CN104718231B - The manufacture method of glycidyl ether based compound, liquid crystal sealing agent and glycidyl ether based compound - Google Patents
The manufacture method of glycidyl ether based compound, liquid crystal sealing agent and glycidyl ether based compound Download PDFInfo
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- CN104718231B CN104718231B CN201380052675.4A CN201380052675A CN104718231B CN 104718231 B CN104718231 B CN 104718231B CN 201380052675 A CN201380052675 A CN 201380052675A CN 104718231 B CN104718231 B CN 104718231B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/31—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings
-
- 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
-
- 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 the manufacture method of a kind of glycidyl ether based compound, the liquid crystal sealing agent comprising above-mentioned glycidyl ether based compound and above-mentioned glycidyl ether based compound, in liquid crystal drip-injection technique, even if when adhesive substrates are carried out with narrow and small sealed width coating of liquid crystalline sealant, liquid crystal sealing agent also strongly bonding can solidify, and be difficult to bring liquid crystal aligning impact.
Description
【Technical field】
The present invention relates to glycidyl ether based compound, the liquid crystal sealing agent comprising glycidyl ether based compound and shrink
The manufacture method of glycerin ether based compound.
【Background technology】
In the manufacture of the liquid crystal indicators 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 arbitrary substrate of 2 plate bases for constituting liquid crystal panel, instil on arbitrary substrate scheduled volume
Liquid crystal, 2 plate bases is sent back to after fitting under vacuo and come in atmospheric pressure filling liquid crystal, solidify liquid crystal sealing agent.
In liquid crystal drip-injection technique, from high speed curable aspect, widely use with epoxy acrylate based compound
Raolical polymerizable compound for host is (public referring for example to Japanese Unexamined Patent Publication 2007-297470 as liquid crystal sealing agent
Report).
【The content of the invention】
【Invent problem to be solved】
But, in recent years, due to the popularization of smart mobile phone, panel type terminal etc., the demand of small panel is increased, due to
The panel design that design is improved, narrow frame are developed, for the requirement of the graph thinning of liquid crystal sealing agent coating increases.Example
Such as, it is desirable to which existing sealed width 1.0mm～1.5mm is halved into such degree.For the requirement, go out in terms of durability
Send out, even if reducing bond area due to the narrowing of sealed width, it is also desirable to which liquid crystal sealing agent is able to maintain that or enters one
Step improves adhesive strength.
In liquid crystal drip-injection technique, sealant is applied to into substrate with frame-shaped and forms frame sealing, in the inner side drip liquid of frame
Crystalline substance, evacuation by panel attachment, carry out UV irradiation make liquid crystal sealing agent photocuring after, in the NI points (nematic phase-each identical of liquid crystal
Property phase point, Nematic Isotropic point) more than temperature carry out thermal curing, heat cure, same is carried out to liquid crystal sealing agent
When make liquid crystal occur orientation.
In the case of larger panel as TV, due to panel it is very big, thus from liquid crystal drip-injection at frame sealing have
The distance having more than certain, after dispenser method is by panel attachment, until when carrying out UV irradiations, liquid crystal is with liquid crystal sealing agent still
Not in contact with, thus liquid crystal sealing agent is just contacted with liquid crystal after photocuring.Or the sealing liquid crystal of liquid crystal and its uncured state
The time of contact of agent is short.
On the other hand, in small panel, due to short to the distance at frame sealing from liquid crystal drip-injection, thus in laminating
Afterwards, when UV irradiations are carried out, liquid crystal sealing agent still contacts (length time of contact) with uncured state with liquid crystal.Therefore, with
Toward comparing, liquid crystal sealing agent liquid crystal pollution in the uncured state becomes problem.
The existing Raolical polymerizable with the epoxide containing epoxy/acrylic acid based compound as host
Liquid crystal sealing agent can't be said and sufficiently respond to the requirement.
The problem of the present invention is to provide a kind of glycidyl ether based compound, the liquid comprising glycidyl ether based compound
The manufacture method of brilliant sealant and glycidyl ether based compound, in liquid crystal drip-injection technique, even if with narrow and small sealing width
When degree coating of liquid crystalline sealant carrys out adhesive substrates, liquid crystal sealing agent also strongly bonding can solidify, and be difficult to liquid crystal aligning
Bring impact.
【The means to solve the problem】
The present invention includes following mode.
[1] a kind of glycidyl ether based compound, which is represented by following formula (1),
【Change 1】
[in formula, n1For the number that the number of 2～30 scopes, m are 1～5 scope；
X is oxygen atom (O), the alkylidene that carbon number is 1～4 or alkylidene that carbon number is 2～4；
Y is alkylidene that carbon number is 2～4 each, independently of the other；
R is hydrogen atom, glycidyl, methylglycidyl, group 1 each, independently of the other：-CH2-CH(OR1)-
CH2-O-R2Or group 2：-CH2-C(CH3)(OR1)-CH2-O-R2(in formula, R1For hydrogen atom or (methyl) acryloyl group, R2For
(methyl) acryloyl group)；
R ' is hydrogen atom or methyl each, independently of the other；
In above-mentioned R, above-mentioned glycidyl, above-mentioned methylglycidyl, above-mentioned group 1 and above-mentioned group 2 it is total
Mean number x is more than 2；
In the case that above-mentioned R includes above-mentioned group 1 or above-mentioned group 2, above-mentioned glycidyl and methylglycidyl
Total mean number y and the ratio (y/z) of total mean number z of above-mentioned group 1 and above-mentioned group 2 be 10/90～90/
10]。
[2] a kind of liquid crystal sealing agent, which includes the glycidyl ether based compound described in above-mentioned [1].
The manufacture method of the glycidyl ether based compound represented by formula (1) [3] as described above described in [1], which includes makes
The operation that compound C represented by following formula (2) is reacted with the compound D represented by following formula (3),
【Change 2】
(in formula, n2For the number of 2～30 scopes；
Y is alkylidene that carbon number is 2～4 each, independently of the other；
R11It is hydrogen atom, glycidyl or methylglycidyl each, independently of the other)；
【Change 3】
[in formula, X is oxygen atom, the alkylidene that carbon number is 1～4 or alkylidene that carbon number is 2～4；
R12It is hydrogen atom, glycidyl, methylglycidyl, group 1 each, independently of the other：-CH2-CH
(OR21)-CH2-O-R22Or group 2：-CH2-C(CH3)(OR21)-CH2-O-R22(in formula, R21For hydrogen atom or (methyl) acryloyl
Base, R22For (methyl) acryloyl group)].
【The effect of invention】
According to the present invention it is possible to provide a kind of glycidyl ether based compound, the liquid comprising glycidyl ether based compound
The manufacture method of brilliant sealant and glycidyl ether based compound, in liquid crystal drip-injection technique, even if with narrow and small sealing width
When degree coating of liquid crystalline sealant carrys out adhesive substrates, liquid crystal sealing agent also strongly bonding can solidify, and be difficult to liquid crystal aligning
Bring impact.
【Description of the drawings】
Fig. 1 be represent embodiment in liquid crystal aligning be zero situation example (compound A-3) microscopic iage.
Fig. 2 be represent embodiment in liquid crystal aligning be zero situation example (compound A-5) microscopic iage.
Fig. 3 be represent embodiment in liquid crystal aligning for × situation example (compound B) microscopic iage.
Fig. 4 is the schematic diagram of the test method for briefly showing adhesive strength.
【Specific embodiment】
Term " operation " in this specification is not only independent operation, even if cannot specify area Do's with other operations
In the case of, as long as the expected purpose of the operation can be reached, also term term.The numerical range that "～" represents is used to represent bag
Containing the numerical value recorded before and after "～" respectively as minima and the scope of maximum.With regard to the amount of each composition in compositionss, in group
When material in compound equivalent to each composition has various, as long as not special declaration, in compositionss, the amount of each composition refers to combination
The total amount of many kinds of substance present in thing.
Additionally, (methyl) acryloyl refers to methacryl and/or acryloyl, (methyl) acrylate refers to metering system
Acid esters and/or acrylate.
[compound A]
The glycidyl ether based compound (hereinafter also referred to compound A) of the present invention is represented by following formula (1).
【Change 4】
In formula, n1For the number that the number of 2～30 scopes, m are 1～5 scope.
X is oxygen atom (O), the alkylidene that carbon number is 1～4 or alkylidene that carbon number is 2～4.Y is each mutual
It independently is the alkylidene that carbon number is 2～4.
