CN105683225B - Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element - Google Patents

Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element Download PDF

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CN105683225B
CN105683225B CN201480058891.4A CN201480058891A CN105683225B CN 105683225 B CN105683225 B CN 105683225B CN 201480058891 A CN201480058891 A CN 201480058891A CN 105683225 B CN105683225 B CN 105683225B
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liquid crystal
crystal display
methyl
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compound
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CN105683225A (en
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林秀幸
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/16—Oxygen atoms, e.g. thioxanthones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/38—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Pyrane Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The high sensitivity of the purpose of the present invention is to provide the pollutions to liquid crystal light low, to long wavelength, sensitization effect also excellent polymerizable monomer and by high-molecular compound obtained from polymerizable monomer polymerization.In addition, the purpose of the present invention is to provide the Photocurable resin composition containing the polymerizable monomer and/or the high-molecular compound, using the Photocurable resin composition manufactured sealing material for liquid crystal display device and the conductive material up and down and liquid crystal display element that are manufactured using the sealing material for liquid crystal display device.The present invention relates to make dialkyl amino yl benzoic acid based compound or with can with the thioxanthone derivates of the functional group of epoxy reaction, with epoxide with unsaturated double-bond or the epoxide with alkoxysilyl react obtained from polymerizable monomer.

Description

Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element
Technical field
The high sensitivity of the present invention relates to the pollutions to liquid crystal light low, to long wavelength, sensitization effect are also excellent poly- Close property monomer and by the polymerizable monomer polymerization obtained from high-molecular compound.Moreover, it relates to contain the polymerization The Photocurable resin composition of property monomer and/or the high-molecular compound is made using the Photocurable resin composition Sealing material for liquid crystal display device and the conductive material up and down and liquid that are manufactured using the sealing material for liquid crystal display device Crystal display element.
Background technique
In recent years, the manufacturing method as liquid crystal display elements such as liquid crystal displays from shortening pitch time, uses liquid crystal The viewpoints such as the optimization of amount consider, such as patent document 1, disclosed in Patent Document 2 used is used to contain curability tree Rouge, Photoepolymerizationinitiater initiater and thermal curing agents photo-thermal and with the sealant of curing type, be referred to as drip technique liquid crystal drop under Mode.
In technique of dripping, firstly, 2 transparent substrates with electrode an on piece formed by distributor it is rectangular The seal pattern of shape.Then, the tiny droplets of liquid crystal are dripped in the frame of transparent substrate in the state that sealant is uncured Entire surface is overlapped another transparent substrate immediately, carries out temporary fixing to light such as sealing irradiation ultraviolet lights.Thereafter, in liquid crystal It is heated when annealing and carries out main solidification, make liquid crystal display element.It, can if carrying out the fitting of substrate under reduced pressure Liquid crystal display element is manufactured with extreme efficiency, technique becomes the mainstream of the manufacturing method of liquid crystal display element currently, this drips.
In addition, popularized in the various mobile devices with liquid crystal display panel such as portable phone, portable game it is present, The miniaturization of device is the project of highly desirable realization.The method of miniaturization as device can enumerate the narrow side of liquid crystal display part Frame, such as the position of sealing is configured under black matrix" (hereinafter also referred to narrow frame design).
However, sealant is configured in the underface of black matrix" in narrow frame design, if therefore carrying out work of dripping Skill, then when making sealant carry out photocuring, the light of irradiation is shielded, and there are the inside that light does not reach sealant, solidification becomes Obtain insufficient problem.If the solidification of sealant like this becomes inadequate, there are uncured sealant ingredient dissolve out to The problem of being easy to produce liquid crystal pollution in liquid crystal.
In patent document 3, it discloses and highly sensitive Photoepolymerizationinitiater initiater is engaged in sealant.However, if only Cooperate highly sensitive Photoepolymerizationinitiater initiater, then can not make the abundant photocuring of sealant.In addition, in patent document 4, disclosing Highly sensitive Photoepolymerizationinitiater initiater and sensitizer combination is engaged in sealant.However, due to using sensitizer, There are problems that being easy to produce liquid crystal pollution.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-133794 bulletin
Patent document 2: International Publication No. 02/092718
Patent document 3: International Publication No. 2011/002028
Patent document 4: Japanese Unexamined Patent Publication 2010-286640 bulletin
Summary of the invention
Subject to be solved by the invention
High sensitivity, the sensitization effect of the object of the present invention is to provide the pollutions to liquid crystal light low, to long wavelength Also excellent polymerizable monomer and by the polymerizable monomer polymerization obtained from high-molecular compound.In addition, mesh of the invention Be, the Photocurable resin composition containing the polymerizable monomer and/or the high-molecular compound, solid using the light is provided The property changed resin combination and manufactured sealing material for liquid crystal display device and made using the sealing material for liquid crystal display device The conductive material up and down and liquid crystal display element made.
