CN104718231A - Glycidyl ether compound, liquid crystal sealant, and method for producing glycidyl ether compound - Google Patents

Glycidyl ether compound, liquid crystal sealant, and method for producing glycidyl ether compound Download PDF

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CN104718231A
CN104718231A CN201380052675.4A CN201380052675A CN104718231A CN 104718231 A CN104718231 A CN 104718231A CN 201380052675 A CN201380052675 A CN 201380052675A CN 104718231 A CN104718231 A CN 104718231A
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compound
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liquid crystal
methyl
compd
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CN104718231B (en
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臼井大晃
堀越良尔
宫崎健介
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Kyoritsu Chemical and Co Ltd
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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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Material Composition (AREA)
  • Physics & Mathematics (AREA)
  • Epoxy Resins (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Epoxy Compounds (AREA)

Abstract

The present invention provides a glycidyl ether compound that scarcely affects liquid crystal molecular alignment and makes it possible for a liquid crystal sealant to adhere strongly and cure even when a liquid crystal sealant is applied in a narrow seal width and bonded to a base in a one-drop-fill method. The present invention also provides a liquid crystal sealant containing the glycidyl ether compound, and a method for producing the glycidyl ether compound.

Description

The manufacture method of glycidyl ether based compound, liquid crystal sealing agent and glycidyl ether based compound
[technical field]
The present invention relates to glycidyl ether based compound, comprise the manufacture method of the liquid crystal sealing agent of glycidyl ether based compound and glycidyl ether based compound.
[background technology]
In the manufacture of the liquid crystal indicators such as liquid crystal panel, widely use liquid crystal drip-injection technique, in the process, such as at the periphery coating of liquid crystalline sealing agent of arbitrary substrate of 2 plate bases of formation liquid crystal panel, arbitrary substrate instils the liquid crystal of predetermined amount, send back in normal atmosphere after 2 plate bases are fitted under vacuo and carry out filling liquid crystal, liquid crystal sealing agent is solidified.
In liquid crystal drip-injection technique, from the aspect of high speed curable, widely use using the epoxy acrylate based compound Raolical polymerizable compound that is host as liquid crystal sealing agent (such as with reference to Japanese Unexamined Patent Publication 2007-297470 publication).
[summary of the invention]
[inventing problem to be solved]
But in recent years, due to popularizing of smart mobile phone, panel type terminal etc., increase the demand of small panel, due to the panel designs that designability improves, narrow frame is developed, and the requirement for the graph thinning of liquid crystal sealing agent coating increases.Such as, require existing sealed width 1.0mm ~ 1.5mm to reduce by half such degree.For this requirement, from the aspect of weather resistance, even if making bond area reduce due to the narrowing of sealed width, also need liquid crystal sealing agent can maintain or improve bonding strength further.
In liquid crystal drip-injection technique, sealing agent is applied to substrate with frame-shaped and forms frame sealing, at the inner side dispenser method of frame, vacuumize panel attachment, carry out UV irradiate make liquid crystal sealing agent photocuring after, temperature more than the NI point (nematic phase-isotropy phase point, Nematic Isotropic point) of liquid crystal carries out thermal curing, and liquid crystal sealing agent is carried out to thermofixation, makes liquid crystal generation orientation simultaneously.
When the larger panel that TV is such, because panel is very large, thus there is from liquid crystal drip-injection to frame sealing place the distance necessarily, after dispenser method is by panel attachment, until when carrying out UV irradiation, liquid crystal contacts not yet with liquid crystal sealing agent, and thus liquid crystal sealing agent just contacts with liquid crystal after photocuring.Or the duration of contact of the liquid crystal sealing agent of liquid crystal and its uncured state is short.
On the other hand, in small panel, due to short to the distance of frame sealing place from liquid crystal drip-injection, thus after laminating, to when carrying out UV irradiation, liquid crystal sealing agent still contacts with liquid crystal (duration of contact is long) with uncured state.Therefore, compared with the past, liquid crystal sealing agent liquid crystal pollution in the uncured state becomes problem.
The existing liquid crystal sealing agent with the Raolical polymerizable that is host of the epoxy compounds containing epoxy/acrylic acid based compound can't be said and fully respond this requirement.
Problem of the present invention is the manufacture method providing a kind of glycidyl ether based compound, the liquid crystal sealing agent comprising glycidyl ether based compound and glycidyl ether based compound, in liquid crystal drip-injection technique, even if when carrying out adhesive substrates with narrow and small sealed width coating of liquid crystalline sealing agent, liquid crystal sealing agent also can strongly bonding solidification, not easily brings impact to liquid crystal aligning.
[solving the means of problem]
The present invention comprises following mode.
[1] a glycidyl ether based compound, it is represented by following formula (1),
[changing 1]
[in formula, n 1be the number of 2 ~ 30 scopes, m is the number of 1 ~ 5 scope;
X is Sauerstoffatom (O), carbonatoms be 1 ~ 4 alkylidene group or carbonatoms be the alkylidene of 2 ~ 4;
Y is separately independently of each other for carbonatoms is the alkylidene group of 2 ~ 4;
R is hydrogen atom, glycidyl, methylglycidyl, group 1:-CH separately independently of each other 2-CH (OR 1)-CH 2-O-R 2or group 2:-CH 2-C (CH 3) (OR 1)-CH 2-O-R 2(in formula, R 1for hydrogen atom or (methyl) acryl, R 2for (methyl) acryl);
R ' is hydrogen atom or methyl separately independently of each other;
In above-mentioned R, the total mean number x of above-mentioned glycidyl, above-mentioned methylglycidyl, above-mentioned group 1 and above-mentioned group 2 is more than 2;
When above-mentioned R comprises above-mentioned group 1 or above-mentioned group 2, the ratio (y/z) of the total mean number y of above-mentioned glycidyl and methylglycidyl and the total mean number z of above-mentioned group 1 and above-mentioned group 2 is 10/90 ~ 90/10].
[2] liquid crystal sealing agent, it comprises 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 in above-mentioned [1], it comprises the operation that the Compound C represented by following formula (2) and the Compound D represented by following formula (3) are reacted
[changing 2]
(in formula, n 2it is the number of 2 ~ 30 scopes;
Y is separately independently of each other for carbonatoms is the alkylidene group of 2 ~ 4;
R 11be hydrogen atom, glycidyl or methylglycidyl independently of each other separately);
[changing 3]
[in formula, X is Sauerstoffatom, carbonatoms be 1 ~ 4 alkylidene group or carbonatoms be the alkylidene of 2 ~ 4;
R 12be hydrogen atom, glycidyl, methylglycidyl, group 1:-CH independently of each other separately 2-CH (OR 21)-CH 2-O-R 22or group 2:-CH 2-C (CH 3) (OR 21)-CH 2-O-R 22(in formula, R 21for hydrogen atom or (methyl) acryl, R 22for (methyl) acryl)].
[effect of invention]
According to the present invention, the manufacture method of a kind of glycidyl ether based compound, the liquid crystal sealing agent comprising glycidyl ether based compound and glycidyl ether based compound can be provided, in liquid crystal drip-injection technique, even if when carrying out adhesive substrates with narrow and small sealed width coating of liquid crystalline sealing agent, liquid crystal sealing agent also can strongly bonding solidification, not easily brings impact to liquid crystal aligning.
[accompanying drawing explanation]
The microscopic iage of Fig. 1 to be the liquid crystal aligning represented in embodiment be example (compd A-3) of the situation of zero.
The microscopic iage of Fig. 2 to be the liquid crystal aligning represented in embodiment be example (compd A-5) of the situation of zero.
To be the liquid crystal aligning represented in embodiment be Fig. 3 × the microscopic iage of example (compd B) of situation.
Fig. 4 is the schematic diagram of the test method briefly showing bonding strength.
[embodiment]
Term " operation " in this specification sheets is not only independently operation, even if when district Do cannot be specified with other operation, as long as the expection object of this operation can be reached, and also this term of term." ~ " numerical range of representing is used to represent to comprise the numerical value recorded before and after " ~ " respectively as the scope of minimum value and maximum value.About the amount of composition each in composition, when the material being equivalent to each composition in the composition exists multiple, only otherwise special declaration, in composition, the amount of each composition refers to the total amount of this many kinds of substance existed in composition.
