CN107267117A - Liquid crystal sealing agent composition, curable resin and (methyl) acrylated curable resin - Google Patents

Liquid crystal sealing agent composition, curable resin and (methyl) acrylated curable resin Download PDF

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Publication number
CN107267117A
CN107267117A CN201710441345.4A CN201710441345A CN107267117A CN 107267117 A CN107267117 A CN 107267117A CN 201710441345 A CN201710441345 A CN 201710441345A CN 107267117 A CN107267117 A CN 107267117A
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methyl
group
formula
rings
curable resin
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CN107267117B (en
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宫崎健介
臼井大晃
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Kyoritsu Chemical and Co Ltd
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Kyoritsu Chemical and Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells

Abstract

The present invention provides liquid crystal sealing agent composition, curable resin and (methyl) acrylated curable resin, and the present invention relates to a kind of liquid crystal sealing agent composition, it includes the curable resin represented by following formula (1).(in formula, X, R1、R2, Y, A ring be defined group, m for 1~7 scope number).

Description

Liquid crystal sealing agent composition, curable resin and (methyl) acrylated curability Resin
The application is divisional application, the China national Application No. 201580005510.0 of its original application, and the applying date is On March 31st, 2015, entitled " the excellent curable resin of flexibility, (methyl) acrylated curability tree after solidification Fat and liquid crystal sealing agent composition ".
Technical field
The present invention relates to can also show excellent flexibility after hardening, be suitable for the curable resin of liquid crystal sealing agent (methyl) acrylated curable resin and the liquid crystal sealing agent composition comprising these curable resins.
Background technology
In the manufacture of the liquid crystal display devices such as liquid crystal panel, liquid crystal drip-injection technique is widely used, in the process, for example In the periphery coating of liquid crystalline sealant of any substrate for 2 plate bases for constituting liquid crystal panel, instil scheduled volume on any substrate Liquid crystal, 2 plate bases is sent back to after fitting under vacuo in atmospheric pressure, so that the filling liquid crystal between substrate, makes liquid crystal Sealant cures.
In liquid crystal drip-injection technique, from high speed curable aspect, widely use with epoxy acrylate based compound Liquid crystal sealing agent is used as the Raolical polymerizable compound of host (referring for example to patent document 1).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-297470 publications
The content of the invention
The invention problem to be solved
In liquid crystal drip-injection technique, sealant is formed into frame sealing with any substrate that frame-shaped is applied in 2 plate bases, By liquid crystal drip-injection to any substrate, two substrates are made to fit under vacuo, carrying out UV irradiations makes liquid crystal sealing agent carry out after photocuring, Temperature more than the NI points (nematic phase-isotropism phase point, Nematic Isotropic point) of liquid crystal carries out heat and supported Shield, heat cure is carried out to liquid crystal sealing agent, while being orientated liquid crystal.
In the case of larger panel as TV, because panel is very big, thus to tool at frame sealing at liquid crystal drip-injection There is the distance more than certain, after dispenser method is by panel attachment, untill UV irradiations are carried out, liquid crystal and its uncured state Liquid crystal sealing agent do not contact or time of contact is short, liquid crystal sealing agent is mainly just contacted after photocuring with liquid crystal.
On the other hand, in recent years, the small-sized liquid crystal surface of increase is needed due to the popularization of smart mobile phone, panel type terminal etc. In plate, due to short to the distance at frame sealing at liquid crystal drip-injection, thus after laminating untill UV irradiations are carried out, liquid crystal is close Envelope agent is contacted with uncured state with liquid crystal or time of contact is long.Therefore, compared with the past, liquid crystal sealing agent is uncured Liquid crystal pollution under state turns into problem.
It is existing using the epoxide containing epoxy/acrylic acid based compound as the Raolical polymerizable of host Liquid crystal sealing agent can't say the requirement for having sufficiently responded to solve the problem.
In addition, in recent years, expect the safety such as Electronic Paper, light weight and be capable of free folding flexible liquid crystal display city Field is expanded.Above-mentioned flexible liquid crystal display replaces conventional upright and outspoken glass substrate using the flexible substrate of plastic foil or the like Manufactured.
On liquid crystal sealing agent, conventional liquid crystal sealing agent is also to form the upright and outspoken solidfied material of comparison, therefore is suitable for glass The bonding of the few substrate of the change in shape of glass etc, but in the flexible display of the soft substrate formation such as film, existing product Understand the change in shape caused by bending or substrate contraction and destroy, peel off, therefore be hardly well suited to the purposes.
From this aspect, as the sealant for being particularly suitable for flexible liquid crystal display, it is necessary to also have after hardening There is the liquid crystal sealing agent of sufficient flexibility.
In view of the foregoing, problem of the invention is to provide a kind of curable resin and the liquid comprising the curable resin Brilliant encapsulant composition, the curable resin can form the solidfied material with flexibility, even if the solidfied material is in bending flexible hydraulic Also adhering state can be maintained in the case of crystal display out of questionly, and the liquid crystal pollution of the curable resin is low, no Influence is easily brought on liquid crystal aligning.
Scheme for solving problem
The present invention includes following mode.
(1) curable resin represented by following formula (1)：
[changing 1]
[in formula, m is the number of 1~7 scope, R1It is hydrogen atom, glycidyl or methylglycidyl each, independently of the other Glyceryl, R2It is hydrogen atom or methyl each, independently of the other, A rings are carbon number and hetero atom number each, independently of the other Add up to the group of more than 5 and the aromatic rings comprising more than 1 or aromatic heterocycle, X be independently of one another hydrogen atom, hydroxyl, Glycidoxypropyl or methyl glycidyl epoxide, Y are following formula (1a)：
[changing 2]
(in formula, Y1Each, independently of the other be carbon number 2~5 alkylidene, n for 1~250 scope number), under State formula (1b)：
[changing 3]
(in formula, Y2It is Direct Bonding each, independently of the other or alkylidene that carbon number is 1 or 2, R3Each mutually It independently is hydrogen atom or methyl, the number of p and q each, independently of the other for more than 0, and their model for adding up to 1~200 The number enclosed) or by the group of the structure of all or part of unsaturated bond progress hydrogenation in above-mentioned formula (1b), on upper State R1And X, it is used as glycidyl or the R of methylglycidyl1With being used as glycidoxypropyl or methyl glycidyl epoxide X total number average value x be more than 1.].
(2) curable resin as described in (1), wherein, in above-mentioned formula (1), the carbon number included in A rings be 4~ 40, oxygen atomicity is 0~5, and nitrogen-atoms numbers are 0~5, and the quantity of ring structure of the number of sulfur atoms to be included in 0~5, and A rings is 1~5.
(3) a kind of (methyl) acrylated curable resin, it is to make the epoxy of the curable resin described in (1) or (2) Obtained from least a portion in base, hydroxyl and unsaturated bond is reacted with (methyl) acrylic acid and/or (methyl) acrylic anhydride.
(4) a kind of liquid crystal sealing agent composition, it is comprising described in the curable resin described in (1) or (2) and/or (3) (methyl) acrylated curable resin.
(5) liquid crystal sealing agent composition as described in (4), wherein, the curability tree in above-mentioned liquid crystal sealing agent composition The content of fat and/or (methyl) acrylated curable resin is 5~95 weight %.
(6) liquid crystal sealing agent composition as described in (4) or (5), wherein, above-mentioned liquid crystal sealing agent composition is further wrapped Containing the compound H with ethylenic unsaturated group and/or epoxy radicals (wherein, not including above-mentioned curable resin and (methyl) Acrylated curable resin).
The effect of invention
According to the present invention it is possible to provide a kind of curable resin and the liquid crystal sealing agent combination comprising the curable resin Thing, the curable resin can form the solidfied material with flexibility, even if the solidfied material is in the feelings of bending flexible liquid crystal display Also adhering state can be maintained under condition out of questionly, and the liquid crystal pollution of the curable resin is low, is difficult to liquid crystal aligning Property brings influence.
Embodiment
The following detailed description of the present invention.It should be noted that (methyl) acryloyl refers to methacryl in this specification And/or acryloyl, (methyl) acrylate is methacrylate and/or acrylate.
[curable resin of the invention]
The curable resin of the present invention is represented by following formula (1).
[changing 4]
The curable resin of the present invention has block, the ether position that is bracketed by subscripting m bracket and specific The soft position that group Y is constituted, it is believed that flexibility, caoutchouc elasticity have been given play in the soft position, thus make the solidification of the present invention The flexibility of property solidfied material obtained from resin solidification is excellent.As shown in formula (1), curable resin of the invention has soft Macromolecular structure, thus, it is believed that the crosslink density appropriateness reduction of the solidfied material of curable resin of the invention also contributes to above-mentioned The performance of flexibility.
In addition, while with above-mentioned soft position, curable resin of the invention, which has, includes this aromatic rings of A rings Structure, the liquid crystal pollution of the curable resin of the invention with this specific structure is low.
(on m)
In formula (1), m is the number of 1~7 scope, is gone out in terms of the viscosity, operability from the curable resin of the present invention Hair, the number of preferably 1~5 scope, the number of more preferably 1~3 scope.The curable resin of the present invention can for example be utilized Aftermentioned manufacture method is manufactured, in this case, the mixture of the different multiple compounds of the number for forming m sometimes.
(on X)
In formula (1), X is hydrogen atom, hydroxyl, glycidoxypropyl or methyl glycidyl epoxide each, independently of the other. In the case that X is hydroxyl, glycidoxypropyl or methyl glycidyl epoxide, as described later, the part can cause crosslinking anti- Should, and (methyl) acryloyl group can also be imported to the part.
From the low aspect of liquid crystal pollution, this X, preferably hydroxyl and glycidoxypropyl are used as.
(on R1)
In above-mentioned formula (1), R1It is hydrogen atom, glycidyl or methylglycidyl each, independently of the other.Such as It is described afterwards, include R1Group can cause cross-linking reaction, and (methyl) acryloyl group can also be imported to the part.Need Illustrate, in the case of numbers of the m for more than 2, the R in each block bracketed by subscripting m bracket1Each other Be it is independent, can it is mutually identical can also be different.
From the low aspect of liquid crystal pollution, such R is used as1, preferably hydrogen atom and glycidyl.
In addition, in the curable resin of the invention represented by above-mentioned formula (1), being used as glycidyl or methylglycidyl Glyceryl R1With X (that is, the R with epoxy radicals as glycidoxypropyl or methyl glycidyl epoxide1And X) it is total Several average value x is more than 1, preferably more than 2.By so making curable resin that there is the bridging property base of certain above quantity Roll into a ball and with above-mentioned soft position, can be also real while curability and the cementability required by liquid crystal sealing agent is ensured The excellent flexibility (hereinafter also referred to as " flexibility after solidification ") of existing solidfied material.
For above-mentioned x, from the liquid crystal sealing agent composition, for example viscous of the aftermentioned curable resin comprising the present invention The aspect of the workability such as the influenceed coating of degree and the physical characteristic such as the intensity after the solidification that crosslink density is influenceed Set out, as described above, it is preferred to be more than 2, more preferably 2~16, more preferably 2~8.
It should be noted that on x, by high performance liquid chromatography (HPLC) and LC Mass (LC-MS) or Gel filtration/permeation chromatography (GPC/GFC) determines the mean molecule quantity and molecular weight distribution of curable resin, and then determines solidification The epoxide equivalent of property resin, so as to calculate the x in above-mentioned formula (1) by its measurement result.
(on R2)
In above-mentioned formula (1), R2It is hydrogen atom or methyl each, independently of the other, from the liquid crystal of the curable resin of the present invention The low aspect of contaminative is set out, preferably hydrogen atom.It should be noted that in the case of numbers of the m for more than 2, by subscripting m Each block for being bracketed of bracket in R2Be also each other it is independent, can it is mutually identical can also be different.
