CN101512421A

CN101512421A - Liquid crystal sealing agent, method for manufacturing liquid crystal display panel using the liquid crystal sealing agent, and liquid crystal display panel

Info

Publication number: CN101512421A
Application number: CNA2007800331021A
Authority: CN
Inventors: 宫胁孝久; 种市大树; 成濑洋; 市川真一郎; 川崎登; 高木正利
Original assignee: Mitsui Chemical Industry Co Ltd
Current assignee: Mitsui Chemicals Inc; Mitsui Chemical Industry Co Ltd
Priority date: 2006-09-07
Filing date: 2007-09-06
Publication date: 2009-08-19
Anticipated expiration: 2027-09-06
Also published as: CN101512421B; JPWO2008029893A1; TW200825113A; CN101914349B; JP5184361B2; HK1148300A1; JP5624634B2; KR101060877B1; TWI473829B; WO2008029893A1; HK1132335A1; TWI405785B; KR101049998B1; TW201329128A; KR20090067159A; CN101914349A; JP2013130873A; KR20110036112A

Abstract

This invention provides a liquid crystal sealing agent which can be applied to liquid crystal display panels. The liquid crystal sealing agent comprises (a) a compound containing a (meth)acryloyl group and a glycidyl group in its molecule and having a number average molecular weight of 500 to 2000, (b) a heat latent curing agent, (c) a radical polymerization initiator, and (d) a filler. The component (a), despite its high molecular weight, has high reactivity and latent curability, and thus simultaneously has a low level of solubility in liquid crystals, a high level of curability, and a high level of viscosity stability. Accordingly, the manufacture of a liquid crystal display panel using the liquid crystal sealing agent is advantageous in that, while maintaining the high level of productivity, the strength of adhesion between a substrate and a cured product of the liquid crystal sealing agent is high and the contamination of the liquid crystal can be suppressed on a low level, resulting in the manufacture of liquid crystal display panels which can realize a high level of display and a high quality.

Description

Liquid crystal sealing agent, use the manufacture method and the display panels of its display panels

Technical field

The present invention relates to liquid crystal sealing agent, use the manufacture method of its display panels, and display panels.

Background technology

In recent years, along with the development of miniature electric machines such as broadband propelling, digital camera and mobile phone, aspect slim, light weight, low power consumption, the needs as the display panels of flat-panel monitor are reached unusual expansion.Display panels has and enclose the structure that liquid crystal is arranged between 2 transparency carrier pasting by liquid crystal sealing agent, is by above-mentioned liquid crystal applied voltages being controlled the orientation of liquid crystal, and the modulation of regulating the light that sees through substrate comes the device of display image.

In the past, display panels is mainly made by the liquid crystal injection mode, described liquid crystal injection mode is that the sealing inlet is made display panels (for example, with reference to patent documentation 1) inject liquid crystal in having the liquid crystal pond of the inlet that is disposed between 2 plate bases after.But, increase along with the needs of display panels, now, the raising of strong request throughput rate in the manufacturing field of display panels, at this situation, with regard to the liquid crystal injection mode, need be when needing spended time and liquid crystal sealing agent is solidified 120～150 ℃ reasons such as temperature heat treated a few hours owing to the injection of liquid crystal, throughput rate is low to become big problem.

Therefore, recently, the manufacture method of the display panels of liquid crystal injection mode as an alternative, mode has caused people's attention under the liquid crystal drop.Mode is meant under the so-called liquid crystal drop, at first, uses point gum machine (dispenser) or serigraphy, forms the seal pattern of frame shape on the either party of 2 plate bases by liquid crystal sealing agent; In described frame or on another substrate, the liquid crystal of the trace that drips; In high vacuum, under the uncured state of liquid crystal sealing agent that 2 plate bases are overlapping; For the liquid crystal sealing agent irradiation ultraviolet radiation between 2 plate bases, make its precuring after, by heating liquid crystal sealing agent is carried out back curing, thereby makes the method for display panels.

By mode under this liquid crystal drop, the time that liquid crystal is enclosed in the liquid crystal pond is short, and because and use up and add hot pressing liquid crystal sealing agent is solidified, thereby also shorten the set time of liquid crystal sealing agent, so, compare with the liquid crystal injection mode, throughput rate improves.As the liquid crystal sealing agent that uses mode under this liquid crystal drop, the liquid crystal sealing agent (for example, with reference to patent documentation 2,3) of light and heat curable has been proposed.

But under the liquid crystal drop in the mode, because liquid crystal directly contacts with the liquid crystal sealing agent of its uncured state, so the composition stripping of liquid crystal sealing agent is in liquid crystal, and liquid crystal is contaminated easily.If liquid crystal is contaminated, then the demonstration of display panels significantly reduces, thereby becomes very big problem.In addition, in the solidfied material of liquid crystal sealing agent, under the residual situation that uncured portion arranged, also can cause the pollution of liquid crystal.This be because, the liquid crystal sealing agent composition of its uncured state from the uncured portion stripping to liquid crystal.If uncured portion remains in the solidfied material of liquid crystal sealing agent, then not only liquid crystal is contaminated, and the bonding strength that constitutes the solidfied material of the substrate of display panels and liquid crystal sealing agent reduces, and the possibility that causes the quality of display panels to reduce is very high.So, consider from pollution that prevents liquid crystal and the viewpoint that improves described bonding strength, expectation proposes such liquid crystal sealing agent: it at short notice, solidify and proceed to the every nook and cranny, uncured portion in the solidfied material is suppressed for minimum this degree curable is well high, and low to the solubleness of liquid crystal.

Up to now, as the liquid crystal sealing agent that improves bonding strength, proposed following liquid crystal sealing agent: its composition is part propylene acidifying (the ア Network リ Le that bisphenol A type epoxy resin and acrylic or methacrylic acid reaction are obtained

) or the epoxy resin (for example, with reference to patent documentation 4) of metering system acidifying.In addition, as the liquid crystal sealing agent that can prevent liquid crystal pollution, following liquid crystal sealing agent has been proposed: the acrylated epoxy resin that comprises have (methyl) acrylic acid series base ((メ ) ア Network リ Le base) and hydroxyl, the number of described (methyl) acrylic acid series base is more than the number (for example, with reference to patent documentation 5) of described hydroxyl.

Patent documentation 1: No. 2004/039885 pamphlet of international publication

Patent documentation 2: TOHKEMY 2001-133794 communique

Patent documentation 3: TOHKEMY 2002-214626 communique

Patent documentation 4: No. the 3162179th, Japan's special permission

Patent documentation 5: TOHKEMY 2005-195978 communique

Summary of the invention

The problem that invention will solve

But the curable of such part propylene acidifying epoxy resin of patent documentation 4 records is low, and is low molecular weight substance, therefore to the solubleness height of liquid crystal, pollutes liquid crystal easily.In addition, with regard to liquid crystal sealing agent, take much count of near the height of the viscosity stability of room temperature, this viscosity stability height suits.Its reason is, if the viscosity of liquid crystal sealing agent is constant near room temperature, is stable, then forms easily the seal pattern of desired line width on substrate, and the yield rate can improve display panels and make the time.To this, the epoxy resin of described part methyl acrylated is because near the viscosity stability room temperature is low, so be inappropriate as the raw material of liquid crystal sealing agent.

And then such acrylated epoxy resin of patent documentation 5 record although viscosity stability is very high, but then, because curable is low, so residually easily in the solidfied material of liquid crystal sealing agent has a uncured portion.Thereby, find to exist that liquid crystal is contaminated, the low problem of bonding strength of the solidfied material of liquid crystal sealing agent and the substrate that constitutes display panels.

So first purpose of the present invention is, provide a kind of not only curable high and the solubleness of liquid crystal is suppressed to very low, and can keep the liquid crystal sealing agent of high viscosity stability.In addition, second purpose of the present invention is, the liquid crystal sealing agent of the application of the invention can keep large-duty while, makes that liquid crystal pollution is prevented and the high display panels of bonding strength of the solidfied material of described liquid crystal sealing agent and the substrate that constitutes display panels.

The means of dealing with problems

The inventor etc. further investigate repeatedly, found that, the molecular weight of the compound of the raw material by being conceived to be used as liquid crystal sealing agent uses the compound that quantizes at the specialized range inner macromolecule, can address the above problem, thereby finish the present invention.

That is, can address the above problem by liquid crystal sealing agent of the present invention.

(1) a kind of liquid crystal sealing agent, it comprises: (a) have (methyl) acryloyl group and glycidyl, number-average molecular weight in the molecule and be 500～2000 compound, (b) hot latent curing agent, (c) radical polymerization initiator and (d) filler.

(2) according to the liquid crystal sealing agent of (1) record, wherein, described (a) composition is the compound of following general formula (I) expression:

In the described general formula (I),

R ₁₁～R ₁₆Represent hydrogen atom or methyl independently of one another, wherein, R ₁₃And R ₁₄Both are not methyl, R ₁₅And R ₁₆Both are not methyl,

X ₁₁And X ₁₂Represent the alkylidene of carbon number 1～10 or the group of general formula (I-1) expression independently of one another,

X ₁₃And X ₁₄The either party represent that the alkylidene of carbon number 1～10, the opposing party represent the group of general formula (I-2) expression,

A represents general formula (I-3a), (I-3b) or the group of (I-3c) representing,

P represents the alkyl of hydrogen atom, carbon number 1～10, the alkoxy or the nitro of carbon number 1～10 independently of one another,

A, b and c represent 0～3 integer independently of one another, and d represents 1～3 integer, and m represents 0～4 integer, here, a+b+c+d+m=6, and a, b and c are not 0 simultaneously,

J represents integer 0 or 1, and k and l represent 0～10 integer separately;

In the described general formula (I-1),

Y ₂₁And Y ₂₂The alkylidene of representing carbon number 1～10 independently of one another,

Y ₂₁With the O combination of acryloyl group in the described general formula (I),

N represents 1～10 integer;

In the described general formula (I-2),

Y ₃₁And Y ₃₂The alkylidene of representing carbon number 1～10 independently of one another,

Y ₃₂O combination with acryloyl group in the described general formula (I);

In the described general formula (I-3a),

R ₄₁And R ₄₂Represent the alkyl of carbon number 1～4, the alkoxy or the nitro of carbon number 1～4 independently of one another,

Z represent singly-bound ,-the O-base ,-the S-base ,-SO ₂-Ji ,-C (R ₄₃) (R ₄₄The group of)-Ji or following general formula (t1) expression, here, R ₄₃And R ₄₄The alkyl or phenyl of representing hydrogen atom, carbon number 1～4 independently of one another;

R and s represent 0～4 integer independently of one another;

In the described general formula (I-3b),

R ₅₁, R ₅₂, R ₅₃And R ₅₄Represent the alkyl of hydrogen atom, carbon number 1～4, the alkoxy or the nitro of carbon number 1～4 independently of one another;

In the described general formula (I-3c),

R ₆₁And R ₆₂The alkyl of representing hydrogen atom or carbon number 1～4 independently of one another.

(3) according to the liquid crystal sealing agent of (1) or (2) record, wherein, the compound of described general formula (I) expression is the compound more than a kind that has acryloyl group, methacryl and epoxy radicals more than 1 in the molecule concurrently.

(4) liquid crystal sealing agent of each record of basis (1)～(3); wherein, described (a) composition is to make (methyl) acrylic acid derivative that has the epoxy compound of 3 or 4 glycidyls in (i) molecule and (ii) have carboxyl react the compound with (methyl) acryloyl group and glycidyl that obtains.

(5) according to the liquid crystal sealing agent of (4) record, wherein, described (i) composition is general formula (i-1), (i-2), (i-3) or (i-4) compound of expression,

R in the described general formula (i-1) ₇₁The alkyl of expression hydrogen atom or carbon number 1～10;

R in the described general formula (i-2) ₇₁The alkyl of expression hydrogen atom or carbon number 1～10;

In the described general formula (i-4),

R ₈₁The alkyl of expression hydrogen atom or carbon number 1～10,

R ₈₂Expression hydrogen atom or methyl.

(6) according to the liquid crystal sealing agent of (4) record, wherein, described (B) composition is the compound of acrylic acid, methacrylic acid, general formula (ii-1) or general formula (ii-2) expression,

In the described general formula (ii-1),

R ₉₁Expression hydrogen atom or methyl,

X ₄₁The group of the alkylidene of expression carbon number 1～10 or following general formula (t2) expression,

X ₄₂The alkylidene of expression carbon number 1～20 or the alkylene group (alkenylene) of carbon number 2～6;

In the described general formula (t2),

Y ₅₁And Y ₅₂The alkylidene of representing carbon number 1～10 independently of one another,

Y ₅₁Represent the acryloyl group in the described general formula (ii-1),

N represents 1～10 integer;

In the described general formula (ii-2),

R ₉₂And R ₉₃Represent hydrogen atom or methyl independently of one another,

X ₆₁The group of representing following general formula (t3) expression,

X ₆₂The alkylidene of expression carbon number 1～10,

X ₆₃The alkylidene of expression carbon number 1～20 or the alkylene group of carbon number 2～6,

I and j represent integer 0 or 1 independently of one another;

In the described general formula (t3),

Y ₇₁And Y ₇₂The alkylidene of representing carbon number 1～10 independently of one another,

The O combination of the acryloyl group in CO base and the described general formula (ii-2).

(7), wherein, further comprise (e) epoxy resin or (f) either party of acyclic compound according to the liquid crystal sealing agent of each record of (1)～(6).

(8) liquid crystal sealing agent of each record of basis (1)～(7), wherein, described (c) composition is the optical free radical polymerization initiator.

(9) liquid crystal sealing agent of each record of basis (1)～(7), wherein, described (c) composition is the hot radical polymerization initiator.

(10) liquid crystal sealing agent of each record of basis (1)～(9), wherein, the use level of described (a) composition is 5～90 mass parts with respect to liquid crystal sealing agent 100 mass parts.

In addition, the problems referred to above are solved by the manufacture method of display panels of the present invention and the display panels that is obtained by this method.

(11) a kind of manufacture method of display panels, it is, by the manufacture method that liquid crystal sealing agent is pasted the display panels that 2 relative plate bases make, this method comprises:

Prepare the operation of the substrate more than 1, described substrate has the viewing area of the frame shape that the liquid crystal sealing agent by each record of (1)～(10) forms in the mode of surrounding the line of pixels column region;

With under the liquid crystal drop in the described viewing area of its uncured state or the operation on another substrate;

With described substrate and the overlapping operation of another substrate that liquid crystal is arranged;

The folded liquid crystal sealing agent of described 2 plate bases is applied light and heat, perhaps apply the either party's of light or heat operation.

(12) display panels that obtains of the manufacture method of display panels by above-mentioned (11) record.

The invention effect

According to the present invention, can provide a kind of not only viscosity stability and curable height, and the bonding strength height of the solidfied material of liquid crystal sealing agent and the substrate that constitutes display panels, and then can prevent the liquid crystal sealing agent of liquid crystal pollution.In addition, also provide a kind of liquid crystal sealing agent of the application of the invention, can keep large-duty manufacture method that obtains the display panels of high-quality display panels simultaneously.

Embodiment

Then, describe the present invention in detail.The feature of liquid crystal sealing agent of the present invention is to comprise: (a) to include (methyl) acryloyl group and glycidyl, number-average molecular weight be 500～2000 compound to molecule, (b) hot latent curing agent, (c) radical polymerization initiator, (d) filler.Below, describe for employed each composition of liquid crystal sealing agent of the present invention.

[(a) have (methyl) acryloyl group and glycidyl, number-average molecular weight in the molecule be 500～2000 compound]

Have (methyl) acryloyl group and glycidyl, number-average molecular weight in (a) of the present invention molecule and be 500～2000 compound (being also referred to as " (a) composition "), be meant that molecule contains the compound that acryloyl group or methacryl and glycidyl, number-average molecular weight are optimized in 500～2000 scopes.Described number-average molecular weight can be that standard is measured with the polystyrene by gel permeation chromatography (GPC).

Aforesaid (a) of the present invention composition, owing to contain (methyl) acryloyl group that shows the curable of hiding, even near therefore such low-temperature region room temperature, its viscosity stability is also high.On the other hand, because have reactive high glycidyl in the molecule, so, can obtain the high good liquid crystal sealing agent of curable with the raw material of (a) composition as liquid crystal sealing agent.Such liquid crystal sealing agent, its storage stability, to the coating height of substrate, even and in the such place of lightproof area, solidify and also can proceed to the every nook and cranny at short notice.The result is, can prevent liquid crystal pollution, and the bonding strength height of the solidfied material of liquid crystal sealing agent and substrate, can keep large-duty display panels that shows that property is good of making simultaneously.