R is hydrogen atom, glycidyl, methylglycidyl, group 1 each, independently of the other：-CH2-CH(OR1)-
CH2-O-R2Or group 2：-CH2-C(CH3)(OR1)-CH2-O-R2(in formula, R1For hydrogen atom or (methyl) acryloyl group, R2For
(methyl) acryloyl group).R ' is hydrogen atom or methyl each, independently of the other.
Above-mentioned glycidyl, above-mentioned methylglycidyl, above-mentioned group 1 and above-mentioned group 2 in above-mentioned R it is total
Mean number x is more than 2；In the case where above-mentioned R includes above-mentioned group 1 or above-mentioned group 2, above-mentioned glycidyl and methyl
The ratio (y/z) of total mean number z of total mean number y and above-mentioned group 1 and above-mentioned group 2 of glycidyl is
10/90～90/10.
Strong cementability from liquid crystal drip-injection technique is (even if with narrow and small sealed width coating of liquid crystalline sealant come base of fitting
During plate liquid crystal sealing agent also can strongly bonding solidification performance) in terms of set out, the n in compound A1For 3～25 scopes
Number, the more preferably number for being preferably 5～20 scopes, the number of 5～15 scopes, the number still more preferably for 7～10 scopes.
It should be noted that n1From number of repeat unit, the i.e. n of the compound (compound C) represented by formula (2)2。
From the coating of liquid crystal sealing agent (for example, point gum machine (dispenser) draw speed and productive temp will not drop
It is low) aspect and liquid crystal sealing agent adapted (not excessively improve compound A viscosity) in terms of set out, in compound A
M be the number of 1～5 scope, the number for being preferably 1～4 scope, the number of more preferably 1～3 scope, be still more preferably 1
The number of～2 scopes.It should be noted that m can be by the reaction equivalent ratio of the compound C of the raw material as compound A and compound D
(inventory) is estimated.
It should be noted that n1GPC is possible with m to be measured.
Y is the alkylidene that carbon number is 2～4 each, independently of the other, specifically, is ethylidene, propylidene, Sanya
Methyl, tetramethylene etc..Y is preferably ethylidene or propylidene, more preferably ethylidene.
The solidification that the workability such as the coating of such as viscosity influence from liquid crystal sealing agent and such as crosslink density affect
Set out in terms of the physical characteristics such as intensity afterwards, the glycidyl, methylglycidyl, 1 and of group in compound A, in R
Total mean number x of group 2 is more than 2, be preferably 2～2m+2, more preferably 2m～2m+2, more preferably 2m+1～
2m+2。
It should be noted that with regard to x, high performance liquid chromatography (HPLC) and liquid chromatographic mass analysis (LC-MS) can be passed through
The mean molecule quantity and molecular weight distribution of compound A are determined, n is determined by GPC1And m, so as to calculate the x.
In compound A, in the case where above-mentioned R includes above-mentioned group 1 or above-mentioned group 2, above-mentioned glycidyl and
The ratio (y/z) of total mean number z of total mean number y and above-mentioned group 1 and above-mentioned group 2 of methylglycidyl
For 10/90～90/10, preferably 20/80～80/20, more preferably 30/70～70/30, more preferably 40/60～60/
40。
From strong cementability aspect, the R in compound A is each independently hydrogen atom, glycidyl, methyl
Glycidyl, group 1 or group 2, preferably hydrogen atom, glycidyl or group 1.Also, R ' is preferably hydrogen atom.
Used in liquid crystal sealing agent in the case of compound A, from make liquid crystal sealing agent guarantee appropriate viscosity in terms of
Set out, the viscosity of compound A be preferably 1000mPas～1000000mPas, more preferably 3000mPas～
700000mPas, more preferably 5000mPas～500000mPas, still more preferably for 7000mPas～
250000mPas, much further preferably from 9000mPas～200000mPas.It should be noted that viscosity can use E
Type viscometer is measured at 25 DEG C.
It should be noted that the viscosity of compound A can for example pass through to change the n in compound A1With m and/or change chemical combination
The presence of the hydroxyl in thing A than etc. being adjusted.
Used in liquid crystal sealing agent in the case of compound A, from strong cementability aspect, the epoxy of compound A
Equivalent is preferably 100g/eq～3000g/eq, more preferably 150g/eq～2000g/eq.
It should be noted that the epoxide equivalent of compound A can utilize the mean molecule quantity and unit repetitives of compound A
Epoxy radix be adjusted.For example, epoxidised ratio can be carried out and to product Q by the hydroxyl to compound P
Epoxy radicals carry out the modified ratio of (methyl) acroleic acid esterification and be adjusted.
In liquid crystal drip-injection technique, even if compound A is not easy to liquid in the case where uncured state is contacted with liquid crystal
Brilliant orientation brings impact (change of NI points is little), is difficult to hinder the orientation of liquid crystal, thus compound A is used as liquid crystal sealing agent
It is preferred.
[liquid crystal sealing agent of inclusion compound A]
The liquid crystal sealing agent (hereinafter also referred to " compositionss ") of inclusion compound A it is strong excellent in adhesion.
From strong cementability and liquid crystal aligning aspect, (for example, may be used in the reaction curability composition of liquid crystal sealing agent
The composition in the presence of light and/or heating etc. reacting and solidifying) in, the content of compound A be preferably 10 weight %～
100 weight %, more preferably 20 weight %～100 weight %, more preferably 30 weight %～100 weight %, further
Preferably 40 weight %～100 weight %, more preferably 50 weight %～100 weight %, more preferably 60 weights
Amount %～100 weight %, more preferably 70 weight %～100 weight %, more preferably 80 weight %～100 weights
Amount %, more preferably 90 weight %～100 weight %, more preferably 100 weight %.
For example, for the host as liquid crystal sealing agent use it is existing with ethylenic unsaturated group and/or
The compound B of epoxy radicals (for example, carries out methacrylated to a part for the epoxy radicals of bisphenol A type epoxy resin to form
Oligomer) for mixture has the liquid crystal sealing agent of compound A together, compared with only using the situation of compound B, strong cementability
Improve a lot.That is, liquid crystal sealing agent go back in addition to inclusion compound A, preferably beyond inclusion compound A with ethylenic not
The compound B of saturated group and/or epoxy radicals.
As the compound B with ethylenic unsaturated group, (methyl) acrylate compounds, aliphatic can be enumerated
Acrylamide compound, ester ring type acrylamide compound, containing aromatic acrylamide compound, N- substituted acrylamides
Based compound.
As (methyl) acrylate compounds, can enumerate to cumylphenoxy ethylene glycol (methyl) acrylate, (first
Base) tert-butyl acrylate, (methyl) ethioxy phenyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid shrink it is sweet
Aliphatic (methyl) acrylate representated by grease, (methyl) acrylate containing aromatic rings.
As the compound containing ethylenic unsaturated group, can enumerate mono-functional, two functionalities, trifunctional or
Multi-functional free-radical polymerised unsaturated compound.
As the free-radical polymerised unsaturated compound of mono-functional, from the side for guaranteeing composition viscosity, film hardness, flexibility
Face is set out, be preferably selected from by (methyl) 2-(Acryloyloxy)ethanol, (methyl) benzyl acrylate, (methyl) tetrahydrofurfuryl acrylate,
(methyl) Isooctyl acrylate monomer, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid bicyclic penta
Ester, (methyl) acrylate epoxide ethyl ester, two cyclopentyloxy ethyl ester of (methyl) acrylic acid, the different Semen Myristicae of (methyl) acrylic acid
Ester, (methyl) lauryl acrylate, (methyl) tert-butyl acrylate and diethylene glycol monoethyl ether (methyl) acrylate composition
The compound of more than a kind in group, more preferably selected from (methyl) isobornyl acrylate, (methyl) acrylic acid tetrahydrochysene bran
The compound of more than a kind in the group of ester, the bicyclic pentyl ester of (methyl) acrylic acid and (methyl) cyclohexyl acrylate composition.
As the free-radical polymerised unsaturated compound of two functionalities, from the side for guaranteeing composition viscosity, film hardness, flexibility
Face is set out, and is preferably selected from by Tricyclodecane Dimethanol two (methyl) acrylate, two (methyl) third of dihydroxymethyl bicyclopentane
Be modified 1,6-HD two (methyl) acrylate, EO modified bisphenol As two (methyl) acrylate, PO of olefin(e) acid ester, EO is modified double
Phenol A bis- (methyl) acrylate, polyester two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, two (first of organosilicon
Base) acrylate and 2,2'-ethylenedioxybis(ethanol). two (methyl) acrylate composition group in more than a kind of compound, more preferably dihydroxy first
Two (methyl) acrylate of base bicyclopentane and/or modified bisphenol A two (methyl) acrylate.Wherein preferably with without hydroxyl
(methyl) acrylate of the bisphenol A skeleton of base, (strain) is commercially available LIGHT-ACRYLATE BP-4EAL (bis-phenols for common prosperity society chemistry
The EO addition product diacrylates of A), BP-4PA (the PO addition product diacrylates of bisphenol-A) etc..