(on A rings)
In above-mentioned formula (1), A rings adding up to more than 5 and wrapping for carbon number and hetero atom number each, independently of the other Group containing the aromatic rings of more than 1 or aromatic heterocycle.Adding up to for carbon number and hetero atom number more than 5 refers to, to A rings If being bonded with the carbon atom and hetero atom, ring atom of composition ring when on the whole with carbon atom or heteroatomic base The whole carbon atoms and hetero atom number that group then includes including these groups add up to more than 5.
On A rings, in terms of viscosity, operability from the curable resin of the present invention and aftermentioned liquid crystal sealing agent composition Set out, the carbon number included preferably wherein is 4~40, oxygen atomicity is 0~5, and nitrogen-atoms numbers are 0~5, and number of sulfur atoms is 0 The quantity of the ring structure included in~5, and A rings is 1~5.
The ring structure (aromatic rings and aromatic heterocycle) included in A rings can be independent a kind, can also there is two or more, on It can be single ring architecture to state ring structure, or condensed cyclic structure.In addition, these ring structures can be with Direct Bonding or by connection Group bonding and there is two or more.
As the example of the linking group, it is 2~4 that can enumerate alkylidene, carbon number that carbon number is 1~4 Alkylidene, ether, ester group, ketone group, thioether group, sulfonyl etc..In addition, in above-mentioned formula (1), be bonded to the oxygen atom and X of A rings with The ring structure of A rings can be bonded by the linking group.
In addition, these ring structures can have substituent independently of one another.As the example of this substituent, it can enumerate Alkyl, alkoxy, acyl group, formoxyl, carboxyl, ester group, cyano group, nitro, sulfo group, amide groups, hydroxyl, sulfydryl, silicyl etc..
As the example of the ring structure included in A rings, phenyl ring, naphthalene nucleus, fluorenes ring, anthracene nucleus, furan nucleus, pyrroles can be enumerated Ring, thiphene ring, imidazole ring, oxazole rings, thiazole ring, pyridine ring, thiazine ring and above-mentioned substituent is bonded with these rings Ring structure etc..
It should be noted that in the case of numbers of the m for more than 2, in each block that subscripting m bracket is bracketed A rings be also each other it is independent, can it is mutually identical can also be different.
(on Y)
Then, in above-mentioned formula (1), Y is following formula (1a), (1b) or by all or part of insatiable hunger in the formula (1b) The group of the structure of hydrogenation is carried out with key.It should be noted that in the case of numbers of the m for more than 2, subscripting m's includes Y in number each block bracketed be also each other it is independent, can it is mutually identical can also be different.
[changing 5]
In formula (1a), Y1It is the alkylidene of carbon number 2~5 each, independently of the other, n is the number of 1~250 scope. As the example of above-mentioned alkylidene, ethylidene, propylidene, trimethylene, tetramethylene and neopentyl etc. can be enumerated.From this hair Set out after the solidification of bright curable resin in terms of flexibility and liquid crystal pollution, Y1Preferably ethylidene or tetramethylene, From above-mentioned flexibility and the operational aspect of the curable resin of the present invention, n is preferably the number of 5~70 scope, is entered One step is preferably the number of 10~50 scope.
It should be noted that in the case of numbers of the n for more than 2, each repetition that subscripting n bracket is bracketed is single Y in member1Be also each other it is independent, can it is mutually identical can also be different.
In addition, in formula (1b), Y2It is Direct Bonding each, independently of the other or alkylidene that carbon number is 1 or 2, R3It is hydrogen atom or methyl each, independently of the other, p and q are more than 0 number each, independently of the other, and they are added up to The number of 1~200 scope.It should be noted that in the case that p, q are more than 2 number, being bracketed with these lower target brackets Repeat unit there is two or more, the R in these each repeat units3It is also independent each other, mutually identical also can may be used With difference.If in addition, above-mentioned p, q scope, then these repeat units can also be randomly bonded.
From flexibility aspect after the operability of the curable resin of the present invention and solidification, p and q sum are preferably The number of 5~70 scope, the number of more preferably 10~50 scope.
(on m, n, p, q)
The m of quantity that is relevant with the formula (1) of described above, representing specific block (repeat unit) can be by aftermentioned hair The input amount of the synthesis material of bright curable resin and the resin (or aftermentioned (methyl) acrylated curable resin) GPC measurement results are estimated.N and p, q aggregate value can be by curable resin (or aftermentioned (methyl) acrylated solidifications Property resin) GPC measurement results estimated, in addition, they can also by the synthesis material of curable resin GPC determine tie Fruit is estimated.In addition, on the respective value of p, q, it is possible to use IR etc. is analyzed.
<The characteristic of curable resin>
The viscosity of the curable resin of present invention mentioned above is usually 1000~2000000mPas.As described later, The curable resin of the present invention is suitable for liquid crystal sealing agent purposes, in the case of for the purposes, from true to liquid crystal sealing agent The sticky aspect for protecting appropriateness is set out, and the viscosity of curable resin is preferably 3000~2000000mPas.Need explanation It is that in this specification, viscosity is in 25 DEG C of numerical value determined using E type viscosimeters.
The viscosity of curable resin such as can by changing the m in formula (1) and/or change curable resin in hydroxyl Base (such as R1For the situation of hydrogen atom) presence ratio etc. be adjusted.
In addition, in the case where curable resin is used for into liquid crystal sealing agent, from take into account cementability and flexibility in terms of Set out, its epoxide equivalent is preferably 400~10000g/eq, more preferably 500~5000g/eq.It should be noted that curability The epoxide equivalent of resin can be included using the mean molecule quantity of curable resin and the bracket of the subscripting m in above-mentioned formula (1) The epoxy radicals of the unit block (repeat unit) got up is (such as the R of glycidyl1) quantity be adjusted.
In addition, the NI points change of the curable resin of the present invention is small.Above-mentioned NI points refer to that liquid crystal is opposite each to same from nematic Property phase (isotropic phase) phase transformation when temperature (phase transition temperature can using differential thermal analysis device by endothermic peak jacking row Determine).The NI points of liquid crystal are determined by the mixing of each composition of liquid crystal is constituted, and are intrinsic value under each proportioning.If liquid crystal is dirty The high raw material of metachromia or sealant are mixed with liquid crystal, then NI points significantly change, on the contrary, the liquid crystal pollution of raw material or sealant In the case of low, the change of NI points is small.
Specifically, the NI points change of curable resin of the invention is usually -5 DEG C~+5 DEG C of scope, is preferably -3 DEG C~+3 DEG C of scope.It should be noted that the details of the assay method of NI points change is said in aftermentioned embodiment It is bright.
[(methyl) acrylated curable resin]
The curable resin of the present invention can react with (methyl) acrylic acid and/or (methyl) acrylic anhydride and form (first Base) acrylated curable resin.The olefinic sites of (methyl) acryloyl group can cause cross-linking reaction, at above-mentioned (methyl) third In the case that alkene is acylated curable resin, it can also be realized while the cementability required by liquid crystal sealing agent is ensured excellent Flexibility.
On (methyl) acryloyl group to the present invention curable resin importing, more specifically, to above-mentioned curability Epoxy radicals (such as R of resin1For the situation of glycidyl), (such as Y is the feelings of the group of formula (1b) for hydroxyl and unsaturated bond Condition) at least a portion carry out.If it should be noted that addition by (methyl) acryloyl group etc. and open epoxy radicals Ring, then can generate hydroxyl, and the importing of (methyl) acryloyl group can also be further carried out to the hydroxyl.
It should be noted that the importing of (methyl) acryloyl group can be by making (methyl) acrylic compounds, such as Acrylic acid, methacrylic acid, there are their acid anhydrides, their ester compounds or their etheride etc. and the present invention Curable resin reacts to carry out.
<The characteristic of (methyl) acrylated curable resin>
(methyl) acrylated curable resin of the present invention is shown in the same manner as the curable resin of the present invention to be used for Preferred characteristic in liquid crystal sealing agent.
That is, the viscosity of (methyl) acrylated curable resin of the invention is usually 1000~2000000mPas, from Ensure that liquid crystal sealing agent appropriate sticky aspect is set out, preferably 3000~2000000mPas.
In addition, the NI points change of (methyl) acrylated curable resin of the present invention is small, the change of its NI point is usually -5 DEG C~+5 DEG C of scope, it is preferably -3 DEG C~+3 DEG C of scope.
[manufacture method of curable resin]
Then, the manufacture method to the curable resin of the present invention is illustrated.
The manufacture method of above-mentioned curable resin includes making following formula (2) or compound E and following formula represented by (3) (4) process of the compound F reactions represented by.
[changing 6]
In formula (2) and (3), Y1、n、Y2、R3, p and q it is as defined above as, R4Be each, independently of the other hydrogen atom, Glycidyl or methylglycidyl.In addition, in formula (3), the repeat unit that the bracket with subscript p or q is bracketed In all or part of unsaturated bond can be hydrogenated.
In addition, in formula (4), as X and A rings are as defined above, R5It is sweet for hydrogen atom, glycidyl or methylglycidyl Oil base.
For example in the-OR for the molecular end for being present in compound E4For glycidoxypropyl or methyl glycidyl epoxide In the case of ,-the OR in compound F5Or in X at least any one be hydroxyl, it is sweet by these glycidyls or methylglycidyl Ring-opening reaction between oil base and hydroxyl, compound F is connected to compound E end.Also, make resulting change as needed Compound (synthetic intermediate G described later, its when intramolecular has more than one epoxy radicals, be the present invention curable resin) In at least a portion of free hydroxyl group (such as the newly-generated hydroxyl by ring-opening reaction) carry out glycidol as described later Base is etherified, so that it is more than 1 to be adjusted to x, the curable resin of the invention when the m obtained in formula (1) is 1.
In addition, in compound F ,-OR5, should-OR in the case of being the group that hydroxyl etc. can make epoxy ring-opening with X5And X It can be reacted with compound E glycidoxypropyl or methyl glycidyl epoxide.In so obtained compound, according to need Free hydroxyl is set to carry out as described later glycidyl etherified, so as to obtain this hair that the m in formula (1) is more than 2 Bright curable resin.It should be noted that m can be adjusted by compound E and F input amount ,-OR5Being with X can When making the group of epoxy ring-opening, the curable resin of the invention that m is 1 can also be obtained by the adjustment of input amount.
It should be noted that compound E and F can be used alone respectively, two or more can also be applied in combination.
The molecular weight of compound E represented by formula (2) or (3) is preferably 500~10000.It should be noted that this explanation In book, molecular weight is the number-average molecular weight that the polystyrene standard determined by GPC converts.
Compound E and F is commercially available, or can easily be prepared by commercially available compound according to known method.For example, R4For hydrogen atom, Y1Compound E for the formula (2) of ethylidene can be obtained with various number of repeat unit (n) as polyethylene glycol Material, appropriate n of the selection with expected range compound.Also, n can also be determined by the GPC of polyethylene glycol and tied Fruit is estimated.
In addition, polyethylene glycol with epichlorohydrin etc. by that can import the compound of glycidyl or methylglycidyl (hereinafter also referred to as " epoxidised compound ") reaction, so as to import glycidyl etc. in the end of polyethylene glycol, this It is meant to R4Glycidyl etc. is easily transformed to by hydrogen atom.This is also applied for described below, R4Or R5For The compound E and F of hydrogen atom other examples.
In addition, R4For hydrogen atom, Y1Compound E for the formula (2) of propylidene can be had as polypropylene ether glycol The material of various number of repeat unit (n).For example, can enumerate EXCENOL420, EXCENOL720, EXCENOL1020, EXCENOL2020 (being manufactured above for Asahi Glass society) etc..
In addition, R4For hydrogen atom, Y1Compound E for the formula (2) of trimethylene for example can be according to Japanese Unexamined Patent Application Publication 2013- Method described in No. 515144 publications, is manufactured as the polytrimethylene ether glycol with various number of repeat unit (n).