In addition, (a) of the present invention composition, its number-average molecular weight is adjusted in 500～2000 the scope.Therefore, have solvent degree for liquid crystal be suppressed very low feature.Usually, the compound that macromolecule quantizes has the tendency of viscosity increased, if but number-average molecular weight is adjusted in the above-mentioned scope, then can not only have been suppressed liquid crystal pollution, and low viscous liquid crystal sealing agent.And then from reducing for the solubleness of liquid crystal and be low viscous viewpoint consideration, (a) number-average molecular weight of composition is preferably 800～1800.

Consider from the viewpoint of the reduction of the raising that takes into account the liquid crystal sealing agent curable and liquid crystal pollution,, preferably have the compound more than a kind of at least 1 acryloyl group, methacryl and epoxy radicals in the molecule concurrently as first (a) composition.Reactive high epoxy radicals etc. to contain quantity many more, then the curable of described compound is high more.In addition, the compound that can become (a) composition is quantized by macromolecule, can prevent liquid crystal pollution more.

When using (a) composition as the raw material of liquid crystal sealing agent, (a) use amount of composition with respect to liquid crystal sealing agent 100 mass parts, is preferably 5～90 mass parts, more preferably 20～60 mass parts.Thereby, the feature of not only aforesaid (a) composition is reflected as the characteristic of preferred liquid crystal sealing agent, and the solidfied material of liquid crystal sealing agent and the bonding strength that constitutes the substrate of display panels increase and become very good, can obtain the display panels of demonstration property excellence.

[first (a) composition]

As (a) of the present invention composition, the compound (being also referred to as " first (a) composition ") of preferably following general formula (I) expression.

In the described general formula (I),

R ₁₁～R ₁₆Represent hydrogen atom or methyl independently of one another,

Wherein, R ₁₃And R ₁₄Both are not methyl, and R ₁₅And R ₁₆Both are not methyl,

A represents following general formula (I-3a), (I-3b) or the group of (I-3c) representing,

J represents integer 0 or 1, and k and l represent 0～10 integer separately;

In the described general formula (I-1),

N represents 1～10 integer;

In the described general formula (I-2),

Y ₃₂O combination with acryloyl group in the described general formula (I);

In the described general formula (I-3a),

Z represent singly-bound ,-the O-base ,-the S-base ,-SO ₂-Ji ,-C (R ₄₃) (R ₄₄The group of)-Ji or following general formula (t1) expression, here, R ₄₃And R ₄₄The alkyl or phenyl of representing hydrogen atom, carbon number 1～4 independently of one another,

R and s represent 0～4 integer independently of one another;

In the described general formula (I-3b),

In the described general formula (I-3c), R ₆₁And R ₆₂The alkyl of representing hydrogen atom or carbon number 1～4 independently of one another.

The compound of formula (I) expression can followingly synthesize: make (i) benzene dicarboxylic acid acid anhydride or benzene tetracarboxylic anhydride and (ii) hydroxyl (methyl) acrylate reactions, generate carboxylic acid ester groups and carboxyl, on (iii) by the carboxyl of above-mentioned reaction generation in conjunction with polynary glycidol ether.

The example of described (i) benzene dicarboxylic acid acid anhydride, benzene tertacarbonic acid's dianhydride or benzene tricarbonic acid's acid anhydride comprises: phthalic anhydride, dodecenyl succinic phthalic anhydride, octenyl phthalic anhydride, 1,2,4,5-benzene tertacarbonic acid dianhydride.These compounds can use separately, perhaps also can multiplely be used in combination.

The example of described (ii) hydroxyl (methyl) acrylate comprises: hydroxy alkyl (carbon number 2～6) (methyl) acrylate, polyalkylene (carbon number 2～6) glycol list (methyl) acrylate, glycerine list (methyl) acrylate, glycerine diacrylate, glycerine acrylate acrylate, pentaerythrite three (methyl) acrylate, cyclohexanedimethanol list (methyl) acrylate, or (carbon number 4～8) modification of their lactone or alkylene oxide (carbon number 2～6) modified compound.These compounds can use separately, perhaps also can multiplely be used in combination.

The example of described (iii) polynary glycidol ether comprises: phenol phenolic varnish type glycidol ether, biphenyl phenolic varnish type glycidol ether, cresols phenolic varnish type glycidol ether, the bisphenol A-type glycidol ether, bisphenol-A D type glycidol ether, Bisphenol F type glycidol ether, diphenyl ether type glycidol ether, thioether type glycidol ether, oxygen thioether type glycidol ether, fluorenes type glycidol ether, diamantane fundamental mode glycidol ether, resorcinol type glycidol ether, catechol type glycidol ether, the hydroquinone type glycidol ether.These compounds can use separately, perhaps also can multiplely be used in combination.

The compound of described general formula (I) expression must be that molecule contains acryloyl group or methacryl and glycidyl.

Polynary glycidol ether is incorporated in the reaction of reactant of benzene dicarboxylic acid acid anhydride or benzene tetracarboxylic anhydride and hydroxyl (methyl) acrylate, consider from the viewpoint that promotes reaction, preferably make temperature of reaction constant in 40～180 ℃ of scopes, more preferably 50～130 ℃.Above-mentioned temperature of reaction is meant that the various raw materials with first (a) composition mix the interior temperature of reaction mixture that obtains.Temperature in the reaction mixture by the serviceability temperature meter etc., can be measured at an easy rate.

In the reaction that makes polynary glycidol ether combination, consider from the viewpoint that promotes reaction, preferably use catalyzer.Here the preferred example of employed catalyzer comprises: organic phosphine compound, tertiary amine compounds, quaternary ammonium compound, organophosphorated salt compounds, glyoxaline compound, organometallics.

The example of described organic phosphine compound comprises triphenylphosphine.The example of described tertiary amine compounds comprises triethylamine, triethanolamine.The example of described quaternary ammonium compound comprises trimethyl ammonium chloride, triethyl benzyl ammonia chloride.The example of described organophosphorated salt compounds comprises Si butyl phosphonium bromide, 4-phenyl phosphonium bromide.The example of described glyoxaline compound comprises glyoxal ethyline.In addition, the example of described organometallics comprises the octenoic acid cobalt.

The use amount of described catalyzer is preferably the amount that can promote the abundance of reacting.Specifically, with respect to the gross mass of reaction mixture, the use amount of catalyzer is preferably 0.01～5.0 quality %.

In the described reaction mixture, also can add polymerization inhibitor as required.So-called polymerization inhibitor is meant the carrying out of the polyreaction in the inhibitory reaction potpourri, the compound that reaction is stopped.Polymerization inhibitor is not particularly limited, and suitably selects for use known compound to get final product.The preferred example of polymerization inhibitor comprises: quinhydrones, methylnaphthohydroquinone, hydroquinone monomethyl ether, phenothiazine, p-tert-butyl catechol, 1,4-benzoquinone and naphthoquinones.These compounds can use separately, perhaps also can multiplely be used in combination.

In addition, can also add organic solvent in the reaction mixture.The example of preferred organic comprises: aromatic series series solvents such as toluene, dimethylbenzene, and ketone series solvents such as cyclohexane, glycol series solvents such as propylene glycol monomethyl ether, but be not particularly limited.These organic solvents can use separately, perhaps also can multiplely be used in combination.

[second (a) composition]

The preferred example of (a) of the present invention composition; except described first (a) composition, also comprise: make (methyl) acrylic acid derivative that has the epoxy compound of 3 or 4 glycidyls in (i) molecule and (ii) have carboxyl react the compound with (methyl) acryloyl group and glycidyl (also becoming " second (a) composition ") that obtains.

The method of making second (a) of the present invention composition is not particularly limited, and for example, can enumerate in the glycidyl that makes in (i) composition 1 or 2 glycidyl and the (ii) method of the carboxyl reaction in the composition.

Described (i) composition that uses as the raw material of second (a) composition, get final product so long as have the compound of 3 or 4 glycidyls in the molecule, be not particularly limited, but in order to obtain preferred (a) composition as the liquid crystal sealing agent raw material, the molecular weight of preferred (i) composition is 400～800 compound.As the preferred example of (i) composition, comprise following general formula (i-1), (i-2), (i-3) or the compound of (i-4) representing with such molecular weight.

R in the described general formula (i-1) ₇₁The alkyl of expression hydrogen atom or carbon number 1～10.

R in the described general formula (i-2) ₇₁The alkyl of expression hydrogen atom or carbon number 1～10.

In the described general formula (i-4),

R ₈₁The alkyl of expression hydrogen atom or carbon number 1～10,

R ₈₂Expression hydrogen atom or methyl.

Described R ₇₁With described R ₈₁The example of the alkyl of the carbon number 1～10 of expression comprises: hydrogen atom, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, hexyl, heptyl, octyl group, 2-ethylhexyl, nonyl and decyl.Wherein, preferred hydrogen atom, methyl, ethyl, more preferably hydrogen atom.

3 officials of described general formula (i-1) expression can epoxy compound, 4 officials of described general formula (i-2) expression can epoxy compound, can be any of commercially available product or composite.During synthetic described epoxy compound, its synthetic method is not particularly limited.During synthetic these compounds, for example, can followingly synthesize:, make 3 nucleomes or the reaction of 4 nucleomes of the phenolic varnish type compound that epihalohydrins and condensation reaction by amphyl and formaldehyde obtain according to known epoxidation reaction.In addition, the example of above-mentioned known epoxidation reaction comprises the known industrially preparing process of the existing epoxy compound that can obtain as the raw material of industry.

And then the compound of described general formula (i-3) and general formula (i-4) expression also is not particularly limited, and can be any of commercially available product or composite.

(ii) composition of the present invention, quantize from the macromolecule of described (a) composition, and described (a) composition is taken into account the high reactivity of this liquid crystal sealing agent during as the raw material of liquid crystal sealing agent and the viewpoint of high viscosity stability is considered, be preferably the compound of acrylic acid, methacrylic acid, following general formula (ii-1) or general formula (ii-2) expression.

In the described general formula (ii-1),

R ₉₁Expression hydrogen atom or methyl,

X ₄₂The alkylidene of expression carbon number 1～20 or the alkylene group of carbon number 2～6.

As the X in the described general formula (ii-1) ₄₁The example of alkylidene of preferred carbon number 1～10 comprise: methylene, ethylidene, methyl ethylidene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexa-methylene, cyclohexylidene, heptamethylene, eight methylene, nine methylene and decamethylene.Wherein, X ₄₁Preferably the alkylidene of carbon number 2～6 or described general formula (t2) expression group.

As the X in the described general formula (ii-1) ₄₂The example of alkylidene of preferred carbon number 1～20 comprise: methylene, ethylidene, methyl ethylidene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexa-methylene, cyclohexylidene, heptamethylene, eight methylene, nine methylene, decamethylene, nine methylene, ten dimethylenes, ten pentamethylenes, ten hexa-methylenes and 18 methylene.

As the X in the described general formula (ii-1) ₄₂The example of alkylene group of preferred carbon number 2～6 comprise :-CH=CH-base ,-CH=CH-CH ₂-Ji ,-CH=CH-CH ₂-CH ₂-Ji ,-CH ₂-CH=CH-CH ₂-Ji.Wherein, as X ₄₂Preferably the alkylidene of carbon numbers 1～6 such as methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexa-methylene and-the CH=CH-base, be more preferably carbon numbers 1～4 such as methylene, ethylidene, trimethylene, tetramethylene alkylidene ,-the CH=CH-base.

In the described general formula (t2),

Y ₅₁With the O combination of acryloyl group in the described general formula (ii-1),

N represents 1～10 integer.

As the Y in the described general formula (t2) ₅₁And Y ₅₂The example of alkylidene of preferred carbon number 1～10 comprise: methylene, ethylidene, methyl ethylidene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexa-methylene, cyclohexylidene, heptamethylene, eight methylene, nine methylene and decamethylene.Wherein, the alkylidene of preferred carbon number 2～6.In addition, the n in the described general formula (t2) represents 1～10 integer, more preferably 1～6 integer.

In the described general formula (ii-2),

X ₆₁The group of representing following general formula (t3) expression,

X ₆₂The alkylidene of expression carbon number 1～10,

I and j represent integer 0 or 1 independently of one another.

In the described general formula (t3), Y ₇₁And Y ₇₂The alkylidene of representing carbon number 1～10 independently of one another, the O combination of the acryloyl group in CO base and the described general formula (ii-2).

As the R in the described general formula (ii-2) ₆₁And R ₆₂The example of alkylidene of preferred carbon number 1～10 comprise: methylene, ethylidene, methyl ethylidene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexa-methylene, cyclohexylidene, heptamethylene, eight methylene, nine methylene and decamethylene.

As the X in the described general formula (ii-2) ₆₃The example of alkylidene of preferred carbon number 1～20 comprise: methylene, ethylidene, methyl ethylidene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexa-methylene, cyclohexylidene, heptamethylene, eight methylene, nine methylene, decamethylene, nine methylene, ten dimethylenes, ten pentamethylenes, ten hexa-methylenes and 18 methylene.

As the X in the described general formula (ii-2) ₆₃The example of alkylene group of preferred carbon number 2～6 comprise :-CH=CH-base ,-CH=CH-CH ₂-Ji ,-CH=CH-CH ₂-CH ₂-Ji ,-CH ₂-CH=CH-CH ₂-Ji.In addition, X ₅₃Preferably the alkylidene of carbon numbers 1～6 such as methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexa-methylene ,-the CH=CH-base, be more preferably carbon numbers 1～4 such as methylene, ethylidene, trimethylene, tetramethylene alkylidene ,-the CH=CH-base.

Y in the described general formula (t3) ₇₁And Y ₇₂Be equivalent to above-mentioned X ₆₁As Y ₇₁And Y ₇₂The example of preferred alkylidene comprise: methylene, ethylidene, methyl ethylidene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexa-methylene, cyclohexylidene, heptamethylene, eight methylene, nine methylene and decamethylene.Wherein, as alkylidene, the more preferably alkylidene of carbon number 2～6.

[manufacture method of the compound of general formula (ii-1) expression]

The compound of described general formula (ii-1) expression, sometimes also make industrial, also can make at an easy rate by " (methyl) acrylic acid derivative " and the esterification of " compound " shown in the reaction equation 1～3 as described later with 2 carboxyls with hydroxyl.Here, the example of described carboxyl also comprises acid halide group, the such precursor that can become carboxyl of anhydride group.

[reaction equation 1]

The reaction of following reaction equation 1 is, have 2 carboxyls general formula (ii-1a) expression compound and have the partial esterification reaction of compound of general formula (ii-1b) expression of hydroxyl.So-called partial esterification reaction is meant the reaction that makes only a part of carboxyl esterification of the compound that has a plurality of carboxyls in the molecule by the compound with hydroxyl.

Reaction equation 1

In the described reaction equation 1,

X ₄₂The alkylidene of expression carbon number 1～20 or the alkylene group of carbon number 2～6,

X ₄₁The group of the alkylidene of expression carbon number 1～10 or described general formula (t2) expression,

R ₉₁Expression hydrogen atom or methyl.

In the reaction of reaction equation 1, the amount ratio of the compound of the compound of described general formula (ii-1a) expression and described general formula (ii-1b) expression is not particularly limited, but owing to need be residual carboxyl in the compound of general formula (ii-1) at the final purpose product, thereby the use amount of preferred hydroxyl be less than the total amount of carboxyl.Specifically, the amount of substance of the compound of described general formula (ii-1a) expression is set at M1, when the amount of substance of the compound of described general formula (ii-1b) expression is set at M2, preferred M1/M2=1.

In the reaction of reaction equation 1, if the use amount of hydroxyl more than the total amount of carboxyl, then esterification is excessively carried out in the reaction mixture of reaction equation 1, so carboxyl is difficult to partly remain in the final purpose product.At this moment, need esterification be stopped so that making residual 1 carboxyl in the final purpose product, be very very difficult but in the stage of the conversion ratio of expecting reaction is stopped, the use amount of therefore preferred each organic group of suitably adjustment.

Described conversion ratio can be held by known analysis means.The preferred example of measuring the analysis means of conversion ratio comprises: liquid chromatography, thin-layer chromatography and IR analytical equipment.In addition, in the reaction equation 1, make the compound that the final purpose product is general formula (ii-1) expression, carry out esterification while preferably measure suitable conversion ratio for more accurate and the refining yield ground of raising.