As free-radical polymerised unsaturated compound more than trifunctional, from guaranteeing composition viscosity, film hardness, flexibility
Aspect set out, be preferably selected from by ECH modified glycerols three (methyl) acrylate (trifunctional), EO modified glycerols three (methyl)
Acrylate (trifunctional), PO modified glycerols three (methyl) acrylate (trifunctional), tetramethylolmethane three (methyl) acrylate
(trifunctional), dipentaerythritol six (methyl) acrylate (six senses) and tetramethylolmethane four (methyl) acrylate (tetrafunctional)
The compound of more than a kind in the group of composition, more preferably three (methyl) acrylate of EO modified glycerols and/or dipentaerythritol
Six (methyl) acrylate.
As the compound B with epoxy radicals, it is preferably selected from by bisphenol A type epoxy compound, bisphenol F type epoxy chemical combination
Thing, bisphenol-A D-ring oxygen compound, novolac type epoxide, cresol novalac type epoxide, naphthalene type epoxy
At least one compound in the group of compound, their hydrogenation compound and alicyclic ring type epoxide composition, more preferably
Selected from least one in the group of bisphenol A type epoxy compound, bisphenol F type epoxy compound and naphthalene type epoxide composition
Compound, more preferably bisphenol A type epoxy compound.
As the concrete example of bisphenol A type epoxy compound, have the manufacture of DIC societies EPICLON 850S, 860,1055,
EPICLON 850CRP etc..As the concrete example of hydrogenated bisphenol A type epoxide, have the manufacture of ADEKA societies KRM-2408,
YX-8034 of JER societies manufacture etc..As the concrete example of bisphenol F type epoxy compound, the EPICLON 830S for having DIC societies to manufacture
Deng.As the concrete example of naphthalene type epoxide, there are EPICLON HP-4032D, HP-7200H of the manufacture of DIC societies etc..As line
Property novolak type epoxy compound concrete example, have DIC societies manufacture EPICLON N-740, N-770 etc..As cresol novalac
The concrete example of type epoxide, has EPICLON N-660, N-670 of the manufacture of DIC societies etc..As alicyclic ring type epoxide
Concrete example, have 3, a 4- epoxy hexanes ylmethyl -3 ', (Daicel societies manufacture Celloxide to 4 '-epoxy hexane carboxylate
2021P)、1,2：Bis- epoxy limonenes of 8,9- (Daicel societies manufacture Celloxide 3000), 1,2- epoxy -4- vinyl cyclohexanes
(Daicel societies manufacture Celloxide 2000), 1,2- epoxy -4- (the 2- oxirane of double (the hydroxymethyl)-n-butyl alcohols of 2,2-
Base) hexamethylene addition product (Daicel societies manufacture EHPE3150) etc..
As the compound B with ethylenic unsaturated group and epoxy radicals, it is also possible to using making the change containing epoxy radicals
Compound and (methyl) acrylic compounds react part (methyl) the Acrylate Modified Epoxy compound for obtaining, more excellent
Choosing makes bisphenol A type epoxy compound and (methyl) acrylic acid react the acrylated epoxy compound in part (methyl) for obtaining
Thing.
Bisphenol A type epoxy resin and (methyl) acrylic acid is made to react the acrylated asphalt mixtures modified by epoxy resin in part (methyl) for obtaining
Fat is for example obtained in the following manner.
Firstly, for bisphenol A type epoxy resin and (methyl) acrylic acid, it is acidified in base catalyst, preferred trivalent organophosphors
In the presence of compound and/or amines, 10 equivalent %～90 equivalent % of (methyl) acrylic acid is made to occur with 1 equivalent of epoxide group
Reaction.Next, carrying out filtering to the reaction product, centrifugation and/or washing etc. are processed, so as to remove base catalysis
Agent, is refined.As base catalyst, it is possible to use that what is commonly used in epoxy resin with (methyl) acrylic acid reaction is known
Base catalyst.In addition it is also possible to using the Polymer Supported base catalyst for being supported with base catalyst on polymer.
In the case of ethylenic unsaturated group is not contained in compound A, as compound B, it is preferably contain as certainly
By base curable compound, using the above-mentioned compound containing ethylenic unsaturated group as suitable example.
The liquid crystal sealing agent of the present invention can be sent out as free radical containing when compound A and/or compound B photopolymerization is made
The Photoepolymerizationinitiater initiater (activating and produce the compound of free radical by light absorbing energy) of source of students.Polymerization initiator is not had
It is particularly limited to, it is possible to use as compound known to polymerization initiator.As polymerization initiator, benzoin can be enumerated
Class, acetophenones, benzophenone, thioxanthene ketone class, α-acyl group oxime esters, glyoxalic acid phenyl ester class, benzil class, azo system chemical combination
The polymerization initiator of thing, diphenyl sulfide based compound, acylphosphine oxide based compound, benzoin ethers and Anthraquinones, preferably exists
Dissolubility in liquid crystal is low, and polymerization of its own reactive group for not occurring to gasify with the analyte in light irradiation draw
Send out agent.As the preferred polymeric initiator of the present invention, for example, the material represented by following formula can be enumerated,
【Change 5】
EY Resin KR-2 (manufacture of KSM societies) etc. can for example be enumerated.
As firming agent, from strong cementability aspect, preferred amine system firming agent, such as organic acid dihydrazide chemical combination
Thing, imidazole and its derivants, dicyandiamide, aromatic amine, epoxide modified polyamine, poly- semicarbazides etc., preferably as organic acid two
The VDH (double (hydrazine the carbonylethyl) -5- isopropyl hydantoin of 1,3-) of hydrazides, ADH (adipic dihydrazide), UDH (7,11- ten
Eight alkane diene -1,18- dicarbapentaborane hydrazides) and LDH (octadecane -1,18- dicarboxyl acid dihydrazides).These firming agent individually can make
With, it is also possible to using two or more.
As photosensitizer, from curable aspect, can for example enumerate carbonyl compound, sulfur-containing organic compound,
Persulfide, oxidoreduction based compound, azo and diazonium compound, halogenide, photo-reduction pigment etc..As photosensitizer,
Specifically, can enumerate：The benzene idol of benzoin methylether, benzoin iso-propylether, α, alpha, alpha-dimethyl epoxide-α-phenyl acetophenone etc
Relation by marriage derivant；Benzophenone, 2,4- dichloro benzophenones, methyl o-benzoylbenzoate, 4,4 '-bis- (diethylamino) hexichol
The benzophenone derivates of ketone etc；The thioxanthene of 2,4- diethyl thioxanthones, CTX, ITX etc
Ketone derivatives；The anthraquinone derivative of 2-chloroanthraquinone, 2-methylanthraquinone etc；N- methylacridine ketone, N- butyl acridones etc
Acridone derivativeses；And α, α-diethoxy acetophenone, benzil, Fluorenone, xanthone, uranyl compound etc..These light
Quick dose can be used alone, or be used in combination of two or more.Preferred photosensitizer is 2,4- diethyl thioxanthones (such as Japan
Chemical medicine DETX-S).
From from the aspect of the curing reaction for promoting curable compound, the liquid crystal sealing agent of the present invention can be containing solidification
Accelerator, can preferably enumerate：The imidazoles such as 2-methylimidazole, 2- ethyl imidazol(e)s and 2-ethyl-4-methylimidazole；2- (diformazans
Amino methyl) tertiary amines such as 11 carbon -7- alkene (DBU) of phenol and 1,8- diazabicyclos [5.4.0]；The phosphines such as triphenylphosphine；
Metallic compounds such as stannous octoate etc..
From control viscosity, further improve the intensity after solidifying, bonding reliability, suppress linear expansivity aspect,
The liquid crystal sealing agent of the present invention can add filler.Filler can use inorganic filler and organic filler.As inorganic filler, can
To enumerate Calcium Carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminium silicate, titanium dioxide, aluminium oxide, Zinc Oxide, silicon dioxide, kaolinite
Soil, Talcum, bead, sericite active hargil, bentonite, aluminium nitride and silicon nitride.As organic filler, can enumerate poly-
Methyl methacrylate, polystyrene, make copolymer, polyester micropartical that their monomer of composition and other monomer copolymerizations obtain,
Polyurethane particulate and rubber particle.