In addition, R4For hydrogen atom, Y1Compound E for the formula (2) of tetramethylene can be obtained as polytetramethylene ether diol There must be the material of various number of repeat unit (n).For example, can enumerate PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000 (being manufactured above for society of Mitsubishi Chemical) etc..
In addition, R3For hydrogen atom, R4Compound E for the formula (3) of hydrogen atom can be imported with the poly- fourth of hydroxyl as end Diene obtains the material with various number of repeat unit (p, q).For example, can enumerate NISSO PB G-1000, G-2000 (with It is upper to be manufactured for Cao Da societies of Japan), Poly bd R-45HT (manufacture of light extraction Xing Chan societies) etc..
In addition, R3For hydrogen atom, R4Part in the repeat unit bracketed by the bracket of hydrogen atom, subscripting p or q Or the compound E of formula (3) that is hydrogenated of whole unsaturated bonds can be imported with the polybutadiene of hydroxyl as end Hydride obtains the material with various number of repeat unit (p, q).For example, NISSO-PBGI-1000, GI-2000 can be enumerated (being manufactured above for Japanese Cao Da societies) etc..
In addition, R3For methyl, R4Compound E for the formula (3) of hydrogen atom can be imported with the poly- isoamyl of hydroxyl as end Diene obtains the material with various number of repeat unit (p, q).For example, Poly ip (manufacture of light extraction Xing Chan societies) etc. can be enumerated.
In addition, R3For methyl, R4Part in the repeat unit bracketed by the bracket of hydrogen atom, subscripting p or q or The compound E for the formula (3) that whole unsaturated bonds is hydrogenated can be imported with the polyisoprene of hydroxyl as end Hydride obtains the material with various number of repeat unit (p, q).For example, EPOL (manufacture of light extraction Xing Chan societies) etc. can be enumerated.
In addition, being used as R5, can for the compound F that hydrogen atom, X are atomicity and ring structure number as defined in hydroxyl, A rings are met To enumerate resorcinol, 2- (4- hydroxy phenyls) ethanol, bisphenol-A, bis-phenol M, bis-phenol P, 1,6- naphthalenediol, 2- ethyl -9,10- anthracenes Double (4- hydroxy-3-methyls phenyl) fluorenes of diphenol, 3,4- thiophene glycol, 9,9- etc..
In addition, being used as R5For the compound F that hydrogen atom, X are atomicity and ring structure number as defined in hydrogen atom, A rings are met, Phenol, 4- α-cumyl phenol, 4- metoxyphenols, 4- oxyquinolines etc. can be enumerated.
On the R in compound E4With the R in compound F5, it is soft after the solidification of resulting curable resin respectively Set out in terms of property and low liquid crystal pollution, preferably R4And R5One of be that hydrogen atom, another one are glycidyl.
For compound E and compound F, in order to generate the curable resin of the present invention, for example, make compound E and chemical combination It is as needed that resulting synthetic intermediate G is in the presence of appropriate catalyst and suitable after thing F reacts in the presence of base When epoxidised compound reaction.Input amount is adjusted in above-mentioned reaction so that m in curable resin is 1~7, be preferably 1~ 5th, the number of more preferably 1~3 scope.Above-claimed cpd can be used alone, and can also make two or more combination With.
On m number, in the case of aftermentioned embodiment, control can be carried out as follows when synthetic intermediate G is synthesized. For example, the epoxy radicals and the equivalent proportion of bisphenol-A (equivalent to compound F) in synthesis example 1 in compound E-1 are changed into 1.0：2.5, if Make this than for 1.0：2.0、1.0：1.5, then m number increase.On the contrary, for 1.0：10、1.0：100、1.0：1000 situations such as Under, it will not also be less than 1.
It should be noted that from the R in the aspect of reactivity, preferred compound E4With the R in compound F5In one Person is hydrogen atom, and another one is glycidyl or methylglycidyl.
As above-mentioned alkali, carried out from being swift in response and synthesis cost aspect, preferably sodium hydroxide, potassium hydroxide etc. Alkali metal hydroxide；The alkali carbonates such as sodium carbonate, potassium carbonate；Tetramethyl ammonium chloride, methyl tricapryl ammonium chloride, methyl The quaternary ammonium salts, more preferably sodium hydroxide or quaternary ammonium salt such as three decyl ammonium chlorides, benzyltrimethylammonium chloride.These alkali are preferably with water-soluble The form of liquid is used, according to circumstances, can also separately be added powder or the alkali of solid with water simultaneously or with water.In addition, These alkali can be used alone, and two or more can also be applied in combination.
On the consumption of alkali, carried out from being swift in response and synthesis cost aspect, in R4For hydrogen atom, R5To shrink In the case of glyceryl, alkali is more than the equivalent of hydroxyl；In R4For glycidyl or methylglycidyl, R5For hydrogen In the case of atom, the consumption of alkali can be catalytic amount, 0.0001~0.1 equivalent of the hydroxyl for being compound F.
On the consumption of epoxidised compound, work as relative to the hydroxyl included in starting compound, preferably 0.05~20 Amount, more preferably 0.05~15 equivalent.The consumption is adjusted by the mean number x of the epoxy radicals in target curable resin, Even if largely excessively being used relative to hydroxyl, x is not more than the mean number of the hydroxyl of starting compound.
As catalyst, from reaction time, cost, reactivity aspect, preferably trimethylamine, trioctylamine, three last of the ten Heavenly stems The tertiary amines such as amine；The seasons such as tetramethyl ammonium chloride, methyl tricapryl ammonium chloride, the decyl ammonium chloride of methyl three, benzyltrimethylammonium chloride Ammonium salt, more preferably quaternary ammonium salt.They can be used alone, and two or more can also be applied in combination.
On the consumption of catalyst, from suppression side reaction, while suitably reaction speed aspect is ensured, relative to original The hydroxyl included in material compound, more preferably preferably 0.0001~0.5 equivalent, 0.01~0.1 equivalent.
Reaction with above-mentioned alkali is preferably at 50~250 DEG C, more preferably at 70~200 DEG C, further preferably 100~170 DEG C carry out, reaction with above-mentioned epoxidised compound preferably 25~100 DEG C, more preferably 30~80 DEG C, further preferably exist 40~60 DEG C of progress.In reaction, the solvent inert in the reaction of hydrocarbon, ether or ketone etc can also be used, but in excess In the case of using epoxidised compound, the compound also can be as solvent function, thus these solvents are not to be required 's.
The refined of curable resin after reaction terminating can conventionally be carried out, for example, by excessive epoxidation Compound is distilled off, and the laggard water-fillings of water-insoluble solvent such as hydrocarbon are added as needed and are washed, by the salt generated and catalyst Remove, it is hereby achieved that being used as the curable resin of the invention of target.
It is the R in compound E from general raw material aspect can be used as compound E and compound F4For contracting Water glyceryl compound E1 (compound E diglycidyl ether compounds；Such as polyethylene glycol diglycidyl base ether), be R in compound F5In the case of compound F1 (such as bisphenol-A) for hydrogen atom, the manufacturer of curable resin of the invention Method preferably includes process 1 and process 2, in process 1, above-claimed cpd E1 is reacted with above-claimed cpd F1, obtains State compound E1 and above-claimed cpd F1 synthetic intermediate G；In process 2, epoxy is carried out to synthetic intermediate G hydroxyl Change, obtain the curable resin that above-mentioned synthetic intermediate G part or all of hydroxyl is at least partially epoxidized.
<The manufacture method of (methyl) acrylated curable resin>
And then, by making curable resin be reacted in the presence of base catalyst with (methyl) acrylic compounds Process 3, imported (methyl) acryloyl so as to obtain at least a portion in epoxy radicals, hydroxyl and unsaturated bond (methyl) acrylated curable resin of the invention of base.
As base catalyst, the known alkali used in the reaction of epoxy resin and (methyl) acrylic acid can be used Property catalyst.Alternatively, it is also possible to using making base catalyst support in the Polymer Supported base catalyst on polymer.As Base catalyst, preferably trivalent organic phosphorus compound, its salt, amines and its salt.These base catalysts can be used alone 1 kind, two or more can also be applied in combination.It should be noted that the basic atom of base catalyst is phosphorus and/or nitrogen.
As trivalent organic phosphorus compound, the alkyl of triethyl phosphine, three n-propyl phosphines, tri-n-butyl phosphine etc can be enumerated Phosphine and its salt；Aryl phosphine and its salt such as triphenylphosphine, three tolylphosphines, three (2,6- Dimethoxyphenyls) phosphines；Phosphorous The tris phosphite classes and its salt etc. such as triphenyl phosphate ester, triethyl phosphite, phosphorous acid three (nonyl phenyl) ester.Wherein preferred triphen Base phosphine.
As the salt of trivalent organic phosphorus compound, ethyltriphenylphosphonium bromide can be enumerated, butyltriphenylphosphonium bromide phosphine, pungent Base triphenylphosphinebromide, decyl triphenylphosphinebromide, isobutyl group triphenylphosphinebromide, propyl group triphenyl phosphine dichloride, amyl group triphen Base phosphonium chloride, hexyltriphenylphosphonium bromide phosphine etc..
As amines, the secondary amine such as diethanol amine can be enumerated；Triethanolamine, dimethyl benzyl amine, three (dimethylaminos Methyl) tertiary amine such as phenol, three (diethylamino methyl) phenol；The azabicyclos of 1,5,7- tri- [4.4.0] decyl- 5- alkene (TBD), 7- Methyl isophthalic acid, the azabicyclos of 5,7- tri- [4.4.0] decyl- 5- alkene (Me-TBD), the carbon -7- alkene of 1,8- diazabicyclos [5.4.0] 11 (DBU), the carbon -7- alkene of 6- dibutylaminos -1,8- diazabicyclos [5.4.0] 11,1,5- diazabicyclos [4.3.0] nonyl- The strong basicity amine such as 5- alkene (DBN), 1,1,3,3- TMGs.The wherein preferred azabicyclos of 1,5,7- tri- [4.4.0] decyl- 5- alkene (TBD)。
As the salt of amines, benzyltrimethylammonium chloride, benzyltriethylammoinium chloride and above-mentioned highly basic can be enumerated Salt of property amine etc..
It is not particularly limited as the polymer for supporting base catalyst, polystyrene can be used through divinyl benzene crosslinked The polymer of polymer, acrylic resin through divinyl benzene crosslinked etc..These polymer, which are not dissolved in, to be passed through The reaction of the curable resin that manufacture method comprising process 1 or comprising process 1 and 2 is obtained and (methyl) acrylic compounds In used solvent (such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene) and raw material, product.In addition, these polymer It can be used alone, two or more can also be applied in combination.
, can be by making base catalyst and insoluble polymer generation chemical bond on Polymer Supported base catalyst Close, or monomer polymerization is carried out after base catalyst is imported into monomer, carry out 3-dimensional using cross-linking monomers such as divinylbenzenes afterwards Crosslinking is manufactured, by such crosslinking, can be formed and gathered insoluble in methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene equal solvent Compound supports base catalyst.
As Polymer Supported base catalyst, specifically, diphenylphosphine base polystyrene, 1,5,7- tri- can be enumerated Azabicyclo [4.4.0] decyl- 5- alkene polystyrene, N, N- (diisopropyl) aminomethylpolystyre.e, N- (methyl polyphenyl second Alkene) -4- (methylamino) pyridine etc..These Polymer Supported base catalysts can be used alone, can also by 2 kinds with On be applied in combination.
As Polymer Supported base catalyst, commercially available product can be used.It is used as commercially available Polymer Supported alkalescence Catalyst, for example, can enumerate PS-PPh3(diphenylphosphine base polystyrene, the manufacture of Biotage societies), PS-TBD (1,5,7- tri- Azabicyclo [4.4.0] decyl- 5- alkene polystyrene, the manufacture of Biotage societies) etc..
In the manufacture method of (methyl) acrylated curable resin of the present invention, by comprising process 1 or including process 1 It is preferably 60 with the 2 obtained curable resin of manufacture method and the temperature in the reaction process of (methyl) acrylic compounds ~120 DEG C, more preferably 80~120 DEG C, more preferably 90~110 DEG C.