In the partial esterification reaction of reaction equation 1, consider, preferably use esterification catalyst from the viewpoint that promotes reaction.So-called esterification catalyst is meant the catalyzer of the esterification of activating carboxy acid and alcohol.The preferred example of such esterification catalyst comprises: mineral acid, organic acid and lewis acid, be not particularly limited, and use known compound to get final product as esterification catalyst.The example of described mineral acid comprises hydrochloric acid, sulfuric acid.The organic acid example comprises methane-sulforic acid, benzene sulfonic acid, p-toluenesulfonic acid.In addition, described lewis acidic example comprises boron trifluoride and aluminium choride.

In order to promote described partial esterification reaction, the use amount of above-mentioned esterification catalyst is preferably measured fully.Consider that from the viewpoint that promotes the partial esterification reaction use amount of esterification catalyst with respect to the gross mass of reaction mixture, is preferably 0.001～50 quality %, more preferably 0.01～30 quality %.

In addition, in the described partial esterification reaction, generate water during reaction.At this moment, in order to promote described reaction, preferably from reaction mixture, remove water byproduct, removing the method for anhydrating from reaction mixture is not particularly limited, comprise and for example use benzene, this boiling point of toluene and the near solvent of water, make the method for water and this solvent azeotropic, perhaps use the method for dewatering agents such as molecular sieve.

The reaction of reaction equation 1 can be carried out in solvent-free, perhaps also can carry out in the solvent that to described reaction is inertia.The example of the suitable solvent that uses comprises hydrocarbon system solvent, ketone series solvent, ester series solvent, ether series solvent and halogen series solvent in the reaction equation 1, but is not particularly limited.

The example of described hydrocarbon system solvent comprises normal hexane, benzene or toluene.The example of described ketone series solvent comprises acetone, methyl ethyl ketone or methyl isobutyl ketone.The example of described ester series solvent comprises ethyl acetate or butyl acetate.The example of described ether series solvent comprises Anaesthetie Ether, tetrahydrofuran Huo diox.In addition, the example of described halogen series solvent comprises methylene chloride, chloroform, phenixin, 1,2-ethylene dichloride or zellon.These solvents can use separately, perhaps also can multiplely be used in combination.

The temperature of reaction of reaction equation 1 is not particularly limited, and efficiently and fully carries out the viewpoint of described partial esterification reaction in the short time and considers, preferred constant in 50～150 ℃ of scopes, more preferably 70～120 ℃.

The reaction time of reaction equation 1, according to kind, combination, the use amount of the compound of the compound of temperature of reaction, described general formula (ii-1a) expression, described general formula (ii-1b) expression or reaction dissolvent etc., suitably set and get final product, be not particularly limited.Consider the situation etc. of carrying out of described partial esterification reaction, be preferably several minutes～100 hours scope in, more preferably 0.5～50 hour, be preferably 1～20 hour especially.

[reaction equation 2]

As described below, the reaction of reaction equation 2 is two following elementary reactions: have 2 acid halide group general formula (ii-1c) expression compound and have the partial esterification reaction of compound of general formula (ii-1b) expression of hydroxyl; And make acid halide group hydrolysis residual in the reaction mixture and generate the compound that the final purpose product is general formula (ii-1).

Reaction equation 2

In the reaction equation 2,

R ₉₁Expression hydrogen atom or methyl,

COL represents acid halide group, and wherein, L represents halogen (Cl or Br).

In the reaction equation 2, need be in the final purpose product residual carboxyl.Therefore, be that the amount of preferred hydroxyl is less than the total amount of acid halide group in the described partial esterification reaction in the reaction of the phase one of reaction equation 2.Here, if the amount of hydroxyl more than the total amount of acid halide group, then need make reaction stop in the stage of the conversion ratio of expecting.But it is very difficult with the conversion ratio of expecting reaction being stopped, thereby not preferred.

Described conversion ratio can be measured by known analysis means.If during reaction equation 2 carries out, suitably measure conversion ratio, then can reaction be stopped or carrying out in the stage of the conversion ratio of expectation.The preferred example of described analysis means comprises liquid chromatography, thin-layer chromatography and IR analytical equipment.

Described partial esterification reaction can be carried out in solvent-free, perhaps also can carry out in the solvent that to described reaction is inertia.The example of such solvent comprises hydrocarbon system solvent, ketone series solvent, ester series solvent, ether series solvent and halogen series solvent.

In the reaction of described partial esterification, generate by-product hydrogen halide (for example hydrogen chloride etc.) by the reaction of acid halide group and hydroxyl.Because such hydrogen halides might make the characteristic of resultant of reaction reduce, and therefore preferably it is removed from reaction mixture.The method of removing hydrogen halides is not particularly limited, as long as use known method, considers that from features such as easy processing dehydrohalogenating agent is of great use.

The preferred example of dehydrohalogenating agent comprises organo-alkali compound or inorganic alkali compound.The example of described organo-alkali compound comprises triethylamine, pyridine, picoline, xylidin, diethylaniline, 1,4-two azo dicyclo [2.2.2] octanes (DABCO) and 1,8-two azo dicyclos [5.4.0] 11 carbon-7-alkene (DBU).In addition, the example of inorganic alkali compound comprises sodium bicarbonate, sodium carbonate, sal tartari, lithium carbonate, NaOH, potassium hydroxide, calcium hydroxide and magnesium oxide.These compounds can use separately, perhaps also can multiplely be used in combination.

The use amount of described dehydrohalogenating agent is not particularly limited, and preferably removes the required sufficient amount of hydrogen halides that generates in the reaction mixture.From the viewpoint, the use amount of dehydrohalogenating agent with respect to 1 mole of hydroxyl, is preferably 0.1～10 mole, more preferably 0.5～5 mole, is preferably 1～3 mole especially.

In the reaction equation 2, the reaction of subordinate phase is a hydrolysis reaction, is to add entry in the reaction mixture that obtains when reacting end by the partial esterification to the phase one to carry out.The method that adds water in the reaction mixture after the partial esterification reaction finishes is not particularly limited, and the disposable adding of water also can be able to be dripped.Wherein, consider, preferably the latter's who is undertaken by dropping method from making the viewpoint that reaction slowly carries out.

The use amount of water in the described hydrolysis reaction is considered from the viewpoint that promotes hydrolysis reaction, with respect to 1 mole of acid halide group remaining in the reaction mixture, is preferably 1～100 mole, more preferably 5～50 moles.

With regard to described hydrolysis reaction, when dripping water,, carry out or stop dripping the operation of water continuously with the conversion ratio of expectation by confirm the conversion ratio in the reaction mixture with known analysis means, carry out or stop thereby making to react.The example of analysis means comprises liquid chromatography, thin-layer chromatography and IR analytical equipment.

In addition, in the described hydrolysis reaction, generated by-product hydrogen halide (for example hydrogen chloride etc.) by the reaction of the water of remaining etheride and interpolation, such hydrogen halides might make the characteristic of resultant of reaction reduce.Therefore preferably remove the hydrogen halides that generates in the reaction mixture as far as possible.The method of removing hydrogen halides is not particularly limited, and considers from viewpoints such as operability, easy acquisitions, preferably uses dehydrohalogenating agent.

The example of described dehydrohalogenating agent comprises organo-alkali compound or inorganic alkali compound.Specifically, the example of described organo-alkali compound comprises triethylamine, pyridine, picoline, xylidin, diethylaniline, 1,4-two azo dicyclo [2.2.2] octanes (DABCO), 1,8-two azo dicyclos [5.4.0] 11 carbon-7-alkene (DBU).On the other hand, the example of described inorganic alkali compound comprises sodium bicarbonate, sodium carbonate, sal tartari, lithium carbonate, NaOH, potassium hydroxide, calcium hydroxide and magnesium oxide.These compounds can use separately, perhaps also can multiplely be used in combination.

The use amount of described dehydrohalogenating agent is not particularly limited, and preferably can fully remove the amount of the hydrogen halides that exists in the reaction mixture.From the viewpoint, the use amount of dehydrohalogenating agent with respect to 1 mole of remaining acid halide group, is preferably 0.5～10 mole, more preferably 1～5 mole.

In the reaction equation 2, the temperature of reaction when reaction of described partial esterification and hydrolysis reaction is not particularly limited, and from promoting the viewpoint consideration of partial esterification reaction, preferred constant in-78～150 ℃ of scopes more preferably-20～100 ℃, is preferably 0～80 ℃ especially.

As for the reaction time in the described partial esterification reaction, wait suitably to set according to the use amount of the compound of the compound of the solvent types of temperature of reaction, use or its combination, general formula (ii-1b) expression and general formula (ii-1c) expression to get final product, be not particularly limited.Consider from the viewpoint that promotes described reaction, be preferably several minutes usually～100 hours, more preferably 30 minutes～50 hours.At this moment, be 1～20 hour if make the reaction time, then can not reduce throughput rate and promote reaction, thereby preferred.

[reaction equation 3]

As follows, the reaction of reaction equation 3 is esterification by ring opening reactions of the compound of the compound of general formula (ii-1e) expression with anhydride group and general formula (ii-1b) expression with hydroxyl.In the reaction of reaction equation 3,, can easily obtain the residual compound that described general formula (ii-1) expression of carboxyl is arranged by the esterification by ring opening reaction.Therefore, in reaction equation 1～3, as the manufacture method of the compound of general formula (ii-1) expression, reaction equation 3 is most preferred.

Reaction equation 3

In the reaction equation 3,

R ₉₁Expression hydrogen atom or methyl.

In the described esterification by ring opening reaction, the proportioning of anhydride group and hydroxyl is not particularly limited, and considers from the viewpoint that promotes described esterification by ring opening reaction, the use amount of hydroxyl with respect to 1 mole of anhydride group, is preferably 0.1～10 mole, more preferably 0.5～5 mole, be preferably 0.8～3 mole especially.

Described esterification by ring opening reaction can be carried out in solvent-free, perhaps also can carry out in the solvent that to described reaction is inertia.The example of such solvent comprises hydrocarbon system solvent, ketone series solvent, ester series solvent, ether series solvent, halogen series solvent, polar solvent, is not particularly limited.

The example of described hydrocarbon system solvent comprises normal hexane, benzene, toluene or dimethylbenzene.The example of described ketone series solvent comprises acetone, methyl ethyl ketone or methyl isobutyl ketone.The example of described ester series solvent comprises ethyl acetate or butyl acetate.The example of described ether series solvent comprises Anaesthetie Ether, tetrahydrofuran Huo diox.The example of described halogen series solvent comprises methylene chloride, chloroform, phenixin, 1,2-ethylene dichloride or zellon.In addition, the example of described polar solvent comprises N, dinethylformamide, N,N-dimethylacetamide, N, N-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO) and sulfolane.These solvents can use separately, perhaps also can multiplely be used in combination.

In the described esterification by ring opening reaction, can use the described catalyst for reaction of activation as required.The example of such catalyzer comprises organic phosphine compound, tertiary amine compounds, quaternary ammonium compound, organophosphorated salt compounds, glyoxaline compound, organometallics class.

The example of described organic phosphine compound comprises triphenylphosphine.The example of described tertiary amine compounds comprises triethylamine, triethanolamine.The example of described quaternary ammonium compound comprises trimethyl ammonium chloride, triethyl benzyl ammonia chloride.The example of described organophosphorated salt compounds comprises Si butyl phosphonium bromide, 4-phenyl phosphonium bromide.The example of described glyoxaline compound comprises glyoxal ethyline.In addition, the example of described organometallics comprises the octenoic acid cobalt.These compounds can use separately, perhaps also can multiplely be used in combination.

The use amount of described catalyzer, the viewpoint that obtains sufficient reaction velocity during from reaction is considered, with respect to the quality of reaction mixture, is preferably in the scope of 0.01～10.0 quality %, more preferably 0.01～5.0 quality %.

The temperature of reaction of described esterification by ring opening reaction is not particularly limited, and considers preferred constant in 0～200 ℃ of scope, more preferably 0～150 ℃ from the viewpoint that makes described reaction high-level efficiency and carry out with producing effect.

As for the reaction time of described esterification by ring opening reaction, just wait suitably to set to get final product, be not particularly limited according to the use amount of the compound of temperature of reaction, general formula (ii-1b) expression, the compound of general formula (ii-1e) expression etc. or solvent types or combination.From described reaction viewpoint efficient and that carry out is considered with producing effect, usually, be preferably several minutes～several 10 hours.

In addition, in the reaction equation 3, also can be on one side confirm conversion ratio by known analysis means, with arbitrarily conversion ratio make reaction carry out or stop on one side.The example of described analysis means comprises liquid chromatography, thin-layer chromatography and IR analytical equipment.

[compound of general formula (ii-2) expression]

Then, the compound of mutual-through type (ii-2) expression describes.The compound of described general formula (ii-2) expression can replace with (methyl) acryloyl group derivant with hydroxyl of following general formula (ii-2a) expression by the compound that the general formula (ii-1b) that will use in the above-mentioned reaction equation 1～3 is represented and make.

In the described general formula (ii-2a),

X ₆₁The group of representing described general formula (t3) expression,

X ₆₂The alkylidene of expression carbon number 1～10,

I and j represent integer 0 or 1 independently of one another.

[reaction equation 4]

The compound of described general formula (ii-2a) expression can be made according to following reaction equation 4.

Reaction equation 4

In the reaction equation 4,

X ₆₁The group of representing described general formula (t3) expression,

X ₆₂The alkylidene of expression carbon number 1～10,

I and j represent integer 0 or 1 independently of one another.

The reaction of above-mentioned reaction equation 4 is; the compound of described general formula (ii-2b) expression by having the glycidyl ether and have the esterification by ring opening reaction of compound of described general formula (ii-2c) expression of alcohol radical, the reaction of (methyl) acryloyl group derivant of synthetic described general formula (ii-2a) expression with hydroxyl.

The esterification by ring opening reaction of reaction equation 4 can be carried out in solvent-free, perhaps also can carry out in the solvent that to described reaction is inertia.The example of such solvent comprises: hydrocarbon system solvents such as normal hexane, benzene, toluene or dimethylbenzene, ketone series solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone, ester series solvents such as Anaesthetie Ether, tetrahydrofuran Huo diox, methylene chloride, chloroform, phenixin, 1, halogen series solvents such as 2-ethylene dichloride or zellon, N, dinethylformamide, N, N-dimethyl acetamide, N, N-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO) and sulfolane isopolarity solvent.These solvents can use separately, perhaps also can multiplely be used in combination.

In the described esterification by ring opening reaction, can use the described catalyst for reaction of activation as required.The example of such catalyzer comprises organic phosphine compounds such as triphenylphosphine, tertiary amines such as triethylamine, triethanolamine, quaternary ammonium salt such as trimethyl ammonium chloride, triethyl benzyl ammonia chloride, organophosphorus salts such as four butyl phosphonium bromides, 4-phenyl phosphonium bromide, imidazoles such as glyoxal ethyline, organometallics classes such as octenoic acid cobalt.These catalyzer can use separately, perhaps also can multiplely be used in combination.

The use amount of described catalyzer, the viewpoint that the time obtains sufficient reaction velocity from reaction consider, the gross mass with respect to the reaction mixture of reaction equation 4 is preferably 0.01～10.0 quality %, more preferably 0.01～5.0 quality %.Among the present invention, when using multiple activation solvent, with the use amount of its total use amount as described catalyzer.

The temperature of reaction of described esterification by ring opening reaction is not particularly limited, and gets final product so long as can carry out the sufficient temperature of described reaction.Described temperature of reaction is constant in 0～200 ℃ of scope preferably, more preferably 0～150 ℃.

As for the reaction time of described esterification by ring opening reaction, wait suitably to set according to kind, combination, the use amount of the use amount of the compound of temperature of reaction, the compound that is used as described general formula (ii-2b) expression of raw material, general formula (ii-2c) expression or solvent or catalyzer etc. to get final product, be not particularly limited.Consider from the viewpoint that described sufficient reacting is carried out, usually, be preferably several minutes～several 10 hours.

In addition, in the reaction equation 4, also can be on one side confirm conversion ratio by known analysis means, with arbitrarily conversion ratio make reaction carry out or stop on one side.The example of described analysis means comprises liquid chromatography, thin-layer chromatography and IR analytical equipment.

[reaction equation 5]

Preferred second (a) of the present invention composition for example can obtain by the reaction shown in the following reaction equation 5.

Reaction equation 5

In the above-mentioned reaction equation 5,

R ₇₁The alkyl of expression hydrogen atom or carbon number 1～10,

R ₉₁Expression hydrogen atom or methyl.

