CN101338177B - Liquid crystal sealing agent, (methyl) acrylic ester compounds used and manufacturing method thereof - Google Patents
Liquid crystal sealing agent, (methyl) acrylic ester compounds used and manufacturing method thereof Download PDFInfo
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- CN101338177B CN101338177B CN2008101318590A CN200810131859A CN101338177B CN 101338177 B CN101338177 B CN 101338177B CN 2008101318590 A CN2008101318590 A CN 2008101318590A CN 200810131859 A CN200810131859 A CN 200810131859A CN 101338177 B CN101338177 B CN 101338177B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
Abstract
The present invention provides a (methyl)acrylate compound which is liquid in room temperature and has low liquid crystal pollution and a liquid crystal sealing compound thereof containing the (methyl)acrylate. The liquid crystal sealing compound is a liquid crystal sealing compound which contains the (methyl)acrylate represented by the formula (I). In the formula (I), A(s) are respectively and independently alkylidene groups with two or three carbon atoms. R1 to R3 are respectively and independently hydrogen atom or methyl. X to Z are respectively and independently alkylidene groups with two to four carbon atoms.
Description
Technical field
The present invention relates to liquid crystal sealing agent and use therein (methyl) acryliccompound and method of manufacture thereof.
Background technology
In recent years, display panels (being also referred to as " liquid crystal panel ") is used as the display panel of various instruments such as TV, portable phone.At present, because productivity is excellent, display panels is made through processing method under the liquid crystal drop.Processing method is the method for manufacture that comprises the display panels of following operation under the so-called liquid crystal drop.1) liquid crystal sealing agent (also abbreviating " sealing agent " as) is coated on the substrate of liquid crystal panel; Be formed for the frame (seal pattern) of filling liquid crystal; 2) base plate bonding of paired liquid crystal panel (the patent documentation 1 etc.) liquid crystal that in above-mentioned frame, drips, 3) and then with it.
During the liquid crystal panel that carries out through processing method under the liquid crystal drop was made, because uncured liquid crystal sealing agent contacts with liquid crystal, the composition of liquid crystal sealing agent was dissolved in liquid crystal easily and pollutes liquid crystal easily.If liquid crystal is polluted by liquid crystal sealing agent, can show bad when then making liquid crystal panel.In case the bad generation of such demonstration just is difficult to improve.Therefore the liquid crystal sealing agent with low liquid crystal pollution property is developed in expectation.
As the raw material of liquid crystal sealing agent, use (methyl) acryliccompound usually.Because above-mentioned reason, (methyl) acryliccompound are necessary for low liquid crystal pollution property.For the viscosity that makes liquid crystal sealing agent keeps flexibility, (methyl) acryliccompound preferably is liquid at normal temperatures in addition.In order to improve the liquid crystal pollution property of liquid crystal sealing agent, reducing as (methyl) acryliccompound of liquid crystal sealing agent main raw material is necessary to the solvability of liquid crystal.Therefore, it is effective making (methyl) acryliccompound become HMW.
As HMW and normal temperature is (methyl) acryliccompound of liquid, and known have (methyl) acryliccompound that has imported the caprolactone chain.For example, what disclose formula (i) expression in the patent documentation 2 is the compound of main framing with the chlorinated isocyanurates ring, and the formula that discloses in the patent documentation 3 is (ii) represented is that the caprolactone modification polyvalent alcohol of raw material gathers (methyl) acryliccompound with the TriMethylolPropane(TMP).What in addition, disclose in the patent documentation 4 that formula (iii) representes is the compound of main framing with the chlorinated isocyanurates ring.
[changing 1]
In the formula (i), l, m, n are 0～3 integer, and l, m, n add up to 0.5～3.
[changing 2]
[changing 3]
R in the formula
1The expression H or
Base,
R representes H or CH in the formula
3Base.
[patent documentation 1] TOHKEMY 2002-214626 communique
The special public clear 61-54788 communique of [patent documentation 2] Japan
[patent documentation 3] japanese kokai publication hei 7-2996 communique
No. 3715840 communique of [patent documentation 4] Japanese Patent
Summary of the invention
The problem that invention will solve
But, disclosed (methyl) acryliccompound in the above-mentioned patent documentation 1～4, compound is used in the fields such as coating or printing-ink that are developed to.Therefore, in the above-mentioned document, for above-mentioned (methyl) acryliccompound being used for liquid crystal sealing agent not record fully.
The contriver waits the preparation of preparation property ground to use the liquid crystal sealing agent of the compound of record in the patent documentation 2, research liquid crystal pollution property.Its result, the situation that the liquid crystal sealing agent of the compound of use patent documentation 2 records pollutes liquid crystal easily becomes clear and definite.The compound of patent documentation 2 record, owing to be the addition reaction synthetic through caprolactone and hydroxyl, it is constant therefore being difficult to make the caprolactone chain length in the compound of polyreaction generation of caprolactone.Thereby infer that because the compound of record is the mixture with compound of various caprolactone chains in the patent documentation 2, the low molecular weight compositions that wherein exists has increased above-mentioned liquid crystal pollution property.
Therefore, under the room temperature in the past higher (methyl) acryliccompound of liquid and molecular weight ratio, be difficult to improve liquid crystal pollution property.
Based on above situation, the object of the present invention is to provide under the room temperature is low (methyl) acryliccompound of liquid, liquid crystal pollution property and the liquid crystal sealing agent that contains it.
The means of dealing with problems
The inventor etc. In view of the foregoing to the result that (methyl) acryliccompound is furtherd investigate, find that (methyl) acryliccompound of formula (I) expression is effective for reducing liquid crystal pollution property.Promptly through the following above-mentioned problem that the invention solves.
[1] contain the liquid crystal sealing agent of (methyl) acryliccompound of formula (I) expression,
[changing 4]
In the formula [I], A is the alkylidene group of carbonatoms 2 or 3 respectively independently, R
1～R
3Be Wasserstoffatoms or methyl independently respectively, X～Z is the alkylidene group of carbonatoms 2～4 respectively independently.
[2] according to [1] described liquid crystal sealing agent, wherein, the A in the above-mentioned general formula (I) is an ethylidene.
[3] according to [1] or [2] described liquid crystal sealing agent; Wherein, Above-mentioned (methyl) acryliccompound is the mixture of the two or more compound in the compound group that is selected from following formula (B1), (B2), (B3) and (E1) representes; And the ratio of the number of the LBu in said mixture base and the number of LEt base is 70: 30～30: 70
[changing 5]
(B1) (B2) (B3) (E1)
In the formula (B1)～(E1), A representes the alkylidene group of carbonatoms 2 or 3 respectively independently, and LBu is the group of following formula (LBu) expression, and LEt is the group of following formula (LEt) expression.
[changing 6]
(LBu)
[changing 7]
[4] according to each described liquid crystal sealing agent of [1]～[3], wherein, further contain epoxy resin, radical polymerization initiator, potentiality epoxy hardener and filler.
[5] according to [4] described liquid crystal sealing agent; Wherein, With respect to 100 mass parts above-mentioned (methyl) acryliccompound, contain the above-mentioned epoxy resin of 5～60 mass parts, the above-mentioned radical polymerization initiator of 0.1～10 mass parts, the above-mentioned potentiality epoxy hardener of 5～40 mass parts and the above-mentioned filler of 10～50 mass parts.
[6] method of manufacture of each described (methyl) acryliccompound of above-mentioned [1]～[3], it comprises:
In the presence of tertiary amine; Make the compound of formula (Im) expression and formula (L1m) expression compound, (L2m) expression compound and (L3m) compound of expression in non-halogen solvent, carry out esterification, and the operation that the hydrogen halide of above-mentioned reaction generation is separated out as amine salt; With
Filter the operation of the reaction mixture that obtains after the above-mentioned reaction; With
With alkali aqueous solution washing through the above-mentioned reaction mixture that removes by filter amine salt after, separatory obtains the operation of organic phase; With
Wash the operation of above-mentioned organic phase with pure water;
[changing 8]
(Im)
In the formula (Im), A is the alkylidene group of carbonatoms 2 or 3, and Halo representes halogen atom;
[changing 9]
[changing 10]
[changing 11]
In the formula (L1m)～(L3m), R
1～R
3Be Wasserstoffatoms or methyl independently respectively, X～Z is the alkylidene group of carbonatoms 2～4 respectively independently.
[7] according to [6] described method of manufacture, wherein, above-mentioned non-halogen solvent is aromatic hydrocarbons, vinyl acetic monomer or MIBK.
[8] according to [6] or [7] described method of manufacture, wherein, above-mentioned tertiary amine is pyridine, triethylamine or xylidine.
[9] (methyl) acryliccompound of formula (B) expression,
[changing 12]
In the formula (B), X
1Be the alkylidene group of carbonatoms 3 or 4, X
2Be the alkylidene group of carbonatoms 2～4 independently respectively, R
1Be Wasserstoffatoms or methyl, R
2Be Wasserstoffatoms or methyl independently respectively.
[10] according to [9] described (methyl) acryliccompound, wherein, the X in the above-mentioned general formula (B)
1Be butylidene, R
1Be Wasserstoffatoms, and X
2Be butylidene or ethylidene.
[11] according to [9] or [10] described (methyl) acryliccompound, the X in the above-mentioned general formula (B)
1And X
2Be butylidene, and R
1And R
2Be Wasserstoffatoms.
[12] a kind of method of manufacture of display panels, it comprises:
Preparation has the operation of first substrate of the seal pattern that each the said liquid crystal sealing agent by above-mentioned [1]～[5] forms; With
Under the uncured state of above-mentioned seal pattern, in the seal pattern frame of above-mentioned first substrate or with second substrate of aforesaid substrate subtend on the drip operation of liquid crystal; With
Operation with above-mentioned first substrate and above-mentioned second superimposed substrate; With
Make above-mentioned liquid crystal sealing agent solidified operation.
[13] display panels that obtains of the method for manufacture through above-mentioned [12] described display panels.
The effect of invention
Can provide under the room temperature through the present invention is low (methyl) acryliccompound of liquid state and liquid crystal pollution property and the liquid crystal sealing agent that contains it.Sealing agent of the present invention is particularly suitable for processing method under the liquid crystal drop, can provide display characteristic excellent display panels.
Embodiment
1. (methyl) acryliccompound
(1) (methyl) acryliccompound
Liquid crystal sealing agent of the present invention contains (methyl) acryliccompound (below be also referred to as " compound of the present invention ") of formula (I) expression.The meaning of so-called (methyl) acryliccompound is the ester cpds of acrylic or methacrylic acid, so-called " (methyl) propenyl " expression " propenyl or methylpropenyl ".