In addition, (methyl) acryloyl refers to methacryloyl and/or acryloyl, and (methyl) acrylate is methacrylate and/or acrylate.
[compd A]
Glycidyl ether based compound (hereinafter also referred to compd A) of the present invention is represented by following formula (1).
[changing 4]
In formula, n 1be the number of 2 ~ 30 scopes, m is the number of 1 ~ 5 scope.
X is Sauerstoffatom (O), carbonatoms be 1 ~ 4 alkylidene group or carbonatoms be the alkylidene of 2 ~ 4.Y is separately independently of each other for carbonatoms is the alkylidene group of 2 ~ 4.
R is hydrogen atom, glycidyl, methylglycidyl, group 1:-CH separately independently of each other 2-CH (OR 1)-CH 2-O-R 2or group 2:-CH 2-C (CH 3) (OR 1)-CH 2-O-R 2(in formula, R 1for hydrogen atom or (methyl) acryl, R 2for (methyl) acryl).R ' is hydrogen atom or methyl separately independently of each other.
The total mean number x of the above-mentioned glycidyl in above-mentioned R, above-mentioned methylglycidyl, above-mentioned group 1 and above-mentioned group 2 is more than 2; When above-mentioned R comprises above-mentioned group 1 or above-mentioned group 2, the ratio (y/z) of the total mean number y of above-mentioned glycidyl and methylglycidyl and the total mean number z of above-mentioned group 1 and above-mentioned group 2 is 10/90 ~ 90/10.
From the aspect of the strong cementability (even if when carrying out adhesive substrates with narrow and small sealed width coating of liquid crystalline sealing agent, liquid crystal sealing agent also can performance of strongly bonding solidification) in liquid crystal drip-injection technique, the n in compd A 1be the number of the number of 3 ~ 25 scopes, preferably number, more preferably 5 ~ 15 scopes of 5 ~ 20 scopes, be further preferably the number of 7 ~ 10 scopes.It should be noted that, n 1derive from 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 (such as, speed of drawing and the productive temp of point gum machine (dispenser) can not reduce) aspect and the aspect of adapted (unduly improving the viscosity of compd A) of liquid crystal sealing agent set out, the m in compd A be 1 ~ 5 scope number, be preferably the number of number, more preferably 1 ~ 3 scope of 1 ~ 4 scope, be further preferably the number of 1 ~ 2 scope.It should be noted that, m can be estimated by the reaction equivalent ratio (charging capacity) of the Compound C of the raw material as compd A and Compound D.
It should be noted that, n 1also GPC can be utilized to measure with m.
Y, separately independently of each other for carbonatoms is the alkylidene group of 2 ~ 4, specifically, is ethylidene, propylidene, trimethylene, tetramethylene etc.Y is preferably ethylidene or propylidene, is more preferably ethylidene.
From the aspect of the physical propertys such as the intensity after the solidification of the workability such as the coating of the such as viscosity influence of liquid crystal sealing agent and such as cross-linking density impact, in compd A, the total mean number x of the glycidyl in R, methylglycidyl, group 1 and group 2 is more than 2, is preferably 2 ~ 2m+2, is more preferably 2m ~ 2m+2, more preferably 2m+1 ~ 2m+2.
It should be noted that, about x, measure molecular-weight average and the molecular weight distribution of compd A by high performance liquid chromatography (HPLC) and liquid chromatographic mass analysis (LC-MS), measure n by GPC 1and m, thus calculate this x.
In compd A, when above-mentioned R comprises above-mentioned group 1 or above-mentioned group 2, the ratio (y/z) of the total mean number y of above-mentioned glycidyl and methylglycidyl and the total mean number z of above-mentioned group 1 and above-mentioned group 2 is 10/90 ~ 90/10, is preferably 20/80 ~ 80/20, is more preferably 30/70 ~ 70/30, more preferably 40/60 ~ 60/40.
From the aspect of strong cementability, the R in compd A is hydrogen atom, glycidyl, methylglycidyl, group 1 or group 2 independently of one another, is preferably hydrogen atom, glycidyl or group 1.Further, R ' is preferably hydrogen atom.
When using compd A in liquid crystal sealing agent, from the aspect of viscosity making liquid crystal sealing agent guarantee appropriateness, the viscosity of compd A is preferably 1000mPas ~ 1000000mPas, is more preferably 3000mPas ~ 700000mPas, more preferably 5000mPas ~ 500000mPas, be further preferably 7000mPas ~ 250000mPas, more more preferably 9000mPas ~ 200000mPas.It should be noted that, viscosity can use E type viscometer to measure at 25 DEG C.
It should be noted that, the viscosity of compd A is such as by changing the n in compd A 1adjust with the existence ratio etc. of the hydroxyl in m and/or change compd A.
When using compd A in liquid crystal sealing agent, from the aspect of strong cementability, the epoxy equivalent (weight) of compd A is preferably 100g/eq ~ 3000g/eq, is more preferably 150g/eq ~ 2000g/eq.
It should be noted that, the epoxy equivalent (weight) of compd A can utilize the epoxy radix of the molecular-weight average of compd A and unit repeating unit to adjust.Such as, by carrying out epoxidised ratio to the hydroxyl of compound P and adjusting the ratio that the epoxy group(ing) of reaction product Q carries out the modification of (methyl) acroleic acid esterification.
In liquid crystal drip-injection technique, even if compd A is when uncured state contacts with liquid crystal, also not easily liquid crystal aligning is brought to impact (change of NI point is little), not easily hinders the orientation of liquid crystal, thus this compd A is preferred as liquid crystal sealing agent.
[liquid crystal sealing agent of inclusion compound A]
The liquid crystal sealing agent (hereinafter also referred to " composition ") of inclusion compound A excellent in adhesion by force.
From the aspect of strong cementability and liquid crystal aligning, liquid crystal sealing agent reaction solidified nature composition (such as, can react under the effect of light and/or heating etc. and the composition solidified) in, the content of compd A is preferably 10 % by weight ~ 100 % by weight, be more preferably 20 % by weight ~ 100 % by weight, more preferably 30 % by weight ~ 100 % by weight, more preferably 40 % by weight ~ 100 % by weight, more preferably 50 % by weight ~ 100 % by weight, more preferably 60 % by weight ~ 100 % by weight, more preferably 70 % by weight ~ 100 % by weight, more preferably 80 % by weight ~ 100 % by weight, more preferably 90 % by weight ~ 100 % by weight, more preferably 100 % by weight.
Such as, for the existing compd B with ethylenic unsaturated group and/or epoxy group(ing) used with the host as liquid crystal sealing agent (such as, a part for the epoxy group(ing) of bisphenol A type epoxy resin is carried out to the oligopolymer of methacrylated) together mixture have the liquid crystal sealing agent of compd A, compared with only using the situation of compd B, strong cementability improves a lot.That is, liquid crystal sealing agent is except inclusion compound A, preferably goes back the compd B with ethylenic unsaturated group and/or epoxy group(ing) beyond inclusion compound A.
As the compd B with ethylenic unsaturated group, can enumerate (methyl) acrylic compound, aliphatic propylene amide compound, ester ring type acrylamide compound, containing aromatic acrylamide compound, N-substituted acrylamide based compound.
As (methyl) acrylic compound, can enumerate aliphatics (methyl) acrylate representated by cumylphenoxy ethylene glycol (methyl) acrylate, (methyl) tert-butyl acrylate, (methyl) ethioxy phenyl ester, (methyl) benzyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylate containing aromatic nucleus.
As the compound containing ethylenic unsaturated group, mono-functional, two functionalities, trifunctional or multi-functional free-radical polymerised unsaturated compound can be enumerated.
As the free-radical polymerised unsaturated compound of mono-functional, from guaranteeing composition viscosity, film hardness, setting out in flexible aspect, is preferably selected from by (methyl) Hydroxyethyl acrylate, (methyl) benzyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid dicyclo pentyl ester, (methyl) acrylate oxygen base ethyl ester, (methyl) vinylformic acid two cyclopentyloxy ethyl ester, the different myristin of (methyl) vinylformic acid, (methyl) lauryl acrylate, the compound of more than a kind in the group of (methyl) tert-butyl acrylate and diethylene glycol monoethyl ether (methyl) acrylate composition, is more preferably and is selected from by (methyl) isobornyl acrylate, (methyl) tetrahydrofurfuryl acrylate, the compound of more than a kind in the group of (methyl) vinylformic acid dicyclo pentyl ester and (methyl) cyclohexyl acrylate composition.