The reaction of reaction equation 5 is; with the compound of described general formula (i-1) expression and the compound of described general formula (ii-1) expression with carboxyl with 3 glycidyls as raw material; carry out the esterification by ring opening reaction one by one, thereby finally generate the reaction (being also referred to as " esterification by ring opening reaction one by one ") of the compound of general formula (iii-2) expression that has glycidyl and (methyl) acryloyl group in the molecule.

In the described reaction of esterification by ring opening one by one, at first, with the compound of described general formula (i-1) expression as initiation material, carboxyl generation esterification by ring opening reaction in the compound of 1 glycidyl that this compound has and described general formula (ii-1) expression, generating 2 officials can epoxy resin be the compound of general formula (iii-1).Then, the esterification by ring opening reaction further takes place in the compound of the compound of general formula (iii-1) expression and general formula (ii-1) expression, finally generates the compound of general formula (iii-2) expression.

The compound of described general formula (iii-2) expression, from the solubleness to liquid crystal suppress very low aspect, high molecular body preferably.In addition, because have glycidyl in the molecule, to the reactive height of epoxide hardening agent, so even also show high curable in the such place of lightproof area.

In the described reaction of esterification by ring opening one by one, the proportioning of glycidyl and carboxyl is not particularly limited, but in reaction equation 5, need be residual glycidyl in the compound of described general formula (iii-1) and the compound that the final purpose product is described general formula (iii-2) in reaction intermediate.Therefore, the use amount of preferred carboxyl is less than the use amount of glycidyl.Specifically, with respect to 1 mole of the compound of described general formula (i-1) expression, the use amount of the compound of described general formula (ii-1) expression is preferably 1～2.8 mole, more preferably 1.3～2.5 moles.

Relative therewith, in the reaction equation 5, if the use amount of carboxyl is more than the use amount of glycidyl, then can promote reaction, therefore 3 glycidyls and all carboxyl generation esterification by ring opening reactions that have of the compound of general formula (i-1) expression, the possibility that generates the compound that following general formula (iv) represents is high.The compound that general formula is (iv) represented is owing to be the high molecular body, thereby the solubleness of liquid crystal is suppressed to very low, and but then, it does not have the reactive high glycidyl with the epoxide hardening agent.Therefore, described compound possibility curable is very low, thereby is not suitable as the raw material of liquid crystal sealing agent.

For partly residual glycidyl in the compound of representing at the compound and the general formula (iii-2) of general formula (iii-1) expression, reaction is stopped, be very difficult but accurately stop to react with the conversion ratio of expecting.Thereby, when carrying out reaction equation 5, preferably adjust the proportioning of glycidyl and carboxyl as mentioned above.

Described general formula (iv) in,

X ₄₁The group of the alkylidene of expression carbon number 1～10 or above-mentioned general formula (t2) expression,

R ₉₁Expression hydrogen atom or methyl.

Described conversion ratio can be grasped by known analysis means.The preferred example of measuring the analysis means of conversion ratio comprises: liquid chromatography, thin-layer chromatography and IR analytical equipment.

The described reaction of esterification by ring opening one by one can be carried out in solvent-free, perhaps also can carry out in the solvent that to described reaction is inertia.The example of such solvent comprises hydrocarbon system solvent, ketone series solvent, ester series solvent, ether series solvent, halogen series solvent, polar solvent.

In the described reaction of esterification by ring opening one by one, can use the described catalyst for reaction of activation as required.The example of such catalyzer comprises organic phosphine compound, tertiary amine compounds, quaternary ammonium compound, organophosphorated salt compounds, glyoxaline compound, organometallics.

In the described catalyzer, the example of described organic phosphine compound comprises triphenylphosphine.The example of described tertiary amine compounds comprises triethylamine, triethanolamine.The example of described quaternary ammonium compound comprises trimethyl ammonium chloride, triethyl benzyl ammonia chloride.The example of described organophosphorated salt compounds comprises Si butyl phosphonium bromide, 4-phenyl phosphonium bromide.The example of described glyoxaline compound comprises glyoxal ethyline.The example of described organometallics comprises the octenoic acid cobalt.These compounds can use separately, perhaps also can multiplely be used in combination.

The use amount of described catalyzer, the viewpoint that obtains sufficient reaction velocity during from reaction is considered, with respect to the gross mass of reaction mixture in the reaction equation 5, is preferably 0.01～10.0 quality %, more preferably 0.01～5.0 quality %.

The temperature of reaction of the described reaction of esterification by ring opening one by one is not particularly limited, and gets final product so long as carry out the sufficient temperature of described reaction, preferably makes described temperature of reaction constant in 0～200 ℃ of scope, more preferably 0～150 ℃.

The reaction time of described esterification by ring opening one by one reaction, wait suitably to set and get final product according to the kind of the use amount of the compound of temperature of reaction, use or solvent or catalyzer etc. or combination, use amount, be not particularly limited.Consider from the viewpoint that promotes described reaction, be preferably several minutes～several 10 hours.

Make the mode that has the compound of glycidyl and (methyl) acryloyl group in the molecule by the reaction of the esterification by ring opening one by one shown in the reaction equation 5 and be not limited to aforesaid way.Promptly, as initiation material is (i) composition, except general formula (i-1), can also use general formula (i-2), (i-3) or (i-4), perhaps, as the described (ii) composition of general formula (ii-1) expression, except the compound of described general formula (ii-1) expression, can also use acrylic acid, methacrylic acid.These compounds are suitably selected to be used in combination to get final product.

(a) of the present invention composition, the theoretical dissolution degree parameter (SP value) of its Fedors is preferably at 10～13 (cal/cm ³) ^1/2Scope.Computing method with regard to solubility parameter (SP value), there are various skills and computing method, the theoretical dissolution degree parametric optimization that uses among the present invention is based on the parameter that the computing method of Fedors invention obtain (with reference to then Hui Chi of Japan, vol.22, no.10 (1986) (53) (566) (Journal of Adhesion Society of Japan) etc.).In these computing method,, therefore can easily calculate solubility parameter because do not need the value of density.The theoretical dissolution degree parameter (SP value) of above-mentioned Fedors is calculated by following formula.

SP value=(∑ Δ e1/ ∑ Δ v1) ^1/2

Wherein, ∑ Δ e1=(Δ H-RT), ∑ Δ v1=mole capacity and

Here, if solubility parameter (SP value) is in above-mentioned scope, then the compound of the described general formula (i-1) of (a) composition expression diminishes to the solubleness of liquid crystal, and the possibility of polluting liquid crystal is suppressed very lowly, so the demonstration raising of display panels and very good.

When synthesizing (a) of the present invention composition with a plurality of compounds as raw material, theoretical dissolution degree parameter (SP value) can be calculated based on the mole fraction sum of each raw material that mixes.The theoretical dissolution degree parametric optimization of calculating here is in above-mentioned scope.

Below, can describe with the composition of above-mentioned (a) composition and usefulness for raw material as liquid crystal sealing agent.

(b) hot latent curing agent

The hot latent curing agent of what is called of the present invention, mix even be meant with hosts such as epoxy resin, usually preserve under the state of resin (room temperature, luminous ray inferior) also not can with functional group's reaction such as epoxy radicals, but the functional group is presented the hardening agent of reactivity by heat or light.

By making liquid crystal sealing agent contain this hot latent curing agent, the viscosity stability of liquid crystal sealing agent improves.Thereby the viscosity stability under the room temperature of described liquid crystal sealing agent obtains good maintenance, so liquid crystal sealing agent is being filled into screen process press or point gum machine, when drawing seal pattern on substrate, can use long-term and stably.Like this, if increase the serviceable life of liquid crystal sealing agent, then can realize the raising of throughput rate in the display panels manufacturing.

As hot latent curing agent of the present invention, the hot latent epoxy resin curing agent of curing accelerator effect is played in preferred use to the epoxy radicals in (a) composition and (e) described later epoxy resin.So-called hot latency epoxy resin is meant to possess the compound that epoxy radicals has hot latency as the functional group.

As hot latent curing agent of the present invention, can use known material.Wherein, having amino amine in the preferred molecule is hot latent curing agent.Amine is hot latent curing agent, is meant to have amino in the molecule, shows the compound of hot latency.This amine is hot latent curing agent, near room temperature not with epoxy reaction, relative therewith, by heating rapidly and epoxy reaction.In addition, usually, amine is that the solidfied material that hot latent curing agent and epoxy resin reaction obtain is a cross-linked polymer, and is therefore low to the solubleness of liquid crystal.The curing rate that influenced by amine is according to kind of kind, use level or the epoxy resin of amine etc. and different.But the amine that the present invention preferably uses is that hot latent curing agent is not particularly limited, from being suitably to select for use the known compound of hot latent curing agent to get final product as amine.

Amine is that the preferred example of hot latent curing agent comprises organic acid dihydrazide compound, imidazoles and derivant thereof, dicyandiamide, aromatic amine, epoxy radicals modified polyamine and polyamino urea etc.These can use separately, perhaps also can multiplely be used in combination.

And then, as hot latent curing agent, preferred especially its fusing point or be material more than 75 ℃ by the softening point temperature that ball and ring method obtains.Viscosity stability under the liquid crystal sealing agent that contains this hot latent curing agent, room temperature is able to keep more well, and further increase the serviceable life when therefore making display panels.

Fusing point or be that amine more than 75 ℃ is that the example of hot latent curing agent comprises dicyandiamide compounds, organic acid dihydrazide and imdazole derivatives by the softening point temperature that ball and ring method obtains.

The example of described dicyandiamide compounds comprises dicyandiamide (209 ℃ of fusing points).The example of described organic acid dihydrazide comprises adipic dihydrazide (181 ℃ of fusing points), 1, two (diazanyl carbonyl the ethyl)-5-isopropyl hydantoins (120 ℃ of fusing points) of 3-.The example of described imdazole derivatives comprises 2,4-diamido-6-(2 '-ethyl imidazole-(1 ')) ethyl triazine (215～225 ℃ of fusing points), 2-phenylimidazole (137～147 ℃ of fusing points).These compounds can use separately, perhaps also can multiplely be used in combination.

The use level of hot latent curing agent with respect to liquid crystal sealing agent 100 mass parts, is preferably 1～25 mass parts, and described use level is 5～15 mass parts more preferably.If the use level of hot latent curing agent is in above-mentioned scope, then the viscosity stability of liquid crystal sealing agent is good.In addition, when described liquid crystal sealing agent is applied to display panels, because the liquid crystal sealing agent that solidifies and the bonding strength height of substrate, so the bonding reliability of display panels improves.Hot latent curing agent used in the present invention preferably waits by WATER-WASHING METHOD, recrystallization method and carries out the high-purity processing.

The liquid crystal sealing agent of the present invention that contains this hot latent curing agent, the liquid type that can be used as effectively uses.The liquid crystal sealing agent of a so-called liquid type is meant major component and the such curing promotion composition stage before use evenly mixing in advance of hot latent curing agent such as epoxy resin, the liquid crystal sealing agent of excellent storage stability.So-called excellent storage stability, even the meaning is to preserve below room temperature, curing reaction also takes place in liquid crystal sealing agent hardly.Specifically, the increment rate of the viscosity of liquid crystal sealing agent when preserving 5 days for 25 ℃ is preferably preserved below 2 times of viscosity of preceding liquid crystal sealing agent.

(c) radical polymerization initiator

So-called radical polymerization initiator of the present invention is meant that absorption produces the compound of free radical from the energy of light or heat.The example of radical polymerization initiator comprises optical free radical polymerization initiator, hot radical polymerization initiator.

Among the present invention,, preferably use the optical free radical polymerization initiator as described (c) composition.So-called optical free radical polymerization initiator is meant the compound that is subjected to rayed and produces free radical,, absorbs luminous energy that is, decomposes, and produces the compound of free radical activity kind.The liquid crystal sealing agent that contains this optical free radical polymerization initiator, because can solidify, so when being used under the liquid crystal drop mode, do not need the back to solidify to wait to solidify to handle by rayed, and, thereby can realize the raising of throughput rate because can shorten the set time of liquid crystal sealing agent.

The optical free radical polymerization initiator can use known compound, is not particularly limited.Its example comprises benzoin based compound, acetophenone compounds, benzophenone compound, thioxanthones compounds, α-acyl group oxime ester compound, benzoin compounds, benzoin ether compounds, benzoyl formic acid ester type compound, benzil compounds, azo based compound, anthraquinone analog compound, diphenyl sulfide based compound, acylphosphine oxide based compound, organic pigment based compound, iron-phthalocyanine based compound.These can use separately, perhaps also can multiplely be used in combination.

Among the present invention, as mentioned above, also can use the hot radical polymerization initiator as described (c) composition.So-called hot radical polymerization initiator is meant that the heating back produces the compound of free radical,, absorbs heat energy that is, decomposes, and produces the compound of free radical activity kind.

If with this hot radical polymerization initiator and optical free radical polymerization initiator and be used for making liquid crystal sealing agent, then after adhesive substrate, further heat after making its precuring by light, thereby liquid crystal sealing agent is fully solidified.At this moment, if only utilize light that liquid crystal sealing agent is solidified, then at the lightproof area that does not have the light direct irradiation, liquid crystal sealing agent is as uncured portion and residual, if but when solidifying, use heat, then no matter whether at lightproof area, can make and solidify each corner that proceeds to liquid crystal sealing agent.Therefore, when described liquid crystal sealing agent was applied to display panels, it was extremely low to obtain liquid crystal pollution, and the display panels of the bonding strength excellence of liquid crystal sealing agent that solidifies and substrate.

The hot radical polymerization initiator can use known compound, is not particularly limited.Its example comprises organic peroxide, azo-compound, replacement ethane compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds.

The example of organic peroxide comprises the compound of classifying in ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxy dicarbonate.

The example of organic peroxide is as follows.Numeral in the bracket is 10 hours half life temperatures (the pure medicine of reference and light Co., Ltd. products catalogue, API Corporation company's products catalogue and above-mentioned polymer handbook).In addition, the example of ketone peroxide class comprises methyl-ethyl-ketone peroxide (109 ℃), cyclohexanone superoxide (100 ℃).

The example of azo-compound comprises that water-soluble azo is that hot radical polymerization initiator, oil-soluble azo are that hot radical polymerization initiator, polymeric azo are the hot radical polymerization initiator.

Water-soluble azo is that the example of hot radical polymerization initiator comprises 2, two (2-(2-imidazoline-2-yl) propane) the di-sulfate dihydrates (46 ℃) of 2 '-azo, 2, two (N-(2-the carboxy ethyl)-2-methyl-prop amidine) hydrates (57 ℃) of 2 '-azo, 2, two (2-(1-(2-the hydroxyethyl)-2-imidazoline-2-yl) propane) dihydrochlorides (60 ℃) of 2 '-azo, 2, two (1-imino group-1-pyrrolidinyl-2-ethyl propane) dihydrochlorides (67 ℃) of 2 '-azo, 2,2 '-azo two (2-methyl-N-(2-hydroxyethyl) propionamide) (87 ℃), 2, two (2-(2-imidazoline-2-yl) propane) dihydrochlorides (44 ℃) of 2 '-azo, 2, two (the 2-methyl-prop amidine) dihydrochlorides (56 ℃) of 2 '-azo, 2,2 '-azo two (2-(2-imidazoline-2-yl) propane) (61 ℃), 2,2 '-azo two (2-methyl-N-(1, two (the hydroxymethyl)-2-hydroxyethyls of 1-) propionamide) (80 ℃).

The oil-soluble azo is that the example of hot radical polymerization initiator comprises 2, two (the 4-methoxyls-2 of 2 '-azo, the 4-methyl pentane nitrile) (30 ℃), dimethyl-2, two (2 Methylpropionic acid ester) (66 ℃) of 2 '-azo, 1,1 '-azo two (cyclohexane-1-nitrile) (88 ℃), 1,1 '-((cyano group-1-Methylethyl) azo) formamide (104 ℃), 2,2 '-azo two (N-cyclohexyl-2-methyl propanamide) (111 ℃), 2,2 '-azo two (2, the 4-methyl pentane nitrile) (51 ℃), 2, two (2-methylbutyronitrile) (67 ℃) of 2 '-azo, 2,2 '-azo two (N-(2-propenyl)-2-methyl propanamide) (96 ℃), 2,2 '-azo two (N-butyl-2-methyl propanamide) (110 ℃).

Polymeric azo is that the example of hot radical polymerization initiator comprises that containing dimethyl silicone polymer unit polymeric azo is the hot radical polymerization initiator, contain polyglycol unit polymeric azo is the hot radical polymerization initiator.In addition, these hot radical polymerization initiators can use separately, perhaps also can multiplely be used in combination.

