP-C of about 30nm, CI Kasei Co.Ltd. makes) and as the 10g N-phenyl-γ-An Bingjisanjiayangjiguiwan of coupling agent, they are dispersed in the resin solution, the 8g mean grain size that adds then as curing accelerator is 3 μ m or littler AMICURE MYH-K (amine adduct: Ajinomoto Fine Techno Co.Ltd. makes), obtains liquid crystal sealing agent of the present invention.
Comparative Examples 1
With 100g liquid bisphenol A type epoxy resin (RE-310S, Nippon Kayaku Co.Ltd. manufacturing) and as the 30g of hardening agent comprise phenol novolac resin (PN-152, the Nippon Kayaku Co.Ltd. makes) heating for dissolving of the compound of 30～50wt% in 30g RHODIASOLVE RPDE as solvent with dicyclo.In the resin solution of gained, by the 60g mean grain size of mixing as inorganic filler with sand mill is ball-aluminium oxide (the NANOTEC ALUMI NASP-C of about 30nm, CI Kasei Co.Ltd. makes) and as the 10g N-phenyl-γ-An Bingjisanjiayangjiguiwan of coupling agent, they are dispersed in the resin solution, the 8g mean grain size that adds then as curing accelerator is 3 μ m or littler AMICUREMYH-K (amine adduct: Ajinomoto Fine Techno Co.Ltd. makes), obtains liquid crystal sealing agent.
Comparative Examples 2
Mix and disperse 100g liquid bisphenol A type epoxy resin (RE-310S, Nippon KayakuCo.Ltd. makes), the 10g adipic dihydrazide as hardening agent, 20g RHODIASOLVERPDE, as the 60g mean grain size of inorganic filler ball-aluminium oxide (NANOTECALUMINA SP-C for about 30nm, CI Kasei Co.Ltd. makes) and, obtain liquid crystal sealing agent as the 10g N-phenyl-γ-An Bingjisanjiayangjiguiwan of coupling agent.Mixing and dispersion adopt three-roller to carry out.Because the liquid crystal sealing agent in the Comparative Examples 2 may solidify because of the heat that sand mill produces, therefore adopt three-roller to substitute sand mill.
Test implementation example 1
(A) viscoelasticity after the measurement solvent evaporates
Liquid crystal sealing agent is coated on the glass baseplate, is that the coating device of 25 μ m is sprawled into the thickness of 25 μ m with it with the gap.Then, the glass baseplate that is coated with sealant is placed on the heating plate that is heated to 90 ℃, left standstill 5 minutes.Make afterwards sealant from glass baseplate scrape from and sealant be configured as the pillars of diameter 20mm, thickness 1mm.Measure the complex viscosity coefficient of gained sample with dynamic viscoelastic measurement mechanism (Rheosol-G5000, UBM Co.Ltd. makes).This dynamic viscoelastic measurement mechanism is provided with as follows:
Cone: the parallel cone of diameter 20mm; Frequency: 0.1Hz;
Strain (strain) angle: 0.1 °; Measure temperature: 30 ℃.The results are shown in the table 1.
(B) when liquid crystal sealing agent precuring with on it, during imposed load, measure the seal width then
Adding the glass fibre that the 1g diameter is 5 μ m (PF-50S, Nippon Electric Glass Co.Ltd. makes) in 100g gained liquid crystal sealing agent as basic at interval, mixes afterwards.With divider this liquid crystal sealing agent is coated on the glass baseplate of 50mm * 50mm, thereby when forming 5 μ m spaces, obtains the sprawling of seal of 1mm, and made it precuring in 5 minutes by heating on 90 ℃ heating plate.Then, on this glass baseplate, stack another glass baseplate of same size under 25 ℃, apply 2kg/cm afterwards
2Load so that sealant is pulverized, and determine the width of the extension of seal with microscope.The results are shown in the table 1.
In the table 1, " well " means that the seal width is 0.3mm or wideer, and " poor " means that the seal width is less than 0.3mm.