As the free-radical polymerised unsaturated compound of two functionalities, from guaranteeing composition viscosity, film hardness, set out in flexible aspect, preferably be selected from by Tricyclodecane Dimethanol two (methyl) acrylate, dihydroxymethyl bicyclopentane two (methyl) acrylate, EO modification 1, 6-hexylene glycol two (methyl) acrylate, EO modified bisphenol A two (methyl) acrylate, PO modified bisphenol A two (methyl) acrylate, polyester two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, the compound of more than a kind in the group of organosilicon two (methyl) acrylate and triglycol two (methyl) acrylate composition, be more preferably dihydroxymethyl bicyclopentane two (methyl) acrylate and/or modified bisphenol A two (methyl) acrylate.Wherein preferably have (methyl) acrylate of the bisphenol A skeleton without hydroxyl, common prosperity society chemistry (strain) is commercially available LIGHT-ACRYLATE BP-4EAL (the EO affixture diacrylate of dihydroxyphenyl propane), BP-4PA (the PO affixture diacrylate of dihydroxyphenyl propane) etc.
As free-radical polymerised unsaturated compound more than trifunctional, from guaranteeing composition viscosity, film hardness, set out in flexible aspect, preferably be selected from by ECH modified glycerol three (methyl) acrylate (trifunctional), EO modified glycerol three (methyl) acrylate (trifunctional), PO modified glycerol three (methyl) acrylate (trifunctional), tetramethylolmethane three (methyl) acrylate (trifunctional), the compound of more than a kind in the group that Dipentaerythritol six (methyl) acrylate (six senses) and tetramethylolmethane four (methyl) acrylate (four senses) form, be more preferably EO modified glycerol three (methyl) acrylate and/or Dipentaerythritol six (methyl) acrylate.
As the compd B with epoxy group(ing), preferably be selected from least one compound in the group be made up of bisphenol A type epoxy compound, bisphenol F type epoxy compound, dihydroxyphenyl propane D type epoxy compounds, novolac type epoxy compounds, cresol novalac type epoxy compounds, naphthalene type epoxy compounds, their plus hydrogenated compound and alicyclic ring type epoxy compounds, be more preferably at least one compound in the group being selected from and being made up of bisphenol A type epoxy compound, bisphenol F type epoxy compound and naphthalene type epoxy compounds, more preferably bisphenol A type epoxy compound.
As the concrete example of bisphenol A type epoxy compound, the EPICLON 850S having DIC society to manufacture, 860,1055, EPICLON 850CRP etc.As the concrete example of hydrogenated bisphenol A type epoxy compounds, the YX-8034 etc. that KRM-2408, JER society having ADEKA society to manufacture manufactures.As the concrete example of bisphenol F type epoxy compound, there is the EPICLON 830S etc. that DIC society manufactures.As the concrete example of naphthalene type epoxy compounds, there are EPICLON HP-4032D, HP-7200H etc. that DIC society manufactures.As the concrete example of novolac type epoxy compounds, DIC society is had to manufacture EPICLON N-740, N-770 etc.As the concrete example of cresol novalac type epoxy compounds, there are EPICLON N-660, N-670 etc. that DIC society manufactures.As the concrete example of alicyclic ring type epoxy compounds, have 3,4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane carboxylicesters (Daicel society manufactures Celloxide 2021P), 1,2:8,9-bis-epoxy limonene (Daicel society manufactures Celloxide 3000), 1,2-epoxy-4-vinyl cyclohexane (Daicel society manufactures Celloxide 2000), 2,1,2-epoxy-4-(2-Oxyranyle) the hexanaphthene affixture (Daicel society manufactures EHPE3150) etc. of two (the hydroxymethyl)-n-butyl alcohol of 2-.
As the compd B with ethylenic unsaturated group and epoxy group(ing); also the compound containing epoxy group(ing) and (methyl) acrylic compounds can be used to react part (methyl) the Acrylate Modified Epoxy compound obtained, more preferably make bisphenol A type epoxy compound and (methyl) vinylformic acid react part (methyl) the acrylated epoxy compounds obtained.
Bisphenol A type epoxy resin and (methyl) vinylformic acid part (methyl) acrylated epoxy resin obtained that reacts such as is obtained in the following manner.
First, for bisphenol A type epoxy resin and (methyl) vinylformic acid, under the existence of basic catalyst, preferably 3 valency organic phosphoric acid compounds and/or amine compound, (methyl) vinylformic acid 10 equivalent % ~ 90 equivalent % and epoxide group 1 equivalent are reacted.Next, this resultant of reaction to be filtered, the process such as centrifugation and/or washing, thus removing basic catalyst, refine.As basic catalyst, known basic catalyst conventional in epoxy resin and (methyl) acrylic acid reaction can be used in.In addition, the Polymer Supported basic catalyst being supported with basic catalyst on polymer can also be used.
In compd A containing ethylenic unsaturated group, as compd B, preferably comprise as radically curing compound, using above-mentioned as be suitable for example containing the compound of ethylenic unsaturated group.
Liquid crystal sealing agent of the present invention can containing the Photoepolymerizationinitiater initiater (activated by light absorbing energy and produce the compound of free radical) when making compd A and/or compd B photopolymerization as free radical occurring source.Polymerization starter is not particularly limited, the known compound of polymerization starter can be used as.As polymerization starter; can enumerate the polymerization starter of bitter almond oil camphor class, acetophenones, benzophenone, thioxanthene ketone, α-acyl group oxime ester class, oxoethanoic acid phenyl ester class, benzil class, Azo, diphenyl sulfide based compound, acylphosphine oxide based compound, benzoin ethers and Anthraquinones, the solvability preferably in liquid crystal is low and himself have the polymerization starter of when the rayed resolvent not reactive group of generating gasification.As preferred polymeric initiator of the present invention, such as, can enumerate the material represented by following formula,
[changing 5]
Such as can enumerate EY Resin KR-2 (manufacture of KSM society) etc.
As solidifying agent, from the aspect of strong cementability, preferred amines system solidifying agent, such as organic acid dihydrazide compound, imidazole and its derivants, Dyhard RU 100, aromatic amine, epoxide modified polyamine, poly-Urea,amino-etc., preferably as the VDH (1 of organic acid dihydrazide, two (hydrazine the carbonylethyl)-5-sec.-propyl glycolylurea of 3-), ADH (adipic dihydrazide), UDH (7,11-octadecane diene-1,18-dicarbapentaborane hydrazides) and LDH (octadecane-1,18-dicarboxyl acid dihydrazide).These solidifying agent can be used alone, and also can use two or more.
As photosensitizers, from the aspect of solidified nature, such as, can enumerate carbonyl compound, sulfur-containing organic compound, persulfide, redox based compound, azo and diazonium compound, halogenide, photoreduction pigment etc.As photosensitizers, specifically, can enumerate: benzoin methylether, benzoin iso-propylether, α, the benzoin derivatives of alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone and so on; Benzophenone, 2,4-dichloro benzophenones, methyl o-benzoylbenzoate, 4, the benzophenone derivates of 4 '-bis-(diethylamino) benzophenone and so on; The thioxanthone derivates of 2,4-diethyl thioxanthone, CTX, ITX and so on; The anthraquinone derivative of 2-chloroanthraquinone, 2-methylanthraquinone and so on; The acridone derivatives of N-methylacridine ketone, N-butyl dihydroketoacridine and so on; And α, α-diethoxy acetophenone, benzil, Fluorenone, xanthone, uranyl compound etc.These photosensitizerss can be used alone, or are used in combination of two or more.Preferred photosensitizers is 2,4-diethyl thioxanthone (such as Japanese chemical drug DETX-S).