Produce the kind of the energy of free radical, no matter light or heat can, (c) use level of composition with respect to liquid crystal sealing agent 100 mass parts, is preferably 0.01～5 mass parts.If making the use level of radical polymerization initiator is more than 0.01 mass parts, then light or the heat by suitably selecting to the liquid crystal sealing agent irradiation can make described liquid crystal sealing agent solidify at short notice.In addition, be below 5 mass parts if make the use level of (c) composition, then the coating of liquid crystal sealing agent is good, and can access the solidfied material that evenly solidifies by rayed.

(d) filler

So-called filler of the present invention is meant for the viscosity by the control liquid crystal sealing agent, improves the intensity make liquid crystal sealing agent solidify the solidfied material that obtains or suppress linear expansivity, thereby improves the purpose such as bonding reliability of liquid crystal sealing agent and the filling agent that uses.

The preferred filler that uses is not particularly limited among the present invention, comprises normally used known material in the field of electronic materials.The example of filler comprises inorganic fillers such as lime carbonate, magnesium carbonate, barium sulphate, magnesium sulphate, alumina silicate, zirconium silicate, iron oxide, titanium dioxide, aluminium oxide (alumina), zinc paste, silicon dioxide, potassium titanate, porcelain earth, talcum, flake asbestos, silica flour, mica, glass fibre, talcum, glass microballoon, sericite atlapulgite, bentonitic clay, aluminium nitride, silicon nitride.

As filler of the present invention, as long as in the scope of the characteristic of not damaging liquid crystal sealing agent, also can use polymethylmethacrylate, polystyrene, constitute their monomer and known organic fillers such as the multipolymer that obtains of other monomer copolymerizations, polyester micropartical, polyurethane particulate, rubber particle.

Wherein, consider preferred inorganic filler from the viewpoint that improves linear expansion coefficient, shape retention.Among this inorganic filler, for reasons such as UV permeability height, more preferably silicon dioxide, talcum.In addition, no matter inorganic or organic, the employed filler of liquid crystal sealing agent of the present invention also can be to carry out the material that graft modification obtains with epoxy resin or silane coupling agent etc.

The shape of filler is not particularly limited, and can be any of setting thing such as spherical, tabular, needle-like or non-setting thing.In addition, the maximum particle diameter of filler is preferably below the 6 μ m, more preferably below the 2 μ m.The particle diameter of filler can be measured by laser diffractometry.If the liquid crystal sealing agent that will contain the filler of this particle diameter is used for the manufacture method of display panels, then can form the extraordinary liquid crystal of the dimensional stability pond of pond spacing.

The use level of filler with respect to 100 mass parts of the liquid crystal sealing agent except that filler, is preferably 1～40 mass parts, more preferably 10～30 mass parts.Through adjusting the liquid crystal sealing agent of filler use level like this, good to the coating of substrate.In addition, filler also can and be used with light-cured resin.Like this and used the photo-curable of liquid crystal sealing agent of filler and light-cured resin good, solidify at short notice.And then because the width of pond spacing remains constant, so dimensional stability is good.

In the liquid crystal sealing agent of the present invention, can also further comprise (e) epoxy resin and (f) acyclic compound or (e) epoxy resin or (f) either party of acyclic compound.

(e) epoxy resin

So-called epoxy resin of the present invention is meant the compound that has the epoxy radicals more than 1 in the molecule.The example of the preferred epoxy of using in the liquid crystal sealing agent of the present invention comprises the polynary glycidyl ether compound of aromatic series, novolac resin, the polynary glycidyl ether compound of phenolic varnish type, glycidyl ether compound class.

The example of the polynary glycidyl ether compound of described aromatic series comprises the compound that aromatic diol compounds and the glycols compound by various glycol modification and chloropropylene oxide reaction thereof obtain.The example of described aromatic diol compounds comprises bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, bisphenol-A D type epoxy resin.In addition, the example of described glycol comprises ethylene glycol, propylene glycol, aklylene glycol.

The example of described novolac resin comprises the compound by phenol or cresols and formaldehyde-derived.The example of the polynary glycidyl ether compound of described phenolic varnish type comprises that with polyalkenyl phenol or its multipolymer etc. be the polyphenol compound of representative and the compound that the chloropropylene oxide reaction obtains.In addition, the example of described glycidyl ether compound comprises the xylylene phenol resin.

Wherein, the example of preferred (e) epoxy resin comprises cresols phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, triphenol methane type epoxy resin, triphenol ethane type epoxy resin, triphenol type epoxy resin, dicyclopentadiene-type epoxy resin, biphenyl type epoxy resin.The example of particularly preferred epoxy resin comprises these acrylic rubber modified epoxy.In the liquid crystal sealing agent of the present invention, these epoxy resin can use separately, perhaps also can multiplely be used in combination.

In addition, the epoxy resin that uses among the present invention, preferably its softening point temperature of measuring by ball and ring method is more than 40 ℃, and more preferably its weight-average molecular weight is 1000～10000.This epoxy resin is low for dissolubility, the diffusivity of liquid crystal.Therefore, the demonstration of the display panels of making by the liquid crystal sealing agent that has used described epoxy resin is good.

The weight-average molecular weight of epoxy resin can be that standard is measured with the polystyrene by gel permeation chromatography (GPC) for example.And then as epoxy resin, the preferred use by molecularly distilled etc. carried out the material that high-purityization has been removed impurity.

The use level of epoxy resin with respect to liquid crystal sealing agent 100 mass parts, is preferably 5～50 mass parts, more preferably 10～30 mass parts.The thermotolerance of such liquid crystal sealing agent is good.But, if described use level less than 5 mass parts, then curing rate is slack-off, if surpass 50 mass parts, then the thermotolerance of liquid crystal sealing agent reduces sometimes.

(f) acyclic compound

So-called acyclic compound of the present invention (ア Network リ Le compound) is meant the compound of the acrylic acid series base (ア Network リ Le base) that has in the molecule more than 1.Acyclic compound of the present invention also comprises (methyl) acryl resin that methacrylic resin is such.The example of acyclic compound comprises acrylate and/or methacrylate monomers or their oligomer, is not particularly limited, and comprises known compound.The water tolerance of liquid crystal sealing agent that contains acyclic compound like this is fabulous, if therefore be applied to display panels, the solidfied material that then can obtain described liquid crystal sealing agent is high with the bonding strength of the substrate that constitutes display panels, and the high-quality display panels of moisture-proof reliability excellence.

The preferred example of acyclic compound (f) composition comprises following material.

The diacrylate and/or the dimethylacrylate of polyglycol, propylene glycol, polypropylene glycol etc.; The diacrylate and/or the dimethylacrylate of three (2-hydroxyethyl) chlorinated isocyanurates; To oxirane or epoxypropane and diacrylate and/or the dimethylacrylate of the glycol that obtain of 1 mole of neopentyl glycol addition more than 4 moles; To the oxirane of 2 moles of 1 mole of bisphenol-A additions or epoxypropane and the diacrylate and/or the dimethylacrylate of the glycol that obtains; To oxirane or two or triacrylate of epoxypropane and the triol that obtain and/or two or trimethyl acrylic ester of 1 mole of trimethylol propane addition more than 3 moles; To oxirane or epoxypropane and diacrylate and/or the dimethylacrylate of the glycol that obtain of 1 mole of bisphenol-A addition more than 4 moles; Three (2-hydroxyethyl) chlorinated isocyanurates triacrylate and/or trimethyl acrylic ester; Trimethylolpropane triacrylate and/or trimethyl acrylic ester, or its oligomer; Pentaerythritol triacrylate and/or trimethyl acrylic ester, or its oligomer; The polyacrylate of dipentaerythritol and/or polymethacrylate; Three (acryloyl group ethyl) chlorinated isocyanurates; Caprolactone modification three (acryloxy ethyl) chlorinated isocyanurates; Caprolactone modification three (methacryloxyethyl) chlorinated isocyanurates; The polyacrylate of alkyl-modified dipentaerythritol and/or polymethacrylate; The polyacrylate of caprolactone modification dipentaerythritol and/or polymethacrylate; Hydroxyl trimethylace tonitric neopentylglycol diacrylate and/or dimethylacrylate; Caprolactone modification hydroxyl trimethylace tonitric neopentylglycol diacrylate and/or dimethylacrylate; Oxirane modified phosphate acrylate and/or dimethylacrylate; Oxirane modified phosphate acrylate and/or dimethylacrylate; Oxirane modification alkylation p thiodipropionic acid ester and/or dimethylacrylate; The low-polyacrylate of neopentyl glycol, trimethylolpropane, pentaerythrite and/or oligomeric methacrylate.

In addition, the example of acyclic compound (f) composition also comprises the resin of whole epoxy radicals of cresols phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, triphenol methane type epoxy resin, triphenol ethane type epoxy resin, triphenol type epoxy resin, dicyclopentadiene-type epoxy resin, biphenyl type epoxy resin etc. and complete (methyl) acrylated of epoxy resin quilt that the reaction of (methyl) acrylic acid obtains.These compounds can use separately, perhaps also can multiplely be used in combination.

Make when containing acyclic compound (f) composition in the liquid crystal sealing agent, preferably with epoxy resin (e) composition and usefulness.At this moment, (e) use level of composition with respect to (f) composition 100 mass parts, is preferably 20～200 mass parts.If by light or heat this liquid crystal sealing agent is solidified, then can access the high solidfied material of glass temperature (Tg).The Tg of the solidfied material of liquid crystal sealing agent can measure by Measurement of Dynamic Viscoelasticity device (DMA).In addition, for obtaining purposes such as highly purified liquid crystal sealing agent, (f) composition preferably uses by WATER-WASHING METHOD etc. by the material of high-purityization.

The example of preferred (methyl) acrylic modified epoxy resin that uses comprises among the present invention: for example make epoxy resin and (methyl) acrylic or methacrylic acid phenenyl ester react the resin that obtains under the base catalyst.The example of described epoxy resin comprises bisphenol-type epoxy resin or phenolic resin varnish type epoxy resin.

With (methyl) acrylic modified epoxy resin of epoxy radicals and (methyl) acrylic acid series base, described (e) composition is shown high intermiscibility in the skeleton.So, contain the liquid crystal sealing agent of (methyl) acrylic modified epoxy resin and described (e) composition, its glass temperature (Tg) height, permanance and thermotolerance height are excellent.And then the bonding strength of the substrate of the solidfied material of this liquid crystal sealing agent and formation display panels increases.

Example as the epoxy resin of the raw material of (methyl) acrylic modified epoxy resin comprises cresols phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, triphenol methane type epoxy resin, triphenol ethane type epoxy resin, triphenol type epoxy resin, dicyclopentadiene-type epoxy resin, biphenyl type epoxy resin.In addition, (methyl) acrylic modified epoxy resin preferably passes through molecularly distilled, washing method etc. by high-purityization.

(g) other adjuvants

In addition, liquid crystal sealing agent of the present invention also can comprise adjuvant as required.The example of the preferred adjuvant that uses comprises coupling agent, ion capturing agent, ion exchanger, levelling agent, pigment, dyestuff, plastifier, defoamers such as hot radical polymerization initiator, silane coupling agent among the present invention.These adjuvants according to purposes, can use separately, perhaps also can multiplely be used in combination.

In addition, in order to ensure the spacing in liquid crystal pond, can also comprise interval dose.Interval dose can be included in the liquid crystal sealing agent, also can be coated in advance on the substrate that constitutes display panels to use.

During preparation Thermocurable sealant,, can also comprise organic solvent in order to improve point gum machine coating or serigraphy.Described organic solvent, preferably it is to the intermiscibility height of the epoxy resin of (e) composition, and boiling point is in 140～220 ℃ scope, and then is inertia to epoxy radicals.This representative examples of organic comprises ketone series solvent, ether series solvent and acetic acid esters series solvent.These can use separately, perhaps also can multiplely be used in combination.

(preparation method of liquid crystal sealing agent)

The method for preparing liquid crystal sealing agent of the present invention is not particularly limited, and can use technique known.In addition, the example of the means of each composition of mixed liquid crystal sealant comprises double-arm stirring machine, roll-type mixing roll, double screw extrusion machine, ball milling mixing roll, planetary stirring machine, but is not particularly limited, and uses known mixing machine to get final product.Liquid crystal sealing agent by arbitrary method is suitably mixed filters with filtrator, removes impurity.Then, implement vacuum defoamation processing back sealing and be filled in vial or the plastic containers, store as required, transport.

(manufacture method of display panels)

Then, the manufacture method to display panels of the present invention describes.The liquid crystal sealing agent of the invention described above can be applied to any of mode under liquid crystal injection mode and the liquid crystal drop.Below, the manufacture method that relates to the display panels of the present invention of mode under liquid crystal injection mode and the liquid crystal drop is described successively.

The manufacture method of display panels of the present invention is, paste the manufacture method of the display panels that 2 relative plate bases make by liquid crystal sealing agent, this method comprises: (1) prepares the operation of the substrate more than 1, and described substrate has the viewing area of the frame shape that forms in the mode of surrounding the line of pixels column region by liquid crystal sealing agent of the present invention; (2) with under the liquid crystal drop in the described viewing area of its uncured state or the operation on another substrate; (3) with described substrate and the overlapping operation of another substrate that liquid crystal is arranged; (4) the folded liquid crystal sealing agent of described 2 plate bases is applied light and heat, perhaps apply the either party's of light or heat operation.

(1) in the operation, preparation is upward disposed the substrate of the viewing area of frame shape with the either party that liquid crystal sealing agent is coated on 2 plate bases.Here, the frame that constitutes by liquid crystal sealing agent is to form in the mode of surrounding the line of pixels column region.

As described liquid crystal sealing agent, above-mentioned of the present invention described liquid crystal sealing agent is useful.Liquid crystal sealing agent not only forms the frame of viewing area etc., but also the effect of the bonding agent that performance is pasted as being used for 2 plate bases are separated certain intervals.In addition, the example of the method for coating of liquid crystalline sealant comprises by the point gum machine coating or by the serigraphy coating on substrate, is not particularly limited, and uses technique known to get final product.When making small-sized display panels, consider, preferably be coated with by serigraphy from the viewpoint of boosting productivity.

The example of 2 plate bases that display panels is used comprises that TFT forms rectangular glass substrate, colored filter, is formed with the substrate of black matrix".The example of the material of substrate comprises plastics such as glass, polycarbonate, polyethylene terephthalate, polyethersulfone, PMMA.

On the relative face of each substrate, also can be formed with alignment films.As alignment films, be not particularly limited, for example can use the known material that comprises organic alignment agent or inorganic alignment agent.In addition, also can be studded with interval dose in advance on the substrate.Interval dose uses the silicon oxide particle of spherical shape usually, keep equably the pond spacing aspect be effective.Usually use is dispersed in interval dose in the face of the state on the substrate in advance or is included in interval dose in the liquid crystal sealing agent.Kind, the size of interval dose are not particularly limited, and according to the size etc. of the pond spacing of expectation, use known material to get final product.

(2) in the operation, be on inboard or another substrate of frame with the viewing area to its uncured state under an amount of liquid crystal drop.Here, another substrate of the liquid crystal that drips is meant the substrate different with the substrate that comprises the viewing area.With under the liquid crystal drop to another substrate the time, liquid crystal drop can be become to substrate overlaps each other the time down in viewing area regional get final product.

In addition, with regard to the liquid crystal that drips, preferably adjust the amount of dripping of liquid crystal so that the liquid crystal that drips is accommodated in the frame according to the size of frame.If like this with under the liquid crystal drop in frame, then the capacity of liquid crystal can not exceed the capacity in the empty pond that frame and substrate surrounded after the stickup.Therefore, can not cause excessive pressure, and the sealing of formation frame can be damaged to frame.

(3) in the operation, there are the substrate of liquid crystal and another substrate overlapping with dripping.Here, overlapping processing is preferably under reduced pressure carried out by vacuum sticker etc.After operation in will reduce pressure under 2 overlapping plate bases return to atmospheric pressure, utilize draught head substrate can be pasted each other.

(4) in the operation, the folded liquid crystal sealing agent of described 2 plate bases is applied light and heat, perhaps apply the either party of light or heat.Thereby in the inside of liquid crystal sealing agent, the effect by radical polymerization initiator produces free radical, and the curing reaction of host and hardening agent obtains promoting, so liquid crystal sealing agent is cured.