[changing 13]
(methyl) acryliccompound of general formula (I) expression is combined with the A as organic group on 3 nitrogen-atoms on the chlorinated isocyanurates ring, so be combined with on each A can the polymeric organic group (below be also referred to as " polymerizable group ").A is the alkylidene group of carbonatoms 2 or 3 respectively independently.What is called independently is respectively that 3 A of expression can be different, also can all be identical group.In the example of carbonatoms 2 or 3 alkylidene group, comprise methyl methylene radical, ethylidene, propylidene (positive propylidene) and isopropylidene.Wherein as the preferred ethylidene of A.The method of manufacture of compound of the present invention specifies at the back, and A is the compound of the present invention of ethylidene, obtains raw material and synthetic easily easily.
R in the polymerizable group
1～R
3Represent Wasserstoffatoms or methyl respectively independently, X～Z representes the alkylidene group of carbonatoms 2～4 respectively independently.Mark "～" among the present invention comprises the value at its two ends.
Compound of the present invention is because A, R in the general formula (I)
1～R
3And X～Z can provide to be liquid and the low liquid crystal sealing agent of liquid crystal pollution property under the room temperature in above-mentioned scope.And then, through optimizing these A, R
1～R
3And X～Z, can provide more excellent liquid crystal sealing agent such as liquid crystal pollution property or bonding strength.Below, describe for the example of preferred The compounds of this invention.
Preferred the 1st example of compound of the present invention is the compound of formula (B) expression.This compound is also referred to as compd B.
[changing 14]
Compd B is that A is the compound of ethylidene in the general formula (I).
In the formula (B), R
1Be Wasserstoffatoms or methyl.R wherein
1Be preferably Wasserstoffatoms.
In the formula (B), X
1Alkylidene group for carbonatoms 3 or 4.
In the example of carbonatoms 3 or 4 alkylidene group, comprise propylidene (positive propylidene), isopropylidene, butylidene (positive butylidene), isobutylene, sec.-butylidene and uncle's butylidene.The excellent in adhesion from as liquid crystal sealing agent time the wherein, X
1Being preferably butylidene is normal-butyl.
In the formula (B), R
2Be Wasserstoffatoms or methyl independently respectively.
In the formula (B), X
2For difference is the alkylidene group of carbonatoms 2～4 independently.In the example of the alkylidene group of carbonatoms 2～4, comprise methyl methylene radical, ethylidene, propylidene (positive propylidene), isopropylidene, butylidene (positive butylidene), isobutylene, sec.-butylidene and uncle's butylidene.X wherein
2Be preferably butylidene or ethylidene.X
2Excellent in adhesion during for butylidene during as liquid crystal sealing agent.X
2Excellent heat resistance during for ethylidene during as liquid crystal sealing agent.
In addition, above-mentioned X
2Can all be butylidene, or all be ethylidene.And then, also can an X
2Be butylidene, another X
2Be ethylidene.X
1Be butylidene, whole X
2For the compound of butylidene is also referred to as " 3Bu type ".X
1Be butylidene, an X
2Be ethylidene, another X
2For the compound of butylidene is also referred to as " 2Bu type ".X
1Be butylidene, whole X
2For the compound of ethylidene is also referred to as " 1Bu type ".Wherein, as compd B, more preferably below shown in compound.
[changing 15]
[changing 16]
[changing 17]
(B3)
In the formula (B1)～(B3), LBu and LEt be with following formula (LBu) and (LBt) expression group.
[changing 18]
[changing 19]
Wherein, be preferably 3Bu type and R especially
1And R
2It all is the compound (being also referred to as " compound B-11 ") of formula (B1) expression of Wasserstoffatoms.This is because the cementability of this compound during as liquid crystal sealing agent is very excellent.
The ratio of the number of the LBu base in compd B 2 or the compd B 1 and LEt base is preferably 70: 30～and 30: 70.
Preferred the 2nd example of compound of the present invention is the compound of formula (E) expression.This compound also can abbreviate compd E as.Compd E is that the A in the general formula (I) is that X～Z is the compound of ethylidene among ethylidene, the polymerizable group L1～L3.
[changing 20]
In the formula (E), R
1～R
3Be Wasserstoffatoms or methyl independently respectively.
This compound is the compound that on the nitrogen-atoms on the chlorinated isocyanurates ring, is combined with 2-(2-(methyl) acryl oxyethyl group) carbonyl ethyl.This substituting group can all be 2-(2-acryl oxyethyl group) carbonyl ethyl.The compound of this moment is also referred to as " acrylate type ".In addition, this substituting group also can all be 2-(2-methacryloyl base oxethyl) carbonyl ethyl.The compound of this moment is also referred to as " methacrylate type ".And then also can be, this substituent part is 2-(2-acryl oxyethyl group) carbonyl ethyl, remaining substituting group is 2-(2-methacryloyl base oxethyl) carbonyl ethyl.The compound of this moment is also referred to as " (methyl) acrylate type ".
As compd E, more preferably methacrylate type.This is because can provide bonding strength excellent liquid crystal sealing agent.Methacrylate type is represented with following formula (E1).
[changing 21]
Compound of the present invention also can contain oligopolymer that the polymerization of (methyl) propenyl the generates impurity that becomes to grade on a small quantity, but preferred high purity.Above-mentioned purity is preferably more than 80%, further is preferably more than 90%, is preferably more than 95% especially.The peak area that obtains when analyzing through HPLC (HPLC) calculates purity.And then the ionic impurity that contains in the preferred compound is less.This is that the liquid crystal pollution property of sealing agent significantly reduces because there is ionic impurity to exist in the liquid crystal sealing agent.In order to reduce ionic impurity, compound of the present invention preferably carry out high purityization through silicagel column is refining.
(2) method of manufacture of (methyl) acryliccompound
The method of manufacture of compound of the present invention is not special to be limited.For example can be according to the method manufacturing of above-mentioned patent documentation 4 records.This method is with 1,3, and 5-three (halogenation formyl radical ethyl) chlorinated isocyanurates and hydroxyalkyl (methyl) propenoate dehydrohalogenation carry out esterification method, comprise following operation particularly.
Hydroxyalkyl (methyl) propenoate and pyridine are dissolved in the operation in the chloroform solvent;
With 1,3,5-three (halogenation formyl radical ethyl) chlorinated isocyanurates is mixed in the said mixture, makes the operation of its reaction;
With saturated aqueous common salt, then wash above-mentioned reaction solution, use the operation of saturated common salt water washing again with the 1N aqueous sodium hydroxide washes;
Separate organic phase, the operation that chloroform etc. obtains the purpose compound is removed in distillation.
But,, therefore preferably make with extra care through refining grade of silicagel column because the compound that obtains with this method contains more ionic impurity.
The reason that contains more impurity with the compound that obtains of method of record in the above-mentioned patent documentation 4 is not confirmed, but can as following, be inferred.
The method of record is used saturated aqueous common salt in the patent documentation 4 in washing procedure.Consider that this is to come the washing reaction mixture, the cause that the branch fluidity of water and organic phase reduces owing to water in washing procedure replaces saturated aqueous common salt.This be because be present in pyridine hydrochloride in the reaction mixture be dissolved in chloroform and water the two.Think in addition this be because, in washing procedure, make water, pyridine hydrochloride is during by chloroform phase transition to water, the purpose compound also is brought into water simultaneously, the refining yield of purpose compound probably can reduce.But when saturated aqueous common salt was used to wash, the sodium ion or the chloride ion in salt solution source were sneaked in the purpose compound easily.Therefore think that in washing procedure, using saturated aqueous common salt is the 1st reason that contains more ionic impurity through the compound that the method for putting down in writing in the patent documentation 4 obtains.
And then contriver etc. clearly learn, when reality attempts implementing the method for record in the patent documentation 4, and the branch fluidity of reaction mixture in washing procedure, though improved when making water, also insufficient.Think that branch fluidity difference is the reason that is present in the interface of organic phase and water owing to amphiphilic materials.Infer that this material mainly is a pyridine hydrochloride.Therefore infer that the branch fluidity that is in the suds difference is the 2nd reason that contains more ionic impurity with the compound that the method for putting down in writing in the patent documentation 4 obtains.
Because above situation, compound of the present invention preferably use following shown in method (below be also referred to as " filtration method ") make.This method comprises:
1) in the presence of tertiary amine; The compound of stating general formula (Im) expression after making with after state general formula (L1m) expression compound, (L2m) expression compound and (L3m) compound of expression in non-halogen solvent, carry out esterification, and the operation separated out as amine salt of the hydrogen halide that above-mentioned reaction is generated; With
The operation of the reaction mixture that 2) obtains after the above-mentioned reaction of filtration; With
3) with alkali aqueous solution washing through the above-mentioned reaction mixture that removes by filter amine salt after, separatory obtains the operation of organic phase; With
4) wash the operation of above-mentioned organic phase with pure water.
1) operation: reaction process
In this reaction process; In the presence of tertiary amine; State 1 of general formula (Im) expression after making; 3,5-three (halogenation formyl radical ethyl) chlorinated isocyanurates (below be also referred to as " compound I m ") and after state general formula (L1m)～(L3m) expression hydroxyalkyl (methyl) propenoate (following also with it and be called " compound L 1m etc. ") in non-halogen solvent, carry out esterification.In this reaction process, obtain compound of the present invention.But the reaction mixture that obtains in this reaction process comprises as 1 of by product, the halogenation hydrogen salt of two [((methyl) acryl alkoxyl group) carbonyl ethyl]-5-(2-carboxy ethyl) chlorinated isocyanurates of 3-or tertiary amine etc.
The halogenation hydrogen salt of tertiary amine (is also referred to as that " tertiary ammonium salt ") also can use in the patent documentation 4 method of record to generate.The method of putting down in writing in the document, owing to use chloroform in the solvent, so tertiary ammonium salt dissolves easily, tertiary ammonium salt is dissolved in the solvent and exists.On the other hand, in this filtration method, because in solvent, use the low non-halogen solvent of tertiary ammonium salt solubleness, tertiary ammonium salt is not dissolved in the solvent and separates out.Therefore, in the operation of back, can from reaction mixture, remove tertiary ammonium salt through filtering.The reaction mixture branch fluidity in the washing procedure of back that does not contain tertiary ammonium salt becomes good.
This operation can be carried out particularly as follows.
The 1st method: in the suspension liquid that is mixed with compound I m and non-halogen solvent, add in advance the method that L1m etc. and tertiary amine are mixed the homogeneous solution that obtains.
The 2nd method: in above-mentioned homogeneous solution, the method for the compound I m of interpolation preparation in advance and the suspension liquid of non-halogen solvent.
The 3rd method: after in above-mentioned homogeneous solution, adding non-halogen solvent, the method for adding compound I m powder.
Wherein, because operability is excellent, preferred the 1st method.At this moment, above-mentioned homogeneous solution adds after can using non-halogen solvent cut.