Further reduce escaping from the filler of non-reactive components is belonged to by mixture from the aspect of gas (ア ウ ト ガ ス),
The mean diameter for constituting the granule of filler is 0.1 μm～3 μm, more preferably 0.5 μm～3 μm.It should be noted that filler is flat
(for example HORIBA societies manufacture laser diffraction/scattering formula particle size distribution analyzer that particle diameter can utilize HORIBA societies to manufacture
Partica LA-950V2) it is measured.
The liquid crystal sealing agent of the present invention contain silane coupler in the range of effect of the present invention having given play to.
From the stability aspect of the solidification intensity of liquid crystal sealing agent of the present invention, as silane coupler, preferably
Selected from least one silane coupler in the group of following substances composition：Tetramethoxy-silicane, tetraethoxysilane, 4 third oxygen
Base silane, tetraisopropoxysilan, four butoxy silanes, dimethoxy diethoxy silane, dimethoxy diisopropoxy silicon
The tetraalkoxysilane classes such as alkane, diethoxy diisopropoxy silane, diethoxy dibutoxy silane；Methyl trimethoxy epoxide silicon
Alkane, MTES, three isopropoxy silane of methyl, ethyl triethoxysilane, three butoxy silane of ethyl, hexamethylene
Ethyl triethoxy silicane alkane, three isopropoxy silane of phenyl, vinyltrimethoxy silane, 3- glycidoxypropyl group trimethoxies
The trialkoxysilanes such as silane, 3- methacryloxypropyl trimethoxy silanes；And dimethyldimethoxysil,ne,
Dimethyldiethoxysilane, diethyldiethoxysilane, diethyl dibutoxy silane, phenylethyl diethoxy silane
Deng dialkoxy base class, more preferably selected from MTMS, MTES, three isopropoxy silicon of methyl
Alkane, ethyl triethoxysilane, three butoxy silane of ethyl, cyclohexyltriethyloxysilane, three isopropoxy silane of phenyl, second
Thiazolinyl trimethoxy silane, 3- glycidoxypropyltrime,hoxysilanes and 3- methacryloxypropyl trimethoxy silicon
At least one trialkoxy silane system silane coupler in the group of alkane composition, further preferred 3- glycidoxypropyl groups front three
TMOS.
[manufacture method of compound A]
The manufacture method of the compound A of the present invention is represented with following formula (3) comprising the compound C made represented by following formula (2)
The operations that react of compound D,
【Change 6】
(in formula, n2For the number of 2～30 scopes, Y is the alkylidene that carbon number is 2～4, R each, independently of the other11Respectively
From independently of one another hydrogen atom, glycidyl or methylglycidyl)；
【Change 7】
[in formula, X is oxygen atom (O), the alkylidene that carbon number is 1～4 or alkylidene that carbon number is 2～4, R12
It is hydrogen atom, glycidyl, methylglycidyl, group 1 each, independently of the other：-CH2-CH(OR21)-CH2-O-R22
Or group 2：-CH2-C(CH3)(OR21)-CH2-O-R22(in formula, R21For hydrogen atom or (methyl) acryloyl group, R22For (methyl)
Acryloyl group)].
From the strong cementability aspect of compound A, to the n in compound C2It is chosen so that the n of compound A1
The n fallen in above range, and compound C2For the number of 3～25 scopes, it is preferably the number, further of 5～20 scopes
Preferably the number of 5～15 scopes, still more preferably for 7～10 scopes number.Also, R11For hydrogen atom compound C point
Son amount (weight average molecular weight) is preferably less than 2000.
Y in compound C is the alkylidene that carbon number is 2～4, and specifically, Y is ethylidene, propylidene, three methylenes
Base, tetramethylene etc..Y is preferably ethylidene or propylidene, more preferably ethylidene.
C and D are commercially available for compound, or easily can be prepared by commercially available compound according to known methods.For example,
For R11For for the compound C of hydrogen atom, Y for ethylidene, it is obtained as Polyethylene Glycol with various number of repeat unit
(n2) compound, can suitably select the n with desired scope2Compound.Also, n2Also can be with n1Similarly calculate
Go out.The molecular weight of Polyethylene Glycol is preferably less than 2000.
Also, for R11For for the compound C of hydrogen atom, Y for propylidene, the tool as polypropylene ether glycol is obtained
There is the compound of various number of repeat unit.Can for example enumerate EXCENOL 420, EXCENOL 720, EXCENOL 1020,
EXCENOL 2020 (being manufactured by Asahi Glass society above) etc..The molecular weight of polypropylene ether glycol is preferably less than 2000.
In addition, for R11For for the compound C of hydrogen atom, Y for trimethylene, for example can be according to Japanese Unexamined Patent Application Publication 2013-
Method described in No. 515144 publications is manufactured in the form of the polytrimethylene ether glycol with various number of repeat unit.
The molecular weight of polytrimethylene ether glycol is preferably less than 2000.
Additionally, for R11For for the compound C of hydrogen atom, Y for tetramethylene, can obtain as polytetramethylene ether
The compound with various number of repeat unit of glycol.PTMG 650, PTMG 850, PTMG 1000, PTMG can for example be enumerated
1300th, PTMG 1500, PTMG 1800, PTMG 2000 (being manufactured by society of Mitsubishi Chemical above) etc..Polytetramethylene ether diol
Molecular weight is preferably less than 2000.
With regard to the R in compound C11With the R in compound D12, from the strong cementability aspect of compound A, difference
It is preferred that R11And R12In one be hydrogen atom, another be glycidyl.
Compound C is reacted according to the mode that can generate compound A with compound D, for example, makes compound C and chemical combination
Thing D is reacted in the presence of base, produces in the presence of appropriate catalyst the reaction of compound C and compound D afterwards
Thing and epoxychloropropane etc. can import the compound of glycidyl or methylglycidyl and be reacted.To above-mentioned reaction
It is adjusted, so that the m in compound A is 1～5, is preferably 1～4, is more preferably 1～3, is still more preferably 1
The number of～2 scopes.
With regard to the number of m, in the case of the embodiment, control can be carried out as follows when the synthesis of synthetic intermediate P is carried out.
For example, the equivalent proportion of the compound C1-1 in embodiment 1-1 and D1 is 1：2.5, and this is than for 1：2.0 or 1：When 1.5, the number of m
Increase.Even if conversely, at this than for 1：10 or 1：100、1：In the case of 1000 grades, the number of m will not also be less than 1.Compound P
In, during m=0, compound D becomes R for hydrogen atom, the compound (i.e. bisphenol-A itself) that X is isopropylidene.
It should be noted that from the aspect of reactivity, the R in preferred compound C11With the R in compound D12In
One be hydrogen atom, another be glycidyl.
As alkali, the alkali such as cost aspect, preferred sodium hydroxide, potassium hydroxide gold is carried out and is synthesized from being swift in response
Category hydroxide；The alkali carbonates such as sodium carbonate, potassium carbonate；More preferably sodium hydroxide.These alkali are preferably with the shape of aqueous solution
Formula is used, according to circumstances, it is also possible to the alkali of powder or solid is simultaneously or separately added with water.
With regard to the consumption of alkali, carry out from being swift in response and synthesize cost aspect, in R11For hydrogen atom, R12For contracting
In the case of water is glyceryl, alkali is more than the equivalent of hydroxyl；In R11For glycidyl, R12In the case of for hydrogen atom,
The consumption of alkali can be catalytic amount, be 0.0001 equivalent～0.1 equivalent of the hydroxyl of compound D, more preferably 0.0001 work as
～0.01 equivalent of amount.For example, in embodiment 1-1, the hydroxyl of 2.5 equivalent=5.0 equivalent of bisphenol-A, it is relative and this, use
The sodium hydroxide of 4% sodium hydroxide solution=0.0015 equivalent of 1.5g, accordingly, with respect to 1 equivalent of hydroxyl, the consumption of alkali is
0.0003 equivalent.
Carrying out rapidly and synthesis cost aspect from reaction, the consumption of the compound such as epoxychloropropane are preferably
0.5 equivalent～20 equivalent, more preferably 0.5 equivalent～15 equivalent.