In the operation of described (4), the temperature the when kind of the light that liquid crystal sealing agent is applied, irradiation time or heating, time etc. are not particularly limited, and wait according to the composition of liquid crystal sealing agent and suitably select to get final product.For example, when by heat liquid crystal sealing agent being solidified, consider that from the viewpoint that promotes liquid crystal sealing agent to solidify preferably making heating-up temperature is 40～90 ℃, making heat time heating time is 1～120 minute.In addition, as required, be heating and curing liquid crystal sealing agent once after, also can be 110～150 ℃ of back curing of carrying out 30～90 minutes.The example of the heater means of liquid crystal sealing agent comprises known heating arrangements such as baking oven, heating plate and hot press, is not particularly limited.

Among the present invention, after the operation of (3), also can comprise 2 overlapping plate bases are returned to atmospheric operation from reducing pressure down.If like this will be under reduced pressure overlapping substrate return to atmospheric pressure environment each other from reducing pressure down, then produce draught head, thereby 2 plate bases are extruded outside two, so substrate is stuck each other in the inboard and the outside of this frame.

In addition, in the mode,, adopt following method under the nearest liquid crystal drop: on substrate, form a plurality of frames by liquid crystal sealing agent, after 2 plate bases are pasted each other, the periphery of frame is cut off, thereby cut out each display panels for the purpose of boosting productivity.Such method also is applicable to the present invention.

The viscosity stability of liquid crystal sealing agent of the present invention keeps very highly, and is low to the solubleness of liquid crystal, and comprises curable high (a) composition, the hardening agent with hot latency, radical polymerization initiator and filler.Make display panels by mode under the liquid crystal drop that uses this liquid crystal sealing agent,, solidify and also fully to carry out, and can when keeping storage stability, high coating, carry out operation even exist under the situation of lightproof area.Thereby in the solidfied material of liquid crystal sealing agent, uncured portion is few, and the pollution that the result can obtain liquid crystal is prevented and the solidfied material of liquid crystal sealing agent and the high display panels of bonding strength of substrate.

In the display panels, the contaminated degree of liquid crystal, i.e. the liquid crystal pollution of display panels, the difference that can order by NI is that △ NI point is estimated.So-called NI point, be meant liquid crystal from nematic phase to the temperature of isotropic phase (etc. direction) when carrying out phase transfer.Phase inversion temperature can use the differential thermal analysis device to be measured by the flex point of exothermic peak.△ NI point is the poor of " the NI point that does not have contaminated liquid crystal " and " the NI point of contaminated liquid crystal ".If raw material that liquid crystal pollution is high or liquid crystal sealing agent mix with liquid crystal, then the Δ NI absolute value of ordering increases.On the other hand, when the liquid crystal pollution of raw material or liquid crystal sealing agent hanged down, the absolute value that Δ NI is ordered reduced.Thereby, mean that the more little liquid crystal pollution of Δ NI point is low more.

Embodiment

Below, enumerate embodiments of the invention and comparative example illustrates in greater detail the present invention.But, the invention is not restricted to mode shown below.

(a) to include (methyl) acryloyl group and glycidyl, number-average molecular weight be 500～2000 compound to molecule

As (a) composition, use compound synthetic in the following synthesis example 1～10 respectively.Wherein, compound synthetic in the synthesis example 1～4 is equivalent to described first (a) composition, and compound synthetic in the synthesis example 7～10 is equivalent to described second (a) composition.In addition, the compound that synthesizes in the synthesis example 5,6, the organic group that has regulation in the molecule, but its number-average molecular weight is outside 500～2000 scope.

In each synthesis example, calculate the acid number of the reaction mixture of any stage sampling in synthetic way by following method, one side is suitably confirmed to react the degree of carrying out by the numerical value of the acid number of calculating and is simultaneously carried out synthetic reaction.This acid number is following calculates: the sample dissolution that will suitably sample from reaction mixture is in Anaesthetie Ether-ethanolic solution, and add the phenolphthalein ethanolic solution, the ethanolic solution (0.1N) that drips KOH becomes colorless up to the solution that obtains, and calculates acid number by the amount of the KOH that consumes.

In addition, measure the number-average molecular weight of the final purpose product that obtains in each synthesis example by following method.Being determined as of number-average molecular weight, (1) are that standard is passed through the mensuration that mensuration that gel permeation chromatography (GPC) carries out and (2) are undertaken by field desorption mass spectrometry (FD-MS method) with the polystyrene.

Synthesis example 1

In the synthesis example 1, by making the reaction of acrylate modified phthalic acid of glycerine acrylate and Bisphenol F diglycidyl ether, the synthetic compd A 1 that contains (methyl) acryloyl group and glycidyl.

At first, in the four-hole boiling flask of the 500ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, with phthalic anhydride 74g (0.5mol), glycerine acrylate acrylate 271g (0.5mol), as the tributyl ammonium bromide 0.7g of catalyzer, mix as the phenothiazine 0.5g of polymerization inhibitor, be warmed to 80 ℃, make its reaction 1 hour, and then, be warmed to 130 ℃, make its reaction 2 hours.

With this resultant of reaction 276g (0.4mol), bisphenol f type epoxy resin (EPOTOHTOYDF-8170C, Toto Kasei KK makes) 125g (0.4mol), as the tributyl ammonium bromide 0.6g of catalyzer, add in the four-hole boiling flask of the 500ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe as the hydroquinone monomethyl ether 0.1g of polymerization inhibitor, mix 80 ℃ of heating, and then its reaction is reached below the 2mgKOH/g up to acid number.Then, this resultant of reaction is separated by silicagel column, obtain compd A 1.The compd A 1 that obtains is carried out HPLC, NMR analyze, results verification is the compound that contains (methyl) acryloyl group and glycidyl.

In addition, when measuring the number-average molecular weight of compd A 1 by GPC, the number-average molecular weight of the compd A 1 that obtains with simple spike is 689.And then, when measuring the number-average molecular weight of compd A 1, be simple spike and same molecular amount (689) by the FD-MS method.

Synthesis example 2

In the synthesis example 2, make 2-hydroxyethylmethacry,ate modification 4-methacryloxyethyl trimellitic acid and the reaction of Bisphenol F diglycidyl ether with following method, thus synthetic compd A 2 with (methyl) acryloyl group and glycidyl.

At first, in the four-hole boiling flask of the 1000ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, with 4-methacryloxyethyl trimellitic anhydride 152g (0.5mol) and 2-hydroxyethylmethacry,ate 58g (0.5mol), as the tributyl ammonium bromide 0.7g of catalyzer, mix as the phenothiazine 0.5g of polymerization inhibitor, be warmed to 80 ℃, make its reaction 1 hour, and then, be warmed to 130 ℃, make its reaction 2 hours.Then, with this resultant of reaction 168g (0.4mol), bisphenol f type epoxy resin (EPOTOHTOYDF-8170C, Toto Kasei KK makes) 125g (0.4mol), as the tributyl ammonium bromide 0.6g of catalyzer, add in the four-hole boiling flask of the 500ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe as the hydroquinone monomethyl ether 0.1g of polymerization inhibitor.After the potpourri that obtains is warmed to 80 ℃, its reaction is reached below the 2mgKOH/g up to acid number.

Dilute this reactant with ethyl acetate 1000g, wash 5 times repeatedly with ultrapure water after, concentrate.Then, this resultant of reaction is separated by silicagel column, obtain compd A 2.The compd A 2 that obtains is carried out HPLC, NMR analyze, results verification is the compound that contains (methyl) acryloyl group and glycidyl.In addition, when measuring the number-average molecular weight of compd A 2 by GPC, the number-average molecular weight of the compd A 2 that obtains with simple spike is 733.When measuring by the FD-MS method, the number-average molecular weight of compd A 2 also is simple spike and same molecular amount.

Synthesis example 3

In the synthesis example 3, make 2-hydroxyl-metacrylate modification phthalic acid and the reaction of Bisphenol F diglycidyl ether with following method, thus synthetic compound A-13 with (methyl) acryloyl group and glycidyl.

At first, in the four-hole boiling flask of the 500ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, with phthalic anhydride 74g (0.5mol), 2-hydroxyethyl methacrylate 65g (0.5mol), as the tributyl ammonium bromide 0.7g of catalyzer, mix as the phenothiazine 0.5g of polymerization inhibitor, be warmed to 80 ℃, make its reaction 1 hour, and then, be warmed to 130 ℃, make its reaction 2 hours.After the reaction, dilute this reactant liquor with ethyl acetate 1000g, wash 5 times repeatedly with ultrapure water after, concentrate.With this resultant of reaction 111g (0.4mol), bisphenol f type epoxy resin (EPOTOHTO YDF-8170C, Toto Kasei KK makes) 125g (0.4mol), as the tributyl ammonium bromide 0.6g of catalyzer, add in the four-hole boiling flask of the 500ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe as the hydroquinone monomethyl ether 0.1g of polymerization inhibitor.After the potpourri that obtains is warmed to 80 ℃, its reaction is reached below the 2mgKOH/g up to acid number.

Dilute this reactant with ethyl acetate 1000g, wash 5 times repeatedly with ultrapure water after, concentrate.Then, this resultant of reaction is separated by silicagel column, obtain compound A-13.By the composition of HPLC, NMR analysis gained compound A-13, results verification is the compound that contains methacryl and glycidyl.In addition, the result by the gpc analysis compound A-13 is, the number-average molecular weight of the compound A-13 that obtains with simple spike is 591.When measuring by the FD-MS method, the number-average molecular weight of compound A-13 also is simple spike and same molecular amount.

Synthesis example 4

In the synthesis example 4, by making carboxylic acid derivates and two phenoxetol fluorenes diglycidyl ether reaction, synthetic compd A 4 with (methyl) acryloyl group and glycidyl.

At first, it is refining to use silica gel that the 6-caprolactone addition product (Daicel KCC makes, trade name pul match (プラ Network セ Le) FA3) of 2-hydroxyethylmethacry,ate is carried out chromatographic column.In five mouthfuls of flasks of the 1000ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, funnel, add sodium hydride 48g and toluene 200g, nitrogen flow down carry out ice-cooled.The 6-caprolactone addition product 229g (0.5mol) of refining 2-hydroxyethylmethacry,ate is dissolved among the toluene 200g, with 2 hours this solution that drips.

Then,, this reaction mixture is filtered, remove unreacted sodium hydride dripping reaction mixture behind this solution keeps 1 hour in ice-cooled after.Afterwards, in reaction mixture, add chloropropylene oxide 185g (2mol), tetramethyl ammonium chloride 5g, hydroquinone monomethyl ether 0.1g, after mixing, stirred 3 hours at 70 ℃ while be blown into dry air.

Afterwards, the reaction mixture that reaction is finished with ultrapure water washing 5 times after, by 120 ℃ of heating decompressions, superfluous impurity such as chloropropylene oxide are removed in distillation, obtain the 6-caprolactone addition product of 2-hydroxyethylmethacry,ate and the resultant of reaction (A4a) of chloropropylene oxide.Then, with this resultant of reaction (A4a) 206g (0.4mol), in advance through refining 6-((6-acryloxy) hexylyloxy) caproic acid (the ARONIX M-5300 of chromatographic column, Toagosei Co., Ltd makes) (molecular weight 300) 120g (0.4mol), as the tributyl ammonium bromide 0.6g of catalyzer, mix as the hydroquinone monomethyl ether 0.1g of polymerization inhibitor, after being warmed to 80 ℃, its reaction is reached below the 2mgKOH/g up to acid number, obtain resultant of reaction (A4b).

Then, with resultant of reaction (A4b) 163g (0.2mol), the 4-methacryloxyethyl trimellitic anhydride 61g (0.2mol) that obtain, mix as the phenothiazine 0.5g of polymerization inhibitor, be warmed to 80 ℃, make its reaction after 1 hour, and then, be warmed to 130 ℃, make its reaction 2 hours, obtain resultant of reaction (A4c).Then, with this resultant of reaction (A4c) 112g (0.1mol), two phenoxetol fluorenes diglycidyl ether (BPEF-G, Osaka gas KCC makes, molecular weight 550) 55g (0.1mol), as the tributyl ammonium bromide 0.2g of catalyzer, add in the four-hole boiling flask of the 300ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe as the hydroquinone monomethyl ether 0.1g of polymerization inhibitor, mix, be warmed to 80 ℃, its reaction is reached below the 2mgKOH/g up to acid number.The resultant of reaction that obtains is separated with silicagel column, obtain compd A 4.

The compd A 4 that obtains is carried out HPLC, NMR analyze, results verification is the compound that contains (methyl) acryloyl group and glycidyl.In addition, the result that compd A 4 is carried out gpc analysis is, the number-average molecular weight of the compd A 4 that obtains with simple spike is 1670.And then when measuring by the FD-MS method, the number-average molecular weight of compd A 4 also is simple spike and same molecular amount.

Synthesis example 5

In the synthesis example 5, the synthetic epoxy resin that bisphenol A type epoxy resin is carried out the methacryl modification.

At first, in the four-hole boiling flask of the 500ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, with bisphenol A type epoxy resin (Chinese mugwort picalon (エピ Network ロ Application) 850CRP, Dainippon Ink. ﹠ Chemicals Inc makes) 175g, methacrylic acid 43g, as the triethanolamine 0.2g of catalyzer, mix as the hydroquinone monomethyl ether 0.2g of polymerization inhibitor, while being blown into dry air, obtain methacrylic acid modified bisphenol A type epoxy resin 110 ℃ of heated and stirred 5 hours.After the resin that obtains used ultrapure water carrying out washing treatment 12 times repeatedly, obtain compound A-45.The compound A-45 that obtains is carried out HPLC, NMR analyze, results verification is the bisphenol A type epoxy resin that 50% epoxy radicals is carried out the methacryl modification.In addition, the compound A-45 that obtains is carried out the result of gpc analysis, number-average molecular weight is 427.

Synthesis example 6

In the synthesis example 6, the synthetic epoxy resin that bisphenol f type epoxy resin is carried out the acryloyl group modification.

At first, in the four-hole boiling flask of the 500ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, with bisphenol f type epoxy resin (Chinese mugwort picalon 850CRP, Dainippon Ink. ﹠ Chemicals Inc makes) 175g, acrylic acid 37g, as the triethanolamine 0.2g of catalyzer, mix as the hydroquinone monomethyl ether 0.2g of polymerization inhibitor, while being blown into dry air, obtain acrylic acid modified bisphenol A type epoxy resin 110 ℃ of heated and stirred 12 hours.The resin that obtains is handled 12 times with the ultrapure water cyclic washing.This resin is carried out HPLC, NMR analyze, results verification is the bisphenol A type epoxy resin (compd A 6) that 50% epoxy radicals is carried out the acryloyl group modification.In addition, the compd A 6 that obtains is carried out the result of gpc analysis, number-average molecular weight is 412.

Synthesis example 7

In the synthesis example 7, can react by epoxy resin synthetic compd A 7 with (methyl) acrylic acid derivative with (methyl) acryloyl group and glycidyl by making phenol phenolic varnish type 3 officials.

At first, possessing stirring machine, gas introduction tube, thermometer, in the four-hole boiling flask of the 2000ml of condenser pipe, packing into can epoxy resin (SR-HP3 as phenol phenolic varnish type 3 officials of the compound of described general formula (i-1) expression, this pharmaceutical industries of slope Co., Ltd. makes, the number-average molecular weight of measuring by FD-MS is 474) 142.4g (0.3mol), methacrylic acid 20.7g (0.3mol), 73.3g (0.3mol) aftermentioned compound B-11, tributyl ammonium bromide 1.45g as catalyzer, phenothiazine 0.01g as polymerization inhibitor, mix 80 ℃ of heating, and then its reaction was reached below the 2mgKOH/g up to acid number in 15 hours.Compound B-11 used herein is the resultant of reaction of 2-hydroxyethyl methacrylate and succinic anhydride.

The reactant liquor 232g that obtains is diluted with toluene 900g and ethyl acetate 300g.Reactant liquor after the dilution is carried out 10 washing operations with ultrapure water with 300g/l time, and the conductivity that concentrates up to water reaches below the 1 μ S/cm, thereby obtains the compd A 7 of 222g.The result who the compd A 7 that obtains is carried out the FD-MS analysis is that number-average molecular weight is 804.

Synthesis example 8

In the synthesis example 8, can react by epoxy resin synthetic epoxy resin with (methyl) acrylic acid derivative with (methyl) acryloyl group and glycidyl by making phenol phenolic varnish type 4 officials.