This operation is thermopositive reaction.Therefore, when reaction was sharply carried out, the excessive temperature of reaction system raise, and existence can not be stablized the situation of reacting.Therefore, when in the 1st and the 2nd method, in a kind of liquid, adding other liquid,, preferably add through dripping down for fear of rapid reaction.The temperature of reaction system is preferably 5～150 ℃ when dripping, more preferably room temperature～60 ℃.Can suitably adjust drop time according to the temperature of reaction system.
After this operation, finish in order to make reaction, preferably with the reaction mixture ageing.Preferably with the temperature of reaction mixture 5～150 ℃, more preferably keep constant to carry out ageing in the scope in room temperature～60 ℃.
The adjustment digestion time makes compound I m in the reaction mixture almost by completely consumed, is preferably 0.1～15 hour, more preferably 2～7 hours.The high more digestion time of temperature of reaction or ageing temperature is short more.But because temperature of reaction or ageing temperature are when high, (methyl) propenyl possibly carry out polymerization, thus preferably reduce temperature of reaction or ageing temperature, and prolong digestion time.Above-mentioned reaction carry out degree, for example can the reaction mixture that the every elapsed time arbitrarily that begin from ageing takes be carried out HPLC and analyze and try to achieve.
[raw material]
Compound I m is with 1,3,5-three (halogenation formyl radical alkyl) chlorinated isocyanurates, 1,3, and the carboxylic acid of 5-three (2-carboxyalkyl) chlorinated isocyanurates carries out carboxylic acid halidesization and obtains etheride, representes with formula (Im).
[changing 22]
In the formula (Im), A is the alkylidene group of carbonatoms 2 or 3, and Halo representes halogen atom.In the example of carbonatoms 2 or 3 alkylidene group, comprise and state group.
Comprise chlorine, bromine and iodine in the example of above-mentioned halogen element.Wherein, as the preferred chlorine of halogen element.Etheride in this, at N, through making 1,3,5-three (2-carboxyalkyl) chlorinated isocyanurates and carbonyl chloride, oxalyl chloride or thionyl chloride react and obtain under the dinethylformamide solvent.
Among the compound I m, mainly contain 1 as impurity, the situation of two (halogenation formyl radical alkyl)-5-(2-carboxyalkyl) chlorinated isocyanurates of 3-is more.This impurity contains carboxyl.This compound is also referred to as " impurity of Im ".The impurity of Im generates in this reaction process as 1 of by product, two [((methyl) acryl alkoxyl group) carbonylic alkyl]-5-(2-carboxyalkyl) chlorinated isocyanurates of 3-.This by product is also referred to as " by product of I ", owing to containing carboxyl thereby being dissolved in the alkali aqueous solution easily.With alkali aqueous solution washing reaction mixture, the by product of this I is present in the reaction mixture this filtration method in the operation of back, and the branch fluidity of this washing reduces.Because above situation, the purity of compound I m is preferably more than 90%, more preferably more than 93%, is preferably more than 95% especially.
The peak area that above-mentioned purity can obtain when analyzing with HPLC is calculated.For example, the purity of compound I m can be through after adding aniline derivatives and being amide compound, carries out HPLC and analyze and try to achieve.Specifically; With 1; 3; The peak area of 5-three (halogenation formyl radical alkyl) chlorinated isocyanurates is made as a1, as 1 of the impurity of Im, the peak area of two (halogenation formyl radical alkyl)-5-(2-carboxyalkyl) chlorinated isocyanurates of 3-is made as impurity peaks beyond a2, other the solvent when being made as a3, comes the purity of computerized compound Im through { a1/ (a1+a2+a3) } * 100.
Compound L 1m, L2m and L3m are the compounds that intramolecularly contains hydroxyl and (methyl) propenyl, and promptly hydroxyalkyl (methyl) propenoate is represented with following formula.
[changing 23]
(L1m) (L2m) (L3m)
In the formula (L1m)～(L3m), R
1～R
3Represent Wasserstoffatoms or methyl respectively independently, X～Z representes the alkylidene group of carbonatoms 2～4 respectively independently.
In the example of these compounds, comprise vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate and (methyl) vinylformic acid 2-hydroxyl isopropyl ester etc., but not special the qualification.
Compound L 1m～L3m can be all identical, also can be all different, and perhaps also can be a part of identical.
Compound L 1m～L3m is whole when identical, can obtain the compound as above-mentioned compound B-11 or E1.
Compound L 1m～L3m part is identical, for example have L2m identical with L3m but with the L1m condition of different.Under this situation, obtain the compound of above-claimed cpd B2 or B3.At this moment; For example; If making compound L 1m mole number and compound L 2m mole number is 1: 1; Then can obtain being selected from the mixture of the two or more compounds in the group that above-claimed cpd B1～E1 forms, the group that derives from compound L 1m in the mixture is 1: 1 with the number ratio of the group that derives from compound L 2m.
The total mole number of the compound L 1m that uses in this filtration method etc. is preferably 2～6 times with respect to compound I m mole number, more preferably 3～4 times, is preferably 3～3.3 times especially.If the total mole number of compound L 1m etc. is in this scope, detersive efficiency and the refining yield of stating washing procedure after then improve.
If the above-mentioned lower value of the total mole ratio of compound L 1m etc. is few, then the refining yield of purpose compound reduces.And if the above-mentioned lower value of the total mole ratio of compound L 1m etc. is little, the halogenation formyl radical ethyl that then is incorporated into 1,3,5 the nitrogen-atoms of compound I m can not be by whole halogenations.Therefore such compound divides fluidity to reduce in the washing procedure of back owing to be amphipathic.On the other hand, if the above-mentioned higher limit of total mole ratio of compound L 1m etc. is big, then can exist unreacted compound L 1m etc. to remain in the reaction mixture, the situation that washing times increases in the washing procedure of back.
[non-halogen solvent]
So-called non-halogen solvent is the organic solvent that does not contain halogen element.As above-mentioned, non-halogen solvent is difficult to dissolve the tertiary ammonium salt that generates in this operation, so can from reaction mixture, easily remove tertiary ammonium salt through the filtration operation of back.Therefore, as above-mentioned, the branch fluidity of the washing procedure of back uprises.In addition, as non-halogen solvent, if use and water or the low solvent of alkali aqueous solution consistency then can further improve this minute fluidity.When dividing fluidity high, there is no need the use saturated aqueous common salt that as patent documentation 4, is in the suds.Therefore, through using non-halogen solvent, can reduce the content of the ionic impurity in the purpose compound.
Because above situation, more preferably the consistency with tertiary ammonium salt, water and alkali aqueous solution is low for non-halogen solvent of the present invention.Comprise hydrocarbon in the example of such solvent, ethers such as phenyl ether, ester classes such as vinyl acetic monomer, and ketone such as MIBK, methyl ethyl ketone.
Wherein, non-halogen solvent of the present invention is preferably as nonpolar hydrocarbon.Comprise aliphatic hydrocarbons such as aromatic hydrocarbonss such as toluene, YLENE and hexane, heptane, octane, decane in the concrete example of hydrocarbon.Be non-halogen solvent when being toluene especially and since with the back operation in the water that uses carry out azeotropic, so dephlegmate from organic phase easily.Non-halogen solvent also can use multiple combination.
The usage quantity of non-halogen solvent is not special to be limited, and in order effectively to react, preferably to adjust and makes that the concentration of the compound I m in the non-halogen solvent is 1～60 quality %, more preferably adjusts and is 10～35 quality %.
[tertiary amine]
So-called tertiary amine is the compound with the Wasserstoffatoms of 3 hydrocarbyl substituted ammonia.Tertiary amine is caught halogen atom that origin comes from compound I m and the hydrogen halide that Wasserstoffatoms generated that derives from compound L 1m etc.
Tertiary amine is not special to be limited.Comprise pyridine, Trimethylamine and xylidine in the example of tertiary amine.Amine below the secondary amine is made an addition to reaction mixture, owing to amine and etheride below the secondary amine react, thereby not preferred.Therefore, tertiary amine does not preferably contain as the amine below the secondary amine of impurity.
The usage quantity of tertiary amine is preferably the sufficient amount that makes the whole hydrogen halide that generate in the reaction mixture become amine salt.Specifically, the mole number of tertiary amine is preferably 2～6 times with respect to the mole number of compound I m, more preferably 3～4 times, is preferably 3～3.3 times especially.
2) operation: filter operation
In this filtration operation, filter 1) reaction process in the reaction mixture that obtains.Thus, can remove the tertiary ammonium salts such as pyridinium salt of separating out in the reaction mixture easily.The method of filter reaction mixture is so long as known method such as suction filtration or pressure filtration get final product.When using strainer, the aperture of strainer is very little, can remove fine tertiary ammonium salt etc., but needs long filtration time.Therefore the next suitably setting of operability can be considered in the aperture of strainer.
3) operation: alkali aqueous solution washing procedure
In this operation, with the alkali aqueous solution washing of sodium hydroxide etc. through the above-mentioned reaction mixture that removes by filter amine salt.Washing is with after in above-mentioned reaction mixture, adding alkali aqueous solution, leaves standstill certain hour after vibrating, and carries out that the separatory of water and organic phase carries out as a circulation.At this moment, the sodium salt that is present in the sodium salt of " by product of I " in the reaction mixture or acid that unreacted compound I m is neutralized generation etc. is extracted into aqueous phase.As above-mentioned, owing to from reaction mixture, removed most tertiary ammonium salt, so the branch fluidity the during washing of this operation is high.And then if use nonpolar non-halogen solvent such as toluene as solvent, then the branch fluidity further improves.Because the purpose compound is present in the organic phase, so aqueous phase discarded behind the separatory only reclaims organic phase.
The alkali aqueous solution that uses in the method for the present invention, the preferably aqueous solution of the mineral compound of alkalescence.Comprise sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate and saleratus in the example of the mineral compound of alkalescence.
The concentration of alkali aqueous solution or usage quantity and washing times, suitably setting makes the washing of reaction mixture fully to get final product.For example, when the concentration about 1/3 quality of use reaction mixture is the alkali aqueous solution of 1 quality %, but the thorough washing reaction mixture.
In the reaction mixture before adding alkali aqueous solution,, preferably add aromatic hydrocarbons, vinyl acetic monomer, MIBK or methyl ethyl ketones such as toluene or YLENE as required in order to improve the branch fluidity of reaction mixture.
Utilize the reaction mixture that alkali aqueous solution carries out or the washing of organic phase, preferably carry out repeatedly.For example, repeatedly carrying out 1 above-mentioned circulation repeatedly gets final product.