It is as catalyst, from response time, catalyst cost, catalyst activity aspect, preferred trimethylamine, three pungent
The tertiary amine of amine, tridecylamine etc；The quaternary ammonium base of tetramethylammonium, three pungent ammonium of methyl, methyl three last of the ten Heavenly stems ammonium, benzyl trimethylammonium etc；Tetramethyl
The quaternary ammonium salt of ammonium chloride, methyl tricapryl ammonium chloride, three decyl ammonium chloride of methyl, benzyltrimethylammonium chloride etc, preferably
Quaternary ammonium salt.
With regard to the consumption of catalyst, from suppression side reaction, from the aspect of while suitably guaranteeing response speed, relative to change
The total amount of the compounds such as compound C, compound D and epoxychloropropane, the consumption of catalyst are preferably 0.01 weight %～10 weight
Amount %, more preferably 0.1 weight %～5 weight %.
Reaction with above-mentioned alkali is preferably at 50 DEG C～250 DEG C, more preferably at 70 DEG C～200 DEG C, further preferably at 100 DEG C
～170 DEG C are carried out, and the reaction with the compound such as above-mentioned epoxychloropropane is preferably at 25 DEG C～100 DEG C, more preferably 30 DEG C～80
DEG C, further preferably carry out at 40 DEG C～60 DEG C.In reaction, it is also possible to which using hydrocarbon, ether or ketone etc is in lazy in the reaction
The solvent of property, but in the case where the compounds such as epoxychloropropane are excessively used, the compound such as epoxychloropropane also can be used as molten
Agent function, thus these solvents are not necessary.
The refined of compound A after reaction terminating conventionally can be carried out, for example, retortable to remove excessive epoxy
The compounds such as chloropropane, add the laggard water-fillings of water-insoluble solvent such as hydrocarbon to wash as needed, remove generated Sal and catalysis
Agent, so as to obtain purpose compound A.
In the manufacture method of the compound A of the present invention, general raw material can be used from as compound C and compound D
From the aspect of, the R in compound C11For compound C1 (the polyalkylene ether glycols diglycidyl ethers of glycidyl；For example
Polyethyleneglycol diglycidylether), the R in compound D12In the case of compound D1 (such as bisphenol-A) for hydrogen atom, the system
The method of making preferably comprises operation 1 and operation 2, in operation 1, makes above-claimed cpd C1 react with above-claimed cpd D1, obtains
To product P of above-claimed cpd C1 and above-claimed cpd D1；In operation 2, epoxy is carried out to the hydroxyl of product P
Change, obtain part or all of product Q being at least partially epoxidized of the hydroxyl of above-mentioned product P.
In this case, further across make product Q in the presence of base catalyst with (methyl) acrylic acid occur
The operation 3 of reaction, is obtained the compound A that group 1 or group 2 have been imported on R.
Used as base catalyst, from raising response rate, being swift in response is carried out and catalyst cost aspect, can be made
The base catalyst commonly used in epoxy resin with (methyl) acrylic acid reaction, it is also possible to supported using base catalyst is made
In the Polymer Supported base catalyst of polymer.As base catalyst, preferred trivalent organic phosphorus compound and/or amine compounds
Thing.The basic atom of base catalyst is phosphorus and/or nitrogen.
As base catalyst, it is possible to use the known alkali commonly used in epoxy resin with (methyl) acrylic acid reaction
Property catalyst.Base catalyst can be additionally made to support the Polymer Supported base catalyst in polymer.As alkali
Property catalyst, preferred trivalent organic phosphorus compound and/or amines.The basic atom of base catalyst is phosphorus and/or nitrogen.
As trivalent organic phosphorus compound, the alkyl of triethyl phosphine, three n-pro-pyl 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, NSC 5284, phosphorous acid three (nonyl phenyl) ester.It is organic as trivalent
The salt of phosphorus compound, can enumerate ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide phosphine, octyl group triphenylphosphinebromide, decyl
Triphenylphosphinebromide, isobutyl group triphenylphosphinebromide, propyl group triphenyl phosphine dichloride, amyl group triphenyl phosphine dichloride, hexyltriphenylphosphonium
Bromide phosphine etc..Wherein triphenylphosphine.
As amines, the secondary amine such as diethanolamine can be enumerated；Triethanolamine, dimethyl benzyl amine, three (dimethylaminos
Methyl) tertiary amine such as phenol, three (diethylamino methyl) phenol；1,5,7- tri- azabicyclos [4.4.0] decyl- 5- alkene (TBD), 7-
Methyl isophthalic acid, 5,7- tri- azabicyclos [4.4.0] decyl- 5- alkene (Me-TBD), 11 carbon -7- alkene of 1,8- diazabicyclos [5.4.0]
(DBU), 11 carbon -7- alkene of 6- dibutylaminos -1,8- diazabicyclos [5.4.0], 1,5- diazabicyclos [4.3.0] nonyl-
Strong basicity amine and its salt such as 5- alkene (DBN), 1,1,3,3- tetramethyl guanidine.Wherein preferred 1,5,7- tri- azabicyclos [4.4.0] decyl-s
5- alkene (TBD).As the salt of amines, benzyltrimethylammonium chloride, benzyltriethylammoinium chloride can be enumerated.
It is not particularly limited as the polymer for supporting base catalyst, polystyrene Jing divinyl benzene crosslinkeds can be used
Polymer, the polymer of acrylic resin Jing divinyl benzene crosslinkeds etc..These polymer are not dissolved in and are passed through
Comprising operation 1 or the epoxy resin that obtains of the manufacture method comprising operation 1 and 2 is used molten with (methyl) acrylic acid reaction
In agent (such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene etc.) and raw material, product.
With regard to Polymer Supported base catalyst, chemical bond can occur with insoluble polymer by making base catalyst
Close, or monomer polymerization is carried out after base catalyst is imported monomer, carry out 3-dimensional using cross-linking monomers such as divinylbenzene afterwards
Crosslinking such that it is able to make and urge insoluble in the Polymer Supported alkalescence in methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene equal solvent
Agent.
As Polymer Supported base catalyst, specifically, can enumerate diphenylphosphine base polystyrene, 1,5,7- tri-
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, it is also possible to share two kinds with
On.
Polymer Supported base catalyst can use commercially available product.As commercially available Polymer Supported base catalysis
Agent, for example, can enumerate PS-PPh3(diphenylphosphine base polystyrene, the manufacture of Biotage societies), PS-TBD (tri- azepines of 1,5,7-
Bicyclic [4.4.0] decyl- 5- alkene polystyrene, the manufacture of Biotage societies).
With regard to the use ratio of Polymer Supported base catalyst, obtain with respect to the manufacture method comprising operation 1 or 2
1 equivalent of epoxy radicals of the epoxy resin for arriving, Polymer Supported alkaline catalyst are preferably 0.5 milliequivalent～5.0 milliequivalent, more excellent
Elect 1.0 milliequivalent～3.0 milliequivalents as.The use ratio of Polymer Supported base catalyst within the above range when, from reaction
It is preferred to set out in terms of rate, response time and catalyst cost.
In the manufacture method of the present invention, by the asphalt mixtures modified by epoxy resin obtained comprising operation 1 or the manufacture method comprising operation 1 and 2
Fat is preferably 60 DEG C～120 DEG C, is more preferably 80 DEG C～120 DEG C, enters one with the temperature in (methyl) acrylic acid reaction process
Step is preferably 90 DEG C～110 DEG C.
Make in the presence of a catalyst by the epoxy resin obtained comprising operation 1 or the manufacture method comprising operation 1 and 2 with
In the case that (methyl) acrylic acid reacts, in order to prevent gelation, appropriate guarantee in reaction system and reaction system is needed
On gas phase oxygen concentration.For example, in the case where energetically air being blown into into reaction system, may cause catalyst
Oxidation, the reduction for causing activity, so that noting.
It is acrylic acid with (methyl) in the epoxy resin by obtaining comprising operation 1 or the manufacture method comprising operation 1 and 2
In reaction, as the inclined acrylated epoxy obtained by the reaction can occur in the presence of ultraviolet isoreactivity energy-ray
Solidification, thus it is preferred that being reacted in the container of masking ultraviolet.Additionally, in order to prevent gas-phase polymerization, by comprising operation 1
Or the epoxy resin that the manufacture method comprising operation 1 and 2 is obtained can be aobvious to epoxy resin with (methyl) acrylic acid reaction
Carry out in the presence of the reflux solvent of good solvent is shown, but in this case, need after termination of the reaction to remove solvent, because
And it is preferred that carrying out under solvent-free.As reflux solvent, acetone, methyl ethyl ketone etc. can be enumerated.