Means for solving the problems
The present invention is to make dialkyl amino yl benzoic acid based compound or with can be with the thiophene of the functional group of epoxy reaction Ton ketone derivatives, with epoxide with unsaturated double-bond or the epoxide with alkoxysilyl reacts and Obtained polymerizable monomer.
The present invention described in detail below.
We have surprisingly found that there is the polymerizable monomer of specific structure, which is polymerize and is obtained High sensitivity, the sensitization effect of the high-molecular compound arrived light low to the pollution of liquid crystal, to long wavelength are also excellent.Therefore, The inventors discovered that by using cooperating, the polymerizable monomer, the high-molecular compound is as Photoepolymerizationinitiater initiater or sensitizer Photocurable resin composition, it is excellent and can inhibit the liquid crystal display element of liquid crystal pollution so as to obtain photo-curable With sealant, so as to complete the present invention.
Polymerizable monomer of the invention be make dialkyl amino yl benzoic acid based compound or have can be with epoxy reaction Functional group thioxanthone derivates (being also referred to simply as " thioxanthone derivates " below), with epoxidation with unsaturated double-bond Close object or epoxide (being also known as " epoxide of the invention " together below) reaction with alkoxysilyl Obtained from.
As above-mentioned dialkyl amino yl benzoic acid based compound, such as can enumerate: following formula (1-1) compound represented, Following formula (1-2) compound represented, following formula (1-3) compound represented, 7- (dimethylamino) coumarin-3-carboxylic acid etc.. Wherein, preferably change shown in following formula (1-1) compound represented, following formula (1-2) compound represented or following formula (1-3) Object is closed, shown in more preferable following formula (2-1) compound represented, following formula (2-2) compound represented or following formula (2-3) Compound.
Above-mentioned thioxanthone derivates have can be with the functional group of epoxy reaction.
As above-mentioned such as hydroxyl, carboxyl, amino can be enumerated etc. with the functional group of epoxy reaction.Wherein, preferably Hydroxy or carboxy.
It as above-mentioned thioxanthone derivates, such as can enumerate: following formula (3) compound represented, 2- amino -9H- thioxanthene - 9- ketone etc..Wherein, preferably following formula (3) compound represented, more preferably following formula (5-1) compound represented or (5-2) Compound represented.
In formula (3), X is hydrogen, group shown in hydroxyl or following formula (4).Each X can be the same or different, but at least One X is group shown in hydroxyl or following formula (4).
The epoxidation of the invention reacted with above-mentioned dialkyl amino yl benzoic acid based compound or above-mentioned thioxanthone derivates Closing object is epoxide with unsaturated double-bond or the epoxide with alkoxysilyl.
Above-mentioned unsaturated double-bond or alkoxysilyl have involved by the polymerization as polymerizable monomer of the invention Polymerism reactive group effect.
It as the functional group with above-mentioned unsaturated double-bond, such as can enumerate: (methyl) acryloxy, vinyl, alkene Propyl etc..Wherein, preferred (methyl) acryloxy.
It should be noted that in the present specification, above-mentioned " (methyl) acryloxy " refers to acryloxy or methyl Acryloxy.
As above-mentioned alkoxysilyl, such as can enumerate: trimethoxysilyl, triethoxysilyl, Methyl dimethoxy oxygroup silicyl, methyl diethoxy silicyl etc..Wherein, preferred trimethoxysilyl.
As epoxide of the invention, it is preferable to use following formula (6-1) or (6-2) compound represented.
In formula (6-1), R1Indicate hydrogen or methyl.In formula (6-2), R2Indicate alkyl that carbon number is 1~10 or carbon number be 1~ 10 alkoxy.Each R2It can be the same or different, but at least one R2The alkoxy for being 1~10 for carbon number.
As making above-mentioned dialkyl amino yl benzoic acid based compound or above-mentioned thioxanthone derivates and epoxidation of the invention It closes object and reacts the method for obtaining polymerizable monomer of the invention, can enumerate: in the presence of basic catalyst, make above-mentioned dioxane Base aminobenzoic acid based compound or above-mentioned thioxanthone derivates and epoxide of the invention are under conditions of 80~130 DEG C The method etc. reacted when stirring 6~72 hours.