From the viewpoint of the curing reaction promoting solidified nature compound, liquid crystal sealing agent of the present invention can contain curing catalyst, preferably can enumerate: the imidazoles such as glyoxal ethyline, 2-ethyl imidazol(e) and 2-ethyl-4-methylimidazole; The tertiary amines such as 2-(dimethylamino methyl) phenol and 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU); The phosphine classes such as triphenylphosphine; The metallic compounds etc. such as stannous octoate.
From controlling viscosity, improving the aspect of the intensity after solidification, bonding reliability, suppression linear expansivity further, liquid crystal sealing agent of the present invention can add filler.Filler can use mineral filler and organic filler.As mineral filler, calcium carbonate, magnesiumcarbonate, barium sulfate, magnesium sulfate, pure aluminium silicate, titanium dioxide, aluminum oxide, zinc oxide, silicon-dioxide, kaolin, talcum, granulated glass sphere, sericite atlapulgite, wilkinite, aluminium nitride and silicon nitride can be enumerated.As organic filler, polymethylmethacrylate, polystyrene, multipolymer, polyester micropartical, polyurethane particulate and rubber particle that their monomer of formation and other monomer copolymerization are obtained can be enumerated.
Reduce ease gas (ア ウ ト ガ ス) further from the viewpoint of the filler being belonged to non-reactive components by mixture, the median size of the particle of formation filler is 0.1 μm ~ 3 μm, is more preferably 0.5 μm ~ 3 μm.It should be noted that, laser diffraction/diffuse transmission type particle size distribution analyzer (the Partica LA-950V2 that such as HORIBA society manufactures) that the median size of filler can utilize HORIBA society to manufacture measures.
Liquid crystal sealing agent of the present invention can contain silane coupling agent in the scope having given play to effect of the present invention.
From the aspect of the stability of the solidification intensity of liquid crystal sealing agent of the present invention, as silane coupling agent, be preferably selected from least one silane coupling agent in the group be made up of following substances: the tetraalkoxysilane class such as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, dimethoxy diethoxy silane, dimethoxy diisopropoxy silane, diethoxy diisopropoxy silane, diethoxy dibutoxy silane, the trialkoxysilanes such as methyltrimethoxy silane, Union carbide A-162, methyl three isopropoxy silane, ethyl triethoxysilane, ethyl three butoxy silane, cyclohexyltriethyloxysilane, phenyl three isopropoxy silane, vinyltrimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-methacryloxypropyl trimethoxy silane, and dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyldiethoxysilane, diethyl dibutoxy silane, the dialkoxy base class such as phenylethyl diethoxy silane, be more preferably and be selected from by methyltrimethoxy silane, Union carbide A-162, methyl three isopropoxy silane, ethyl triethoxysilane, ethyl three butoxy silane, cyclohexyltriethyloxysilane, phenyl three isopropoxy silane, vinyltrimethoxy silane, at least one trialkoxy silane system silane coupling agent in the group of 3-glycidoxypropyltrime,hoxysilane and 3-methacryloxypropyl trimethoxy silane composition, preferred 3-glycidoxypropyltrime,hoxysilane further.
[manufacture method of compd A]
The manufacture method of compd A of the present invention comprises the operation that the Compound C represented by following formula (2) and the Compound D represented by following formula (3) are reacted,
[changing 6]
(in formula, n 2be the number of 2 ~ 30 scopes, Y separately independently of each other for carbonatoms is the alkylidene group of 2 ~ 4, R 11be hydrogen atom, glycidyl or methylglycidyl independently of each other separately);
[changing 7]
[in formula, X is Sauerstoffatom (O), carbonatoms be 1 ~ 4 alkylidene group or carbonatoms be the alkylidene of 2 ~ 4, R 12be hydrogen atom, glycidyl, methylglycidyl, group 1:-CH independently of each other separately 2-CH (OR 21)-CH 2-O-R 22or group 2:-CH 2-C (CH 3) (OR 21)-CH 2-O-R 22(in formula, R 21for hydrogen atom or (methyl) acryl, R 22for (methyl) acryl)].
From the aspect of the strong cementability of compd A, to the n in Compound C 2carry out the n selecting to make compd A 1fall into above-mentioned scope, and the n in Compound C 2be the number of the number of 3 ~ 25 scopes, preferably number, more preferably 5 ~ 15 scopes of 5 ~ 20 scopes, be further preferably the number of 7 ~ 10 scopes.Further, R 11for the molecular weight (weight-average molecular weight) of the Compound C of hydrogen atom is preferably less than 2000.
Y in Compound C to be carbonatoms be 2 ~ 4 alkylidene group, specifically, Y is ethylidene, propylidene, trimethylene, tetramethylene etc.Y is preferably ethylidene or propylidene, is more preferably ethylidene.
Compound C and D have commercially available, or easily can be prepared by commercially available compound according to known method.Such as, for R 11for hydrogen atom, Y are the Compound C of ethylidene, can obtain, as polyoxyethylene glycol, there is various number of repeat unit (n 2) compound, suitably can select the n with desired scope 2compound.Further, n 2also can with n 1similarly calculate.The molecular weight of polyoxyethylene glycol is preferably less than 2000.
Further, for R 11for hydrogen atom, Y are the Compound C of propylidene, the compound with various number of repeat unit as polypropylene ether glycol can be obtained.Such as can 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 R 11for hydrogen atom, Y are the Compound C of trimethylene, such as, can manufacture with the form of the polytrimethylene ether glycol with various number of repeat unit according to the method described in Japanese Unexamined Patent Application Publication 2013-515144 publication.The molecular weight of polytrimethylene ether glycol is preferably less than 2000.
In addition, for R 11for hydrogen atom, Y are the Compound C of tetramethylene, the compound with various number of repeat unit as polytetramethylene ether diol can be obtained.Such as can enumerate PTMG 650, PTMG 850, PTMG 1000, PTMG 1300, PTMG 1500, PTMG 1800, PTMG 2000 (being manufactured by society of Mitsubishi Chemical above) etc.The molecular weight of polytetramethylene ether diol is preferably less than 2000.
About the R in Compound C 11with the R in Compound D 12, from the aspect of the strong cementability of compd A, preferred R respectively 11and R 12in one be hydrogen atom, another is glycidyl.
Compound C and Compound D are reacted according to the mode that can generate compd A, such as, Compound C and Compound D are reacted in the presence of base, and the compound making the reaction product of Compound C and Compound D and epoxy chloropropane etc. can import glycidyl or methylglycidyl under the existence of suitable catalyzer afterwards reacts.Above-mentioned reaction adjusted, is 1 ~ 5 to make the m in compd A, be preferably 1 ~ 4, more preferably 1 ~ 3, be further preferably the number of 1 ~ 2 scope.
About the number of m, in the case of the embodiment, can control as follows when carrying out the synthesis of synthetic intermediate P.Such as, the equivalence ratio of Compound C 1-1 and the D1 in embodiment 1-1 is 1:2.5, and this is than during for 1:2.0 or 1:1.5, and the number of m increases.Otherwise even if when this than for 1:10 or 1:100,1:1000 etc., the number of m also can not be less than 1.In compound P, during m=0, Compound D becomes the compound (i.e. dihydroxyphenyl propane itself) that R is hydrogen atom, X is isopropylidene.
It should be noted that, from reactive aspect, the R in preferred compound C 11with the R in Compound D 12in one be hydrogen atom, another is glycidyl.
As alkali, from the aspect of carrying out and synthesizing cost that is swift in response, the alkali metal hydroxides such as preferred sodium hydroxide, potassium hydroxide; The alkaline carbonate such as sodium carbonate, salt of wormwood; More preferably sodium hydroxide.These alkali preferably use in form of an aqueous solutions, according to circumstances, also can with water simultaneously or separate the alkali adding powder or solid.
About the consumption of alkali, from the aspect of carrying out and synthesizing cost that is swift in response, at R 11for hydrogen atom, R 12when for glycidyl, alkali is more than the equivalent of hydroxyl; At R 11for glycidyl, R 12when for hydrogen atom, the consumption of alkali can be catalytic amount, for the hydroxyl of Compound D 0.0001 equivalent ~ 0.1 equivalent, be more preferably 0.0001 equivalent ~ 0.01 equivalent.Such as, in embodiment 1-1, the hydroxyl of dihydroxyphenyl propane 2.5 equivalent=5.0 equivalent, relatively therewith, use the sodium hydroxide of 4% sodium hydroxide solution=0.0015 equivalent of 1.5g, therefore, relative to hydroxyl 1 equivalent, the consumption of alkali is 0.0003 equivalent.