(C) water-intake rate of test liquid crystal sealing agent
The liquid crystal sealing agent of gained is coated with into the thickness of 25 μ m on glass baseplate.Coating heats 10 minutes down with dry solvent at 100 ℃, and solidifies 60 minutes down at 150 ℃.Then, the glass baseplate of coating is put into Constant Temperature and Humidity Chambers 24 hours under 60 ℃, 90% atmosphere, calculate water-intake rate according to the weight ratio of putting into before and after the Constant Temperature and Humidity Chambers.The results are shown in the table 1.
(D) rate of perviousness of test liquid crystal sealing agent
Test according to JIS-Z0208.That is, the liquid crystal sealing agent of gained is coated with into the thickness of 50 μ m on Kapton.Coating heats 10 minutes down with dry solvent at 100 ℃, and solidifies 60 minutes down at 150 ℃.Then, peel off liquid crystal sealing agent, and make it further to solidify 60 minutes down at 150 ℃ from Kapton.In moisture vapor transmission cup, put into an amount of lime chloride,, and place cup, seal cup with paraffin then according to the liquid crystal sealing agent of moisture vapor transmission cup cutting curing.Afterwards, moisture vapor transmission cup is put into Constant Temperature and Humidity Chambers 24 hours under 60 ℃, 90% atmosphere, calculate water-intake rate according to the weight ratio of putting into before and after the Constant Temperature and Humidity Chambers.The results are shown in the table 1.
Table 1: the assessment result of liquid crystal sealing agent
| Test event | Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 |
| (A) (B) seal width test (C) water-intake rate (%) (60 ℃ of viscoelasticity (Pas), 90%Rh, 24 hours) (D) rate of perviousness (%) (g/m 224 hours) | 1110 good 1.0 40 | 107000 differ from 1.0 42 | 1020 good 3.7 80 |
Shown in (A) of table 1, the viscoelasticity of the liquid crystal sealing agent of embodiment 1 after solvent evaporates is less than the viscoelasticity of the liquid crystal sealing agent of Comparative Examples 1, and the liquid crystal sealing agent of Comparative Examples 1 has very high viscosity.Therefore, can think in the process of producing liquid crystal indicator, the liquid crystal sealing agent of embodiment 1 lamination up and down the pressure load during base material less than the liquid crystal sealing agent of Comparative Examples 1, so under the situation of the liquid crystal sealing agent that adopts embodiment 1, can in the shorter time, implement alignment procedures.In addition, shown in (B) of table 1, after precuring, the liquid crystal sealing agent of embodiment 1 state at room temperature is better than the liquid crystal sealing agent of Comparative Examples 1.In addition, as (C) of table 1 with (D), water-intake rate among the embodiment 1 and rate of perviousness are all good than Comparative Examples 2.
Embodiment 2
(1) synthetic liquid crystal sealing agent
Epoxy resin (RE-600NM with 100g formula (1) expression, Nippon Kayaku Co.Ltd. makes, it comprises the compound of n=0 in the formula (1) of 65～80wt%) and comprise the phenol novolac resin (PN-152 of the compound of 30～50wt% with dicyclo as the 30g of hardening agent, Nippon Kayaku Co.Ltd. makes) (boiling point is 200～230 ℃ to heating for dissolving under the 1013.25hPa, and 20 ℃ of following vapour pressures are 6Pa at the 10gRHODIASOLVE RPDE as solvent; Contain 57～63wt% dimethyl glutarate, 21～27wt% dimethyl succinate and 12～20wt% dimethyl adipate; Rhodia Nikka Co.Ltd. makes) in.In the resin solution of gained, by the 60g mean grain size of mixing as inorganic filler with sand mill is ball-aluminium oxide (the NANOTEC ALUMINA SP-C of about 30nm, CI Kasei Co.Ltd. makes) and as the 10g N-phenyl-γ-An Bingjisanjiayangjiguiwan of coupling agent, they are dispersed in the resin solution, the 8g mean grain size that adds then as curing accelerator is 3 μ m or littler AMICURE MYH-K (amine adduct: Ajinomoto Fine Techno Co.Ltd. makes), obtains liquid crystal sealing agent of the present invention.