Make the curable resin obtained by the manufacture method comprising process 1 or comprising process 1 and 2 in the presence of a catalyst In the case of the reaction of (methyl) acrylic compounds, in order to prevent gelation, it is necessary to suitably ensure in reaction system and anti- Answer the oxygen concentration of the gas phase in system.For example, in the case where being blown into air into reaction system on one's own initiative, may cause and urge The oxidation of agent, the reduction for causing activity, thus should be noted.
On the curable resin and (methyl) propylene obtained by the manufacture method comprising process 1 or comprising process 1 and 2 The reaction of sour based compound, because (methyl) the acrylated curable resin obtained by the reaction can be because of ultraviolet isoreactivity Energy-ray and solidify, thus preferably masking ultraviolet container in reacted.In addition, in order to prevent gas phase from gathering Close, the curable resin and (methyl) acrylic acid series chemical combination obtained by the manufacture method comprising process 1 or comprising process 1 and 2 The reaction of thing can be carried out in the presence of the reflux solvent of good solvent is shown to curable resin, but in such case Under, need to remove solvent after termination of the reaction.Thus, above-mentioned reaction is preferably in solvent-free lower progress., can be with as reflux solvent Enumerate acetone, methyl ethyl ketone, toluene etc..
[liquid crystal sealing agent composition]
They (are hereinafter also referred to as by the curable resin and (methyl) acrylated curable resin of the present invention in the lump " curable resin of the invention etc. ") there are the various characteristics of described above, preferred viscosity during with as liquid crystal sealing agent, Flexibility after low liquid crystal pollution and excellent solidification.
Therefore, using the present invention curable resin etc. liquid crystal sealing agent composition it is operational excellent, in liquid crystal drop Even if in the case of contacting with liquid crystal with uncured state in note technique, being not easy to bring the orientation of liquid crystal influence, because This is difficult the orientation for hindering liquid crystal, and in the flexible device of flexible liquid crystal display etc in the case of use, even if Bending is clamped with the flexible base board of the liquid crystal sealing agent after solidification, by its excellent flexibility and stress relaxation effect, also not Easily occur the rupture of sealing liquid crystal part and the stripping from substrate etc..
Specifically, the viscosity of liquid crystal sealing agent composition of the invention is usually 1000~2000000mPas, preferably For 10000~1000000mPas.In addition, the viscosity of liquid crystal sealing agent composition can pass through curable resin of the invention Deng structure or being adjusted as the addition of the composition containing composition, solvent of liquid crystal sealing agent composition of illustrating below.
For the liquid crystal sealing agent composition of the invention of this curable resin comprising the present invention etc., from softness Property in terms of set out, make the storage modulus of its liquid crystal sealing agent solidfied material after solidifying generally under room temperature (25 DEG C) for 1.0 × 103~3.0 × 109Pa, preferably 1.0 × 103~1.0 × 109Pa.It should be noted that the assay method of storage modulus is rear It is described in detail in the item for stating embodiment.
In addition, from flexibility aspect, liquid crystal obtained from making the liquid crystal sealing agent composition solidification of the present invention is close The glass transition temperature (Tg) of envelope agent solidfied material is usually less than 80 DEG C, be preferably less than 40 DEG C, be more preferably less than 30 DEG C, More preferably room temperature (25 DEG C) below, particularly preferably -80~25 DEG C.
The curable resin of the liquid crystal sealing agent composition of the present invention comprising the present invention etc., above-mentioned liquid crystal sealing agent composition In the content of curable resin etc. be usually 5~95 weight %, the influence from flexibility, cementability and to liquid crystal aligning Aspect is set out, preferably 10~95 weight %.
In addition, the present invention liquid crystal sealing agent composition can be according to required by the purposes various characteristics, do not damaging The various composition of following explanation is further included in the range of the effect of the present invention.
<Compound H>
In addition to curable resin of the present invention etc., liquid crystal sealing agent composition of the invention, which can also be included, to be solidified into Point, for example, for the host as liquid crystal sealing agent use it is existing have ethylenic unsaturated group and/or epoxy radicals Compound H (for example, oligomer of methacrylated is carried out to a part of epoxy radicals of bisphenol A type epoxy resin) For mixture has a liquid crystal sealing agent composition of the curable resin etc. of the present invention together, with the situation phase using only compound H Than the flexibility of liquid crystal sealing agent solidfied material is greatly improved.
As the compound H with ethylenic unsaturated group, (methyl) acrylate compounds, aliphatic can be enumerated Acrylamide compound, ester ring type acrylamide compound, contain aromatic acrylamide compound, N- substituted acrylamides Based compound.
As above-mentioned (methyl) acrylate compounds, it can enumerate to cumylphenoxy ethylene glycol (methyl) acrylic acid Ester, (methyl) tert-butyl acrylate, (methyl) ethioxy phenyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid Aliphatic (methyl) acrylate representated by ethylene oxidic ester, (methyl) acrylate containing aromatic rings.
In addition, as the compound H with ethylenic unsaturated group, mono-functional, two functionalities, three can also be enumerated Functionality or multi-functional free-radical polymerised unsaturated compound.
As the free-radical polymerised unsaturated compound of above-mentioned mono-functional, from ensuring the viscous of liquid crystal sealing agent composition Degree, flexible aspect are set out, and are preferably selected from by (methyl) hydroxy-ethyl acrylate, (methyl) benzyl acrylate, (methyl) propylene Sour tetrahydrochysene chaff ester, (methyl) Isooctyl acrylate monomer, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) The bicyclic pentyl ester of acrylic acid, (methyl) acrylate epoxide ethyl ester, the cyclopentyloxy ethyl ester of (methyl) acrylic acid two, (methyl) propylene Sour dicyclopentenyl epoxide ethyl ester, the different myristin of (methyl) acrylic acid, (methyl) lauryl acrylate, the tertiary fourth of (methyl) acrylic acid More than a kind of compound in the group of ester and diethylene glycol monoethyl ether (methyl) acrylate composition, more preferably selected from by (first Base) isobornyl acrylate, (methyl) tetrahydrofurfuryl acrylate, the bicyclic pentyl ester of (methyl) acrylic acid, the ring of (methyl) acrylic acid two More than a kind of compound in the group that amylene epoxide ethyl ester and (methyl) cyclohexyl acrylate are constituted.
As the above-mentioned free-radical polymerised unsaturated compound of two functionalities, from ensuring the viscous of liquid crystal sealing agent composition Degree, flexible aspect are set out, and are preferably selected from by Tricyclodecane Dimethanol two (methyl) acrylate, dihydroxymethyl bicyclopentane Two (methyl) acrylate, EO are modified 1,6-HD two (methyl) acrylate, EO modified bisphenol As two (methyl) acrylic acid (such as ARONIXM-6100, East Asia are synthesized for ester, PO modified bisphenol As two (methyl) acrylate, polyester two (methyl) acrylate Society manufactures), polyethylene glycol two (methyl) acrylate (such as 4G, Xin Zhong village chemical industry society manufacture) and (first of organosilicon two Base) acrylate (such as EBECRYL 350, DAICEL-ALLNEX societies manufacture) composition group in more than a kind of compound, More preferably (methyl) acrylate of dihydroxymethyl bicyclopentane two and/or EO or PO modified bisphenol As two (methyl) acrylate. There is (methyl) acrylate of bisphenol A skeleton wherein preferably without hydroxyl, as such (methyl) acrylate, altogether (strain) is commercially available has LIGHT-ACRYLATE BP-4EAL (the EO addition products diacrylate of bisphenol-A), BP-4PA (double for flourish society chemistry Phenol A PO addition products diacrylate) etc..
As above-mentioned trifunctional or multi-functional free-radical polymerised unsaturated compound, from ensuring liquid crystal sealing agent group The viscosity of compound, flexible aspect are set out, and are preferably selected from being changed by EO modified glycerols three (methyl) acrylate (trifunctional), PO Property glycerine three (methyl) acrylate (trifunctional), pentaerythrite three (methyl) acrylate (trifunctional), dipentaerythritol six More than a kind in the group of (methyl) acrylate (six functions) and pentaerythrite four (methyl) acrylate (tetrafunctional) composition Compound, more preferably EO modified glycerols three (methyl) acrylate.
Then, as the compound H with epoxy radicals, it is preferably selected from by bisphenol A type epoxy compound, bisphenol-f type ring Oxygen compound, bisphenol-A D-ring oxygen compound, phenol novolak-type epoxy compound, cresol novolak type epoxy chemical combination Thing, naphthalene type epoxide, resorcinol type epoxide, their hydrogenation compound and alicyclic ring type epoxide composition At least one of group compound, more preferably selected from by bisphenol A type epoxy compound, bisphenol F type epoxy compound, naphthalene type At least one of the group of epoxide and resorcinol type epoxide composition compound, more preferably bisphenol-A Type epoxide.
As the concrete example of bisphenol A type epoxy compound, there are EPICLON850S, 860,1055, EXA- that DIC societies manufacture 850CRP etc..
As the concrete example of hydrogenated bisphenol A type epoxide, what KRM-2408, JER society for having ADEKA societies to manufacture manufactured YX-8034 etc..
As the concrete example of bisphenol F type epoxy compound, there are EPICLON 830S of DIC societies manufacture etc..
As the concrete example of naphthalene type epoxide, there are EPICLON HP-4032D, HP-7200H of the manufacture of DIC societies etc..
As the concrete example of phenol novolak-type epoxy compound, there are DIC societies to manufacture EPICLON N-740, N-770 Deng.
As the concrete example of cresol novolak type epoxy compound, there are EPICLON N-660, N-670 that DIC societies manufacture Deng.
As the concrete example of resorcinol type epoxide, there are the Denacol EX- that Nagase ChemteX societies manufacture 201 etc..
As the concrete example of alicyclic ring type epoxide, there are 3,4- epoxy hexanes ylmethyl -3 ', 4 '-epoxy hexane Carboxylate (Daicel societies manufacture Celloxide 2021P), 1,2：(Daicel societies manufacture Celloxide to the epoxy limonenes of 8,9- bis- 3000), 1,2- epoxies -4- vinyl cyclohexanes (Daicel societies manufacture Celloxide 2000), double (the methylol) -1- fourths of 2,2- 1,2- epoxies -4- (2- Oxyranyles) hexamethylene addition product (Daicel societies manufacture EHPE3150) of alcohol etc..
As the compound H with ethylenic unsaturated group and epoxy radicals, can enumerate makes the chemical combination containing epoxy radicals Thing and (methyl) acrylic compounds react obtained part (methyl) Acrylate Modified Epoxy compound, are used as this Compound, preferably makes bisphenol A type epoxy resin and (methyl) acrylic acid react obtained part (methyl) acrylated ring Oxygen compound.
It is above-mentioned bisphenol A type epoxy resin and (methyl) acrylic acid is reacted obtained part (methyl) acrylated ring Oxygen tree fat is for example obtained in the following manner.
First, make bisphenol A type epoxy resin with (methyl) acrylic acid in base catalyst, preferably trivalent organic phosphoric acid chemical combination Reacted in the presence of thing and/or amines.On reaction ratio now, make (methyl) third relative to the equivalent of epoxy radicals 1 Olefin(e) acid is 10~90 equivalent % ratio.Next, the reaction product is filtered, centrifuged and/or washed etc. Reason, so as to remove base catalyst, is refined.As above-mentioned base catalyst, it can use in epoxy resin and (methyl) The known base catalyst used in the reaction of acrylic acid.In addition it is also possible to using being supported with base catalysis on polymer The Polymer Supported base catalyst of agent.
As described above, various compound H can be contained in the liquid crystal sealing agent composition of the present invention, but consolidating in the present invention In the case of not containing ethylenic unsaturated group in the property changed resin etc., as above-claimed cpd H, preferably as radical polymerization The above-mentioned compound with ethylenic unsaturated group of property compound.