Carrying out rapidly and the aspect of synthesizing cost from reaction, the consumption of the compounds such as epoxy chloropropane is preferably 0.5 equivalent ~ 20 equivalent, is more preferably 0.5 equivalent ~ 15 equivalent.
As catalyzer, from the aspect of reaction times, catalyzer cost, catalyst activity, the tertiary amine of preferred Trimethylamine 99, trioctylamine, tridecylamine and so on; The quaternary ammonium hydroxide of tetramethylammonium, the pungent ammonium of methyl three, methyl three ammonium in the last of the ten Heavenly stems, benzyl TMA (TriMethylAmine) and so on; The quaternary ammonium salt of tetramethyl ammonium chloride, methyl tricapryl ammonium chloride, methyl three decyl ammonium chloride, benzyl trimethyl ammonium chloride and so on, preferred quaternary ammonium salt.
About the consumption of catalyzer, from the viewpoint of suppressing side reaction, simultaneously suitably guaranteeing speed of response, relative to the total amount of the compounds such as Compound C, Compound D and epoxy chloropropane, the consumption of catalyzer is preferably 0.01 % by weight ~ 10 % by weight, is more preferably 0.1 % by weight ~ 5 % by weight.
With the reaction of above-mentioned alkali preferably 50 DEG C ~ 250 DEG C, more preferably 70 DEG C ~ 200 DEG C, preferably further to carry out at 100 DEG C ~ 170 DEG C, with the reaction of the compounds such as above-mentioned epoxy chloropropane preferably 25 DEG C ~ 100 DEG C, more preferably 30 DEG C ~ 80 DEG C, preferably further to carry out at 40 DEG C ~ 60 DEG C.When reacting, also the solvent in the reaction in inertia of hydrocarbon, ether or ketone and so on can be used, but when compounds such as excessive use epoxy chloropropane, the compounds such as epoxy chloropropane also can be used as solvent and play function, thus these solvents are not for necessary.
The refining of compd A after reaction terminating can conventionally carry out, such as, the compounds such as the epoxy chloropropane that retortable removing is excessive, wash after adding the water-insoluble solvent such as hydrocarbon as required, remove the salt and catalyzer that generate, thus obtain object compd A.
In the manufacture method of compd A of the present invention, from the viewpoint of using general raw material as Compound C and Compound D, the R in Compound C 11for Compound C 1 (the polyalkylene ether glycols diglycidylether of glycidyl; Such as polyethyleneglycol diglycidylether), R in Compound D 12when Compound D 1 (such as dihydroxyphenyl propane) for hydrogen atom, this manufacture method preferably comprises operation 1 and operation 2, in operation 1, above-claimed cpd C1 and above-claimed cpd D1 is reacted, obtains the reaction product P of above-claimed cpd C1 and above-claimed cpd D1; In operation 2, epoxidation is carried out to the hydroxyl of reaction product P, obtain part or all reaction product Q be at least partially epoxidized of the hydroxyl of above-mentioned reaction product P.
In this case, further across the operation 3 making reaction product Q react with (methyl) vinylformic acid under basic catalyst exists, the compd A having imported group 1 or group 2 on R can be obtained.
As basic catalyst, from raising reactivity, be swift in response and carry out the aspect with catalyzer cost, basic catalyst conventional in epoxy resin and (methyl) acrylic acid reaction can be used in, basic catalyst also can be used to support Polymer Supported basic catalyst in polymkeric substance.As basic catalyst, preferably 3 valency organo phosphorous compounds and/or amine compound.The basic atom of basic catalyst is phosphorus and/or nitrogen.
As basic catalyst, known basic catalyst conventional in epoxy resin and (methyl) acrylic acid reaction can be used in.Basic catalyst can be used in addition to support Polymer Supported basic catalyst in polymkeric substance.As basic catalyst, preferably 3 valency organo phosphorous compounds and/or amine compound.The basic atom of basic catalyst is phosphorus and/or nitrogen.
As 3 valency organo phosphorous compoundss, alkylphosphines class and the salt thereof of triethyl phosphine, three n-propyl phosphines, tri-n-butyl phosphine and so on can be enumerated; Aryl phosphine class and the salt thereof such as triphenylphosphine, three tolylphosphine, three (2,6-Dimethoxyphenyl) phosphines; Tris phosphite class and the salt etc. thereof such as triphenyl phosphite, triethyl-phosphite, tricresyl phosphite (nonyl phenyl) ester.As the salt of 3 valency organo phosphorous compoundss, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide phosphine, octyl group triphenylphosphinebromide, decyl triphenylphosphinebromide, isobutyl-triphenylphosphinebromide, propyl group triphenyl phosphine dichloride, amyl group triphenyl phosphine dichloride, hexyltriphenylphosphonium bromide phosphine etc. can be enumerated.Wherein triphenylphosphine.
As amine compound, the secondary amine such as diethanolamine can be enumerated; The tertiary amine such as trolamine, dimethyl benzyl amine, three (dimethylamino methyl) phenol, three (diethylamino methyl) phenol; 1,5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene (TBD), 7-methyl isophthalic acid, 5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene (Me-TBD), 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU), 6-dibutylamino-1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1,5-diazabicyclo [4.3.0]-5-in ninth of the ten Heavenly Stems alkene (DBN), 1,1, strong basicity amine and the salt thereof such as 3,3-tetramethyl guanidine.Wherein preferred 1,5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene (TBD).As the salt of amine compound, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride can be enumerated.
Be not particularly limited as the polymkeric substance supporting basic catalyst, polystyrene can be used through the polymkeric substance of divinyl benzene crosslinked, acrylic resin through the polymkeric substance etc. of divinyl benzene crosslinked.These polymkeric substance are insoluble in solvent (such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene etc.) used in the epoxy resin that obtained by the manufacture method comprising operation 1 or comprise operation 1 and 2 and (methyl) acrylic acid reaction and raw material, resultant.
About Polymer Supported basic catalyst, by making basic catalyst and insoluble polymer generation chemical bonding, or monomer polymerization is carried out after basic catalyst is imported monomer, utilize the cross-linking monomers such as Vinylstyrene to carry out 3 dimensions to be afterwards cross-linked, thus the Polymer Supported basic catalyst be insoluble in methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene equal solvent can be made.
As Polymer Supported basic catalyst, specifically, diphenylphosphine base polystyrene, 1 can be enumerated, 5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene polystyrene, N, N-(di-isopropyl) aminomethylpolystyre.e, N-(methylated polystyrene)-4-(methylamino) pyridine etc.These Polymer Supported basic catalysts can be used alone, and also can share two or more.
Polymer Supported basic catalyst can use commercially available product.As commercially available Polymer Supported basic catalyst, such as, PS-PPh can be enumerated 3(diphenylphosphine base polystyrene, Biotage society manufacture), PS-TBD (1,5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene polystyrene, Biotage society manufacture).
About the usage ratio of Polymer Supported basic catalyst, with respect to epoxy group(ing) 1 equivalent of the epoxy resin that the manufacture method comprising operation 1 or 2 obtains, Polymer Supported alkaline catalyzer is preferably 0.5 milliequivalent ~ 5.0 milliequivalent, is more preferably 1.0 milliequivalent ~ 3.0 milliequivalents.When the usage ratio of Polymer Supported basic catalyst is in above-mentioned scope, be preferred from the aspect of reactivity, reaction times and catalyzer cost.
In manufacture method of the present invention, the temperature in the epoxy resin obtained by the manufacture method comprising operation 1 or comprise operation 1 and 2 and (methyl) acrylic acid reaction process is preferably 60 DEG C ~ 120 DEG C, be more preferably 80 DEG C ~ 120 DEG C, more preferably 90 DEG C ~ 110 DEG C.