(2) produce liquid crystal indicator
With the hectographic printing method will be coated on such as the liquid crystal aligning material of polyimide material array base material (this array base material comprises glass and active element, distribution and transparency electrode are arranged thereon) and color filter side group material (this color filter side group material above have and comprise red, blue and green color filter, the black matrix that shading is used is with the transparency electrode that contains the relative substrate of ITO conduct) on.Then, these base materials were temporarily cured under 50～100 ℃ 1～10 minute, and, obtain liquid crystal aligning layer, then two base materials are all carried out liquid crystal molecular orientation and handle, as polishing (rubbing) 160～220 ℃ of following actual curing 0.5～3 hour.
Then, by silk screen print method above-mentioned liquid crystal sealing agent is coated on the color filter side group material.An amount of glass fibre with required diameter is joined in the liquid crystal sealing agent, with holding unit thickness (cell thickness).The initial viscosity η 1 of liquid crystal sealing agent A is 22.5Pas.About 7 hours of continuous fibers reticulated printing is used for the base material of liquid crystal panel with manufacturing, and the viscosities il 2 of this liquid crystal sealing agent after printing continuously is 28.4Pas.That is, η 2＜60, η 2/ η 1=1.26.
After sealant printed continuously, the shape of seal was satisfactory, non-cracking and spot, and the mesh that plates for screen printing does not take place yet stops up.
After the sealant printing, adopt heating plate that sealant is temporarily cured under 50～100 ℃ and desolvated (residual solvent is less than 10ppm) to remove in 1～30 minute.
On the other hand, adopt the spherical base at interval that is made of plastics that array side group material is sprayed to form element thickness by dry spraying process.
Afterwards, color filter side group material and array side base material is temporarily bonded to each other to together, after the position alignment, make these relative base materials under 150～200 ℃, carry out heat pressure adhesive 0.5～3 hour with this relative base material lamination and fixing, thereby form the uniform thickness in the given range.
The base material that these are relative cuts into given shape, by vacuum pouring (vacuumpouring) method nematic liquid crystalline material is injected wherein then, and with ultraviolet curing resin sealed cast hole to obtain liquid crystal indicator.
The defectives such as the fracture such as seal, attenuation and spot that may be caused by sealant printing (seal printing) do not appear in liquid crystal indicator made according to the method for the present invention.
Comparative Examples 3
(1) synthetic liquid crystal sealing agent
With 100g liquid bisphenol A type epoxy resin (RE-310S, Nippon Kayaku Co.Ltd. makes) and comprise the phenol novolac resin (PN-152 of the compound of 30～50wt% with dicyclo as the 30g of hardening agent, Nippon Kayaku Co.Ltd. manufacturing) heating for dissolving is in the 30g propylene-glycol diacetate (boiling point is 190 ℃ under the 1013.25hPa, and 20 ℃ of following vapour pressures are 31Pa) as solvent.In the resin solution of gained, by the 60g mean grain size of mixing as inorganic filler with sand mill is ball-aluminium oxide (the NANOTEC ALUMINASP-C of about 30nm, CI Kasei Co.Ltd. makes) and as the 10g N-phenyl-γ-An Bingjisanjiayangjiguiwan of coupling agent, they are dispersed in the resin solution, the 8g mean grain size that adds then as curing accelerator is 3 μ m or littler AMICURE MYH-K (Ajinomoto FineTechno Co.Ltd. manufacturing), obtains liquid crystal sealing agent.
(2) produce liquid crystal indicator
Mode according to identical with embodiment 2 forms liquid crystal aligning layer on array side base material and color filter side group material, then they are carried out orientation process.
Then, by silk screen print method above-mentioned liquid crystal sealing agent B is coated on the color filter side group material.An amount of glass fibre with required diameter is joined in the liquid crystal sealing agent with holding unit thickness.The initial viscosity η 1 of this liquid crystal sealing agent is 30.5Pas.The continuous fibers reticulated printing was made the base material that is used for liquid crystal panel in about 7 hours, and the viscosities il 2 of this liquid crystal sealing agent after printing continuously is 102Pas.That is, η 2＞60, η 2/ η 1=3.34.
After sealant printed continuously, the shape of seal was causing confusion aspect wide, the narrow part of seal.In addition, the local fracture of seal occurs, and plates for screen printing is stopped up partly.