In addition, compound H described above can be used alone, two or more can also be applied in combination.
<Photoepolymerizationinitiater initiater>
The liquid crystal sealing agent composition of the present invention can contain make the present invention curable resin etc. (and containing In the case of make compound H) photopolymerization when as free radical occurring source Photoepolymerizationinitiater initiater.It is not special to Photoepolymerizationinitiater initiater Limit, known compound can be used, be can be used alone, two or more can also be applied in combination.
As above-mentioned Photoepolymerizationinitiater initiater, can enumerate benzoin class, acetophenones, benzophenone, thioxanthene ketone class, α- Acyl group oxime esters, glyoxalic acid phenyl ester class, benzil class, Azo, diphenyl sulfide based compound, acylphosphine oxide system Compound, benzoin ethers and Anthraquinones etc., the dissolubility preferably in liquid crystal it is low and its own in light irradiation, analyte is not The Photoepolymerizationinitiater initiater with reactive group gasified.
<Sensitising agent>
The liquid crystal sealing agent composition of the present invention generally carries out photocuring, in order to improve sensitivity now to light, can be with Contain sensitising agent., can be without particular limitation using existing known various compounds as above-mentioned sensitising agent, sensitising agent can To be used alone a kind, two or more can also be applied in combination.
As above-mentioned sensitising agent, from curability aspect, for example, carbonyls, organic sulfur chemical combination can be enumerated Thing, persulfide, redox based compound, azo and diazonium compound, halide, photo-reduction pigment etc..
As sensitising agent, it can specifically enumerate：The acridone derivatives of N- methylacridines ketone, N- butyl acridones etc； And α, α-diethoxy acetophenone, benzil, Fluorenone, xanthone, uranyl compound etc., also, it is used as above-mentioned photopolymerization Also include the material as sensitising agent function in the material that the example of initiator is enumerated.
<Curing agent>
From the cementability aspect for the liquid crystal sealing agent composition for improving the present invention, above-mentioned liquid crystal sealing agent composition In can contain curing agent.Above-mentioned curing agent is not particularly limited, known compound can be used.
As above-mentioned curing agent, from cementability aspect, preferably amine system curing agent, such as organic acid dihydrazide chemical combination Thing, imidazole and its derivants, dicyandiamide, aromatic amine, epoxide modified polyamine, poly- semicarbazides etc..These curing agent can be single 1 kind is solely used, two or more can also be applied in combination.
<Curing accelerator>
From the curing reaction for promoting cure component (curable resin of the invention etc. and the compound H of described above etc.) From the aspect of, liquid crystal sealing agent composition of the invention can contain curing accelerator, and curing accelerator can be used alone 1 Kind, two or more can also be applied in combination.
As its preference, it can enumerate：The imidazoles such as 2-methylimidazole, 2- ethyl imidazol(e)s and 2-ethyl-4-methylimidazole Class；The tertiary amines such as 2- (dimethylamino methyl) phenol and the carbon -7- alkene (DBU) of 1,8- diazabicyclos [5.4.0] 11；Triphenyl The phosphines such as phosphine；Metallic compounds such as stannous octoate etc..
<Filler>
From control viscosity, bonding reliability, suppress linear expansivity aspect, liquid crystal sealing agent composition of the invention Filler can be contained.As above-mentioned filler, inorganic filler and organic filler can be used, they can be used alone, and also may be used So that two or more to be applied in combination.
As above-mentioned inorganic filler, can enumerate calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, alumina silicate, titanium dioxide, Aluminum oxide, zinc oxide, silica, kaolin, talcum, bead, sericite atlapulgite, bentonite, aluminium nitride and nitrogen SiClx etc..
As above-mentioned organic filler, can enumerate polymethyl methacrylate, polystyrene, make their monomer of composition with Copolymer that other monomer copolymerizations are obtained, polyester micropartical, polyurethane particulate, rubber particle and by comprising with high-vitrification Core-shell particle that the core of the shell of the copolymer of transition temperature and copolymer with lower glass transition temperatures is constituted etc..As Core-shell particle, can enumerate ZEFIAC serial (F351 etc.) of GANZ Chemical societies manufacture etc..
The side from the ease gas (ア ウ ト ガ ス) of liquid crystal sealing agent is reduced as the filler of non-reactive components from by mixture Face considers that the average grain diameter for constituting the particle of filler is usually 0.1~3 μm, more preferably 0.5~3 μm.It should be noted that Laser diffraction/scattering formula particle size distribution analyzer (such as HORIBA that the average grain diameter of filler can be manufactured using HORIBA societies The Partica LA-950V2 of society's manufacture) it is measured.
<Silane coupler>
The liquid crystal sealing agent composition of the present invention can contain silane coupler in the range of effect of the present invention has been given play to. Silane coupler can be used alone, and two or more can also be applied in combination.
From take into account make the present invention liquid crystal sealing agent composition solidification liquid crystal sealing agent solidfied material cementability and Set out in terms of flexibility, as silane coupler, be preferably selected from least one of the group that is made up of following substances silane Coupling agent：Tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, two Methoxyl group diethoxy silane, dimethoxy diisopropoxy silane, diethoxy diisopropoxy silane, the fourth of diethoxy two The tetraalkoxysilane class such as TMOS；MTMS, MTES, the isopropoxy silicon of methyl three Alkane, ethyl triethoxysilane, the butoxy silane of ethyl three, cyclohexyltriethyloxysilane, the isopropoxy silane of phenyl three, second Alkenyl trimethoxy silane, 3- glycidoxypropyltrime,hoxysilanes, 3- methacryloxypropyl trimethoxy silicon The trialkoxysilanes such as alkane；And dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl diethoxy silicon The dialkoxy base class such as alkane, diethyl dibutoxy silane, phenylethyl diethoxy silane, among these, are more preferably selected from By MTMS, MTES, the isopropoxy silane of methyl three, ethyl triethoxysilane, ethyl Three butoxy silanes, cyclohexyltriethyloxysilane, the isopropoxy silane of phenyl three, vinyltrimethoxy silane, 3- epoxies At least one of group of propoxypropyl trimethoxy silane and 3- methacryloxypropyl trimethoxy silanes composition Trialkoxy silane system silane coupler, further preferred 3- glycidoxypropyltrime,hoxysilanes.
Embodiment
Illustrate the present invention by the following examples, but the present invention and be not limited to the examples restriction.Need explanation , the compound used in embodiment and comparative example manufactures as follows.
[comparing synthesis example 1] acrylated bisphenol A type epoxy resin of part methyl
By bisphenol A type epoxy resin (EXA850CRP, Dainippon Ink Chemicals's manufacture) 340.0g, methacrylic acid (Tokyo Into society's manufacture) 90.4g, triphenylphosphine (manufacture of Tokyo chemical conversion society) 0.5g and BHT (dibutyl hydroxy toluene) 100mg mixing, 100 DEG C are stirred 6 hours.Obtain the acrylated bisphenol A type epoxy resin 418.0g of part methyl of light yellow clear dope.
[synthesis example 1] methacrylation curable resin 1
(1) by polyethylene glycol #1000 (manufacture of LION societies) 2000.0g (4.0 equivalents/hydroxyl), epichlorohydrin 2220.0g (6.0 Equivalent), benzyltrimethylammonium chloride 74.3g (0.10 equivalent) is added to and is provided with machine mixer, thermometer, temperature adjustment In device, condenser, 5 liters of three neck round bottom flask of Dean-Stark trap and dropping funel.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 600.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.
After addition terminates, continue to stir 3 hours.Next, reactant mixture is cooled into room temperature, chloroform 3L is added, is used 3L water is cleaned 6 times.The solvent of organic phase obtained by being removed by vacuum distillation, obtains 1150.0g white waxy solids Compound E-1.
(2) compound E-1 (950.0g (1.7 equivalents/epoxy radicals)) and bisphenol-A (988.0g (2.5 equivalent)) are added to In eggplant type flask, carrying out heating stirring makes liquid temperature reach 150 DEG C.4%NaOH aqueous solution 2.9g are added, it is small in 150 DEG C of stirrings 6 When.
Liquid temperature is cooled to for less than 60 DEG C, chloroform 2L is added, is cleaned 6 times with 1%NaOH aqueous solution 2L, 6 are cleaned with water 2L It is secondary.
Magnesium sulfate is added into resulting organic phase, solid constituent is filtered out by filtering etc. after drying, passes through to depressurize and steams Evaporate and the solvent of resulting organic phase is distilled off, 997.0g is obtained using in the form of light yellow clear dope as in synthesis The reactant G-1 of mesosome.
(3) reactant G-1 (997.0g), epichlorohydrin (1423.0g) and benzyltrimethylammonium chloride (47.5g) are added to It is provided with 5 liter three of machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel In mouth round-bottomed flask.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 384.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.
Next, reactant mixture is cooled into room temperature, chloroform 2L is added, is cleaned with 2L water 6 times.Pass through vacuum distillation The solvent of organic phase obtained by removing, obtains the resin 1 of 982.0g thick pale yellow things.
(4) 100.0g resins 1, methacrylic acid 8.6g, triphenylphosphine 0.5g and BHT20mg are mixed, stirred at 100 DEG C Mix 5 hours.Obtain the methacrylation curable resin 1 of 107.0g thick pale yellow things.
[synthesis example 2] methacrylation curable resin 2
(1) by polytetramethylene ether diol (PTMG) 1000 (manufacture of society of Mitsubishi Chemical) 500.0g (1.0 equivalents/hydroxyl), Epichlorohydrin 555.0g (6.0 equivalent), benzyltrimethylammonium chloride 18.6g (0.10 equivalent) be added to be provided with machine mixer, In thermometer, thermoregulator, condenser, 2 liters of three neck round bottom flask of Dean-Stark trap and dropping funel.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 150.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.
Next, reactant mixture is cooled into room temperature, chloroform 1L is added, is cleaned with 1L water 4 times.Pass through vacuum distillation The solvent of organic phase obtained by removing, obtains the compound E-2 of 459.0g white waxy solids.
(2) compound E-2 (132.0g (0.20 equivalent/epoxy radicals)) and bisphenol-A (114.0g (2.5 equivalent)) are added to In eggplant type flask, carrying out heating stirring makes liquid temperature reach 150 DEG C.4%NaOH aqueous solution 0.3g are added, it is small in 150 DEG C of stirrings 6 When.Liquid temperature is cooled to for less than 60 DEG C, chloroform 500mL is added, is cleaned 3 times, cleaned with water 1L 3 times with 1%NaOH aqueous solution 1L.
Magnesium sulfate is added into resulting organic phase, solid constituent is filtered out by filtering etc. after drying, passes through to depressurize and steams Evaporate and the solvent of resulting organic phase is distilled off, 140.0g is obtained using in the form of light yellow clear dope as in synthesis The reactant G-2 of mesosome.
(3) reactant G-2 (140.0g), epichlorohydrin (195.0g) and benzyltrimethylammonium chloride (6.5g) are added to peace 1 liter three mouthfuls equipped with machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel In round-bottomed flask.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 53.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.Next, reactant mixture is cooled into room temperature, chloroform 500mL is added, 4 are cleaned with 500mL water It is secondary.The solvent of organic phase obtained by being removed by vacuum distillation, obtains the resin 2 of 129.0g thick pale yellow things.
(4) 48.6g resins 2, methacrylic acid 4.3g, triphenylphosphine 0.3g and BHT10mg are mixed, in 100 DEG C of stirrings 6 hours.Obtain the methacrylation curable resin 2 of 50.6g thick pale yellow things.
[synthesis example 3] methacrylation curable resin 3
(1) by NISSO-PB G-1000 (Japanese Cao Da societies manufacture) 350.0g (0.50 equivalent/hydroxyl), epichlorohydrin 370.0g (8.0 equivalent), benzyltrimethylammonium chloride 9.3g (0.10 equivalent) be added to be provided with machine mixer, thermometer, In thermoregulator, condenser, 2 liters of three neck round bottom flask of Dean-Stark trap and dropping funel.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 75.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.