When making the epoxy resin obtained by the manufacture method comprising operation 1 or comprise operation 1 and 2 react with (methyl) vinylformic acid in the presence of a catalyst, in order to prevent gelation, need the oxygen concn suitably ensureing the gas phase in reaction system and in reaction system.Such as, when being blown into air energetically in reaction system, the oxidation of catalyzer may being caused, cause active reduction, thus should be noted that.
In the epoxy resin obtained by the manufacture method comprising operation 1 or comprise operation 1 and 2 with (methyl) acrylic acid reaction, because the inclined acrylated epoxy be obtained by reacting by this can be solidified under the effect of ultraviolet isoreactivity energy-ray, thus preferably to react covering in ultraviolet container.In addition, in order to prevent vapour phase polymerization, the epoxy resin obtained by the manufacture method comprising operation 1 or comprise operation 1 and 2 and (methyl) acrylic acid reaction can be carried out under the existence of reflux solvent epoxy resin being demonstrated to good solvent, but in this case, need except desolventizing after termination of the reaction, thus preferably to carry out under solvent-free.As reflux solvent, acetone, methyl ethyl ketone etc. can be enumerated.
In manufacture method of the present invention, after the epoxy resin making to be obtained by the manufacture method comprising operation 1 or comprise operation 1 and 2 and (methyl) vinylformic acid are reacted, obtain inclined acrylated epoxy by removing Polymer Supported basic catalyst.As the method for removing Polymer Supported basic catalyst, preferably adopt and filter or centrifugation.
As the method for filtering Polymer Supported basic catalyst, such as, can enumerate the method that use mesh is nylon wire NY-10HC (manufacture of Sefar society of Switzerland) the filtering Polymer Supported basic catalyst of 10 μm.
As the method for Polymer Supported basic catalyst being carried out to centrifugation, can enumerate by using separating centrifuge to carry out the method that solid-liquid separation removes Polymer Supported basic catalyst.
[embodiment]
Illustrate the present invention by the following examples, but the present invention is not by the restriction of these embodiments.It should be noted that, only otherwise special declaration, " % " is weight basis.
[comparative example 1-2] (compd B)
By bisphenol A type epoxy resin, (EXA850CRP, Dainippon Ink Chemicals manufacture; Also the compound as comparative example 1-1 uses) 340g, methacrylic acid (Tokyo change into society manufacture) 90.4g, triphenylphosphine (Tokyo changes into society and manufactures) 0.5g and BHT 100mg mix, 100 DEG C of stirrings 6 hours.
Obtain the compd B 418g for pale yellow transparent dope.
[synthesis example 1] (Compound C 1-1)
Polyoxyethylene glycol #200 (200g (2 equivalents/hydroxyl)), epoxy chloropropane 1110g (6 equivalent), benzyl trimethyl ammonium chloride 37.1g (0.1 equivalent) are joined in three mouthfuls of round-bottomed flasks of 2 liters that are provided with machine mixer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel.Next, mixture is stirred under the high vacuum of 70 holders (torr), is heated to about 50 DEG C to 55 DEG C simultaneously, makes epoxy chloropropane vigorous reflux.Add to lentamente in mixture with the 48% solution NaOH of the times of 2 hours by 300g.After generating azeotrope, send the epoxy chloropropane in water/epoxy chloropropionate alkylating mixture back to reaction system immediately, proceed to stir simultaneously.Add after terminating, continue stirring 3 hours.Next, reaction mixture is cooled to room temperature, adds chloroform 1L, clean 6 times with the water of 1L.Removed the solvent of obtained organic phase by underpressure distillation, obtain the Compound C 1-1 (171g) of light yellow transparent liquid.
[synthesis example 2] (Compound C 1-2)
Except making the polyoxyethylene glycol #200 in synthesis example 1 be except polyoxyethylene glycol #300 (300g), to carry out equally with synthesis example 1, obtaining the Compound C 1-2 (222g) of light yellow transparent liquid.
[synthesis example 3] (Compound C 1-4)
Polyoxyethylene glycol #1000 (250g (0.5 equivalent/hydroxyl)), epoxy chloropropane 277g (6 equivalent), benzyl trimethyl ammonium chloride 9.28g (0.1 equivalent) are joined in three mouthfuls of round-bottomed flasks of 1 liter that is provided with machine mixer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel.Next, mixture is stirred under the high vacuum of 70 holders (torr), is heated to about 50 DEG C to 55 DEG C simultaneously, makes epoxy chloropropane vigorous reflux.Add to lentamente in mixture with the 48%NaOH solution of the times of 2 hours by 75g.After generating azeotrope, send the epoxy chloropropane in water/epoxy chloropropionate alkylating mixture back to reaction system immediately, proceed to stir simultaneously.Add after terminating, continue stirring 3 hours.Next, reaction mixture is cooled to room temperature, adds chloroform 500mL, clean 6 times with the water of 500mL.Removed the solvent of obtained organic phase by underpressure distillation, obtain the Compound C 1-4 (138g) into white waxy solid.
[embodiment 1-1] (compd A-1)
(1) Compound C 1-1 (145g (1 equivalent/epoxy group(ing))) and dihydroxyphenyl propane (Compound D 1) (570g (2.5 equivalent)) are joined in eggplant type flask, carry out heated and stirred and make liquid temperature reach 150 DEG C.Add 4%NaOH aqueous solution 1.5g, stir 2 hours at 150 DEG C.Being cooled to liquid temperature is less than 60 DEG C, adds chloroform 500mL, utilize 1%NaOH aqueous solution 1L clean 6 times, utilize water 1L to clean 3 times.Magnesium sulfate is added in obtained organic phase, solids component is leached by filtration etc. after dry, by underpressure distillation by the solvent of obtained organic phase distillation removing, obtain the reaction product P-1 (290g) as synthetic intermediate using the form of clear yellow viscous thing.
(2) reaction product P-1 (170g), epoxy chloropropane (495g) and benzyl trimethyl ammonium chloride (16.5g) are joined in three mouthfuls of round-bottomed flasks of 2 liters that are provided with machine mixer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel.Next, mixture is stirred under the high vacuum of 70 holders (torr), is heated to about 50 DEG C to 55 DEG C simultaneously, makes epoxy chloropropane vigorous reflux.Add to lentamente in mixture with the 48%NaOH solution of the times of 2 hours by 133g.After generating azeotrope, send the epoxy chloropropane in water/epoxy chloropropionate alkylating mixture back to reaction system immediately, proceed to stir simultaneously.Add after terminating, continue stirring 3 hours.Next, reaction mixture is cooled to room temperature, adds chloroform 1L, clean 6 times with the water of 1L.Removed the solvent of obtained organic phase by underpressure distillation, obtain compd A-1 (reaction product Q-1) 206g into faint yellow dope.
[embodiment 1-2] (compd A-2)
(1) Compound C 1-2 (230g (1 equivalent/epoxy group(ing))) and dihydroxyphenyl propane (Compound D 1) (570g (2.5 equivalent)) are joined in eggplant type flask, carry out heated and stirred and make liquid temperature reach 150 DEG C.Add 4%NaOH aqueous solution 1.5g, stir 2 hours at 150 DEG C.Being cooled to liquid temperature is less than 60 DEG C, adds chloroform 500mL, utilize 1%NaOH aqueous solution 1L clean 6 times, utilize water 1L to clean 3 times.Magnesium sulfate is added in obtained organic phase, solids component is leached by filtration etc. after dry, by underpressure distillation by the solvent of obtained organic phase distillation removing, obtain the reaction product P-2 (366g) as synthetic intermediate using the form of clear yellow viscous thing.
(2) reaction product P-2 (203g), epoxy chloropropane (495g) and benzyl trimethyl ammonium chloride (16.5g) are joined in three mouthfuls of round-bottomed flasks of 2 liters that are provided with machine mixer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel.Next, mixture is stirred under the high vacuum of 70 holders (torr), is heated to about 50 DEG C to 55 DEG C simultaneously, makes epoxy chloropropane vigorous reflux.Add to lentamente in mixture with the 48%NaOH solution of the times of 2 hours by 133g.After generating azeotrope, send the epoxy chloropropane in water/epoxy chloropropionate alkylating mixture back to reaction system immediately, proceed to stir simultaneously.