Afterwards, according to the mode identical with embodiment 2, lamination also cuts this base material and injects liquid crystal, obtains liquid crystal indicator.The ratio such as the defective of seal fracture, attenuation and element thickness inequality that is occurred is about 5%.
Embodiment 3
(1) synthetic liquid crystal sealing agent
Epoxy resin (RE-600NM with 30g formula (1) expression, Nippon Kayaku Co.Ltd. makes, it comprises the compound of the middle n=0 of formula (1) of 65～80wt%), 70g bisphenol A type epoxy resin (RE-310S, Nippon Kayaku Co.Ltd. makes) and (contain 57～63wt% dimethyl glutarate at 7g RHODIASOLVERPDE as solvent as phenol novolac resin (PN-152, the Nippon Kayaku Co.Ltd. makes) heating for dissolving that the 30g of hardening agent contains the compound with dicyclo of 30～50wt%, 21～27wt% dimethyl succinate and 12～20wt% dimethyl adipate; Rhodia Nikka Co.Ltd. makes) and 3g butyl cellosolve (Wako Jun-Yaku Kogyo Co.Ltd. manufacturing) in.
In the resin solution of gained, by the 25g mean grain size of mixing as inorganic filler with sand mill is amorphous alumina (the ALUMICRON FAL-0.05B of about 30nm, FujimiIncorporated makes) and the 25g mean grain size be silicon dioxide (the CRYSYALITE 1FF of the pulverizing of 0.5 μ m, Tatsumori Co.Ltd. makes) and as the 9g N-phenyl-γ-An Bingjisanjiayangjiguiwan of coupling agent, they are dispersed in the resin solution, the 7g mean grain size that adds then as curing accelerator is 3 μ m or littler AMICUREMYH-K (Ajinomoto Fine Techno Co.Ltd. manufacturing), obtains liquid crystal sealing agent of the present invention.
(2) produce liquid crystal indicator
With the hectographic printing method will be coated on such as the liquid crystal aligning material of polyimide material array base material (this array base material comprises glass and given active element, distribution and transparency electrode are arranged thereon) and color filter substrate (this color filter substrate above have and comprise red, blue and green color filter, the black matrix that shading is used and contain the transparency electrode of ITO) on.Then, these base materials were temporarily cured under 50～100 ℃ 1～10 minute, and, obtain liquid crystal aligning layer, then two base materials are all carried out liquid crystal molecular orientation and handle as polishing 160～220 ℃ of following actual curing 0.5～3 hour.
Then, by silk screen print method above-mentioned liquid crystal sealing agent is coated on the color filter side group material.An amount of glass fibre with required diameter is joined in the liquid crystal sealing agent with holding unit thickness.When batch process is used for the base material of liquid crystal panel, in the dirt pocket of air flows downward, carry out serigraphy continuously.Processing time is about 7 hours.
When the sealant printing begins and continuously the enclosure shape after the printing is satisfactory, foam, fracture and spot (referring to Fig. 1) do not occur.In addition, after the printing, the mesh that plates for screen printing do not occur stops up continuously.
After the sealant printing, under 50～100 ℃, temporarily cured 1～30 minute with heating plate.The purpose of temporarily curing is in order to remove the solvent in the sealant.The preferred temperature of temporarily curing selected in the following manner: make and under this temperature, only leave solvent behind the removal of solvents, and this temperature is lower than the heat activation temperature of hardening agent less than 10ppm.Even can go down to desolventize at the temporary transient stoving temperature that is higher than 100 ℃, but owing to taken place to thicken and curing reaction under this temperature, the precision machining of element thickness tends to deterioration, this respect must be noted that.
On the other hand, adopt the spherical base at interval that is made of plastics that array side group material is sprayed to form element thickness by dry spraying process.Afterwards, sealant is temporarily cured the basic spraying of color filter substrate afterwards and the spherical interval of employing base material afterwards temporarily to be bonded together, and aligned position, make these relative base materials under 150～200 ℃, carry out heat pressure adhesive 0.5～3 hour with this relative base material lamination and fixing then, thereby form the uniform thickness in the given range.
Do not carry out if above-mentioned hot pressing and step for adhering are not the hot pressing sheeters by normal pressure or decompression, but undertaken, can not cause problem yet by the multilayer sheeter.