In the manufacture method of the present invention, make by obtaining comprising operation 1 or the manufacture method comprising operation 1 and 2
After epoxy resin is reacted with (methyl) acrylic acid, inclined ester-epoxy is obtained by removing Polymer Supported base catalyst
Resin.Method as Polymer Supported base catalyst is removed, it is preferred to use filter or centrifugation.
Method as being filtered to Polymer Supported base catalyst, it is 10 μm that can for example enumerate using mesh
The method that nylon wire NY-10HC (manufacture of Sefar societies of Switzerland) filters Polymer Supported base catalyst.
Method as being centrifuged to Polymer Supported base catalyst, can enumerate by using centrifugation
The method that machine carries out solid-liquid separation to remove Polymer Supported base catalyst.
【Embodiment】
The present invention is illustrated by the following examples, but the present invention is not limited by these embodiments.Need explanation
As long as, not special declaration, " % " is weight basis.
[comparative example 1-2] (compound B)
By bisphenol A type epoxy resin (EXA850CRP, Dainippon Ink Chemicals's manufacture；The compound for also serving as comparative example 1-1 makes
With) 340g, methacrylic acid (Tokyo chemical conversion society manufacture) 90.4g, triphenylphosphine (manufacture of Tokyo chemical conversion society) 0.5g and BHT
100mg mixes, and stirs 6 hours at 100 DEG C.
Obtain the compound B 418g for pale yellow transparent dope.
[synthesis example 1] (compound C1-1)
By Polyethylene Glycol #200 (200g (2 equivalents/hydroxyl)), epoxychloropropane 1110g (6 equivalent), benzyl trimethyl chlorine
Change ammonium 37.1g (0.1 equivalent) is added to and is provided with machine mixer, thermometer, thermoregulator, condenser, Dean-Stark
In the three neck round bottom flask of 2 liters of water knockout drum and Dropping funnel.Next, mixture is stirred under the fine vacuum of 70 supports (torr)
Mix, while 50 DEG C are heated to about to 55 DEG C, make epoxychloropropane vigorous reflux.With the times of 2 hours by 48% solution of 300g
NaOH is added slowly in mixture.After generating azeotropic mixture, immediately by the epoxychloropropane in water/epoxychloropropane mixture
Send reaction system back to, while proceeding stirring.After addition terminates, continue stirring 3 hours.Next, reactant mixture is cold
But to room temperature, chloroform 1L is added, 6 times is cleaned with the water of 1L.The solvent of the organic faciess obtained by being removed by vacuum distillation, is obtained
The compound C1-1 (171g) of light yellow transparent liquid.
[synthesis example 2] (compound C1-2)
Polyethylene Glycol #200 in make synthesis example 1 is, in addition to Polyethylene Glycol #300 (300g), equally to enter with synthesis example 1
OK, obtain the compound C1-2 (222g) of light yellow transparent liquid.
[synthesis example 3] (compound C1-4)
By Polyethylene Glycol #1000 (250g (0.5 equivalent/hydroxyl)), epoxychloropropane 277g (6 equivalent), benzyl trimethyl
Ammonium chloride 9.28g (0.1 equivalent) is added to and is provided with machine mixer, thermometer, thermoregulator, condenser, Dean-
In the three neck round bottom flask of 1 liter of Stark water knockout drums and Dropping funnel.Next, by mixture 70 supports (torr) Gao Zhen
Empty lower stirring, while being heated to about 50 DEG C to 55 DEG C, makes epoxychloropropane vigorous reflux.With the times of 2 hours by the 48% of 75g
NaOH solution is added slowly in mixture.After generating azeotropic mixture, immediately by the epoxy chlorine in water/epoxychloropropane mixture
Propane sends reaction system back to, while proceeding stirring.After addition terminates, continue stirring 3 hours.Next, reaction is mixed
Thing is cooled to room temperature, adds chloroform 500mL, cleans 6 times with the water of 500mL.Organic faciess obtained by being removed by vacuum distillation
Solvent, obtain the compound C1-4 (138g) for white waxy solid.
[embodiment 1-1] (compound A-1)
(1) by compound C1-1 (145g (1 equivalent/epoxy radicals)) and bisphenol-A (compound D1) (570g (2.5 equivalent))
It is added in eggplant type flask, carrying out heated and stirred makes liquid temperature reach 150 DEG C.Addition 4%NaOH aqueous solution 1.5g, stir at 150 DEG C
Mix 2 hours.Liquid temperature is cooled to for less than 60 DEG C, chloroform 500mL is added, is cleaned 6 times, utilized water using 1%NaOH aqueous solutions 1L
1L is cleaned 3 times.Magnesium sulfate is added in resulting organic faciess, solid constituent is leached by filtration etc. after being dried, by decompression
The solvent of resulting organic faciess is distilled off by distillation, and the reaction as synthetic intermediate is obtained using in the form of clear yellow viscous thing
Product P-1 (290g).
(2) product P-1 (170g), epoxychloropropane (495g) and benzyltrimethylammonium chloride (16.5g) are added
Enter to being provided with 2 liters of machine mixer, thermometer, thermoregulator, condenser, Dean-Stark water knockout drums and Dropping funnel
Three neck round bottom flask in.Next, mixture is stirred under the fine vacuum of 70 supports (torr), while being heated to about 50 DEG C extremely
55 DEG C, make epoxychloropropane vigorous reflux.The 48%NaOH solution of 133g is added slowly to into mixture with the times of 2 hours
In.After generating azeotropic mixture, the epoxychloropropane in water/epoxychloropropane mixture is sent back to reaction system immediately, while continuing
It is stirred.After addition terminates, continue stirring 3 hours.Next, reactant mixture is cooled to room temperature, chloroform 1L is added, used
The water of 1L is cleaned 6 times.The solvent of the organic faciess obtained by being removed by vacuum distillation, obtains the compound for faint yellow dope
A-1 (product Q-1) 206g.
[embodiment 1-2] (compound A-2)
(1) by compound C1-2 (230g (1 equivalent/epoxy radicals)) and bisphenol-A (compound D1) (570g (2.5 equivalent))
It is added in eggplant type flask, carrying out heated and stirred makes liquid temperature reach 150 DEG C.Addition 4%NaOH aqueous solution 1.5g, stir at 150 DEG C
Mix 2 hours.Liquid temperature is cooled to for less than 60 DEG C, chloroform 500mL is added, is cleaned 6 times, utilized water using 1%NaOH aqueous solutions 1L
1L is cleaned 3 times.Magnesium sulfate is added in resulting organic faciess, solid constituent is leached by filtration etc. after being dried, by decompression
The solvent of resulting organic faciess is distilled off by distillation, and the reaction as synthetic intermediate is obtained using in the form of clear yellow viscous thing
Product P-2 (366g).
(2) product P-2 (203g), epoxychloropropane (495g) and benzyltrimethylammonium chloride (16.5g) are added
Enter to being provided with 2 liters of machine mixer, thermometer, thermoregulator, condenser, Dean-Stark water knockout drums and Dropping funnel
Three neck round bottom flask in.Next, mixture is stirred under the fine vacuum of 70 supports (torr), while being heated to about 50 DEG C extremely
55 DEG C, make epoxychloropropane vigorous reflux.The 48%NaOH solution of 133g is added slowly to into mixture with the times of 2 hours
In.After generating azeotropic mixture, the epoxychloropropane in water/epoxychloropropane mixture is sent back to reaction system immediately, while continuing
It is stirred.
After addition terminates, continue stirring 3 hours.Next, reactant mixture is cooled to room temperature, chloroform 1L, profit are added
6 times are cleaned with the water of 1L.The solvent of the organic faciess obtained by being removed by vacuum distillation, obtains the chemical combination for faint yellow dope
Thing A-2 (product Q-2) 241g.
[embodiment 1-3] (compound A-3)
(1) Denacol EX-830 (compound C1-3) (268g (1 equivalents/ring that Nagase chemte X societies are manufactured
Epoxide)) and bisphenol-A (compound D1) (570g (2.5 equivalent)) be added in eggplant type flask, carrying out heated and stirred reaches liquid temperature
To 150 DEG C.Addition 4%NaOH aqueous solution 1.5g, stir 2 hours at 150 DEG C.Liquid temperature is cooled to for less than 60 DEG C, chloroform is added
500mL, is cleaned 6 times using 1%NaOH aqueous solutions 1L, is cleaned 3 times using water 1L.Sulphuric acid is added in resulting organic faciess
Magnesium, is leached solid constituent by filtration etc. after being dried, the solvent of resulting organic faciess is distilled off by vacuum distillation, with
The form of clear yellow viscous thing obtains product P-3 (375g) as synthetic intermediate.