Add after terminating, continue stirring 3 hours.Next, reaction mixture is cooled to room temperature, adds chloroform 1L, utilize the water of 1L to clean 6 times.Removed the solvent of obtained organic phase by underpressure distillation, obtain compd A-2 (reaction product Q-2) 241g into faint yellow dope.
[embodiment 1-3] (compd A-3)
(1) the Denacol EX-830 (Compound C 1-3) (268g (1 equivalent/epoxy group(ing))) Nagase chemte X society manufactured and dihydroxyphenyl propane (Compound D 1) (570g (2.5 equivalent)) join in eggplant type flask, carry out heated and stirred and make liquid temperature reach 150 DEG C.Add 4%NaOH aqueous solution 1.5g, stir 2 hours at 150 DEG C.Being cooled to liquid temperature is less than 60 DEG C, adds chloroform 500mL, utilize 1%NaOH aqueous solution 1L clean 6 times, utilize water 1L to clean 3 times.Magnesium sulfate is added in obtained organic phase, solids component is leached by filtration etc. after dry, by underpressure distillation by the solvent of obtained organic phase distillation removing, obtain the reaction product P-3 (375g) as synthetic intermediate using the form of clear yellow viscous thing.
(2) reaction product P-3 (200g), epoxy chloropropane (452g) and benzyl trimethyl ammonium chloride (15.1g) are joined three mouthfuls of round-bottomed flasks of 2 liters that are provided with machine mixer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel.Next, mixture is stirred under the high vacuum of 70 holders (torr), is heated to about 50 DEG C to 55 DEG C simultaneously, makes epoxy chloropropane vigorous reflux.Add to lentamente in mixture with the 48%NaOH solution of the times of 2 hours by 122g.After generating azeotrope, send the epoxy chloropropane in water/epoxy chloropropionate alkylating mixture back to reaction system immediately, proceed to stir simultaneously.Add after terminating, continue stirring 3 hours.Next, reaction mixture is cooled to room temperature, adds chloroform 1L, clean 6 times with the water of 1L.Removed the solvent of obtained organic phase by underpressure distillation, obtain compd A-3 (reaction product Q-3) 228g into faint yellow dope.
[embodiment 1-4] (compd A-4)
(1) Compound C 1-4 (130g (0.23 equivalent/epoxy group(ing))) and dihydroxyphenyl propane (Compound D 1) (131g (2.5 equivalent)) are joined in eggplant type flask, carry out heated and stirred and make liquid temperature reach 150 DEG C.Add 4%NaOH aqueous solution 0.3g, stir 2 hours at 150 DEG C.Being cooled to liquid temperature is less than 60 DEG C, adds chloroform 500mL, utilize 1%NaOH aqueous solution 1L clean 6 times, utilize water 1L to clean 3 times.Magnesium sulfate is added in obtained organic phase, solids component is leached by filtration etc. after dry, by underpressure distillation by the solvent of obtained organic phase distillation removing, obtain the reaction product P-4 (154g) as synthetic intermediate using the form of clear yellow viscous thing.
(2) reaction product P-4 (140g), epoxy chloropropane (207g) and benzyl trimethyl ammonium chloride (6.94g) are joined three mouthfuls of round-bottomed flasks of 2 liters that are provided with machine mixer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel.Next, mixture is stirred under the high vacuum of 70 holders (torr), is heated to about 50 DEG C to 55 DEG C simultaneously, makes epoxy chloropropane vigorous reflux.Add to lentamente in mixture with the 48%NaOH solution of the times of 2 hours by 56g.After generating azeotrope, send the epoxy chloropropane in water/epoxy chloropropionate alkylating mixture back to reaction system immediately, proceed to stir simultaneously.Add after terminating, continue stirring 3 hours.Next, reaction mixture is cooled to room temperature, adds chloroform 1L, clean 6 times with the water of 1L.Removed the solvent of obtained organic phase by underpressure distillation, obtain compd A-4 (reaction product Q-4) 142g into faint yellow dope.
[embodiment 1-5] (compd A-5)
Compd A-3 (reaction product Q-3) 320g, methacrylic acid (Tokyo changes into society and manufactures) 43.05g, triphenylphosphine (basic catalyst, Tokyo change into society and manufacture) 0.25g and BHT 50mg are mixed, stirs 8 hours at 100 DEG C.Obtain the compd A-5 (357g) for faint yellow dope.
[embodiment 2-1 ~ 9 and comparative example 2-1]
Respectively by compd A-1 ~ 5 (embodiment 1-1 ~ 5) and compd B (comparative example 1-2) and EY ResinKR-2 (KSM society manufactures), ZEFIAC (ゼ Off ァ ア ッ Network) F351 (GANZ CHEMICAL CO., LTD. manufacture), SEAHOSTAR KE-C50HG (Japanese catalyst society manufactures), KBM-403 (silane coupling agent: SHIN-ETSU HANTOTAI's chemical industry manufactures) and Ajicure VDH (1, two (hydrazine the carbonylethyl)-5-sec.-propyl glycolylurea of 3-, AJINOMOTO FINETECHNO society manufactures) mix according to the combined amount (weight part) shown in table 1, three-roll mill (made C-43/4 × 10 of aboveground making) is used to carry out fully mixing afterwards, obtain the liquid crystal sealing agent of embodiment 2-1 ~ 9 and comparative example 2-1.
[test conditions]
For compd A-1 ~ 5 (embodiment 1-1 ~ 5), EPICRON 850CRP (comparative example 1-1) and compd B (comparative example 1-2), measure viscosity and epoxy equivalent (weight) respectively, evaluation approach, measure the change of NI point; For the liquid crystal sealing agent of embodiment 2-1 ~ 9 and the liquid crystal sealing agent of comparative example 2-1 ~ 3, evaluate bonding strength respectively, measure the change of NI point.
(1) viscosimetric analysis
Use E type viscometer (Dong Ji industry society manufactures RE105U), measure at 25 DEG C.
Following selection rotor and rotating speed.
Compd A-1:3 ° × R7.7 rotor, rotating speed 5rpm
Compd A-2:3 ° × R7.7 rotor, rotating speed 10rpm
Compd A-3:3 ° × R14 rotor, rotating speed 5rpm
Compd A-4:3 ° × R14 rotor, rotating speed 20rpm
Compd A-5:3 ° × R7.7 rotor, rotating speed 5rpm
EPICLON 850CRP:3 ° × R14 rotor, rotating speed 20rpm
Compd B: 3 ° × R7.7 rotor, rotating speed 10rpm
(2) epoxy equivalent (weight) measures
Measure under the condition described in JIS K 7236:2001.
(3) NI point change detection
In ampoule, add compd A-1 ~ 5 (embodiment 1-1 ~ 5), EPICRON 850CRP (comparative example 1-1), compd B (comparative example 1-2), the liquid crystal sealing agent of embodiment 2-1 ~ 9 and the liquid crystal sealing agent 0.1g of comparative example 2-1 ~ 3 respectively, add liquid crystal (MLC-11900-080, Merck society manufacture) 1g further.This bottle to be put in 120 DEG C of baking ovens 1 hour, leave standstill in room temperature thereafter, take out lcd segment afterwards returning to room temperature (25 DEG C), with 0.2 μm of metre filter, make evaluation liquid crystalline sample.The mensuration of NI point uses differential scanning type calorimeter (manufacture of DSC, PerkinElmer society, PYRIS6), and being sealing in aluminium sample disc by evaluation liquid crystalline sample 10mg, is measure under the condition of 5 DEG C/min at heat-up rate.It should be noted that, be sealing in aluminium sample disc by above-mentioned liquid crystal 10mg, is measure, using measurement result as blank under the condition of 5 DEG C/min at heat-up rate.
Heat absorption summit (phase transition temperature) TB of blank and the poor TE-TB of heat absorption summit (phase transition temperature) TE of evaluation liquid crystal are changed as NI point.
From reduce impurity suppressing its stripping liquid crystal, stably guarantee the orientation of liquid crystal, improve display characteristic in consider, NI point changes more little more preferred.