From the viewpoint of reactivity, above-mentioned dialkyl amino yl benzoic acid based compound or above-mentioned thioxanthone derivates and this The reaction of the epoxide of invention preferably carries out in the presence of trivalent organophosphorus acid compound and/or amine compounds.
As making above-mentioned dialkyl amino yl benzoic acid based compound or above-mentioned thioxanthone derivates and epoxidation of the invention Above-mentioned dialkyl amino yl benzoic acid based compound or above-mentioned thioxanthone derivates and epoxy compound of the invention when conjunction object reaction The use ratio of object, with molar ratio computing, preferably above-mentioned dialkyl amino yl benzoic acid based compound or above-mentioned thioxanthone derivates: Epoxide=1 of the invention: 1~10: 1.By making above-mentioned dialkyl amino yl benzoic acid based compound or above-mentioned thioxanthones The use ratio of derivative and epoxide of the invention is the range, has photoreactivity so as to manufacture with high yield The polymerizable monomer of the invention of group.
As making above-mentioned dialkyl amino yl benzoic acid based compound or above-mentioned thioxanthone derivates and epoxy of the invention The basic catalyst that uses when compound reacts, such as can enumerate: triphenylphosphine, triethylamine, tripropyl amine (TPA), tetramethylethylenediamine, Dimethyllaurylamine, triethyl benzyl ammonia chloride, trimethyl cetyl ammonium bromide, tetrabutylammonium bromide, trimethyl butyl bromine Change phosphorus, tetrabutyl phosphonium bromide phosphorus etc..Wherein, triphenylphosphine.
In addition, above-mentioned basic catalyst, which can also be supported, is used as Polymer Supported basic catalyst in polymer.
As sheet obtained from reacting above-mentioned dialkyl amino yl benzoic acid based compound with epoxide of the invention The polymerizable monomer (hereinafter also referred to " polymerizable monomer from dialkyl amino yl benzoic acid based compound ") of invention, concrete example Following formula (7-1)~(7-6) compound represented can such as be enumerated.
In formula (7-1)~(7-3), R1Indicate hydrogen or methyl.In formula (7-4)~(7-6), R2Indicate that carbon number is 1~10 alkane The alkoxy that base or carbon number are 1~10.Each R2It can be the same or different, but at least one R2The alcoxyl for being 1~10 for carbon number Base.
As the polymerism for keeping above-mentioned thioxanthone derivates of the invention obtained from reacting with epoxide of the invention Monomer (hereinafter also referred to " polymerizable monomer from thioxanthone derivates "), specifically can for example enumerate following formula (8-1)~(8- 4) compound represented etc..
In formula (8-1), (8-2), R1Indicate hydrogen or methyl.In formula (8-3), (8-4), R2Indicate that carbon number is 1~10 alkyl Or the alkoxy that carbon number is 1~10.Each R2It can be the same or different, but at least one R2The alcoxyl for being 1~10 for carbon number Base.
High-molecular compound (hereinafter also referred to " high score of the invention obtained from polymerizable monomer of the invention is polymerize Sub- compound ") it is also one of present invention.
As by the polymerism from dialkyl amino yl benzoic acid based compound above-mentioned among polymerizable monomer of the invention The method of monomer polymerization, such as cationic polymerization, anionic polymerisation, free radical polymerization can be enumerated etc..Wherein, preferably make in toluene Lysed compound is in the presence of the radical polymerization initiators such as azodiisobutyronitrile in 60~100 DEG C of condition in solvent The method reacted when stirring 4~12 hours.
Make as when the above-mentioned polymerizable monomer from dialkyl amino yl benzoic acid based compound is carried out cationic polymerization Cationic polymerization catalyst, such as can enumerate: the inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid etc. Sulfonic acid such as carboxylic acid, Loprazolam, ethane sulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid etc..Wherein, preferred hydrochloric acid.
Make as when the above-mentioned polymerizable monomer from dialkyl amino yl benzoic acid based compound is carried out anionic polymerisation Anionic polymerization catalyst, such as can enumerate: the lithium alkylides such as n-BuLi, s-butyl lithium, tert-butyl lithium ,-two lithium fourth of Isosorbide-5-Nitrae Two lithiums of alkylidenes such as alkane (Isosorbide-5-Nitrae-ジ リ チ オ Block タ Application) (ア Le キ レ Application ジ リ チ ウ Si), phenyl lithium, lithium Stilbene, lithium naphthalene, sodium naphthalene, Potassium naphthalene, n-butyl magnesium, n-hexyl magnesium, calcium ethoxide, calcium stearate, tert-butyl alcohol strontium, barium ethoxide, barium isopropylate, ethyl mercaptan barium, tertiary fourth Alcohol barium, barium phenolate, lignocaine barium, barium stearate etc..Wherein, preferred n-BuLi.