(2) product P-3 (200g), epoxychloropropane (452g) and benzyltrimethylammonium chloride (15.1g) are added
Enter to being provided with 2 liters of machine mixer, thermometer, thermoregulator, condenser, Dean-Stark water knockout drums and Dropping funnel
Three neck round bottom flask.Next, mixture is stirred under the fine vacuum of 70 supports (torr), while being heated to about 50 DEG C to 55
DEG C, make epoxychloropropane vigorous reflux.The 48%NaOH solution of 122g is added slowly to into mixture with the times of 2 hours
In.After generating azeotropic mixture, the epoxychloropropane in water/epoxychloropropane mixture is sent back to reaction system immediately, while continuing
It is stirred.After addition terminates, continue stirring 3 hours.Next, reactant mixture is cooled to room temperature, chloroform 1L is added, used
The water of 1L is cleaned 6 times.The solvent of the organic faciess obtained by being removed by vacuum distillation, obtains the compound for faint yellow dope
A-3 (product Q-3) 228g.
[embodiment 1-4] (compound A-4)
(1) by compound C1-4 (130g (0.23 equivalent/epoxy radicals)) and bisphenol-A (compound D1), ((2.5 work as 131g
Amount)) it is added in eggplant type flask, carrying out heated and stirred makes liquid temperature reach 150 DEG C.Addition 4%NaOH aqueous solution 0.3g, 150
DEG C stirring 2 hours.Liquid temperature is cooled to for less than 60 DEG C, chloroform 500mL is added, and 6 times, profit is cleaned using 1%NaOH aqueous solutions 1L
3 times are cleaned with water 1L.Magnesium sulfate is added in resulting organic faciess, solid constituent is leached by filtration etc. after being dried, is passed through
The solvent of resulting organic faciess is distilled off by vacuum distillation, is obtained as synthetic intermediate using in the form of clear yellow viscous thing
Product P-4 (154g).
(2) product P-4 (140g), epoxychloropropane (207g) and benzyltrimethylammonium chloride (6.94g) are added
Enter to being provided with 2 liters of machine mixer, thermometer, thermoregulator, condenser, Dean-Stark water knockout drums and Dropping funnel
Three neck round bottom flask.Next, mixture is stirred under the fine vacuum of 70 supports (torr), while being heated to about 50 DEG C to 55
DEG C, make epoxychloropropane vigorous reflux.The 48%NaOH solution of 56g is added slowly in mixture with the times of 2 hours.
After generating azeotropic mixture, the epoxychloropropane in water/epoxychloropropane mixture is sent back to reaction system immediately, while proceeding
Stirring.After addition terminates, continue stirring 3 hours.Next, reactant mixture is cooled to room temperature, chloroform 1L is added, with 1L's
Water is cleaned 6 times.The solvent of the organic faciess obtained by being removed by vacuum distillation, obtains the compound A-4 for faint yellow dope
(product Q-4) 142g.
[embodiment 1-5] (compound A-5)
By compound A-3 (product Q-3) 320g, methacrylic acid (manufacture of Tokyo chemical conversion society) 43.05g, triphenyl
Phosphine (base catalyst, the manufacture of Tokyo chemical conversion society) 0.25g and BHT 50mg mixing, stirs 8 hours at 100 DEG C.Obtain as light
The compound A-5 (357g) of clear yellow viscous thing.
[embodiment 2-1～9 and comparative example 2-1]
Respectively by compound A-1～5 (embodiment 1-1～5) and compound B (comparative example 1-2) and EY ResinKR-2
(manufacture of KSM societies), ZEFIAC (ゼ Off ァ ア ッ Network) F351 (GANZ CHEMICAL CO., LTD. are manufactured), SEAHOSTAR KE-
C50HG (Japanese catalyst society manufacture), KBM-403 (silane couplers：SHIN-ETSU HANTOTAI's chemical industry manufacture) and Ajicure VDH (1,
Double (hydrazine the carbonylethyl) -5- isopropyl hydantoin of 3-, the manufacture of AJINOMOTO FINETECHNO societies) according to mixed shown in table 1
Resultant (weight portion) is mixed, and is fully kneaded using three-roll mill (made C-43/4 × 10 are made on well) afterwards, is obtained
To embodiment 2-1～9 and the liquid crystal sealing agent of comparative example 2-1.
[experimental condition]
For compound A-1～5 (embodiment 1-1～5), EPICRON 850CRP (comparative example 1-1) and compound B (ratios
Compared with example 1-2), viscosity and epoxide equivalent are determined respectively, evaluation approach determines the change of NI points；For the liquid of embodiment 2-1～9
Brilliant sealant and the liquid crystal sealing agent of comparative example 2-1～3, evaluate adhesive strength respectively, determine the change of NI points.
(1) viscosimetric analysis
Using E type viscometers (Dong Ji industries society manufactures RE105U), it is measured at 25 DEG C.
It is following to select rotor and rotating speed.
Compound A-1：3 ° × R7.7 rotors, rotating speed 5rpm
Compound A-2：3 ° × R7.7 rotors, rotating speed 10rpm
Compound A-3：3 ° × R14 rotors, rotating speed 5rpm
Compound A-4：3 ° × R14 rotors, rotating speed 20rpm
Compound A-5：3 ° × R7.7 rotors, rotating speed 5rpm
EPICLON 850CRP：3 ° × R14 rotors, rotating speed 20rpm
Compound B：3 ° × R7.7 rotors, rotating speed 10rpm
(2) epoxide equivalent is determined
In JIS K 7236：It is measured under conditions of described in 2001.
(3) NI points change detection
Compound A-1～5 (embodiment 1-1～5), EPICRON 850CRP (comparative example 1- are separately added in ampoule bottle
1), the liquid crystal sealing agent 0.1g of compound B (comparative example 1-2), the liquid crystal sealing agent of embodiment 2-1～9 and comparative example 2-1～3,
Liquid crystal (MLC-11900-080, the manufacture of Merck society) 1g is added further.The bottle is put into 1 hour in 120 DEG C of baking ovens, thereafter
Be stored at room temperature, lcd segment taken out afterwards room temperature (25 DEG C) is returned to, filtered with 0.2 μm of filter, make evaluation liquid crystal
Sample.The measure of NI points uses differential scanning type calorimeter (manufacture of DSC, PerkinElmer society, PYRIS6), by evaluation liquid
Brilliant sample 10mg is sealing in aluminium sample disc, is measured under conditions of programming rate is for 5 DEG C/min.It should be noted that
Above-mentioned liquid crystal 10mg is sealing in aluminium sample disc, is measured under conditions of programming rate is for 5 DEG C/min, knot will be determined
Fruit is used as blank.
By blank heat absorption summit (phase transition temperature) TB with heat absorption summit (phase transition temperature) TE's of evaluation liquid crystal
Difference TE-TB changes as NI points.
From the dissolution for impurity being reduced to suppress which in liquid crystal, stably guarantee the orientation of liquid crystal, improve display characteristic
From the aspect of, the change of NI points is more little more preferred.
(4) orientation evaluation
In the ITO with alignment films (Sunever SE-7492, the manufacture of Nissan Chemical Industries society) of 2 rubbed process
It is close to carry out so that compound A-1 is carried out a coating between 15mm on the face of the monolithic of glass substrate (60mm × 70mm × 0.7mmt)
Envelope, makes a diameter of below the 2mm after laminating fit the face of another, after injection liquid crystal, in 120 DEG C of hot-air oven during coating
Thermal curing 1 hour, makes the panel for evaluation approach.
Compound A-1 is replaced with into compound A-2～5, EPICLON 850CRP, compound B respectively, is made for evaluating
The panel of orientation.
Friction treatment is carried out as follows.
Using air point gum machine (dispenser), will orientation liquid Sunever SE-7492 (manufacture of Nissan Chemical Industries society)
Instil TN6070 substrates (the FPD Solutions societies manufacture ITO being dried after (0.3MPa, 5.3sec) is cleaned to pure water
Substrate), 10 second 5000rpm is reached in Jing using spin coater afterwards and even spread (alignment films are carried out under conditions of being kept for 20 seconds
Thickness isCondition).After coating, prebake (85 DEG C, 1min) on hot plate, using (230 are bakeed after baking oven
℃、60min).Using cotton friction roller under rotating speed 500rpm with the speed conveying substrate of 600mm/min, being pressed into 0.4mm
Amount carries out friction treatment.Mode of the substrate in 90 ° of rotations (intersection) according to opposite specifies frictional direction.By base after friction treatment
Plate is impregnated in pure water, carries out ultrasound wave cleaning.Be dried using 120 DEG C of baking oven, make after friction treatment with taking
To the ito glass substrate of film.