Possessing stirring machine, gas introduction tube, thermometer, in the four-hole boiling flask of the 2000ml of condenser pipe, packing into can epoxy resin (YL-7284 as phenol phenolic varnish type 4 officials of the compound of described general formula (i-2) expression, japan epoxy resin Co., Ltd. makes, number-average molecular weight 636) 318g (0.5mol), 104g (0.45mol) aftermentioned compound B-11 and 110g (0.45mol) compd B 2, tributyl ammonium bromide 2.1g as catalyzer, phenothiazine 0.05g as polymerization inhibitor, mix 80 ℃ of heating, and then its reaction was reached below the 2mgKOH/g up to acid number in 15 hours.Compd B 2 used herein is resultant of reaction of 4-hydroxybutyl acrylate and succinic anhydride.

The reactant liquor 530g that obtains is diluted with toluene 1200g and ethyl acetate 600g.Reactant liquor after the dilution is carried out 10 washing operations with ultrapure water with 500g/l time, and the conductivity that concentrates up to water reaches below the 1 μ S/cm, thereby obtains the compound A-28 of 509g.The result who the compound A-28 that obtains is carried out the FD-MS analysis is that number-average molecular weight is 1111.

Synthesis example 9

In the synthesis example 9, phenol phenolic varnish type 4 officials can be reacted by epoxy resin with (methyl) acrylic acid derivative with following method, thus synthetic epoxy resin with (methyl) acryloyl group and glycidyl.

Possessing stirring machine, gas introduction tube, thermometer, in the four-hole boiling flask of the 2000ml of condenser pipe, packing into can epoxy resin (YL-7284 as phenol phenolic varnish type 4 officials of the compound of described general formula (i-2) expression, japan epoxy resin Co., Ltd. makes, number-average molecular weight 636 by FD-MS method mensuration) 318g (0.5mol), 425g (0.9mol) aftermentioned compd B 3, tributyl ammonium bromide 2.1g as catalyzer, phenothiazine 0.05g as polymerization inhibitor, mix 80 ℃ of heating, and then its reaction was reached below the 2mgKOH/g up to acid number in 15 hours.Compd B 3 used herein is resultant of reaction of 3 moles of modified methyl acrylics of caprolactone and succinic anhydride.

The reactant liquor 740g that obtains is diluted with toluene 1200g and ethyl acetate 600g.Reactant liquor after the dilution is carried out 10 washing operations with ultrapure water with 600g/l time, and the conductivity that concentrates up to water reaches below the 1 μ S/cm, thereby obtains the compd A 9 of 730g.The compd A 9 that obtains is carried out the result that FD-MS analyzes, and number-average molecular weight is 1770.

Synthesis example 10

In the synthesis example 10, can react by epoxy resin synthetic epoxy resin with (methyl) acrylic acid derivative with (methyl) acryloyl group and glycidyl by making 3 officials.

Possessing stirring machine, gas introduction tube, thermometer, in the four-hole boiling flask of the 2000ml of condenser pipe, pack into as 3 officials of the compound of described general formula (i-4) expression can epoxy resin VG-3102 (Mitsui Chemicals, Inc makes, the number-average molecular weight of measuring by the FD-MS method is 460) 184g (0.4mol), 92g (0.40mol) aftermentioned compound B-11 and 97.6g (0.40mol) compd B 2, tributyl ammonium bromide 2.0g as catalyzer, phenothiazine 0.05g as polymerization inhibitor, mix 80 ℃ of heating, and then its reaction was reached below the 2mgKOH/g up to acid number in 8 hours.

The reactant liquor 370g that obtains is diluted with toluene 900g and ethyl acetate 300g.Reactant liquor after the dilution is carried out 10 washing operations with ultrapure water with 300g/l time, and the conductivity that concentrates up to water reaches below the 3 μ S/cm, thereby obtains the compd A 10 of 361g.The compd A 10 that obtains is carried out the result that FD-MS analyzes, and number-average molecular weight is 934.

Below, (synthesis example of B1～B3) describes to (methyl) acrylic acid derivative of using in the above-mentioned synthesis example.

(synthesizing of compound B-11)

In the four-hole boiling flask of the 2000ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, with succinic anhydride 420g (4.2mol), 2-hydroxyethyl methacrylate 656g (5.0mol), as the phenothiazine 0.05g mixing of polymerization inhibitor, be warmed to 110 ℃ of reactions 5 hours.With this resultant of reaction with toluene 2500g dilution, wash 6 times repeatedly with ultrapure water 800g after, concentrated, obtain the compound B-11 of 850g.The compound B-11 that obtains is carried out HPLC, NMR analyze, the resultant of reaction that results verification obtains 2-hydroxyethyl methacrylate and succinic anhydride is the purpose compound B-11.

(synthesizing of compd B 2)

In the four-hole boiling flask of the 2000ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, with succinic anhydride 480g (4.8mol), 4-hydroxybutyl acrylate 577g (4mol), as the phenothiazine 0.05g mixing of polymerization inhibitor, be warmed to 110 ℃ of reactions 5 hours.With this resultant of reaction with toluene 2000g dilution, wash 5 times repeatedly with ultrapure water 1000g after, concentrated, obtain the compd B 2 of 920g.The compd B 2 that obtains is carried out HPLC, NMR analyze, the resultant of reaction that results verification obtains 4-hydroxybutyl acrylate and succinic anhydride is a purpose compd B 2.

(synthesizing of compd B 3)

In the four-hole boiling flask of the 2000ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, with 3 moles of addition product 472g of 6-caprolactone (1.0mol) of succinic anhydride 120g (1.2mol), refining 2-hydroxyethyl methacrylate, mix, be warmed to 110 ℃ of reactions 5 hours as the phenothiazine 0.05g of polymerization inhibitor.3 moles of addition products of 6-caprolactone of so-called refining 2-hydroxyethyl methacrylate are refining things of column chromatography of 3 moles of addition products of 6-caprolactone (pul match FA3, Daicel KCC makes) of commercially available 2-hydroxyethyl methacrylate.

With this resultant of reaction with toluene 2000g dilution, wash 10 times repeatedly with ultrapure water 1000g after, concentrated, obtain the compd B 3 of 584g.The compd B 3 that obtains is carried out HPLC, NMR analyze, the resultant of reaction that results verification obtains 3 moles of modified methyl acrylics of caprolactone and succinic anhydride is a purpose compd B 3.

(b) hot latent curing agent

As hot latent curing agent, to (i) 1,3 pairs of (diazanyl carbonyl the ethyl)-5-isopropyl hydantoins (AJICURE VDH-J, Ajinimoto Fine Techno Co. Inc. makes), (ii) adipic dihydrazide (ADH, Japanese fine chemistry Co., Ltd. makes) is suitably selected to use for these 2 kinds.

(c) radical polymerization initiator

As radical polymerization initiator, use be the 1-hydroxy-cyclohexyl phenyl ketone that plays the effect of optical free radical polymerization initiator (Irgacure 184, and Ciba company makes).

(d) filler

As filler, use be spherical silicon dioxide (1 mean grain size 0.7 μ m) (admafine A-802, ADMATECH Co., Ltd. make).

(e) epoxy resin

As epoxy resin, use be the solid shape epoxy resin of orthoresol phenolic varnish type (EOCN-1020-75, Nippon Kayaku K. K makes).

(f) acyclic compound

As (f) composition, suitably select following compound to use: (i) with the dimethylacrylate (epoxy-ester 3000M, Kyoeisha Chemical Co., Ltd. makes) of bisphenol A-type resin with toluene and ultrapure water dilute, cyclic washing 12 times and the compound that carries out the high-purity processing; (ii) with bisphenol-A, EO addition product diacrylate (BISCOAT#700, organic chemistry Co., Ltd. in Osaka makes) with toluene and ultrapure water dilute, cyclic washing 12 times and the compound that carries out the high-purity processing.

(g) other adjuvants

As adjuvant, use be γ-glycidoxy trimethoxy silane (KBM403, Shin-Etsu Chemial Co., Ltd makes) of selling as silane coupling agent.

In addition, in each embodiment and the comparative example, measure and estimated the viscosity stability of liquid crystal sealing agent, the bonding strength of liquid crystal sealing agent, the demonstration of display panels respectively, and estimated the characteristic of liquid crystal sealing agent.Each measure specific as follows shown in.The bonding strength of described liquid crystal sealing agent is that the bonding strength of measuring the liquid crystal sealing agent of the bonding strength of the liquid crystal sealing agent of (1) light or heat curing, (2) heat curing is estimated for these 2 kinds.In addition, the demonstration of display panels, it is to estimate: the demonstration of the display panels that the display panels that (1) makes according to usual method, the demonstration that (2) have the display panels of lightproof area, (3) are only made by heat curing by the sample of measuring following three kinds of patterns.

(viscosity stability of liquid crystal sealing agent)

Viscosity number when using 25 ℃ of E type viscometer determining liquid crystal sealing agents.During viscosimetric analysis, liquid crystal sealing agent 100 mass parts are packed in the tygon container made, after the sealing, preserved 5 days at 25 ℃.Then, through after specified time limit, with the viscosity number of 25 ℃ of E type viscometer determinings.Then, the value of use measuring, calculating with the viscosity number before sealing is 100 o'clock, through the rate of change of the viscosity number after 25 ℃/5 days.At this moment, estimate the viscosity stability of liquid crystal sealing agent with following 2 ranks: described rate of change is 20% to be evaluated as the viscosity stability height when following, is good (zero); It is low that existence is evaluated as viscosity stability when surpassing 20% variation, is bad (*).

(bonding strength of liquid crystal sealing agent)

1. the bonding strength of the liquid crystal sealing agent that solidifies of light and heat

At first, the circle of liquid crystal sealing agent serigraphy on the alkali-free glass of 25mm * 45mm * thick 5mm becoming diameter 1mm of the glass fibre 1 quality % of 5 μ m will be added with.Then, will paste with cross, fix with anchor clamps then with the paired same glass of this substrate, with ultraviolet lamp (Ushio Electric Inc's manufacturing) to shining 100mW/cm herein ²Ultraviolet ray, liquid crystal sealing agent is solidified.At this moment, making ultraviolet illumination energy is 2000mJ.

For make liquid crystal sealing agent solidify the test film that obtains by light, use baking oven to make test film in 60 minutes 120 ℃ of heat treated.As for the planar stretch intensity of the test film of finishing, use cupping machine (210 types, INTESCO company makes), set draw speed 2mm/ minute, be that parallel direction is shelled and drawn for the glass bottom surface, thereby measuring planar stretch intensity.Here, described bonding strength is that size according to planar stretch intensity is evaluated as 2 ranks.That is, be that average evaluation more than the 10MPa is bonding strength good (zero) with pulling strengrth, be bonding strength low poor (*) with pulling strengrth less than the average evaluation of 10MPa.

2. the bonding strength of the liquid crystal sealing agent of heat curing

At first, will be added with the circle of liquid crystal sealing agent serigraphy on the alkali-free glass of 25mm * 45mm * thick 5mm becoming diameter 1mm of the glass fibre 1 quality % of 5 μ m, same glass that will be paired with it carries out cross to be pasted, and fixing.Then, use baking oven to 2 plate bases of this stickup 120 ℃ of heat treated 60 minutes, only liquid crystal sealing agent is solidified by heat curing, make test film.

As for the planar stretch intensity of the test film of finishing, use cupping machine (210 types, INTESCO company makes) to measure.At this moment, the mensuration of planar stretch intensity, the evaluation of measurement result, identical with the method that illustrates in the bonding strength of the liquid crystal sealing agent that solidifies at above-mentioned (A) light and heat.

(demonstration of display panels)

1. by carrying out the demonstration that light and heat solidifies the display panels of making

Use is added with the liquid crystal sealing agent of the glass fibre 1 quality % of 5 μ m, is having on the 40mm of transparency electrode and alignment films * 45mm glass substrate (manufacturing of RT-DM88PIN EHC company), draws the frame type of 35mm * 40mm with live width 0.5mm, thick 50 μ m.Use point gum machine (ShotMaster, Musashi Engineering Inc. makes) during drafting.

Then, the liquid crystal material that the panel content amount after will pasting each other with substrate is suitable (MLC-11900-00, Merck ﹠ Co., Inc. make), use point gum machine critically drip with the paired glass substrate of the substrate that is formed with seal pattern on.Then, under the decompression of 90Pa, with 2 sheet glass substrates are overlapping make liquid crystal sealed after, with ultraviolet lamp (Ushio Electric Inc's manufacturings), shine 100mW/cm ²Ultraviolet ray, liquid crystal sealing agent is solidified.At this moment, making the ultraviolet irradiation energy is 2000mJ.What light source used is metal halide lamp.In the mensuration of accumulation light quantity, use be mensuration wavelength coverage with 300～390nm, peak sensitivity wavelength is the ultraviolet ray accumulation quantometer (UVR-T35 opens up general Kanggong department and makes) of 365nm.In addition, by light liquid crystal sealing agent is solidified after, and then, after 60 minutes, liquid crystal sealing agent is solidified 120 ℃ of heat treated.

The deflection film is pasted on the two sides of 2 plate bases after stickup separately, makes display panels.For this display panels, apply the voltage of 5V with continuous-current plant, thereby drive display panels.At this moment, whether near the liquid crystal display function the sealing that is formed by liquid crystal sealing agent by range estimation observation just works orderly from the driving initial stage, and benchmark according to the rules is with the demonstration of 2 level evaluation display panels.Here, to arrive that the average evaluation of performance liquid crystal display function is demonstration property good (zero) till the edge of sealing, from beginning to be demonstration property obviously poor (*) near the edge of sealing to the average evaluation of till it is more than 0.3mm, not bringing into play Presentation Function towards the frame inboard.

2. have the demonstration of the display panels of lightproof area

Then, will be with the panel content amount after pasting suitable liquid crystal material (MLC-11900-00, Merck ﹠ Co., Inc. makes) uses point gum machine critically to drip.Then, under the decompression of 90Pa, with 2 sheet glass substrates overlapping after, apply loading and fix, and then, use aluminium strip to cover hermetic unit as the substrate of front, make not direct irradiation of ultraviolet ray.Then,, liquid crystal sealing agent is solidified, make the display panels that has lightproof area by light and heat according to the method identical with the assay method of above-mentioned display panels.

For the Presentation Function of the display panels of finishing, measure, estimate according to the method identical with above-mentioned " 1. solidifying the evaluation method of the demonstration of the display panels of making " by carrying out light and heat.Here, the benchmark of the demonstration of evaluating liquid LCD panel is same as described above, so detailed.

3. the demonstration of the display panels of only making by heat curing

Then, the liquid crystal material that the panel content amount after will pasting each other with substrate is suitable (MLC-11900-00, Merck ﹠ Co., Inc. makes) uses point gum machine critically to drip.Then, under the decompression of 90Pa, with 2 sheet glass substrates overlapping after, 120 ℃ of heating 60 minutes, liquid crystal sealing agent is solidified with baking oven.

Alignment films is pasted on the two sides of 2 plate bases after stickup separately, makes display panels.For this display panels, apply the voltage of 5V with continuous-current plant, display panels is driven.At this moment, whether near the liquid crystal display function the sealing that is formed by liquid crystal sealing agent by range estimation observation just works orderly from the driving initial stage, and benchmark according to the rules is with the demonstration of 2 level evaluation display panels.Here, the benchmark of the demonstration of evaluating liquid LCD panel is same as the above-mentioned method, therefore omits explanation.

Embodiment 1

Will be as the o-cresol phenolic resin varnish (EOCN-1020-75 of (e) composition, Nippon Kayaku K. K's manufacturing) 5 mass parts heating for dissolving are at the epoxy-ester (3000M through high purity process, Kyoeisha Chemical Co., Ltd.'s manufacturing) in 10 mass parts, makes uniform solution.In cooled this solution, add 52 mass parts compd As 1 as (a) composition, (Irgacure 184 as the 1-hydroxy-cyclohexyl phenyl ketone of the performance optical free radical initiating agent effect of (c) composition, Ciba company makes) 2 mass parts, as 1 of (b) composition, two (diazanyl carbonyl the ethyl)-5-isopropyl hydantoins (AJICUREVDH-J of 3-, Ajinimoto Fine Techno Co. Inc. makes) 10 mass parts, spherical silicon dioxide (admafine A-802 as (d) composition, ADMATECH Co., Ltd. makes) 20 mass parts, γ-glycidoxy trimethoxy silane (KBM403 as (g) composition, Shin-Etsu Chemial Co., Ltd makes) 1 mass parts, carry out premixed with mixer.And then, carry out mixingly reaching below the 5 μ m with three-roller up to solid material, filter with the filtrator (MSP-10-E10S, ADVANTEC company makes) of mesh 10 μ m.Handle by the filtrate that obtains being carried out vacuum defoamation, make liquid crystal sealing agent (P1).