When utilizing alkali aqueous solution repetitive scrubbing organic phase, preferred monitoring on one side is as 1 of the by product of the I in the organic phase, two [((methyl) acryl alkoxyl group) the carbonylic alkyl]-5-(2-carboxyalkyl) of 3-on one side the concentration of chlorinated isocyanurates wash.To carry out the concentration that HPLC analyzes the by product of asking I except that the organic phase of desolvating.Be specifically; Will through HPLC analyze obtain 1; 3; The peak area that the peak area of 5-three (halogenation formyl radical alkyl) chlorinated isocyanurates is made as the by product of x1, I is made as x2, when the impurity peak area aggregate value beyond other the solvent is made as x3, and the value of calculating through { x2/ (x1+x2+x3) } * 100.During washing, the amount of preferably carrying out repeatedly until the by product of I is below 1%.
4) operation: pure water washing procedure
In this operation, wash the organic phase that preceding operation obtains with pure water.Thus, can remove the alkali aqueous solution of sneaking into organic phase, can from organic phase, remove through the inexpungible impurity of neutralizing treatment simultaneously.In the inexpungible impurity of neutralizing treatment, hydroxyalkyl (methyl) propenoate such as inclusion compound L1m.Pure water washs not special qualification of amount of nonrecoverable pure water, obtains the washing effect of excellence for 1/3 quality left and right sides Shi Ke of organic phase.
Utilize the washing of the organic phase that pure water carries out, while preferably monitor the total concentration of compound L 1m in the organic phase etc. and the specific conductivity of water is washed.To carry out HPLC except that the organic phase of desolvating and analyze the total concentration of asking compound L 1m etc.Be specifically, will be made as y1 through the peak area that HPLC analyzes hydroxyalkyl (methyl) propenoate that obtains, when peak area summation in addition is made as y2 (removing solvent peak), the value of calculating through (y2/ (y1+y2)) * 100.
Specific conductivity is asked through well-established law and is got final product.Because the amount of specific conductivity and the contained ionic impurity of aqueous phase is proportional, therefore can be used as the concentration index of the ionic impurity in the organic phase.
Preferred total concentration of washing compound L 1m in above-mentioned organic phase etc. repeatedly is below 1%, and the specific conductivity of water is below the 2 μ S/cm.
Above-mentioned 3) and 4) operation, can be to carry out 3 repeatedly) operation after, carry out 4 repeatedly) operation, also can be to hocket 3 repeatedly) and 4).But, preferred the former method when considering detersive efficiency.
[concentrating]
From the organic phase of carrying out thorough washing, separate the purpose compound, preferably organic phase is concentrated and separate.Comprise vaporizer in the example of the equipment of concentrated organic phase.Preferably in organic phase, add stopper etc. when concentrated.In the example of stopper, comprise quinones such as quinhydrones, the 4-tertiary butyl-quinhydrones, and 2, phenols such as the 4-tertiary butyl-phenol, 4-methoxyphenol.
As 1,3 of isolating purpose compound, the purity of 5-three [(4-(methyl) acryl alkoxyl group) carbonylic alkyl] chlorinated isocyanurates is analyzed through HPLC and to be measured.This purity is total peak area that the peak area with the purpose compound is made as m1, impurity in addition when being made as m2, the value of calculating through (m1/ (m1+m2)) * 100.The purity of the purpose compound of measuring like this is preferably more than 90%.
2. sealing agent
So-called display panels is meant encloses the tabular device that forms between two transparent substrates with liquid-crystal compsn (liquid crystal).The material that will be used to enclose liquid crystal is called sealing agent or liquid crystal sealing agent.Usually, display panels is two plate bases to be vacated certain interval come bondingly, liquid crystal is enclosed this space make, so liquid crystal sealing agent (also abbreviate as " sealing agent) double as is used for two plate base adherent caking agents.
(1) (methyl) acryliccompound
Sealing agent of the present invention contains the compound of the invention described above as principal constituent.Sealing agent can contain separately states compound, also can contain multiple different compounds.When sealing agent contains multiple different compounds, preferably contain and be selected from (B 1), (B2), (B3) and (E1) mixture of the two or more compounds in the compound group of expression.At this moment, the number of LBu in this mixture base is preferably 70: 30 with the ratio of the number of Let base～and 30: 70, more preferably 60: 40～40: 60, further be preferably 50: 50.This is very excellent because contain the sealing agent cementability of such mixture.
The ratio of the number of LBu base and the number of LEt base is at the mixture of above-mentioned scope, can synthetic compound B-11 in advance and compd E 1 be become expected value (for example 1: 1) according to mixed in molar ratio and mix and obtain.In addition, this mixture, of compound method of manufacture of the present invention, be to be synthetic obtaining under with the condition of the expected value (for example 1: 1) of molar ratio computing according to making as the Intake Quantity of the compound L 1m of raw material and compound L 2m.The number of the LBu base of the mixture value that obtains is like this analyzed through NMR with the ratio of the number of Let base and is tried to achieve.
Compound of the present invention is the necessary composition of liquid crystal sealing agent, preferably in 100 mass parts liquid crystal sealing agents, contains 5～90 mass parts, further preferably contains 20～60 mass parts.This content is in the above-mentioned scope time, the liquid crystal pollution property reduction of liquid crystal sealing agent, and it is good that the display characteristic of display panels also becomes.In the present invention, "～" comprises the value at its two ends.
It is solidifying agent, filler, other additive that liquid crystal sealing agent of the present invention can further comprise epoxy resin, radical polymerization initiator, hot potentiality amine.
(2) epoxy resin
So-called epoxy resin is meant that intramolecularly has an above epoxy group(ing) and do not have the compound of (methyl) propenyl.Epoxy resin is that known material gets final product.Comprise following material in its example.
The polynary glycidyl ether compound of the aromatic series that the reaction of aromatic diol class and epoxy chloropropane obtains; The phenol novolac-type epoxy resin that the reaction of novolac-type resol or polyalkenyl phenol Polyphenols and epoxy chloropropane obtains; The glycidyl ether compound class of xylylene resol; Triphenol type epoxy resin; And dicyclopentadiene-type epoxy resin.Sealing agent of the present invention can contain multiple these different epoxy resin.In addition, these epoxy resin preferably carry out high purityizatioies through molecular distillation method etc.
In the example of the polynary glycidyl ether compound of aromatic series, comprise bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, dihydroxyphenyl propane D type epoxy resin, diphenyl ether type epoxy resin and biphenyl type epoxy resin.
The content of epoxy resin with respect to 100 mass parts compound of the present invention, is preferably 5～60 mass parts, further is preferably 10～20 mass parts.The content of epoxy resin is the sealing agent in the above-mentioned scope, can provide bonding safety excellent display panels.
(3) radical polymerization initiator
So-called radical polymerization initiator is meant and absorbs the compound that energy produces radical.In the example of radical polymerization initiator, comprise optical free radical polymerization starter, hot radical polymerization starter.So-called optical free radical polymerization starter is meant to receive the compound that rayed produces radical, that is, absorb luminous energy, decompose the compound that produces the radical kind.So-called hot radical polymerization starter is meant the compound that adds the thermogenesis radical, that is, absorb heat energy, decompose the compound that produces the radical kind.Sealing agent of the present invention, can comprise optical free radical polymerization starter, hot radical polymerization starter any or the two.
The optical free radical polymerization starter that contains in the sealing agent of the present invention is not special to be limited.In the example of optical free radical polymerization starter, comprise bitter almond oil camphor based compound, phenyl methyl ketone class, benzophenone, thioxanthene ketone, α-acyl group oxime ester (acyloxime ester) class, phenylglyoxylic acid ester class, dibenzoyl class, azo based compound, diphenyl sulfide based compound, acylphosphine oxide based compound, organic pigment based compound, iron-phthalocyanine system, bitter almond oil camphor class, benzoin ethers and anthraquinone class.Sealing agent of the present invention can comprise multiple these optical free radical polymerization starters.
The content of optical free radical polymerization starter with respect to compound 100 mass parts of the present invention, is preferably 0.1～10 mass parts.Through making above-mentioned content is more than 0.1 mass parts, and sealing agent becomes good by the solidified nature that rayed produces.Be below 10 mass parts through making above-mentioned content in addition, can make the stability of concentration of liquid crystal sealing agent good, can obtain uniform cured body during photocuring.
The hot radical polymerization starter that contains in the sealing agent of the present invention, not special the qualification.In the example of hot radical polymerization starter, comprise organo-peroxide or azo cpd and replace ethane compounds.These compounds can be used alone or in combination.In the example of organo-peroxide, comprise ketone peroxide, ketal peroxide, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxy dicarbonate.Sealing agent of the present invention can contain multiple these hot radical polymerization starters.
(4) potentiality epoxy hardener
So-called potentiality epoxy hardener is meant, even be mixed in the epoxy resin, under preservation state usually resin also hardly with epoxy reaction, but through heating and epoxy reaction, make the solidifying agent of epoxy resin cure.Its viscosity stability of sealing agent that contains the potentiality epoxy hardener is excellent.
The potentiality solidifying agent that contains in the sealing agent of the present invention is not special to be limited, and it is the potentiality epoxy hardener that preferred intramolecularly contains amino amine.Amine is in the example of potentiality epoxy hardener, comprises organic acid dihydrazide compound, imidazoles and verivate thereof, Dyhard RU 100, aromatic amine, epoxide modified polyamine and gathers Urea,amino-.
The potentiality epoxy hardener, preferred especially fusing point or the softening point temperature of measuring through ring and ball method are more than 75 ℃.The sealing agent that contains such potentiality epoxy hardener, the viscosity stability under the room temperature are very excellent.Therefore, even such sealing agent is filled in screen process press or the point gum machine because on substrate, describe seal pattern for a long time, viscosity is also stable, and does not damage operability.
Fusing point or be that amine more than 75 ℃ is in the example of potentiality solidifying agent through the softening point temperature that ring and ball method is measured comprises Dyhard RU 100 Dyhard RU 100 classes such as (209 ℃ of fusing points); Adipic dihydrazide (181 ℃ of fusing points), 1, two (diazanyl the carbonyl ethyl)-5-sec.-propyl NSC 9226 organic acid dihydrazides such as (120 ℃ of fusing points) of 3-; 2,4-diamino--6-[2 '-ethyl imidazole-(1 ')]-ethyl triazine (215 ℃～225 ℃ of fusing points), 2-phenylimidazole imdazole derivatives such as (137～147 ℃ of fusing points).
Sealing agent of the present invention can contain multiple these potentiality epoxy hardeners.The content of potentiality epoxy hardener with respect to compound 100 mass parts of the present invention, is preferably 5～40 mass parts, more preferably 25～35 mass parts.The content of potentiality epoxy hardener is the sealing agent of above-mentioned scope, can provide bonding safety excellent display panels.So in addition sealing agent viscosity stability is also excellent.The potentiality epoxy hardener that the present invention uses preferably carry out high purityization through WATER-WASHING METHOD, recrystallization method etc.