Next, reactant mixture is cooled into room temperature, chloroform 500mL is added, is cleaned with 500mL water 6 times.By subtracting The solvent of resulting organic phase is distilled off in pressure, obtains the compound E-3 of 298.0g clear viscous things.
(2) by compound E-3 (96.5g (0.10 equivalent/epoxy radicals)), bisphenol-A (68.5g (3.0 equivalent)), benzyl front three Ammonium chloride 0.9g (0.050 equivalent) and methyl iso-butyl ketone (MIBK) 100.0g are added in eggplant type flask, using liquid temperature as 120 DEG C of side Formula is heated to reflux, while stirring 20 hours.Liquid temperature is cooled to for less than 60 DEG C, chloroform 300mL is added, uses the 1%NaOH aqueous solution 300mL is cleaned 5 times, is cleaned with water 300mL 5 times.
Magnesium sulfate is added into resulting organic phase, solid constituent is filtered out by filtering etc. after drying, passes through to depressurize and steams Evaporate and the solvent of resulting organic phase is distilled off, 75.5g is obtained using in the form of light yellow clear dope as in synthesis The reactant G-3 of mesosome.
(3) reactant G-3 (75.5g), epichlorohydrin (112.5g) and benzyltrimethylammonium chloride (2.8g) are added to peace 500 milliliters equipped with machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel In three neck round bottom flask.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 23.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.
Next, reactant mixture is cooled into room temperature, chloroform 300mL is added, is cleaned with 300mL water 6 times.By subtracting The solvent of resulting organic phase is distilled off in pressure, obtains the resin 3 of 54.4g thick pale yellow things.
(4) 50.0g resins 3, methacrylic acid 3.3g, triphenylphosphine 0.2g and BHT10mg are mixed, 5 is stirred at 100 DEG C Hour.Obtain the methacrylation curable resin 3 of 47.0g thick pale yellow things.
[synthesis example 4] methacrylation curable resin 4
(1) by NISSO-PB GI-1000 (Japanese Cao Da societies manufacture) 300.0g (0.40 equivalent/hydroxyl), epichlorohydrin 296.0g (8.0 equivalent), benzyltrimethylammonium chloride 7.4g (0.10 equivalent) be added to be provided with machine mixer, thermometer, In thermoregulator, condenser, 2 liters of three neck round bottom flask of Dean-Stark trap and dropping funel.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 60.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.
Next, reactant mixture is cooled into room temperature, chloroform 500mL is added, is cleaned with 500mL water 6 times.By subtracting The solvent of resulting organic phase is distilled off in pressure, obtains the compound E-4 of 264.0g clear viscous things.
(2) by compound E-4 (80.0g (0.060 equivalent/epoxy radicals)), bisphenol-A (57.1g (4.0 equivalent)), benzyl three Ammonio methacrylate 0.9g (0.080 equivalent) and methyl iso-butyl ketone (MIBK) 100.0g are added in eggplant type flask, using liquid temperature as 120 DEG C Mode is heated to reflux, while stirring 20 hours.Liquid temperature is cooled to for less than 60 DEG C, addition chloroform 300mL is water-soluble with 1%NaOH Liquid 300mL is cleaned 5 times, is cleaned with water 300mL 5 times.
Magnesium sulfate is added into resulting organic phase, solid constituent is filtered out by filtering etc. after drying, passes through to depressurize and steams Evaporate and the solvent of resulting organic phase is distilled off, 80.0g is obtained using in the form of thick pale yellow thing as synthetic intermediate Reactant G-4.
(3) reactant G-4 (80.0g), epichlorohydrin (88.8g) and benzyltrimethylammonium chloride (3.0g) are added to installation There are 500 milliliters of machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel In three neck round bottom flask.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 24.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.
Next, reactant mixture is cooled into room temperature, chloroform 300mL is added, is cleaned with 300mL water 6 times.By subtracting The solvent of resulting organic phase is distilled off in pressure, obtains the resin 4 of 56.0g thick pale yellow things.
(4) 50.0g resins 4, methacrylic acid 3.0g, triphenylphosphine 0.2g and BHT10mg are mixed, in 100 DEG C of stirrings 12 hours.Obtain the methacrylation curable resin 4 of 47.0g thick pale yellow things.
[synthesis example 5] methacrylation curable resin 5
(1) by compound E-2 (96.0g (0.15 equivalent/epoxy radicals)), 4- α-cumyl phenol (30.0g (1.0 equivalent)), Benzyltrimethylammonium chloride 1.4g (0.050 equivalent) is added in eggplant type flask, is heated to reflux by liquid temperature in the way of 120 DEG C, Stir 30 hours simultaneously.Liquid temperature is cooled to for less than 60 DEG C, 125.0g is obtained using in the form of thick pale yellow thing as in synthesis The reactant G-5 of mesosome.
(2) reactant G-5 (125.0g), epichlorohydrin (150.0g) and benzyltrimethylammonium chloride (2.8g) are added to peace 500 milliliters equipped with machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel Three neck round bottom flask in.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 30.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.
Next, reactant mixture is cooled into room temperature, chloroform 500mL is added, is cleaned with 500mL water 6 times.By subtracting The solvent of resulting organic phase is distilled off in pressure, obtains the resin 5 of 130.0g thick pale yellow things.
(3) 63.5g resins 5, methacrylic acid 4.3g, triphenylphosphine 0.1g and BHT13mg are mixed, 6 is stirred at 100 DEG C Hour.Obtain the methacrylation curable resin 5 of 66.0g thick pale yellow things.
[synthesis example 6] methacrylation curable resin 6
(1) compound E-2 (64.0g (0.10 equivalent/epoxy radicals)) and resorcinol (27.5g (2.5 equivalent)) are added Into eggplant type flask, by liquid temperature in the way of 120 DEG C heating stirring.4%NaOH aqueous solution 0.2g are added, 24 are stirred at 120 DEG C Hour.Liquid temperature is cooled to for less than 60 DEG C, chloroform 300mL is added, is cleaned with water 300mL 4 times.
Magnesium sulfate is added into resulting organic phase, solid constituent is filtered out by filtering etc. after drying, passes through to depressurize and steams Evaporate and the solvent of resulting organic phase is distilled off, 60.5g is obtained using in the form of light yellow clear dope as in synthesis The reactant G-6 of mesosome.
(2) reactant G-6 (60.5g), epichlorohydrin (102.0g) and benzyltrimethylammonium chloride (3.4g) are added to peace 500 milliliters equipped with machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel Three neck round bottom flask in.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 28.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.Next, reactant mixture is cooled into room temperature, chloroform 300mL is added, 6 are cleaned with 300mL water It is secondary.The solvent of organic phase obtained by being removed by vacuum distillation, obtains the resin 6 of 48.0g thick pale yellow things.
(3) 44.6g resins 6, methacrylic acid 4.3g, triphenylphosphine 0.1g and BHT10mg are mixed, in 100 DEG C of stirrings 14 hours.Obtain the methacrylation curable resin 6 of 42.8g thick pale yellow things.
[synthesis example 7] methacrylation curable resin 7
(1) by compound E-2 (53.0g (0.080 equivalent/epoxy radicals)) and 2- (4- hydroxyphenyls) ethanol, ((1.0 work as 11.1g Amount)) be added in eggplant type flask, by liquid temperature in the way of 120 DEG C heating stirring.Add benzyltrimethylammonium chloride (3.0g (0.20 equivalent)), stirred 24 hours at 120 DEG C.Liquid temperature is cooled to for less than 60 DEG C, chloroform 300mL is added, uses 1%NaOH water Solution 300mL is cleaned 1 time, is cleaned with water 300mL 5 times.
Magnesium sulfate is added into resulting organic phase, solid constituent is filtered out by filtering etc. after drying, passes through to depressurize and steams Evaporate and the solvent of resulting organic phase is distilled off, 59.0g is obtained using in the form of light yellow clear dope as in synthesis The reactant G-7 of mesosome.
(2) reactant G-7 (59.0g), epichlorohydrin (93.3g) and benzyltrimethylammonium chloride (3.1g) are added to installation There are 500 milliliters of machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel In three neck round bottom flask.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 25.2g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.Next, reactant mixture is cooled into room temperature, chloroform 300mL is added, 6 are cleaned with 300mL water It is secondary.The solvent of organic phase obtained by being removed by vacuum distillation, obtains the resin 7 of 50.5g thick pale yellow things.
(3) 47.3g resins 7, methacrylic acid 5.2g, triphenylphosphine 0.1g and BHT10mg are mixed, 7 is stirred at 100 DEG C Hour.Obtain the methacrylation curable resin 7 of 51.0g thick pale yellow things.
[synthesis example 8] methacrylation curable resin 8
(1) compound E-2 (94.0g (0.15 equivalent/epoxy radicals)) and phenol (21.2g (1.5 equivalent)) are added to eggplant In shape flask, by liquid temperature in the way of 120 DEG C heating stirring.Benzyltrimethylammonium chloride (2.8g (0.10 equivalent)) is added, 120 DEG C are stirred 24 hours.Liquid temperature is cooled to for less than 60 DEG C, methyl iso-butyl ketone (MIBK) 300mL is added, uses the 1%NaOH aqueous solution 300mL is cleaned 2 times, is cleaned with water 300mL 4 times.
Magnesium sulfate is added into resulting organic phase, solid constituent is filtered out by filtering etc. after drying, passes through to depressurize and steams Evaporate and the solvent of resulting organic phase is distilled off, 90.0g is obtained using in the form of light yellow clear dope as in synthesis The reactant G-8 of mesosome.
(2) reactant G-8 (90.0g), epichlorohydrin (130.0g) and benzyltrimethylammonium chloride (2.6g) are added to peace 500 milliliters equipped with machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel Three neck round bottom flask in.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 21.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.Next, reactant mixture is cooled into room temperature, chloroform 300mL is added, 6 are cleaned with 300mL water It is secondary.The solvent of organic phase obtained by being removed by vacuum distillation, obtains the resin 8 of 80g thick pale yellow things.
(3) 57.6g resins 8, methacrylic acid 3.5g, triphenylphosphine 0.1g and BHT10mg are mixed, in 100 DEG C of stirrings 13 hours.Obtain the methacrylation curable resin 8 of 59.2g thick pale yellow things.
[synthesis example 9] methacrylation curable resin 9
(1) by double (the 4- hydroxy-3-methyls phenyl) fluorenes of compound E-2 (63.0g (0.10 equivalent/epoxy radicals)) and 9,9- (95.0g (2.5 equivalent)), n-butyl alcohol (80.0g) are added in eggplant type flask, are heated to reflux at 120 DEG C.Add benzyl trimethyl Ammonium chloride (0.9g (0.050 equivalent)), is stirred 20 hours in 120 DEG C of stirrings.Liquid temperature is cooled to for less than 60 DEG C, chloroform is added 300mL, is cleaned 14 times with 1%NaOH aqueous solution 300mL, is cleaned with water 300mL 5 times.
Magnesium sulfate is added into resulting organic phase, solid constituent is filtered out by filtering etc. after drying, passes through to depressurize and steams Evaporate and the solvent of resulting organic phase is distilled off, 56.0g is obtained using in the form of light yellow clear dope as in synthesis The reactant G-9 of mesosome.
(2) reactant G-9 (56.0g), epichlorohydrin (111.0g) and benzyltrimethylammonium chloride (2.2g) are added to peace 500 milliliters equipped with machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel Three neck round bottom flask in.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 18.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.Next, reactant mixture is cooled into room temperature, chloroform 300mL is added, 6 are cleaned with 300mL water It is secondary.The solvent of organic phase obtained by being removed by vacuum distillation, obtains the resin 9 of 54.0g thick pale yellow things.