Embodiment 2

As (a) composition, use the compd A 2 of 52 mass parts to replace compd As 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (P2).

Embodiment 3

As (a) composition, use the compound A-13 of 52 mass parts to replace compd A 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (P3).

Embodiment 4

As (a) composition, use the compd A 4 of 52 mass parts to replace compd As 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (P4).

Embodiment 5

Will be as the o-cresol phenolic resin varnish (EOCN-1020-75 of (e) composition, Nippon Kayaku K. K's manufacturing) 5 mass parts heating for dissolving are at the epoxy-ester (3000M through high purity process, Kyoeisha Chemical Co., Ltd.'s manufacturing) in 24 mass parts, makes uniform solution.In cooled this solution, add compd A 2 as 20 mass parts of (a) composition, 1-hydroxy-cyclohexyl phenyl ketone (Irgacure184 as the performance optical free radical initiating agent effect of (c) composition, Ciba company makes) 5 mass parts, as 1 of (b) composition, two (diazanyl carbonyl the ethyl)-5-isopropyl hydantoins (AJICUREVDH-J of 3-, Ajinimoto Fine Techno Co. Inc. makes) 15 mass parts, spherical silicon dioxide (admafine A-802 as (d) composition, ADMATECH Co., Ltd. makes) 30 mass parts, γ-glycidoxy trimethoxy silane (KBM403 as (g) other adjuvants, Shin-Etsu Chemial Co., Ltd makes) 1 mass parts, carry out premixed with mixer.Then, carry out mixingly reaching below the 5 μ m, filter with the filtrator (MSP-10-E10S, ADVANTEC company makes) of mesh 10 μ m up to solid material with three-roller.Handle by the filtrate that obtains being carried out vacuum defoamation, make liquid crystal sealing agent (P5).Embodiment 6

Will be as the o-cresol phenolic resin varnish (EOCN-1020-75 of (e) composition, Nippon Kayaku K. K's manufacturing) 6 mass parts heating for dissolving are at the epoxy-ester (3000M through high purity process, Kyoeisha Chemical Co., Ltd.'s manufacturing) in 6 mass parts, makes uniform solution.In cooled this solution, add compd A 2 as 9 mass parts of (a) composition, the compound A-45 of 26 mass parts, the compd A of 26 mass parts-6, (Irgacure 184 as the 1-hydroxy-cyclohexyl phenyl ketone of the performance optical free radical polymerization initiator effect of (c) composition, Ciba company makes) 2 mass parts, as 1 of (b) composition, two (diazanyl carbonyl ethyl)-5-isopropyl hydantoins (the AJICURE VDH-J of 3-, Ajinimoto Fine Techno Co. Inc. makes) 10 mass parts, spherical silicon dioxide (admafine A-802 as (d) composition, the manufacturing of ADMATECH Co., Ltd.) γ-glycidoxy trimethoxy silane (KBM403 of 14 mass parts and conduct (g) composition, Shin-Etsu Chemial Co., Ltd makes) 1 mass parts, carry out premixed with mixer.Then, reach below the 5 μ m up to solid material, with filtrator (MSP-10-E10S, ADVANTEC company makes) this mixing thing of filtration of mesh 10 μ m with three-roller is mixing.Handle by the filtrate that obtains being carried out vacuum defoamation, make liquid crystal sealing agent (P6).

Embodiment 7

Will be as the compd A 2 of 81 mass parts of (a) composition, as 1 of (b) composition, two (diazanyl carbonyl ethyl)-5-isopropyl hydantoins (the AJICURE VDH-J of 3-, Ajinimoto Fine Techno Co. Inc.'s manufacturing) spherical silicon dioxide (the admafine A-802 of 10 mass parts, conduct (d) composition, the manufacturing of ADMATECH Co., Ltd.) γ-glycidoxy trimethoxy silane (KBM403 of 8 mass parts and conduct (g) composition, Shin-Etsu Chemial Co., Ltd makes) 1 mass parts, carry out premixed with mixer.Then, reach below the 5 μ m up to solid material, with filtrator (MSP-10-E10S, ADVANTEC company makes) this mixing thing of filtration of mesh 10 μ m with three-roller is mixing.Handle by the filtrate that obtains being carried out vacuum defoamation, make liquid crystal sealing agent (P7).

Embodiment 8

Will be as the o-cresol phenolic resin varnish (EOCN-1020-75 of (e) composition, Nippon Kayaku K. K makes) 5 mass parts heating for dissolving at (f) composition promptly through bisphenol-A, the EO addition product diacrylate (BISCOAT#V700 of high purity process, the manufacturing of Osaka organic chemistry Co., Ltd.) in 10 mass parts, makes uniform solution.In cooled this solution, add compd A 7 as 52 mass parts of (a) composition, (Irgacure 184 as the 1-hydroxy-cyclohexyl phenyl ketone of the performance optical free radical polymerization initiator effect of (c) composition, Ciba company makes) 2 mass parts, adipic dihydrazide (ADH as (b) composition, Japan fine chemistry Co., Ltd. makes) 10 mass parts, spherical silicon dioxide (admafine A-802 as (d) composition, the manufacturing of ADMATECH Co., Ltd.) γ-glycidoxy trimethoxy silane (KBM403 of 20 mass parts and conduct (g) composition, Shin-Etsu Chemial Co., Ltd makes) 1 mass parts, carry out premixed with mixer.Then, carry out mixingly reaching below the 5 μ m, use the filtrator (MSP-10-E10S, ADVANTEC company makes) of mesh 10 μ m to filter this mixing thing then up to solid material with three-roller.Handle by the filtrate that obtains being carried out vacuum defoamation, make liquid crystal sealing agent (P8).

Embodiment 9

As (a) composition, use the compound A-28 of 52 mass parts to replace compd A 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (P9).

Embodiment 10

As (a) composition, use the compd A 9 of 52 mass parts to replace compd As 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (P10).

Embodiment 11

As (a) composition, use the compd A 10 of 52 mass parts to replace compd As 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (P11).

Embodiment 12

Will be as the o-cresol phenolic resin varnish (EOCN-1020-75 of (e) composition, Nippon Kayaku K. K's manufacturing) 15 mass parts heating for dissolving are at bisphenol-A, EO addition product diacrylate (BISCOAT#V700 through high purity process, the manufacturing of Osaka organic chemistry Co., Ltd.) in 22 mass parts, make uniform solution, and then cool off.In cooled this solution, add compd A 7 as 20 mass parts of (a) composition, (Irgacure 184 as the 1-hydroxy-cyclohexyl phenyl ketone of the performance optical free radical initiating agent effect of (c) composition, Ciba company makes) 2 mass parts, adipic dihydrazide (ADH as (b) composition, Japan fine chemistry Co., Ltd. makes) 15 mass parts, spherical silicon dioxide (admafine A-802 as (d) composition, the manufacturing of ADMATECH Co., Ltd.) γ-glycidoxy trimethoxy silane (KBM403 of 25 mass parts and conduct (g) composition, Shin-Etsu Chemial Co., Ltd makes) 1 mass parts, carry out premixed with mixer.Then, carry out mixingly reaching below the 5 μ m, filter this mixing thing with the filtrator (MSP-10-E10S, ADVANTEC company makes) of mesh 10 μ m up to solid material with three-roller.Handle by the filtrate that obtains being carried out vacuum defoamation, make liquid crystal sealing agent (P12).

Comparative example 1

As (a) composition, use the compound A-45 of 52 mass parts to replace compd A 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (Q1).

Comparative example 2

As (a) composition, use the compd A 6 of 52 mass parts to replace compd As 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (Q2).

Comparative example 3

As (a) composition, use the compd A 6 of the compound A-45 of 26 mass parts and 26 mass parts to replace compd As 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (Q3).

Comparative example 4

As (a) composition, use the epoxy-ester 3000M of 62 mass parts to replace compd A 1 and the epoxy-ester 3000M that uses among the embodiment 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (Q4).

Comparative example 5

As (a) composition, that uses 52 mass parts replaces compd A 7 according to the synthetic Compound C 1 of following synthetic method, in addition, with embodiment 8 identical operations, make liquid crystal sealing agent (Q5).

(synthesizing of Compound C 1)

In the four-hole boiling flask of the 500ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, with bisphenol A type epoxy resin (Chinese mugwort picalon 850CRP, Dainippon Ink. ﹠ Chemicals Inc makes) 175g, methacrylic acid 43g, as the triethanolamine 0.2g of catalyzer, mix as the hydroquinone monomethyl ether 0.2g of polymerization inhibitor, while be blown into dry air with potpourri 110 ℃ of heated and stirred 5 hours, obtain Compound C 1.This Compound C 1 usefulness ultrapure water cyclic washing that obtains is handled 12 times.Compound C 1 is carried out HPLC, NMR analyze, results verification is the bisphenol A type epoxy resin that 50% epoxy radicals is carried out the methacryl modification.In addition, the Compound C 1 that obtains is carried out the result that FD-MS analyzes, number-average molecular weight is 426.

Comparative example 6

As (a) composition, that uses 52 mass parts replaces compd As 7 according to the synthetic Compound C 2 of following synthetic method, in addition, with embodiment 8 identical operations, make liquid crystal sealing agent (Q6).

(synthesizing of Compound C 2)

In the four-hole boiling flask of the 500ml that possesses stirring machine, gas introduction tube, thermometer, condenser pipe, with bisphenol A type epoxy resin (Chinese mugwort picalon 850CRP, Dainippon Ink. ﹠ Chemicals Inc makes) 175g, acrylic acid 37g, as the triethanolamine 0.2g of catalyzer, mix as the hydroquinone monomethyl ether 0.2g of polymerization inhibitor, while be blown into dry air with potpourri 110 ℃ of heated and stirred 12 hours, obtain Compound C 2.These Compound C 2 usefulness ultrapure water cyclic washings that obtain are handled 12 times.Compound C 2 is carried out HPLC, NMR analyze, results verification is the bisphenol A type epoxy resin that 50% epoxy radicals is carried out the acryloyl group modification.In addition, the Compound C 2 that obtains is carried out the result that FD-MS analyzes, number-average molecular weight is 412.

Comparative example 7

As (a) composition, use the Compound C 2 of described Compound C 1,26 mass parts of 26 mass parts to replace compd As 1, in addition, with embodiment 1 identical operation, make liquid crystal sealing agent (Q7).

Comparative example 8

The diacrylate that uses the bisphenol A type epoxy resin of 52 mass parts is epoxy-ester (3000A, Kyoeisha Chemical Co., Ltd.'s manufacturing) compd A 7 that uses among the replacement embodiment 8, in addition, with embodiment 8 identical operations, make liquid crystal sealing agent (Q8).

To be shown in table 1,2 for each evaluation result conclusive table of the liquid crystal sealing agent that obtains in embodiment 1～12, the comparative example 1～8.

Shown in table 1,2, use the liquid crystal sealing agent of liquid crystal sealing agent P1～P12 of the present invention, with regard near projects of the demonstration the sealing of near the demonstration its sealing of display panels of above-mentioned viscosity stability, bonding strength and use, lightproof area, it is good that evaluation result is confirmed to be.And then, even only make under the situation of described liquid crystal sealing agent curing, also can confirm the bonding strength height by heat curing, and the demonstration excellence of display panels.

Relative therewith; shown in comparative example 1～6; although being to have the compound of (methyl) acryloyl group and epoxy radicals concurrently but its number-average molecular weight is lower than 500 the compound liquid crystal sealing agent as raw material; it is low to be viscosity stability; and the demonstration inequality of liquid crystal has taken place near sealing; thereby demonstration property is low, and it is all poor than each embodiment to confirm.In addition, shown in comparative example 4,8, with the liquid crystal sealing agent of the metering system acidifying epoxy resin different with structure of the present invention as raw material, its viscosity stability and bonding strength are all very low, can be confirmed to be significance difference.

Industrial utilizability

The viscosity stability of liquid crystal sealing agent of the present invention and curing property height are good. Therefore, can with The seal pattern live width attenuates or to the change the outfit possibility of increased frequency of liquid crystal sealing agent of the devices such as point gum machine Suppress very lowly, thereby can improve yield rate, can under the condition that shortens hardening time, make liquid crystal Show panel. And, described liquid crystal sealing agent, because the solubility to liquid crystal can be suppressed very low, because of This also is suitable for mode under the liquid crystal drop.

The application is based on application number JP2006-243057, the JP2006-243059 of application on September 7th, 2006 Advocate preferential with application number JP2006-350198, the JP2006-350317 of application on December 26th, 2006 Power. The content of the specification record of these applications all is incorporated in the present specification.

Claims

1. liquid crystal sealing agent, it comprises: (a) have (methyl) acryloyl group and glycidyl and number-average molecular weight in the molecule and be 500～2000 compound, (b) hot latent curing agent, (c) radical polymerization initiator and (d) filler.

2. according to the liquid crystal sealing agent of claim 1 record, wherein, described (a) composition is the compound of following general formula (I) expression:

In the described general formula (I),

R ₁₁～R ₁₆Represent hydrogen atom or methyl independently of one another, wherein, R ₁₃And R ₁₄Both are not methyl, and R ₁₅And R ₁₆Both are not methyl,

X ₁₁And X ₁₂Represent the alkylidene of carbon number 1～10 or the group of following general formula (I-1) expression independently of one another,

X ₁₃And X ₁₄The either party represent that the alkylidene of carbon number 1～10, the opposing party represent the group of following general formula (I-2) expression,

A, b and c represent 0～3 integer independently of one another, and d represents 1～3 integer, and m represents 0～4 integer, here, a+b+c+d+m=6, and a, b and c all are not 0,

J represents integer 0 or 1, and k and 1 represents 0～10 integer separately;

In the described general formula (I-1),

N represents 1～10 integer;

In the described general formula (I-2),

Y ₃₂O combination with acryloyl group in the described general formula (I);

In the described general formula (I-3a),

R and s represent 0～4 integer independently of one another;

In the described general formula (I-3b),

3. according to the liquid crystal sealing agent of claim 1 record, wherein, the compound of described general formula (I) expression is the compound more than a kind that has acryloyl group, methacryl and epoxy radicals more than 1 in the molecule concurrently.

4. according to the liquid crystal sealing agent of claim 1 record; wherein, described (a) composition is to make (methyl) acrylic acid derivative that has the epoxy compound of 3 or 4 glycidyls in (i) molecule and (ii) have carboxyl react the compound with (methyl) acryloyl group and glycidyl that obtains.

5. according to the liquid crystal sealing agent of claim 4 record, wherein, described (i) composition is following general formula (i-1), (i-2), (i-3) or (i-4) compound of expression,

In the described general formula (i-4), R ₈₁The alkyl of expression hydrogen atom or carbon number 1～10, R ₈₂Expression hydrogen atom or methyl.

6. according to the liquid crystal sealing agent of claim 4 record, wherein, described (ii) composition is the compound of acrylic acid, methacrylic acid, following general formula (ii-1) or general formula (ii-2) expression,

In the described general formula (ii-1),

R ₉₁Expression hydrogen atom or methyl,

X ₄₂The alkylidene of expression carbon number 1～20 or the alkylene group of carbon number 2～6;

In the described general formula (t2),

N represents 1～10 integer;

In the described general formula (ii-2),

X ₆₁The group of representing following general formula (t3) expression, X ₆₂The alkylidene of expression carbon number 1～10,

I and j represent integer 0 or 1 independently of one another;

In the described general formula (t3),

7. according to the liquid crystal sealing agent of claim 1 record, wherein, further comprise (e) epoxy resin or (f) either party of acyclic compound.

8. according to the liquid crystal sealing agent of claim 1 record, wherein, described (c) composition is the optical free radical polymerization initiator.

9. according to the liquid crystal sealing agent of claim 1 record, wherein, described (c) composition is the hot radical polymerization initiator.

10. according to the liquid crystal sealing agent of claim 1 record, wherein, the content of described (a) composition is 5～90 mass parts with respect to liquid crystal sealing agent 100 mass parts.

11. the manufacture method of a display panels, it is, by the manufacture method that liquid crystal sealing agent is pasted the display panels that 2 relative plate bases make, this method comprises:

Prepare the operation of the substrate more than 1, described substrate has the viewing area of the frame shape that the liquid crystal sealing agent by claim 1 record forms in the mode of surrounding the line of pixels column region;

12. the display panels that the manufacture method of the display panels by claim 11 record obtains.