(5) filler
So-called filler is meant the weighting agent that the intensity of viscosity controller with sealing agent, cured article improves, linear expansivity is controlled to be purpose and add.The contained filler of sealing agent of the present invention is not special to be limited, but the filler that the preferred electron material is used.In the example of such filler, comprise mineral filler and organic filler.
In the example of mineral filler, comprise lime carbonate, magnesiumcarbonate, permanent white, sal epsom, pure aluminium silicate, zirconium silicate, red stone, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon-dioxide, potassium titanate, kaolin, talcum, granulated glass sphere, sericite atlapulgite, wilkinite, aluminium nitride AlN and silicon nitride.In the example of organic filler, comprise polymethylmethacrylate, PS, TEB 3K and other monomeric multipolymers, vinylbenzene and other monomeric multipolymers, polyester micropartical, polyurethane particulate and rubber particle.In above-mentioned filler, from the preferred mineral filler of the viewpoint of low linear expansion property, shape-holding property, from the viewpoint of photopermeability more preferably silicon-dioxide, talcum.
The shape of filler is not special to be limited, and can be setting or amorphous such as spherical, tabular, needle-like.The content of filler with respect to compound 100 mass parts of the present invention, is preferably 10～50 mass parts, more preferably 35～45 mass parts.The sealing agent that contains the filler of above-mentioned scope, bonding strength is excellent.
(6) other additive
Sealing agent of the present invention can contain following additive as required.Coupling agents such as silane coupling agent, a part contain compound, ion capturing agent, ionite, flow agent, pigment, dyestuff, thermoplastic polymer, skimmer of glycidyl and (methyl) propenyl etc.And then in order to ensure the lamellar spacing (cell gap) of expectation, sealing agent of the present invention can contain barrier sheet.
A part contains the compound of glycidyl and (methyl) propenyl, and epoxy resin such as bisphenol-type epoxy resin or novolac-type epoxy resin and the reaction of (methyl) acrylic or methacrylic acid phenenyl ester are obtained.The compound that a part contains glycidyl and (methyl) propenyl is also referred to as modified epoxy.Because modified epoxy has epoxy group(ing) and (methyl) propenyl concurrently in resin matrix, the intermiscibility of compound of the present invention and epoxy resin is excellent, therefore uniform cured article can be provided.
Sealing agent of the present invention also can contain the solvent that is useful on modulation viscosity.Solvent so long as known solvent get final product.Comprise ketone solvents such as pimelinketone in its example; Ether solvents such as diglyme, methyl carbitol, ethyl carbitol, diethylene glycol monobutyl ether; Acetic ester solvents such as diethylene glycol diacetate, alkoxyl group diglycol monotertiary acetic ester, and non-polar solvent such as toluene, YLENE.
When sealing agent of the present invention contained solvent, in the manufacturing process of display panels, a side liquid-crystal display was preferably carried out temporary transient Procuring with this liquid crystal sealing agent and is handled with after forming seal pattern on the substrate under 50～100 ℃ temperature.The content of solvent is preferably below 20% with respect to sealing agent, more preferably below 10%.The content of solvent is difficult to reduce the display characteristic of display panels at the sealing agent of this scope.
The liquid crystal pollution property of sealing agent, as after state can through make display panels, show state when driving display panel is estimated.The liquid crystal of display panel is replied poorly if liquid crystal is contaminated, and it is bad that show state becomes.
In addition, also can in beaker, heat mixing, more contaminated liquid crystal and do not have the NI point of contaminated liquid crystal to estimate the liquid crystal pollution property of sealing agent with sealing agent or as (methyl) acryliccompound and the liquid crystal of its principal constituent.
So-called NI point be liquid crystal from nematic phase to the temperature of isotropic phase (isotropic phase) when carrying out phase transition.Phase inversion temperature can use the differential thermal analysis device to be measured by the flex point of exothermic peak.Δ NI point is the poor of " the NI point that does not have contaminated liquid crystal " and " the NI point of contaminated liquid crystal ".When raw material that liquid crystal pollution property is high or sealing agent liquid crystal mixed, it is big that the absolute value that Δ NI is ordered becomes.On the contrary, when the liquid crystal pollution property of raw material or sealing agent was hanged down, the absolute value that Δ NI is ordered diminished.
Compound of the present invention or contain its sealing agent, when carrying out following test, the absolute value that preferred Δ NI is ordered is less than 0.8 ℃ material, and more preferably the Δ NI absolute value of ordering is less than 0.4 ℃ material.Test is carried out as follows: the sealing agent that will mix compound of the present invention with 1: 10 mass ratio or contain it and the material of liquid crystal are 120 ℃ of heating after 1 hour, with above-mentioned method mensuration Δ NI point.
2. the preparation of sealing agent
Sealing agent preparation method of the present invention is not special to be limited.Sealing agent can obtain above-mentioned sealing agent with known method with raw materials mix.In the blending means example, comprise the method for known mixing machineries such as using double blade mixer, roller mixing roll, twin screw extruder, ball milling mixing roll and planetary stirring machine.The blended sealing agent finally filters with strainer, and vacuum defoamation is handled the back sealing and is filled in vial or the polythene container, preserves, transports.
3. the method for manufacture of display panels
Use sealing agent of the present invention to make not special qualification of method of display panels, but following preferred method of manufacture is described.
Display panels of the present invention preferably passes through following operation, is that so-called liquid crystal drop laxative remedy is made said operation:
1) preparation has the operation of first substrate of the seal pattern that is formed by sealing agent of the present invention;
2) under the uncured state of above-mentioned seal pattern, in the seal pattern frame of above-mentioned first substrate or with the drip operation of liquid crystal of second substrate of aforesaid substrate subtend;
3) with the operation of above-mentioned first substrate and above-mentioned second superimposed substrate; And
4) make the operation of above-mentioned sealant cures.
Above-mentioned 1) operation～3) can be carried out through known method.Above-mentioned 4) operation can temporarily solidify sealing agent by irradiates light, heats afterwards to make its after fixing, also can only make sealant cures through heating.The display panels of making like this shows that condition of poor is few, has good display characteristic.
[embodiment]
Specify the present invention through embodiment, but the present invention is not limited to this.In addition, below " % ", " part " of record are represented " quality % ", " mass parts " respectively.
[preparations of the material that uses in embodiment, the comparative example etc.]
(1) (methyl) acryliccompound
(methyl) acryliccompound is synthetic through following synthetic example.
Synthesizing of [synthetic example 1] methacrylate compound (A1)
Operate equally with the embodiment 1 of patent documentation 4, make 1,3,5-three (2-carboxy ethyl) chlorinated isocyanurates and 2-hydroxyethyl methacrylate reaction obtain containing 1,3, the reaction solution of 5-three [2-(2-methacryloyl base oxethyl) carbonyl ethyl] chlorinated isocyanurates.
With saturated aqueous common salt with this reaction solution washing 3 times after, concentrate the chloroform phase.The enriched material that obtains is carried out silicagel column make with extra care, separate 1,3,5-three [2-(2-methacryloyl base oxethyl) carbonyl ethyl] chlorinated isocyanurates.The purity of this compound as after analyze through HPLC stating and try to achieve.Its result is calculated as 98% by the peak area ratio of HPLC.
Synthesizing of [synthetic example 2] acryliccompound (A2)
Except using vinylformic acid 2-hydroxy methacrylate to replace the 2-hydroxyethyl methacrylate, with the operation equally of synthetic example 1, synthesising title compound.
Synthesizing of [synthetic example 3] (methyl) propenoate mixture (A3)
Except half the (mole converts) with 2-hydroxyethyl methacrylate replaces with the vinylformic acid 2-hydroxy methacrylate, use with synthetic example 1 same method and obtain the title mixture.
Synthesizing of [synthetic example 4] (methyl) propenoate mixture (A4)
Except the mixture (mol ratio 1: 1) that uses vinylformic acid 4-hydroxyl butyl ester and 2-hydroxyethyl methacrylate replaces the 2-hydroxyethyl methacrylate,, obtain the title mixture with the operation equally of synthetic example 1.The mixture that obtains is the mixture of above-claimed cpd B1 and B2 and B3.This mixture
1The mensuration result of H-NMR such as the following stated.Measure with EX270 type nuclear magnetic resonance device (NEC's system, 270MHz, CDCl
3, room temperature) carry out.Measure the FT-IR of this compound in addition, confirmed to derive from the absorption peak of tricarbimide ring.
H(a)：6.41ppm(1.5H)、H(b)：5.83ppm(1.5H)、H(c、j)：6～6.2ppm(3H)、H(d、g、i、m、n、p)：4～4.5ppm(18H)、H(e、f)：1.79ppm(6H)、H(h、o)：2.68ppm(6H)、H(k)：5.60ppm(1.5H)、H(1)：1.95ppm(4.5H)
[changing 24]
Synthesizing of [synthetic example 5] acryliccompound (A5)
Except using vinylformic acid 4-hydroxyl butyl ester to replace the 2-hydroxyethyl methacrylate,, obtain title compound with the operation equally of synthetic example 1.The compound that obtains is the compound of above-mentioned formula (B1) expression.The purity of this compound is 97.5 area % through the HPLC analytical calculation.
This compound
1The mensuration result of H-NMR (condition is identical with synthetic routine 4) is like the following stated.In addition, measure the FT-IR of this compound, confirmed to derive from the absorption peak of tricarbimide ring.
H(a)：6.41ppm(3H)、H(b)：5.83ppm(3H)、H(c)：6.12ppm(3H)、H(d、g、i)：4～4.4ppm(18H)、H(e、f)：1.79ppm(12H)、H(h)：2.66ppm(6H)
[changing 25]
Synthesizing of [synthetic example 6] propenoate mixture (A6)
Except half the (mole converts) with vinylformic acid 4-hydroxyl butyl ester replaces with the vinylformic acid 2-hydroxy methacrylate, use with synthetic example 5 same methods and obtain propenoate mixture (A6).This mixture
1The mensuration result of H-NMR (condition is identical with synthetic routine 4) is like the following stated.Measure the FT-IR of this compound in addition, confirmed to derive from the absorption peak of tricarbimide ring.
H(a、q)：6.3～6.5ppm(3H)、H(b、r)：5.75～5.95ppm(3H)、H(c、s)：6～6.25ppm(3H)、H(d、g、i、t、u、w)：4～4.6ppm(18H)、H(e、f)：1.79ppm(6H)、H(h、v)：2.55～2.85ppm(6H)
(2) other compositions
Use following material.