(3) 51.0g resins 9, methacrylic acid 4.3g, triphenylphosphine 0.1g and BHT10mg are mixed, 9 is stirred at 100 DEG C Hour.Obtain the methacrylation curable resin 9 of 49.8g thick pale yellow things.
[synthesis example 10] methacrylation curable resin 10
(1) by PEG-2000 (manufacture of Dong Bang chemical industry society) 1000.0g (1.0 equivalents/hydroxyl), epichlorohydrin 925.0g (10 equivalent), benzyltrimethylammonium chloride 18.6g (0.10 equivalent), which are added to, is provided with machine mixer, thermometer, temperature tune In 5 liters of three neck round bottom flask for saving device, condenser, Dean-Stark trap and dropping funel.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 150.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.
After addition terminates, continue to stir 3 hours.Next, reactant mixture is cooled into room temperature, chloroform 1L is added, is used 1L water is cleaned 3 times.The solvent of organic phase obtained by being removed by vacuum distillation, obtains the change of 760.0g white waxy solids Compound E-5.
(2) compound E-5 (220.0g (0.20 equivalent/epoxy radicals)) and bisphenol-A (31.0g (1.4 equivalent)) are added to In eggplant type flask, by liquid temperature in the way of 110 DEG C heating stirring.Benzyltrimethylammonium chloride 1.9g is added, 20 are stirred at 110 DEG C Hour.
Liquid temperature is cooled to for less than 60 DEG C, chloroform 300mL is added, is cleaned 3 times with 1%NaOH aqueous solution 300mL, use water 300mL is cleaned 6 times.
Magnesium sulfate is added into resulting organic phase, solid constituent is filtered out by filtering etc. after drying, passes through to depressurize and steams Evaporate and the solvent of resulting organic phase is distilled off, 110.0g is obtained using in the form of light yellow clear dope as in synthesis The reactant G-10 of mesosome.
(3) reactant G-10 (108.0g), epichlorohydrin (175.0g) and benzyltrimethylammonium chloride (2.3g) are added to It is provided with 1 liter of machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel In three neck round bottom flask.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 19.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.
Next, reactant mixture is cooled into room temperature, chloroform 300mL is added, is cleaned with 300mL water 6 times.By subtracting The solvent of resulting organic phase is distilled off in pressure, obtains the resin 10 of 92.0g white waxy solids.
(4) by 21.7g resins 10, methacrylic acid 1.1g, benzyltrimethylammonium chloride 0.1g, toluene 50.0g and BHT15mg is mixed, and is stirred 7 hours at 100 DEG C.Next, reactant mixture is cooled into room temperature, chloroform 100mL is added, is used 100mL water is cleaned 3 times.The solvent of organic phase obtained by being removed by vacuum distillation, obtains 17.0g white waxy solids Methacrylation curable resin 10.
[synthesis example 11] methacrylation curable resin 11
(1) by polytetramethylene ether diol (PTMG) 2000 (manufacture of society of Mitsubishi Chemical) 500.0g (0.50 equivalent/hydroxyl), Epichlorohydrin 463.0g (10 equivalent), benzyltrimethylammonium chloride 9.3g (0.10 equivalent) are added to and are provided with machine mixer, temperature In 2 liters of three neck round bottom flask for spending meter, thermoregulator, condenser, Dean-Stark trap and dropping funel.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 75.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.
After addition terminates, continue to stir 3 hours.Next, reactant mixture is cooled into room temperature, chloroform 1L is added, is used 1L water is cleaned 3 times.The solvent of organic phase obtained by being removed by vacuum distillation, obtains the change of 450.0g white waxy solids Compound E-6.
(2) compound E-6 (127.0g (0.10 equivalent/epoxy radicals)) and bisphenol-A (15.0g (1.4 equivalent)) are added to In eggplant type flask, by liquid temperature in the way of 110 DEG C heating stirring.Benzyltrimethylammonium chloride 0.9g is added, 20 are stirred at 110 DEG C Hour.
Liquid temperature is cooled to for less than 60 DEG C, chloroform 300mL is added, is cleaned 3 times with 1%NaOH aqueous solution 300mL, use water 300mL is cleaned 6 times.
Magnesium sulfate is added into resulting organic phase, solid constituent is filtered out by filtering etc. after drying, passes through to depressurize and steams Evaporate and the solvent of resulting organic phase is distilled off, 120.0g is obtained using in the form of light yellow clear dope as in synthesis The reactant G-11 of mesosome.
(3) reactant G-11 (117.0g), epichlorohydrin (125.0g) and benzyltrimethylammonium chloride (2.5g) are added to It is provided with 1 liter of machine mixer, thermometer, thermoregulator, condenser, Dean-Stark trap and dropping funel In three neck round bottom flask.
Next, mixture is stirred under 50 supports (torr) high vacuum, while being heated to about 50 DEG C to 60 DEG C, make table Chloropharin vigorous reflux.The 20.0g 48%NaOH aqueous solution is added slowly in mixture with the times of 2 hours.Generation is altogether Boil after thing, send the epichlorohydrin in water/epichlorohydrin mixture back to reaction system immediately, while proceeding stirring.Addition is terminated Afterwards, continue to stir 3 hours.
Next, reactant mixture is cooled into room temperature, chloroform 300mL is added, is cleaned with 300mL water 6 times.By subtracting Pressure is distilled off, by the solvent removing of resulting organic phase, obtaining the resin 11 of 92.0g thick pale yellow things.
(4) 55.0g resins 11, methacrylic acid 2.6g, triphenylphosphine 0.1g and BHT10mg are mixed, in 100 DEG C of stirrings 7 hours.Obtain the methacrylation curable resin 11 of 54.0g thick pale yellow things.
[manufacture of Photoepolymerizationinitiater initiater]
The Photoepolymerizationinitiater initiater used in embodiment and comparative example is manufactured as follows.
<The manufacture of Photoepolymerizationinitiater initiater 1>
By Denacol EX-830 (PEG400 diglycidyl ether Nagase ChemteX societies manufacture) 26.8g (0.10 equivalent/epoxy radicals), 4- dimethylaminobenzoic acids 16.5g (1.0 equivalent), benzyltrimethylammonium chloride 3.7g (0.20 Equivalent), MIBK (methyl iso-butyl ketone (MIBK)) 25.0g be added in flask, 110 DEG C stir 24 hours.Reactant mixture is cooled down To room temperature, it is dissolved in chloroform 50g, is cleaned with water 100ml 6 times.The solvent under reduced pressure of organic phase is distilled off, 35.3g is obtained Photoepolymerizationinitiater initiater 1.
<The manufacture of Photoepolymerizationinitiater initiater 2>
By Denacol EX-830 (PEG400 diglycidyl ether Nagase ChemteX societies manufacture) 26.8g (0.10 equivalent/epoxy radicals), 2- hydroxyl -9H- thioxanthene-9-ones 22.8g (1.0 equivalent), benzyltrimethylammonium chloride 3.7g (0.20 Equivalent), MIBK40.0g be added in flask, 110 DEG C stir 72 hours.Reactant mixture is cooled to room temperature, chlorine is dissolved in In imitative 50g, cleaned with water 100ml 6 times.The solvent under reduced pressure of organic phase is distilled off, 36.2g Photoepolymerizationinitiater initiaters 2 are obtained.
[embodiment 1~11 and comparative example 1]
The acrylated bisphenol A type epoxy resin of part methyl, the methyl that synthesis example and comparing is manufactured in synthesis example respectively Acrylated curable resin 1~11 and Photoepolymerizationinitiater initiater 1 and 2 and EH-5030S (the ADEKA manufactures for being used as curing agent (polynary amine compound)) mixed according to the combined amount (parts by weight) shown in table 1 below, afterwards using three-roll mill (well C-43/4 manufactured by upper making × 10) fully kneaded, obtains the liquid crystal sealing agent combination of embodiment 1~11 and comparative example 1 Thing.
For synthesis example and comparing each compound manufactured in synthesis example and each liquid crystal sealing agent composition, by with Under experiment evaluated.
[experimental condition]
On the acrylated bisphenol A type epoxy resin of part methyl, methacrylation curable resin 1~9 and 11, survey Determine epoxide equivalent, viscosity and the change of NI points,
On methacrylation curable resin 10, epoxide equivalent and the change of NI points are determined,
On Photoepolymerizationinitiater initiater 1 and 2, viscosity and the change of NI points are determined,
On curing agent (EH-5030S), the change of NI points is determined,
Determine the Tg and various temperature of the solidfied material of the liquid crystal sealing agent composition manufactured in embodiment 1~11 and comparative example 1 Storage modulus under degree.
(1) epoxide equivalent is determined
In JISK7236：Determined under conditions of described in 2001.
(2) viscosimetric analysis
Using E types viscosimeter (Dong Ji industries society manufactures RE105U), it is measured at 25 DEG C.
Following selection rotor and rotating speed.
The acrylated bisphenol A type epoxy resin of part methyl：3 ° × R7.7 rotors, rotating speed 10rpm
Methacrylation curable resin 1：3 ° × R7.7 rotors, rotating speed 15rpm
Methacrylation curable resin 2：3 ° × R7.7 rotors, rotating speed 15rpm
Methacrylation curable resin 3：3 ° × R7.7 rotors, rotating speed 0.5rpm
Methacrylation curable resin 4：3 ° × R7.7 rotors, rotating speed 0.2rpm
Methacrylation curable resin 5：1 ° of 34 ' × R24 rotors, rotating speed 2.0rpm
Methacrylation curable resin 6：3 ° × R14 rotors, rotating speed 5.0rpm
Methacrylation curable resin 7：1 ° of 34 ' × R24 rotors, rotating speed 5.0rpm
Methacrylation curable resin 8：1 ° of 34 ' × R24 rotors, rotating speed 2.0rpm
Methacrylation curable resin 9：3 ° × R7.7 rotors, rotating speed 2.0rpm
Methacrylation curable resin 11：3 ° × R7.7 rotors, rotating speed 15rpm
(3) NI points change is determined
The acrylated bisphenol A type epoxy resin of part methyl, methacrylation curability are separately added into ampoule bottle Resin 1~11, Photoepolymerizationinitiater initiater 1 and 2, curing agent (EH-5030S) 0.1g, further add liquid crystal (MLC-11900-080, Merck society manufactures) 1g.The bottle is put into 120 DEG C of baking ovens 1 hour, is being stored at room temperature thereafter, room temperature (25 DEG C) is being returned to After take out lcd segment, filtered with 0.2 μm of filter, evaluation liquid crystalline sample be made.
The measure of NI points will be evaluated using differential scanning type calorimeter (manufacture of DSC, Perkin Elmer societies, PYRIS6) It is sealing into aluminium sample disc, is measured under conditions of programming rate is 5 DEG C/min with liquid crystalline sample 10mg.Need explanation , above-mentioned liquid crystal 10mg is sealing into aluminium sample disc, is measured, will survey under conditions of programming rate is 5 DEG C/min Result is determined as blank.
By heat absorption summit (phase transition temperature) TE's of heat absorption summit (phase transition temperature) TB of blank and evaluation liquid crystal Poor TE-TB changes as NI points.From suppress liquid crystal sealing agent containing dissolution of the composition in liquid crystal, stably ensure liquid crystal From the aspect of orientation, raising display characteristic, the absolute value of NI points change is smaller more preferred.
(4) Tg is determined
On the liquid crystal sealing agent composition manufactured in embodiment 1~11 and comparative example 1, it is molded in long 5cm, width 5mm, thickness In 0.5mm mould, with accumulated light 3000mJ/cm2Irradiation ultraviolet radiation (UV irradiation units：UVX-01224S1、USHIO INC. society manufacture, 100mW/cm2/ 365nm, 30 seconds) solidify it, afterwards, utilize 120 DEG C hot-air ovens carry out 1 hour heat Solidification, is made solidfied material test film.