For resulting panel, the state of orientation of the liquid crystal at seal point (point coated portion) edge is confirmed.Really
Recognizing is carried out using optical microscope, polaroid is clipped liquid crystal test box (テ ス ト セ Le) with the state of cross Nicols, is passed through
Transmission is observed, for liquid crystal (hereinafter referred to as blank liquid crystal) and the sealing point edge of seal point and the mid portion of seal point
The state of liquid crystal be compared.
The uneven part different from the state in blank liquid crystal seen by sealing point edge is being sealed into the one of point edge
Part and situation less than 50 μm or the feelings of this uneven part are not observed in sealing margin completely from sealing point edge
Condition is evaluated as zero；
By this uneven part in a part for sealing point edge and from sealing point edge more than 50 μm of situation or
This uneven part is observed all around sealing point edge but this uneven part is little from sealing point edge
△ is evaluated as in 50 μm of situations；
To all observe around sealing point edge that this uneven part and this uneven part are poly- from close
Seal point edge rise more than 50 μm of situation be evaluated as ×.
It should be noted that it is believed that above-mentioned uneven part represents that liquid crystal aligning is bad.
Fig. 1, in 2 it is following situations：In the orientation of the liquid crystal of the sealing point edge of compound A-3 (Fig. 1) and A-5 (Fig. 2)
Under state, the uneven portions different from the state of blank liquid crystal seen by sealing point edge are not observed completely in sealing point edge
Situation about dividing；Or this uneven part sealing point edge a part and from sealing point edge less than 50 μm (zero).
It is following situations in Fig. 3：Under the state of orientation of the liquid crystal of the sealing point edge of compound B, this uneven part is in sealing
Around point edge all and from sealing point edge more than 50 μm (×).
(5) evaluation of adhesive strength
The summary of test method is shown in Fig. 4.
Respectively the liquid crystal sealing agent point of embodiment 2-1～9 and comparative example 2-1～3 is coated on and is scattered with 6 μm of septs
15mm × the 3mm of (30mm × 30mm × 0.5mmt), the position of 15mm × 21mm on ito glass substrate, according to laminating during coating
The diameter of liquid crystal sealing agent is the mode of 1.5～2.5mm φ and carries out coating afterwards.Thereafter, glass adhering substrate (23mm ×
23mm × 0.5mmt), with illumination 3000mJ/cm2Irradiation ultraviolet radiation (UV irradiation units：UVX-01224S1, USHIO INC. societies
Manufacture, with 100mW/cm2/ 365nm irradiates 30 seconds) solidified, thereafter, thermosetting in 1 hour is carried out using 120 DEG C of hot-air ovens
Change, make for evaluating the test film of adhesive strength.The autoplotter AGS-500 manufactured using society of Shimadzu Seisakusho Ltd., will examination
The glass substrate for testing piece is fixed, and the position of ito glass substrate 15mm × 25mm is punched out with the speed of 5mm/min, is evaluated
Adhesive strength.Evaluation result is listed in table 1.
The Japanese patent application disclosure of No. 2012-227417 is brought into this specification by reference integrally
In.
For the whole documents described in this specification, patent application and technical standard, each document, patent application and
The degree that technical standard is included in this specification by reference is identical with the degree of the situation which is specifically recorded respectively.
Claims (2)
1. application of the glycidyl ether based compound that formula (1) is represented in liquid crystal sealing agent is prepared, the liquid crystal sealing agent bag
Containing the glycidyl ether based compound that content is 60 weight %～100 weight %,
【Change 8】
In formula (1), n1For the number of 2～30 scopes, m is the number of 1～5 scope；
X is oxygen atom, the alkylidene that carbon number is 1～4 or alkylidene that carbon number is 2～4；
Y is alkylidene that carbon number is 2～4 each, independently of the other；
R is hydrogen atom, glycidyl, methylglycidyl, group 1 each, independently of the other：-CH2-CH(OR1)-CH2-
O-R2Or group 2：-CH2-C(CH3)(OR1)-CH2-O-R2, in the formula of group 1 and group 2, R1For hydrogen atom or (methyl) propylene
Acyl group, R2For (methyl) acryloyl group；
R ' is hydrogen atom or methyl each, independently of the other；
In the R, the glycidyl, the methylglycidyl, the group 1 and the group 2 it is total average
Number x is more than 2；
In the case that the R includes the group 1 or the group 2, the conjunction of the glycidyl and methylglycidyl
Ratio y/z of total mean number z of meter mean number y and the group 1 and the group 2 is 10/90～90/10.
2. it is as claimed in claim 1 to apply, wherein, the liquid crystal sealing agent is further comprising with ethylenic unsaturated group
And/or the compound B of epoxy radicals, do not include the glycidyl ether based compound in compound B.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-227417 | 2012-10-12 | ||
| JP2012227417 | 2012-10-12 | ||
| PCT/JP2013/077036 WO2014057871A1 (en) | 2012-10-12 | 2013-10-04 | Glycidyl ether compound, liquid crystal sealant, and method for producing glycidyl ether compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104718231A CN104718231A (en) | 2015-06-17 |
| CN104718231B true CN104718231B (en) | 2017-03-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380052675.4A Active CN104718231B (en) | 2012-10-12 | 2013-10-04 | The manufacture method of glycidyl ether based compound, liquid crystal sealing agent and glycidyl ether based compound |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6310852B2 (en) |
| KR (1) | KR102056074B1 (en) |
| CN (1) | CN104718231B (en) |
| TW (1) | TWI586695B (en) |
| WO (1) | WO2014057871A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI662055B (en) * | 2014-03-31 | 2019-06-11 | 日商協立化學產業股份有限公司 | Curable resin, (meth) acrylic curable resin, and liquid crystal sealant composition having excellent softness after curing |
| JP6601634B2 (en) * | 2017-03-31 | 2019-11-06 | 協立化学産業株式会社 | Modified resin and curable resin composition containing the same |
| JP7148332B2 (en) | 2018-09-07 | 2022-10-05 | 積水化学工業株式会社 | Liquid crystal display element sealant, vertical conduction material, and liquid crystal display element |
| KR20240023110A (en) * | 2021-06-22 | 2024-02-20 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal display elements and liquid crystal display elements |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55161817A (en) * | 1979-06-05 | 1980-12-16 | Sumitomo Chem Co Ltd | Preparation of epoxy resin |
| JP3637126B2 (en) * | 1996-01-25 | 2005-04-13 | ナミックス株式会社 | Sealant for liquid crystal display cell and liquid crystal display cell using the same |
| JP2006124698A (en) | 2001-05-16 | 2006-05-18 | Sekisui Chem Co Ltd | Curing resin composition, and sealant and end-sealing material for display element |
| WO2004027502A1 (en) * | 2002-09-19 | 2004-04-01 | Mitsui Chemicals, Inc. | Sealing composition for liquid crystal displays and process for production of liquid crystal display panels |
| US20050010022A1 (en) * | 2003-07-09 | 2005-01-13 | Yasuo Chiba | Epoxy resin compositions |
| JP2007297470A (en) * | 2006-04-28 | 2007-11-15 | Dainippon Ink & Chem Inc | Curable composition, its cured product, sealing agent for liquid crystal display element, liquid crystal display element and vinyl group-containing epoxy resin |
-
2013
- 2013-10-04 JP JP2014540827A patent/JP6310852B2/en active Active
- 2013-10-04 WO PCT/JP2013/077036 patent/WO2014057871A1/en active Application Filing
- 2013-10-04 CN CN201380052675.4A patent/CN104718231B/en active Active
- 2013-10-04 KR KR1020157011942A patent/KR102056074B1/en active IP Right Grant
- 2013-10-09 TW TW102136533A patent/TWI586695B/en active
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| Publication number | Publication date |
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| KR20150068448A (en) | 2015-06-19 |
| TW201428018A (en) | 2014-07-16 |
| TWI586695B (en) | 2017-06-11 |
| WO2014057871A1 (en) | 2014-04-17 |
| CN104718231A (en) | 2015-06-17 |
| JP6310852B2 (en) | 2018-04-11 |
| JPWO2014057871A1 (en) | 2016-09-05 |
| KR102056074B1 (en) | 2019-12-16 |
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