(4) orientation evaluation
2 on the face of the monolithic of the ito glass substrate (60mm × 70mm × 0.7mmt) with alignment films (Sunever SE-7492, Nissan Chemical Industries society manufacture) of friction treatment with 15mm between compd A-1 is carried out a coating to seal, the diameter after laminating is made to be that below 2mm fits the face of another sheet during coating, after injecting liquid crystal, the hot-air oven thermal curing 1 hour of 120 DEG C, make the panel being used for evaluation approach.
Compd A-1 is replaced with respectively compd A-2 ~ 5, EPICLON 850CRP, compd B, make the panel being used for evaluation approach.
Friction treatment is carried out as follows.
Use air point gum machine (dispenser), orientation liquid Sunever SE-7492 (manufacture of Nissan Chemical Industries society) is instiled (0.3MPa, 5.3sec) to pure water cleaning, carried out dry TN6070 substrate (FPD Solutions society manufacture ito substrate), utilize spin coater through within 10 seconds, reaching 5000rpm and carrying out even spread under keeping the condition of 20 seconds (orientation thickness is afterwards condition).After coating, prebake (85 DEG C, 1min), cures after utilizing baking oven (230 DEG C, 60min) on hot plate.Use cotton friction roller with the speed conveying substrate of 600mm/min, carries out friction treatment with the amount of being pressed into of 0.4mm under rotating speed 500rpm.The mode being 90 ° of rotations (intersection) according to the substrate on opposite specifies frictional direction.Friction treatment metacoxa is impregnated in pure water, carries out ultrasonic cleaning.Utilize the baking oven of 120 DEG C to carry out drying, make the ito glass substrate with alignment films after friction treatment.
For obtained panel, the state of orientation of the liquid crystal at seal point (some coated portion) edge is confirmed.Confirm to utilize opticmicroscope to carry out, polaroid is clipped liquid crystal test box (テ ス ト セ Le) with the state of cross Nicols, observed by transmission, seal point and the liquid crystal (hereinafter referred to as blank liquid crystal) of middle portion of seal point are compared with the state of the liquid crystal at seal point edge.
The part of the uneven part different from the state of blank liquid crystal seen by seal point edge at seal point edge is less than the situation of 50 μm or is zero at the average evaluation that sealing the margin does not observe this uneven part completely from seal point edge;
By the part of this uneven part at seal point edge and from seal point edge more than 50 μm situation or around seal point edge, all observe this uneven part but the average evaluation that this uneven part is less than 50 μm from seal point edge is △;
To all observe this uneven part around seal point edge and this uneven part average evaluation that gathers more than 50 μm from seal point edge for ×.
It should be noted that, it is believed that above-mentioned uneven part represents that liquid crystal aligning is bad.
Be following situation in Fig. 1,2: under the state of orientation of the liquid crystal at the seal point edge of compd A-3 (Fig. 1) and A-5 (Fig. 2), do not observe the situation of the uneven part different from the state of blank liquid crystal seen by seal point edge at seal point edge completely; Or the part of this uneven part at seal point edge and being less than from seal point edge 50 μm (zero).Be following situation in Fig. 3: under the state of orientation of the liquid crystal at the seal point edge of compd B, this uneven part around seal point edge all and from seal point edge more than 50 μm (×).
(5) evaluation of bonding strength
The summary of test method has been 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 the 15mm × 3mm of (30mm × 30mm × 0.5mmt), the position of 15mm × 21mm on the ito glass substrate being scattered with 6 μm of spacers, the mode being 1.5 ~ 2.5mm φ according to the diameter of liquid crystal sealing agent after laminating during coating carries out a coating.Thereafter, glass adhering substrate (23mm × 23mm × 0.5mmt), with illumination 3000mJ/cm 2irradiation ultraviolet radiation (UV irradiating unit: UVX-01224S1, USHIO INC. society manufactures, with 100mW/cm 2/ 365nm irradiates 30 seconds) be cured, thereafter, utilizing the hot-air oven of 120 DEG C to carry out thermofixation in 1 hour, making the test film for evaluating bonding strength.The autoplotter AGS-500 using society of Shimadzu Seisakusho Ltd. to manufacture, fixes the glass substrate of test film, punching is carried out with the speed of 5mm/min in the position of ito glass substrate 15mm × 25mm, evaluates bonding strength.Evaluation result lists in table 1.
The disclosure entirety of No. 2012-227417, Japanese patent application is brought in this specification sheets by reference.
For the whole documents described in this specification sheets, patent application and technological standard, the degree that each document, patent application and technological standard are included in this specification sheets is by reference identical with the degree of the situation that it is specifically recorded respectively.

Claims (7)

1. a glycidyl ether based compound, it is represented by following formula (1),
[changing 8]
In formula (1), n 1be the number of 2 ~ 30 scopes, m is the number of 1 ~ 5 scope;
X is Sauerstoffatom, carbonatoms be 1 ~ 4 alkylidene group or carbonatoms be the alkylidene of 2 ~ 4;
Y is separately independently of each other for carbonatoms is the alkylidene group of 2 ~ 4;
R is hydrogen atom, glycidyl, methylglycidyl, group 1:-CH separately independently of each other 2-CH (OR 1)-CH 2-O-R 2or group 2:-CH 2-C (CH 3) (OR 1)-CH 2-O-R 2, in the formula of group 1 and group 2, R 1for hydrogen atom or (methyl) acryl, R 2for (methyl) acryl;
R ' is hydrogen atom or methyl separately independently of each other;
In described R, the total mean number x of described glycidyl, described methylglycidyl, described group 1 and described group 2 is more than 2;
When described R comprises described group 1 or described group 2, the ratio y/z of the total mean number y of described glycidyl and methylglycidyl and the total mean number z of described group 1 and described group 2 is 10/90 ~ 90/10.
2. a liquid crystal sealing agent, it comprises glycidyl ether based compound according to claim 1.
3. liquid crystal sealing agent as claimed in claim 2, wherein, in described liquid crystal sealing agent, the content of described glycidyl ether based compound is 10 % by weight ~ 90 % by weight.
4. liquid crystal sealing agent as claimed in claim 2 or claim 3, wherein, described liquid crystal sealing agent comprises the compd B with ethylenic unsaturated group and/or epoxy group(ing) further, does not comprise described glycidyl ether based compound in this compd B.
5. the manufacture method of the glycidyl ether based compound represented by formula according to claim 1 (1), it comprises the operation that the Compound C represented by following formula (2) and the Compound D represented by following formula (3) are reacted,
[changing 9]
In formula (2), n 2it is the number of 2 ~ 30 scopes;
Y is separately independently of each other for carbonatoms is the alkylidene group of 2 ~ 4;
R 11be hydrogen atom, glycidyl or methylglycidyl independently of each other separately;
[changing 10]
In formula (3), X is Sauerstoffatom, carbonatoms be 1 ~ 4 alkylidene group or carbonatoms be the alkylidene of 2 ~ 4;
R 12be hydrogen atom, glycidyl, methylglycidyl, group 1:-CH independently of each other separately 2-CH (OR 21)-CH 2-O-R 22or group 2:-CH 2-C (CH 3) (OR 21)-CH 2-O-R 22, in the formula of group 1 and group 2, R 21for hydrogen atom or (methyl) acryl, R 22for (methyl) acryl.
6. manufacture method as claimed in claim 5, wherein, is the R in described formula (2) in described Compound C 11for the R that the Compound C 1 of glycidyl, described Compound D are in described formula (3) 12for hydrogen atom Compound D 1 when, described operation comprises operation 1 and operation 2, in operation 1, described Compound C 1 and described Compound D 1 is reacted, and obtains the reaction product P of described Compound C 1 and described Compound D 1; In operation 2, epoxidation is carried out to the hydroxyl of described reaction product P, obtain part or all reaction product Q be at least partially epoxidized of the hydroxyl of described reaction product P.
7. manufacture method as claimed in claim 6, wherein, this manufacture method comprises operation 3 further, in operation 3, described reaction product Q is reacted under basic catalyst exists with (methyl) vinylformic acid.
CN201380052675.4A 2012-10-12 2013-10-04 The manufacture method of glycidyl ether based compound, liquid crystal sealing agent and glycidyl ether based compound Active CN104718231B (en)

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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
CN117203577A (en) * 2021-06-22 2023-12-08 积水化学工业株式会社 Sealing agent for liquid crystal display element and liquid crystal display element

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