The base material that these are relative cuts into given shape, for example wherein injects nematic liquid crystalline material by the vacuum pouring normal direction then, and with ultraviolet curing resin sealed cast hole.Liquid crystal indicator made according to the method for the present invention do not occur may by the sealant printshop cause such as defectives such as seal fracture, attenuation and spots.
As mentioned above, by adopting liquid crystal sealing agent of the present invention, can be under the situation that does not produce the enclosure shape problem, efficient, high repeatability ground produces liquid crystal indicator.
Industrial applicibility
Heat-setting liquid crystal sealing agent of the present invention can be produced liquid crystal indicator very effectively, in making the process of liquid crystal indicator, and at lamination up and down during base material, the time that alignment procedures only need be lacked; And when adopting the vacuum clamping method to carry the up and down base material that utilizes uncured liquid crystal sealing agent lamination by promoting upper substrate, the up and down separation of base material can not appear; And it has good moisture-proof reliability.
Summary of drawings
Fig. 1 is the photo of glass baseplate, the glass baseplate of liquid crystal sealing agent of the embodiment of the invention 3 of having taken from serigraphy thereon.
Claims (18)
1, a kind of liquid crystal sealing agent is characterized in that comprising the epoxy resin by following formula (1) expression: [formula (1)]
(in the formula, n represents average degree of polymerization, is 0～5 positive number), hardening agent, curing accelerator and inorganic filler.
2, according to the liquid crystal sealing agent of claim 1, wherein this epoxy resin contains formula (1) compound of the wherein n=0 of 50～95wt%.
3, according to the liquid crystal sealing agent of claim 1 or 2, wherein bisphenol A type epoxy resin and this epoxy resin together use.
4, according to each liquid crystal sealing agent in the claim 1～3, wherein this hardening agent is a novolac resin.
5, according to the liquid crystal sealing agent of claim 4, wherein this novolac resin contains the compound with dicyclo of 20～80wt%.
6, according to each liquid crystal sealing agent in the claim 1～5, wherein this curing accelerator is potential curing accelerator.
7, according to the liquid crystal sealing agent of claim 6, wherein this potential curing accelerator is amine adduct and has the mean grain size that is no more than 6 μ m.
8, according to each liquid crystal sealing agent in the claim 1～7, wherein this inorganic filler is aluminium oxide and/or silicon dioxide.
9, according to each liquid crystal sealing agent in the claim 1～8, wherein this inorganic filler is the silicon dioxide of amorphous alumina and/or pulverizing.
10, according to each liquid crystal sealing agent in the claim 1～9, it comprises organic solvent.
11, according to the liquid crystal sealing agent of claim 10, wherein the boiling point of this organic solvent under 1013.25hPa is not less than 200 ℃ and the vapour pressure under 20 ℃ and is not higher than 20Pa.
12, according to the liquid crystal sealing agent of claim 10 or 11, wherein this organic solvent is a dibasic acid dimethyl ester.
13, according to the liquid crystal sealing agent of claim 12, it contains butyl cellosolve in addition as organic solvent.
14, according to each liquid crystal sealing agent in the claim 1～13, it contains coupling agent.
15, according to the liquid crystal sealing agent of claim 14, wherein this coupling agent is an amino silicane coupling agent.
16, adopt the liquid crystal indicator that seals according to each liquid crystal sealing agent in the claim 1～15.
17, a kind of method that is used to produce liquid crystal indicator, this liquid crystal indicator comprises and is positioned in the middle of the base material that contains color filter layer and the base material that contains the liquid crystal aligning layer on electrode layer and adopts the fixing liquid crystal material of liquid crystal sealing agent, the method is characterized in that to comprise by serigraphy and will be coated on the step of step on one of described base material, another base material of heat pressure adhesive and this liquid crystal material is poured into step in the gap between the described base material according to each liquid crystal sealing agent in the claim 1～15.