For resulting solidfied material test film, Measurement of Dynamic Viscoelasticity device (DMA, Seiko Instruments is utilized Society's manufacture, DMS6100), it is stretching to make deformation pattern, is risen with frequency 1.0Hz, in -50 DEG C~100 DEG C of scopes with 2 DEG C/min Temperature, is measured simultaneously.It regard the summit temperature in the losstangenttanδ of resulting result as Tg.
(5) storage modulus is determined
On the liquid crystal sealing agent composition manufactured in embodiment 1~11 and comparative example 1, enter under conditions of same with Tg The making of row solidfied material test film and using Measurement of Dynamic Viscoelasticity device (manufacture of DMA, Seiko Instruments societies, DMS6100 measure).In resulting result, the value of storage modulus at each temperature is extracted out.
Evaluation result and the mixing composition one of embodiment 1~11 and the liquid crystal sealing agent composition of comparative example 1 by more than Rise and be shown in table 1 below.
【Table 1】

Claims (11)

1. a kind of liquid crystal sealing agent composition, it includes the curable resin represented by following formula (1),
In formula, m is the number of 1~7 scope,
X is independently of one another hydrogen atom, hydroxyl, glycidoxypropyl or methyl glycidyl epoxide,
R1It is each, independently of the other hydrogen atom, glycidyl or methylglycidyl,
R2It is each, independently of the other hydrogen atom or methyl,
A rings are the conduct for adding up to more than 5 and including more than 1 of carbon number and hetero atom number each, independently of the other The group of the ring structure of aromatic rings or aromatic heterocycle,
It is mutually only in X in the case where at least one of X is the ring structure Direct Bonding of hydrogen atom and X and A rings on Y It is on the spot hydroxyl, glycidoxypropyl or methyl glycidyl epoxide and is bonded at least one of oxygen atom and X of A rings In the case of being bonded with the ring structure of A rings by linking group, and/or the ring structure of the A rings in X bondings is more than 1 In the case of the condensed ring or aromatic heterocycle of aromatic rings, Y is following formula (1a), following formula (1b) or by the portion in the formula (1b) Point or whole unsaturated bonds carry out hydrogenation structure group,
In formula (1a), Y1It is the alkylidene of carbon number 2~5 each, independently of the other, n is the number of 1~250 scope,
In formula (1b), Y2It is that Direct Bonding or carbon number are 1 or 2 alkylidene, R each, independently of the other3Each mutually solely It is on the spot hydrogen atom or methyl, the number of p and q each, independently of the other for more than 0, and their scope for adding up to 1~200 Number,
In the case of other than the above, Y is the formula (1b) or enters all or part of unsaturated bond in the formula (1b) The group of the structure of row hydrogenation,
Herein, the linking group is to be selected from the alkylidene for being 1~4 by carbon number, the alkylidene that carbon number is 2~4, ether One or more of group that base, ester group, ketone group, thioether group and sulfonyl are constituted,
On the R1And X, it is used as glycidyl or the R of methylglycidyl1With being used as glycidoxypropyl or methyl contracting The average value x of the X of water glycerine epoxide total number is more than 1.
2. a kind of liquid crystal sealing agent composition, it includes (methyl) acrylated curable resin, is somebody's turn to do (methyl) acrylated solid The property changed resin is at least a portion in epoxy radicals, hydroxyl and the unsaturated bond of the curable resin represented by following formula (1) On be imported with (methyl) acryloyl group,
In formula, m is the number of 1~7 scope,
X is independently of one another hydrogen atom, hydroxyl, glycidoxypropyl or methyl glycidyl epoxide,
R1It is each, independently of the other hydrogen atom, glycidyl or methylglycidyl,
R2It is each, independently of the other hydrogen atom or methyl,
A rings are the conduct for adding up to more than 5 and including more than 1 of carbon number and hetero atom number each, independently of the other The group of the ring structure of aromatic rings or aromatic heterocycle,
It is mutually only in X in the case where at least one of X is the ring structure Direct Bonding of hydrogen atom and X and A rings on Y It is on the spot hydroxyl, glycidoxypropyl or methyl glycidyl epoxide and is bonded at least one of oxygen atom and X of A rings In the case of being bonded with the ring structure of A rings by linking group, and/or the ring structure of the A rings in X bondings is more than 1 In the case of the condensed ring or aromatic heterocycle of aromatic rings, Y is following formula (1a), following formula (1b) or by the portion in the formula (1b) Point or whole unsaturated bonds carry out hydrogenation structure group,
In formula (1a), Y1It is the alkylidene of carbon number 2~5 each, independently of the other, n is the number of 1~250 scope,
In formula (1b), Y2It is that Direct Bonding or carbon number are 1 or 2 alkylidene, R each, independently of the other3Each mutually solely It is on the spot hydrogen atom or methyl, the number of p and q each, independently of the other for more than 0, and their scope for adding up to 1~200 Number,
In the case of other than the above, Y is the formula (1b) or enters all or part of unsaturated bond in the formula (1b) The group of the structure of row hydrogenation,
Herein, the linking group is to be selected from the alkylidene for being 1~4 by carbon number, the alkylidene that carbon number is 2~4, ether One or more of group that base, ester group, ketone group, thioether group and sulfonyl are constituted,
On the R1And X, it is used as glycidyl or the R of methylglycidyl1With being used as glycidoxypropyl or methyl contracting The average value x of the X of water glycerine epoxide total number is more than 1.
3. liquid crystal sealing agent composition as claimed in claim 1, wherein, the liquid crystal sealing agent composition is further included (methyl) acrylated curable resin, it is in the solidification represented by following formula (1) to be somebody's turn to do (methyl) acrylated curable resin (methyl) acryloyl group is imported with least a portion in epoxy radicals, hydroxyl and the unsaturated bond of property resin,
In formula, m is the number of 1~7 scope,
X is independently of one another hydrogen atom, hydroxyl, glycidoxypropyl or methyl glycidyl epoxide,
R1It is each, independently of the other hydrogen atom, glycidyl or methylglycidyl,
R2It is each, independently of the other hydrogen atom or methyl,
A rings are the conduct for adding up to more than 5 and including more than 1 of carbon number and hetero atom number each, independently of the other The group of the ring structure of aromatic rings or aromatic heterocycle,
It is mutually only in X in the case where at least one of X is the ring structure Direct Bonding of hydrogen atom and X and A rings on Y It is on the spot hydroxyl, glycidoxypropyl or methyl glycidyl epoxide and is bonded at least one of oxygen atom and X of A rings In the case of being bonded with the ring structure of A rings by linking group, and/or the ring structure of the A rings in X bondings is more than 1 In the case of the condensed ring or aromatic heterocycle of aromatic rings, Y is following formula (1a), following formula (1b) or by the portion in the formula (1b) Point or whole unsaturated bonds carry out hydrogenation structure group,
In formula (1a), Y1It is the alkylidene of carbon number 2~5 each, independently of the other, n is the number of 1~250 scope,
In formula (1b), Y2It is that Direct Bonding or carbon number are 1 or 2 alkylidene, R each, independently of the other3Each mutually solely It is on the spot hydrogen atom or methyl, the number of p and q each, independently of the other for more than 0, and their scope for adding up to 1~200 Number,
In the case of other than the above, Y is the formula (1b) or enters all or part of unsaturated bond in the formula (1b) The group of the structure of row hydrogenation,
Herein, the linking group is to be selected from the alkylidene for being 1~4 by carbon number, the alkylidene that carbon number is 2~4, ether One or more of group that base, ester group, ketone group, thioether group and sulfonyl are constituted,
On the R1And X, it is used as glycidyl or the R of methylglycidyl1With being used as glycidoxypropyl or methyl contracting The average value x of the X of water glycerine epoxide total number is more than 1.
4. such as liquid crystal sealing agent composition according to any one of claims 1 to 3, wherein, in the formula (1), wrapped in A rings The carbon number contained is 4~40, and oxygen atomicity is 0~5, and nitrogen-atoms numbers are 0~5, and number of sulfur atoms is bag in 0~5, and A rings The quantity of the ring structure contained is 1~5.
5. such as liquid crystal sealing agent composition according to any one of claims 1 to 3, wherein, the liquid crystal sealing agent composition In curable resin and/or the content of (methyl) acrylated curable resin be the weight % of 5 weight %~95.
6. such as liquid crystal sealing agent composition according to any one of claims 1 to 3, wherein, the liquid crystal sealing agent composition The compound H with ethylenic unsaturated group and/or epoxy radicals is further included, wherein, compound H does not include the solidification Property resin and (methyl) acrylated curable resin,
Compound H with ethylenic unsaturated group be (methyl) acrylate compounds, aliphatic propylene amide compound, Ester ring type acrylamide compound, containing aromatic acrylamide compound or N- substituted acrylamide based compounds,
Compound H with epoxy radicals is selected from by bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol-A D-ring Oxygen compound, phenol novolak-type epoxy compound, cresol novolak type epoxy compound, naphthalene type epoxide, At least one of the group of benzenediol type epoxide, their hydrogenation compound and alicyclic ring type epoxide composition chemical combination Thing,
Compound H with ethylenic unsaturated group and epoxy radicals is to make the compound containing epoxy radicals and (methyl) acrylic acid Based compound reacts obtained part (methyl) Acrylate Modified Epoxy compound.
7. such as liquid crystal sealing agent composition according to any one of claims 1 to 3, wherein, said composition is used for liquid crystal drip-injection Technique.
8. such as liquid crystal sealing agent composition according to any one of claims 1 to 3, wherein, said composition is used for flexible liquid crystal Display.
9. the curable resin represented by following formula (1),
In formula, m is the number of 1~7 scope,
X is independently of one another hydrogen atom, hydroxyl, glycidoxypropyl or methyl glycidyl epoxide,
R1It is each, independently of the other hydrogen atom, glycidyl or methylglycidyl,
R2It is each, independently of the other hydrogen atom or methyl,
A rings are the conduct for adding up to more than 5 and including more than 1 of carbon number and hetero atom number each, independently of the other The group of the ring structure of aromatic rings or aromatic heterocycle,
It is mutually only in X in the case where at least one of X is the ring structure Direct Bonding of hydrogen atom and X and A rings on Y It is on the spot hydroxyl, glycidoxypropyl or methyl glycidyl epoxide and is bonded at least one of oxygen atom and X of A rings In the case of being bonded with the ring structure of A rings by linking group, and/or the ring structure of the A rings in X bondings is more than 1 In the case of the condensed ring or aromatic heterocycle of aromatic rings, Y is following formula (1a), following formula (1b) or by the portion in the formula (1b) Point or whole unsaturated bonds carry out hydrogenation structure group,
In formula (1a), Y1It is the alkylidene of carbon number 2~5 each, independently of the other, n is the number of 1~250 scope,
In formula (1b), Y2It is that Direct Bonding or carbon number are 1 or 2 alkylidene, R each, independently of the other3Each mutually solely It is on the spot hydrogen atom or methyl, the number of p and q each, independently of the other for more than 0, and their scope for adding up to 1~200 Number,
In the case of other than the above, Y is the formula (1b) or enters all or part of unsaturated bond in the formula (1b) The group of the structure of row hydrogenation,
Herein, the linking group is to be selected from the alkylidene for being 1~4 by carbon number, the alkylidene that carbon number is 2~4, ether One or more of group that base, ester group, ketone group, thioether group and sulfonyl are constituted,
On the R1And X, it is used as glycidyl or the R of methylglycidyl1With being used as glycidoxypropyl or methyl contracting The average value x of the X of water glycerine epoxide total number is more than 1.
10. curable resin as claimed in claim 9, wherein, in the formula (1), the carbon number included in A rings is 4 ~40, oxygen atomicity is 0~5, and nitrogen-atoms numbers are 0~5, and number of sulfur atoms is the quantity of the ring structure included in 0~5, and A rings For 1~5.
11. a kind of (methyl) acrylated curable resin, it is the epoxy in the curable resin described in claim 9 or 10 (methyl) acryloyl group is imported with least a portion in base, hydroxyl and unsaturated bond.
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