Epoxy resin: ortho-cresol novolac-type solid epoxy (EOCN-1020-75: Japanese chemical drug system)
The optical free radical polymerization starter: (IRGACURE 184: the Ciba corporate system) for 1-hydroxyl-cyclohexyl-phenyl-ketone
The hot radical polymerization starter: 1,1-azo two (2,4-hexanaphthene-1-nitrile) (V-40 :) with the pure medicine system of light
The potentiality epoxy hardener: 1, two (diazanyl the carbonyl ethyl)-5-sec.-propyl NSC 9226 (AmicureVDH: 120 ℃ of aginomoto system, fusing points) of 3-
Filler: spherical silicon dioxide (Severs spy-S-30 (シ one Off オ ス タ one-S-30): Japanese catalyzer system)
Additive: as γ-glycidoxypropyl Trimethoxy silane (KBM403: SHIN-ETSU HANTOTAI's chemical industry system) of silane coupling agent
Modified epoxy: following synthetic routine 7 resins that obtain
[synthetic example 7]
Bisphenol f type epoxy resin (Ai Putuote YDF-8170C (エ Port ト one ト YDF-8170C): Dongdu system of changing into) 160g, vinylformic acid 36g, trolamine 0.2g packs in the four-hole boiling flask of the 500ml that stirrer, gas introduction tube, TM, prolong are housed.Then, with these under the dry air air-flow, 110 ℃, 5 hours heated and stirred react, and obtain the propenyl modified epoxy.The resin that obtains is with ultrapure water washing 12 times.
[various evaluation method]
1) the liquid crystal pollution property evaluation test of raw material and liquid crystal sealing agent
Accurate weighing (methyl) acryliccompound 0.03g and liquid crystal (MLC-11900-000: Merck system) 0.3g in the beaker of 1ml were 120 ℃ of heating 1 hour.After heating stopped, more contaminated liquid crystal and do not have the NI point of contaminated liquid crystal was calculated Δ NI point.When using low raw material of liquid crystal pollution property or liquid crystal sealing agent, the absolute value that Δ NI is ordered diminishes.
To (methyl) propenoate mixture and with after state method preparation sealing agent likewise ask Δ NI point respectively.
2) show state of the display panels after light and thermofixation test
A) prepare transparency electrode and the 40mm * 45mm glass substrate (RT-DM88PIN:EHC system) that posts alignment films.
After usefulness, state in the liquid crystal sealing agent of method preparation, add the spun glass of 5 μ m of mixing 1%.The sealing agent is filled in point gum machine (SHOTMASTER: Musashi engineering corporation system), on aforesaid substrate, paint the seal pattern of the frame type of 35mm * 40mm with the line drawing of live width 0.5mm, the thick 50 μ m of line.
B) then, use point gum machine to drip in paired glass substrate with suitable liquid crystal material (MLC-11900-000: the Merck system) precision of plate inner capacities after fitting.And then, under the decompression of 90Pa, make that liquid crystal is sealed with this two substrates is superimposed.
C) use the prosperous motor system UV irradiation equipment of excellent will, with 100mW/cm
2Uviolizing illumination to the irradiation energy of above-mentioned superimposed substrate irradiation 2000mJ, carry out photocuring.Light source uses metal halide lamp, uses total range of wavelength, peak susceptibility wavelength with 300nm～390nm to add up quantorecorder (UVR-T35: open up general health corporate system) as the ultraviolet ray of 365nm in the mensuration of accumulative total light quantity.
D) carry out photocuring through ultraviolet ray after, further carried out after fixing in 60 minutes 120 ℃ of heating.
On the two sides of glass substrate paste polarization film e) thereafter.
Use continuous-current plant under the impressed voltage of 5V, to drive this display panels and estimate Presentation Function.Whether near the liquid-crystal display function of specifically, estimating liquid crystal sealing agent began to work orderly from the driving initial stage.What show is unusual, is from producing towards liquid crystal display part near the sealing agent, therefore judging to the distance at sealing agent edge through the display abnormality zone.When not observing display abnormality, when promptly above-mentioned distance is almost nil display characteristic is evaluated as well (zero), when above-mentioned distance surpasses 0.3mm display characteristic is evaluated as poor significantly (*).
3) the liquid-crystal display state of the display panels after thermofixation test
With above-mentioned a)～b) operation likewise, obtain superimposed substrate.
F) then, carried out after fixing in 60 minutes 120 ℃ of heating.
Then, paste polarization film on the two sides of glass substrate.
Use continuous-current plant under the impressed voltage of 5V, to drive this display panels, estimate Presentation Function.Concrete evaluation method and above-mentioned is carried out equally.
4) test of the liquid crystal sealing agent determining bonding strength after light and the thermofixation
Preparation is stated after usefulness in the liquid crystal sealing agent of method preparation and is added with the sealing agent of the spun glass of 5 μ m as spacer.Then, on the non-alkali glass of 25mm * 45mm thickness 5mm, sealing agent silk screen printing become the round shape of diameter 1mm, paired same glass cruciform is bonding, fix.Use the prosperous system UV irradiation equipment of excellent will, with 100mW/cm
2Uviolizing illumination to the irradiation energy of this glass irradiation 2000mJ, carry out photocuring.And then, afterwards at 120 ℃ of after fixing that carry out 60 minutes, the preparation test film.
The INTESCO corporate system), to measure planar stretch intensity in draw speed 2mm/ minute the test film that obtains is used tensile testing machine (210 types:.During the bonding strength of this decision method more than obtaining 10MPa, be evaluated as bonding strength good (zero), be evaluated as when obtaining the bonding strength less than 10MPa poor (*).
5) test of the liquid crystal sealing agent determining bonding strength after the thermofixation
With above-mentioned same operation, prepare two sheet glass that cruciform is pasted.Then, this glass is carried out 60 minutes heat treated at 120 ℃, the test film that thermofixation obtains is only carried out in preparation.The test film that obtains is estimated as above-mentioned.
6) viscosity stability
100 mass parts liquid crystal sealing agents are packed into seal in the Vilaterm container made.Directly preserved through 5 days at 25 ℃, measure through the time the viscosity of sealing agent after changing.Through the time the viscosity of sealing agent after changing, 25 ℃ of viscosity numbers during with the sealing measured are in advance represented as 100 o'clock ratio.The rate of rise of viscosity is 20% to be evaluated as storage stability good (zero) when following, and said rate of rise surpasses at 20% o'clock and is evaluated as storage stability poor (*).
[embodiment 1]
With mixing machine material shown in following is carried out pre-mixing, then using three rollers to carry out mixing is below the 5 μ m until solid material.Then after strainer (MSP-10-E10S:ADVANTEC system) the filtration said composition with aperture 10 μ m, carry out the vacuum defoamation processing and obtain liquid crystal sealing agent (P1).
35 parts of methacrylate compound (material that synthetic example 1 obtains)
10 parts of potentiality epoxy hardeners
5 parts of epoxy resin
2 parts of optical free radical polymerization starters
15 parts of fillers
5 parts of propenyl modified epoxies (material that synthetic example 7 obtains)
1 part of silane coupling agent
The sealing agent that obtains is through state method evaluation.
[embodiment 2]
Except the compound (A2) that uses synthetic example 2 to obtain replaces likewise operating with embodiment 1 compound (A1), obtain liquid crystal sealing agent (P2).The sealing agent that obtains is through state method evaluation.
[embodiment 3]
Except the compound (A3) that uses synthetic example 3 to obtain replaces likewise operating with embodiment 1 compound (A1), obtain liquid crystal sealing agent (P3).The sealing agent that obtains is through state method evaluation.
[embodiment 4]
Except the mixture (A4) that uses synthetic example 4 to obtain replaces likewise operating with embodiment 1 compound (A1), obtain liquid crystal sealing agent (P4).The sealing agent that obtains is through state method evaluation.
[embodiment 5]
Except the compound (A5) that uses synthetic example 5 to obtain replaces likewise operating with embodiment 1 compound (A1), obtain liquid crystal sealing agent (P5).The sealing agent that obtains is through state method evaluation.
[embodiment 6]
Except using compound (A1) and compound (A5) are replaced likewise operating with embodiment 1 compound (A1) with 1: 1 blended mixture of mass ratio, obtain liquid crystal sealing agent (P6).The sealing agent that obtains is through state method evaluation.
[embodiment 7]
Except the mixture (A6) that uses synthetic example 6 to obtain replaces likewise operating with embodiment 1 compound (A1), obtain liquid crystal sealing agent (P7).The sealing agent that obtains is through state method evaluation.
[embodiment 8]
Except half the (mass conversion) with compound (A1) replaces with the mixture (A6), likewise operate with embodiment 1, obtain liquid crystal sealing agent (P8).The sealing agent that obtains is through state method evaluation.
[embodiment 9～16]
Except using as 1 of hot radical polymerization starter; 1-azo two (2; 4-hexanaphthene-1-nitrile) replaces 1-hydroxyl-cyclohexyl-beyond phenyl-ketone, likewise operate, obtain liquid crystal sealing agent (T1)～(T8) with embodiment 1～8 as the optical free radical polymerization starter.The sealing agent that obtains is through state method evaluation.
[comparative example 1]
Except the propenoate (R1) that uses above-mentioned formula (i) expression replaces likewise operating with embodiment 1 compound (A1), obtain liquid crystal sealing agent (C1).
Aforesaid propylene ester compound (R1) synthesizes according to the reference example and the embodiment of patent documentation 2.1 mole of 5-three (2-hydroxyethyl) chlorinated isocyanurates, the alcohol that open loop addition 6-caprolactone is 2.5 moles have been obtained with respect to 1,3.And then, make this alcohol and vinylformic acid carry out esterification, obtain containing the reaction mixture of object.Then, with 1% aqueous sodium hydroxide solution and then with this reaction mixture of ultrapure water washing, carry out high purityization.
[comparative example 2]
Except the acryliccompound (R2) that uses above-mentioned formula (ii) to represent replaces likewise operating with embodiment 1 compound (A1), obtain liquid crystal sealing agent (C2).
Aforesaid propylene ester compound (R2) synthesizes according to the embodiment 1 of patent documentation 3.Obtained with respect to 1 mole of TriMethylolPropane(TMP) the alcohol that open loop addition 6-caprolactone is 3 moles.And then, make this alcohol and vinylformic acid carry out esterification, obtain containing the reaction mixture of object.Then, with 1% aqueous sodium hydroxide solution and then with this reaction mixture of ultrapure water washing, carry out high purityization.
[comparative example 3]
Except using as 1 of hot radical polymerization starter, 1-azo two (2,4-hexanaphthene-1-nitrile) replaces the 1-hydroxyl-cyclohexyl-beyond phenyl-ketone, likewise operate with comparative example 1 as the optical free radical polymerization starter, obtains liquid crystal sealing agent (C3).