18, according to the method that is used to produce liquid crystal indicator of claim 17, wherein this liquid crystal sealing agent satisfies η 2＜60 (Pas) and η 2/ η 1＜1.5 (wherein, η 1 is coated with this liquid crystal sealing agent viscosity before by serigraphy, and η 2 implements printing this liquid crystal sealing agent viscosity afterwards continuously).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP357529/2003 | 2003-10-17 | ||
| JP2003357529 | 2003-10-17 | ||
| JP192772/2004 | 2004-06-30 | ||
| JP244571/2004 | 2004-08-25 |
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| CN1867861A true CN1867861A (en) | 2006-11-22 |
| CN100414398C CN100414398C (en) | 2008-08-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004800303102A Expired - Fee Related CN100414398C (en) | 2003-10-17 | 2004-10-15 | Sealant for liquid crystal, liquid-crystal display made with the same, and process for produicng the display |
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| CN (1) | CN100414398C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875832A (en) * | 2009-04-28 | 2010-11-03 | 日本化药株式会社 | Liquid crystal sealing agent and use the liquid crystal display of this liquid crystal sealing agent |
| CN102472929A (en) * | 2010-03-25 | 2012-05-23 | 三井化学株式会社 | Liquid crystal sealing agent, method for producing liquid crystal display panel using same, and liquid crystal display panel |
| WO2015010433A1 (en) * | 2013-07-22 | 2015-01-29 | 京东方科技集团股份有限公司 | Frame-sealing adhesive composition, method for preparing same, and liquid crystal panel having same |
| CN114185204A (en) * | 2021-11-19 | 2022-03-15 | Tcl华星光电技术有限公司 | Preparation method of liquid crystal display panel and liquid crystal display panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5283616A (en) * | 1976-01-01 | 1977-07-12 | Semedain Kk | Digiycidyl oxyalkyl benzene |
| JPH05262850A (en) * | 1992-03-18 | 1993-10-12 | Nippon Kayaku Co Ltd | Sealing composition for liquid crystal cell, and liquid crystal display element |
| JPH10274775A (en) * | 1997-03-31 | 1998-10-13 | Optrex Corp | Production of liquid crystal display device |
| JP3863253B2 (en) * | 1997-06-27 | 2006-12-27 | 株式会社日立製作所 | Liquid crystal display element and manufacturing method thereof |
| JPH11246743A (en) * | 1998-02-27 | 1999-09-14 | Mitsui Chem Inc | Resin composition for sealing liquid crystal |
| KR100414698B1 (en) * | 1999-04-01 | 2004-01-13 | 미쯔이카가쿠 가부시기가이샤 | Sealing material composition for liquid crystal |
| JP2001142079A (en) * | 1999-11-11 | 2001-05-25 | Nippon Kayaku Co Ltd | Liquid crystal sealing agent and liquid crystal cell |
| JP4622131B2 (en) * | 2001-03-28 | 2011-02-02 | 住友ベークライト株式会社 | Resin paste for semiconductor and semiconductor device |
| JP4730501B2 (en) * | 2001-08-16 | 2011-07-20 | 信越化学工業株式会社 | Liquid epoxy resin composition and semiconductor device using the same |
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2004
- 2004-10-15 CN CNB2004800303102A patent/CN100414398C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875832A (en) * | 2009-04-28 | 2010-11-03 | 日本化药株式会社 | Liquid crystal sealing agent and use the liquid crystal display of this liquid crystal sealing agent |
| CN101875832B (en) * | 2009-04-28 | 2015-06-10 | 日本化药株式会社 | Liquid crystal sealant and liquid crystal display unit using the same |
| CN102472929A (en) * | 2010-03-25 | 2012-05-23 | 三井化学株式会社 | Liquid crystal sealing agent, method for producing liquid crystal display panel using same, and liquid crystal display panel |
| CN102472929B (en) * | 2010-03-25 | 2014-07-30 | 三井化学株式会社 | Liquid crystal sealing agent, method for producing liquid crystal display panel using same, and liquid crystal display panel |
| WO2015010433A1 (en) * | 2013-07-22 | 2015-01-29 | 京东方科技集团股份有限公司 | Frame-sealing adhesive composition, method for preparing same, and liquid crystal panel having same |
| CN114185204A (en) * | 2021-11-19 | 2022-03-15 | Tcl华星光电技术有限公司 | Preparation method of liquid crystal display panel and liquid crystal display panel |
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| Publication number | Publication date |
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| CN100414398C (en) | 2008-08-27 |
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