[comparative example 4]
Except using as 1 of hot radical polymerization starter, 1-azo two (2,4-hexanaphthene-1-nitrile) replaces the 1-hydroxyl-cyclohexyl-beyond phenyl-ketone, likewise operate with comparative example 2 as the optical free radical polymerization starter, obtains liquid crystal sealing agent (C4).
For compound (mixture), as above-mentioned, measure Δ NI point.Its result is shown in table 1.
[table 1]
1) propenoate (R3) be following shown in compound.
[changing 26]
The system Aronix M315 of Toagosei Co., Ltd
Measure Δ NI point for the sealing agent of preparation as stated.Its result is shown in table 2.
[table 2]
| Sample | ΔNI(℃) | |
| Embodiment 1 | Sealing agent (P1) | 0.10 |
| Embodiment 2 | Sealing agent (P2) | 0.10 |
| Embodiment 3 | Sealing agent (P3) | 0.20 |
| Embodiment 4 | Sealing agent (P4) | 0.15 |
| Embodiment 5 | Sealing agent (P5) | 0.20 |
| Embodiment 6 | Sealing agent (P6) | 0.15 |
| Embodiment 7 | Sealing agent (P7) | 0.20 |
| Embodiment 8 | Sealing agent (P8) | 0.10 |
| Embodiment 9 | Sealing agent (T1) | 0.10 |
| Embodiment 10 | Sealing agent (T2) | 0.10 |
Table 2,
| Embodiment 11 | Sealing agent (T3) | 0.10 |
| Embodiment 12 | Sealing agent (T4) | 0.15 |
| Embodiment 13 | Sealing agent (T5) | 0.20 |
| Embodiment 14 | Sealing agent (T6) | 0.15 |
| Embodiment 15 | Sealing agent (T7) | 0.20 |
| Embodiment 16 | Sealing agent (T8) | 0.10 |
| Comparative example 1 | Sealing agent (C1) | 1.20 |
| Comparative example 2 | Sealing agent (C2) | 1.00 |
| Comparative example 3 | Sealing agent (C3) | 1.10 |
| Comparative example 4 | Sealing agent (C4) | 1.00 |
For the sealing agent for preparing as stated, estimate liquid crystal show state, bonding strength and bonding stability, the result is shown in table 3,4.Table 3 expression is carried out the performance of the sealing agent of photocuring and thermofixation for P1～P8 and C1, C2, and the performance of the sealing agent of thermofixation is carried out in table 4 expression for T1～T8 and C3, C4.
[table 3]
[table 4]
Synthesizing of [embodiment 17] high-purity compound
In the flask that stirrer, TM, tap funnel and prolong are housed, pack 1,3 into, 5-three (chloroformyl ethyl) chlorinated isocyanurates 188.3g (0.47 mole, HPLC purity 98%) and toluene 732g obtain suspension liquid.Then, when this suspension liquid is stirred, drip vinylformic acid 4-hydroxyl butyl ester 203.3g (1.41 moles), pyridine 111.4g (1.41 moles) and the mixed uniformly solution of toluene 732g.Drip and at room temperature carried out 2 hours.When carrying out dripping of solution on one side with the liquid temperature of TM mensuration suspension liquid on one side, the liquid temperature of suspension liquid rises to 35 ℃ during dropping.
The suspension liquid that has dripped complete soln is at room temperature carried out ageing in 5 hours.Begin to aging period from the dropping of solution, reaction mixture is the slurries that contain white crystals.These slurries comprise solvent, be dissolved in the purpose compound of this solvent, be not dissolved in the pyridine hydrochloride of solvent precipitate, be not dissolved in the raw material 1,3 of solvent, 5-three (chloroformyl ethyl) chlorinated isocyanurates.When ageing stops, exist hardly in the reaction mixture undissolved 1,3,5-three (chloroformyl ethyl) chlorinated isocyanurates.Reaction mixture after use strainer (the paulownia mountain makes made, No.5A) this ageing of suction filtration is removed pyridine hydrochloride from reaction mixture.In addition, with the pyridine hydrochloride of toluene 300g washing and recycling, reclaim these toluene and be mixed in the filtrating that the front obtains.
Then, among the reaction mixture 2200g after removing pyridine hydrochloride, add the aqueous sodium hydroxide solution 600g of 1 quality % after, vibrate, place certain hour.So the mixture of reaction mixture and aqueous sodium hydroxide solution (below be called " mixture of washing ") is from leaving standstill beginning water and toluene separatory mutually after 10 minutes.The mixture of washing is made up of transparent toluene phase and transparent water, does not have the emulsion phase, and the interface is clear and definite.
After from the mixture of washing, removing water, add the aqueous sodium hydroxide solution 600g of 1 quality % in mutually again, vibrate, place separatory behind the certain hour at toluene.Then, from the mixture of this washing, remove water after, the toluene that obtains through the HPLC assay determination 1 in mutually, the content of two [((methyl) acryl butoxy) carbonyl ethyl]-5-(2-carboxy ethyl) chlorinated isocyanurates of 3-.Its result, the content of the toluene of this compound in mutually confirms as 0.5% after removing and desolvating.
Then, add pure water 600g in mutually, after vibrating, leave standstill certain hour, carry out separatory again at the toluene that obtains.Confirming separatory from leaving standstill the time point that begins through 10 minutes.Visual when observing down toluene mutually with the mixture of pure water (below be called " mixture of water washing "), affirmation toluene is clear and definite with the interface of water, does not have the emulsion phase.
Then, from the mixture of water washing, remove toluene that water obtains mutually in, add pure water 600g again, after vibrating, leave standstill certain hour, carry out separatory, repeatedly 6 such operations.After the 6th time operation stopped, when measuring vinylformic acid 4-hydroxyl butyl ester content in mutually of the toluene that obtains, content was 0.01%.In addition, the specific conductivity of the 6th water that obtain of operation is 0.8 μ S/cm.Thus, through above-mentioned a series of washing, can confirm to have removed ionic impurity fully mutually from toluene.
The toluene that finally obtains mutually in, add the phenothiazine of 0.016g as stopper.Use and bathe temperature, obtain 1,3,5-three [(4-acryl butoxy) carbonyl ethyl] chlorinated isocyanurates 293g at 50 ℃ of under reduced pressure concentrated these toluene solutions of the about constant vaporizers of maintenance.
Through 1,3 of HPLC assay determination preparation, be 91% during the purity of 5-three [(4-acryl butoxy) carbonyl ethyl] chlorinated isocyanurates.With respect to raw material 1,3,5-three (chloroformyl ethyl) chlorinated isocyanurates, the object yield is 78%, is high yield.The specific conductivity of water is 1.2 μ S/cm during ionic impurity in (methyl) acryliccompound that obtains through following method evaluation in addition.Confirm that this compound ions property impurity has been reduced to the level that liquid crystal sealing agent can be used for electronic machine so.
[embodiment 18]
Except the 2-hydroxyethyl methacrylate that uses equivalent (mole conversion) replaces the vinylformic acid 4-hydroxyl butyl ester, use with all identical method of embodiment 17 and synthesize 1,3,5-three [(2-methacryloyl base oxethyl) carbonyl ethyl] chlorinated isocyanurates.Its result obtain 1,3,5-three [(2-methacryloyl base oxethyl) carbonyl ethyl] chlorinated isocyanurates is 267g.
Through the HPLC assay determination obtain 1,3, during the purity of 5-three [(2-methacryloyl base oxethyl) carbonyl ethyl] chlorinated isocyanurates, relevant purity is 92%.Through calculating with respect to 1,3 with the same methods of embodiment 17, the object yield of 5-three (chloroformyl ethyl) chlorinated isocyanurates, its as a result yield be 76%.
In addition, when measuring the ionic impurity in (methyl) acryliccompound that obtains, the specific conductivity of water is 1.2 μ S/cm, confirms that ionic impurity has been reduced to the such level that can be used for electronic machine of liquid crystal sealing agent.
HPLC of the present invention analyzes and the mensuration of ionic impurity amount is carried out as follows.
[HPLC analysis]
.HPLC post: YMC-Pack ODS-A A-312 150 * 6.0mm I.D.S-5 μ m, 12nm
. elutriant: acetonitrile/0.1 quality % phosphoric acid water=65/35 (volume ratio)
. flow: 1ml/ minute
.UV detector wavelength: 210nm
. IR: 20 μ l
. inject sample: with 0.01g (not containing solvent converts) with dilution in acetonitrile to 50ml
For example; Will be through 1,3 of HPLC assay determination, the peak area of 5-three [(4-acryl butoxy) carbonyl ethyl] chlorinated isocyanurates is made as m1; When the total peak area of impurity in addition is made as m2; Calculate 1,3 according to (m1/ (m1+m2)) * 100, the purity of 5-three [(4-acryl butoxy) carbonyl ethyl] chlorinated isocyanurates.
[measuring method of ionic impurity amount]
The amount of the ionic impurity in (methyl) acryliccompound is as followsly estimated through specific conductivity.
The measuring method of specific conductivity: get 3g as the reaction mixture of determination object and (methyl) acryliccompound of manufacturing, mixed toluene 30g and ultrapure water 30g therein.What ultrapure water used is the ultrapure water after just having made with extra care.Then, leave standstill organic phase and water separatory after this mixed solution that vibrates.Then, use conductance measurement meter (DKK.TOA CORPORATION system, EC METERCM-21P) to measure the specific conductivity (μ S/cm) of the water that from mixed solution, takes out.
[reference example 1]
In the flask that stirrer, TM, tap funnel and prolong are housed, the chloroform 1227g that packs into, 2-hydroxyethyl methacrylate 203g (1.56 moles) and pyridine 113.4g (1.43 moles) stir and process uniform mixture.Use 50 minutes and in this mixture, add 1,3,5-three (2-chloroformyl ethyl) carbonyl ethyl chlorinated isocyanurates 188.3g (0.47 mole) while cooling off.During this period, during with the liquid temperature of TM assaying reaction mixture, be to rise to 42 ℃ by 25 ℃.In addition, add in the above-claimed cpd process, the color of reaction mixture is a water white transparency.
With the solution that obtains like this 65 ℃ of ageings 1 hour.Reaction mixture adds saturated aqueous common salt 588g after making near liquid temperature to the room temperature of the reaction mixture after the ageing, makes with extra care.So though reaction mixture is the state that carries out separatory as the chloroform of organic phase mutually with water, chloroform be gonorrhoea mutually, and chloroform mutually and the interface of water exist emulsion equal, the branch fluidity is poor.
Add 1 quality % sodium hydroxide solution 588g in mutually and vibrate from the reaction mixture of separatory, removing chloroform that water obtains, leave standstill certain hour.After leaving standstill, chloroform forms interface more clearly mutually, and water and chloroform be separatory mutually.The chloroform that obtains behind the separatory has some gonorrhoeas mutually.Wash the chloroform that behind separatory, obtains once more with 1 quality % sodium hydroxide solution 588g and remove the chloroform phase that water obtains mutually.After this, use saturated aqueous common salt 588g with chloroform phase repetitive scrubbing 5 times as stated.
After this, separate (methyl) acryliccompound from chloroform mutually through well-established law.Use when having stated the ionic impurity that contains in this compound of method evaluation, the specific conductivity of water is 265 μ S/cm.By this results verification, the level that contains ionic impurity in this compound makes liquid crystal sealing agent not be suitable for electronic machine.
But, (methyl) acryliccompound that obtains like this, refining through silicagel column, can ionic impurity be reduced to the level applicable to electronic machine such as liquid crystal sealing agent.
By above can be clear and definite, compound of the present invention at room temperature is liquid, and uses the liquid crystal sealing agent of this compound to have extremely low liquid crystal pollution property, sealing agent raw material and the liquid crystal sealing agent particularly used as processing method under the liquid crystal drop are excellent.
Applicability in the industry
Can provide liquid crystal pollution property low-down liquid crystal sealing agent through the present invention.Sealing agent of the present invention is particularly suitable for processing method under the liquid crystal drop, shows that for making good display panels is effective.In addition, compound of the present invention is because considerably less, the high purity of ionic impurity also is useful as the electronic material beyond the liquid crystal sealing agent with caking agent or cementing agent.
Please advocate the right of priority of application number JP2007-205896 that applies for based on the application number JP2007-179096 of application on July 6th, 2007, the application number JP2007-179097 of application on July 6th, 2007, on August 7th, 2007 and the application number JP2008-145021 that applied on June 2nd, 2008 in this.The content of this application specification sheets and accompanying drawing record is fully incorporated in the present specification.
Claims (9)
1. liquid crystal sealing agent; It contains (methyl) acryliccompound, epoxy resin, radical polymerization initiator, potentiality epoxy hardener and the filler of formula (I) expression; Said (methyl) acryliccompound with respect to 100 mass parts; Contain the said epoxy resin of 5～60 mass parts, the said radical polymerization initiator of 0.1～10 mass parts, the said potentiality epoxy hardener of 5～40 mass parts and the said filler of 10～50 mass parts
[changing 1]
In the formula (I), A is the alkylidene group of carbonatoms 2 or 3 respectively independently, R
1～R
3Be Wasserstoffatoms or methyl independently respectively, X～Z is the alkylidene group of carbonatoms 2～4 respectively independently.
2. liquid crystal sealing agent according to claim 1, wherein, the A in the said general formula (I) is an ethylidene.
3. liquid crystal sealing agent according to claim 1; Wherein, Said (methyl) acryliccompound is for being selected from following formula (B1), (B2), (B3) and (E1) mixture of the two or more compound in the group of the compound of expression; And the ratio of the number of the LBu in said mixture base and the number of LEt base is 70: 30～30: 70
[changing 2]
In the formula (B1)～(E1), A representes the alkylidene group of carbonatoms 2 or 3 respectively independently, and LBu is the group of following formula (LBu) expression, and LEt is the group of following formula (LEt) expression,
[changing 3]
[changing 4]
4. a liquid crystal sealing agent contains (methyl) acryliccompound that formula (B) is represented,
[changing 5]
In the formula (B), X
1Be the alkylidene group of carbonatoms 3 or 4, X
2Be the alkylidene group of carbonatoms 2～4 independently respectively, R
1Be Wasserstoffatoms or methyl, R
2Be Wasserstoffatoms or methyl independently respectively.
5. liquid crystal sealing agent according to claim 4, wherein, the X in the said general formula (B)
1Be butylidene, R
1Be Wasserstoffatoms, and X
2Be butylidene or ethylidene.
6. liquid crystal sealing agent according to claim 4, wherein, the X in the said general formula (B)
1And X
2Be butylidene, and R
1And R
2Be Wasserstoffatoms.
7. the method for manufacture of (methyl) acryliccompound of formula (B) expression, it comprises:
In the presence of tertiary amine; Make compound, formula (L1m) expression of formula (Im) expression compound, (L2m) expression compound and (L3m) compound of expression in non-halogen solvent, carry out esterification, and the operation separated out as amine salt of the hydrogen halide that said reaction is generated; With
Filter the operation of the reaction mixture that obtains after the said reaction; With
Through behind the said reaction mixture that removes by filter amine salt, separatory obtains the operation of organic phase with the alkali aqueous solution washing; With
Wash the operation of said organic phase with pure water;
[changing 6]
In the formula (B), X
1The alkylidene group of representing carbonatoms 3 or 4, X
2The alkylidene group of representing carbonatoms 2～4 respectively independently, R
1Expression Wasserstoffatoms or methyl, R
2Represent Wasserstoffatoms or methyl respectively independently;
[changing 7]
In the formula (Im), A is an ethylidene, and Halo representes halogen atom;
[changing 8]
[changing 9]
[changing 10]
In the formula (L1m)～(L3m), R
1～R
3Represent Wasserstoffatoms or methyl respectively independently, X～Z representes the alkylidene group of carbonatoms 2～4 respectively independently.
8. the method for manufacture of a display panels, it comprises:
Preparation has the operation of first substrate of the seal pattern that is formed by the described liquid crystal sealing agent of claim 1; With
Under the uncured state of said seal pattern, in the seal pattern frame of said first substrate or with second substrate of said substrate subtend on the drip operation of liquid crystal; With
Operation with said first substrate and said second superimposed substrate; With
Make said liquid crystal sealing agent solidified operation.
9. the display panels that obtains of the method for manufacture through the said display panels of claim 8.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007179096 | 2007-07-06 | ||
| JP2007179097 | 2007-07-06 | ||
| JP2007-179097 | 2007-07-06 | ||
| JP2007179097 | 2007-07-06 | ||
| JP2007179096 | 2007-07-06 | ||
| JP2007-179096 | 2007-07-06 | ||
| JP2007205896 | 2007-08-07 | ||
| JP2007205896 | 2007-08-07 | ||
| JP2007-205896 | 2007-08-07 | ||
| JP2008145021 | 2008-06-02 | ||
| JP2008-145021 | 2008-06-02 | ||
| JP2008145021A JP4224526B1 (en) | 2007-07-06 | 2008-06-02 | Liquid crystal sealing agent, (meth) acrylic acid ester compound used therefor, and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101338177A CN101338177A (en) | 2009-01-07 |
| CN101338177B true CN101338177B (en) | 2012-07-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008101318590A Active CN101338177B (en) | 2007-07-06 | 2008-07-01 | Liquid crystal sealing agent, (methyl) acrylic ester compounds used and manufacturing method thereof |
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|---|---|
| JP (1) | JP4224526B1 (en) |
| KR (2) | KR100949630B1 (en) |
| CN (1) | CN101338177B (en) |
| HK (1) | HK1127077A1 (en) |
| TW (1) | TWI341428B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5337526B2 (en) * | 2009-02-24 | 2013-11-06 | 国立大学法人 東京大学 | Method for bonding metal and resin, method for producing circuit forming component using the same, and circuit forming component |
| JP5348423B2 (en) * | 2010-02-08 | 2013-11-20 | 株式会社スリーボンド | Sealant for liquid crystal dropping method |
| CN102958693B (en) * | 2010-06-21 | 2015-07-08 | Dic株式会社 | Oxygen-barrier film and adhesive |
| JP5565588B2 (en) * | 2011-03-22 | 2014-08-06 | スリーボンドファインケミカル株式会社 | Sealant for liquid crystal dropping method |
| JP5764425B2 (en) * | 2011-08-09 | 2015-08-19 | 積水化学工業株式会社 | Manufacturing method of sealant for liquid crystal display element |
| CN103207522A (en) * | 2012-01-11 | 2013-07-17 | 东洋油墨Sc控股株式会社 | Color composition for color filter and color filter |
| JP5386012B2 (en) * | 2012-06-20 | 2014-01-15 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
| JP5340474B1 (en) * | 2012-11-22 | 2013-11-13 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
| JP2014215474A (en) * | 2013-04-25 | 2014-11-17 | 東洋インキＳｃホールディングス株式会社 | Coloring composition for color filter, and color filter |
| KR101569333B1 (en) * | 2013-03-06 | 2015-11-13 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
| JP6754933B2 (en) * | 2014-04-09 | 2020-09-16 | 協立化学産業株式会社 | Liquid crystal sealant applicable to flexible liquid crystal panels |
| JP6046866B1 (en) * | 2015-05-08 | 2016-12-21 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| JP6097454B1 (en) * | 2015-09-02 | 2017-03-15 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN108051956B (en) * | 2017-12-28 | 2020-07-31 | 深圳市华星光电技术有限公司 | Manufacturing method of liquid crystal panel, frame glue and manufacturing method thereof |
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| CN1682149A (en) * | 2002-09-19 | 2005-10-12 | 三井化学株式会社 | Sealing composition for liquid crystal displays and process for production of liquid crystal display panels |
| JP3715840B2 (en) * | 1999-07-26 | 2005-11-16 | 四国化成工業株式会社 | Novel ester compound having isocyanuric acid ring and process for producing the same |
| WO2006120998A1 (en) * | 2005-05-09 | 2006-11-16 | Sekisui Chemical Co., Ltd. | Sealing material for the liquid crystal dispensing method, transferring material and liquid crystal display devices |
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| JP4531566B2 (en) * | 2002-11-01 | 2010-08-25 | 三井化学株式会社 | Liquid crystal sealant composition and method for producing liquid crystal display panel using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3715840B2 (en) * | 1999-07-26 | 2005-11-16 | 四国化成工業株式会社 | Novel ester compound having isocyanuric acid ring and process for producing the same |
| CN1682149A (en) * | 2002-09-19 | 2005-10-12 | 三井化学株式会社 | Sealing composition for liquid crystal displays and process for production of liquid crystal display panels |
| WO2006120998A1 (en) * | 2005-05-09 | 2006-11-16 | Sekisui Chemical Co., Ltd. | Sealing material for the liquid crystal dispensing method, transferring material and liquid crystal display devices |
Non-Patent Citations (3)
| Title |
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| JP特开2002－371069A 2002.12.26 |
| JP特开2003－119231A 2003.04.23 |
| JP特许3715840B2 2005.11.16 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI341428B (en) | 2011-05-01 |
| KR100949630B1 (en) | 2010-03-26 |
| HK1127077A1 (en) | 2009-09-18 |
| KR20090115843A (en) | 2009-11-09 |
| TW200903119A (en) | 2009-01-16 |
| JP2009058933A (en) | 2009-03-19 |
| KR20090004681A (en) | 2009-01-12 |
| JP4224526B1 (en) | 2009-02-18 |
| KR101343205B1 (en) | 2013-12-20 |
| CN101338177A (en) | 2009-01-07 |
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