Make as when the above-mentioned polymerizable monomer from dialkyl amino yl benzoic acid based compound is carried out free radical polymerization Radical polymerization initiator, such as can enumerate: azodiisobutyronitrile, two cyclohexanenitrile of azo, bis- (2, the 4- dimethyl-pentens of azo Nitrile) etc. azo compounds, benzoyl peroxide, lauroyl peroxide, adjacent chlorobenzoyl peroxide, O-methoxy benzoyl peroxide Formyl, peroxidating 3,5, the organic peroxies such as 5- trimethyl acetyl, the peroxidating 2 ethyl hexanoic acid tert-butyl ester, di-tert-butyl peroxide Compound etc..Wherein, preferred azodiisobutyronitrile.
As the side for polymerizeing the polymerizable monomer from thioxanthone derivates above-mentioned among polymerizable monomer of the invention Method, such as can enumerate: using the polymerization etc. of sol-gal process in the presence of acidic catalyst or basic catalyst, but preferably Polymerizable monomer of the invention to be dissolved in alcohol solvent is mixed with water, in 60~120 DEG C under acidic catalyst The method that condition is reacted when stirring 2~24 hours.
As the acidic catalyst used when polymerizeing the above-mentioned polymerizable monomer from thioxanthone derivates, such as can arrange Lift: the carboxylic acids such as the inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, Loprazolam, ethane sulfonic acid, benzene sulfonic acid, Sulfonic acid such as p-methyl benzenesulfonic acid etc..Wherein, preferred hydrochloric acid.
As the basic catalyst used when polymerizeing the above-mentioned polymerizable monomer from thioxanthone derivates, hydrogen can be enumerated Organic compounds such as the inorganic compounds such as sodium oxide molybdena, potassium hydroxide, ammonia, amine compounds etc..Wherein, preferred sodium hydroxide.
The preferred lower limit of the degree of polymerization of high-molecular compound of the invention is 3.High-molecular compound of the invention gathers It is right when being 2, being dimer, in the feelings for being used for sealing material for liquid crystal display device as Photoepolymerizationinitiater initiater or sensitizer Under condition, it cannot sufficiently inhibit liquid crystal pollution sometimes.The preferred lower limit of the degree of polymerization of high-molecular compound of the invention is 10.
In addition, the preferred upper limit of the degree of polymerization of high-molecular compound of the invention is 1000.Producing high-molecular of the invention When closing the degree of polymerization of object greater than 1000, sealing material for liquid crystal display device is being used for as Photoepolymerizationinitiater initiater or sensitizer In the case of, coating is deteriorated sometimes.The preferred upper limit of the degree of polymerization of high-molecular compound of the invention is 100.
The preferred lower limit of the number-average molecular weight of high-molecular compound of the invention is 2000, the preferred upper limit is 30,000.This When the number-average molecular weight of the high-molecular compound of invention is less than 2000, liquid crystal is being used for as Photoepolymerizationinitiater initiater or sensitizer In the case where display element sealant, it cannot sufficiently inhibit liquid crystal pollution sometimes.The number of high-molecular compound of the invention is equal When molecular weight is greater than 30,000, in the case where being used for sealing material for liquid crystal display device as Photoepolymerizationinitiater initiater or sensitizer, Coating is deteriorated sometimes.The preferred lower limit of the number-average molecular weight of high-molecular compound of the invention is 5000, more preferably The upper limit is 10,000.
It should be noted that in the present specification, above-mentioned number-average molecular weight is surveyed using gel permeation chromatography (GPC) Value that is fixed and being found out by polystyrene conversion.When as the number-average molecular weight to be converted by GPC measurement based on polystyrene Column, such as ShodexLF-804 (manufacture of Showa electrician company) can be enumerated etc..
High-molecular compound of the invention is also excellent to high sensitivity, the sensitization effect of the light of long wavelength, therefore preferably uses Make Photoepolymerizationinitiater initiater or sensitizer.
Photocuring containing curable resin and polymerizable monomer of the invention and/or high-molecular compound of the invention Property resin combination is also one of present invention.
From the viewpoint of not reacted with curable resin after being just above coated with to substrate etc. and preventing liquid crystal pollution, this The Photocurable resin composition of invention preferably comprises high-molecular compound of the invention.High-molecular compound of the invention has Effect as Photoepolymerizationinitiater initiater or sensitizer.
For the content of the high-molecular compound of the invention in Photocurable resin composition of the invention, relatively In 100 parts by weight of curable resin, preferred lower limit is 0.5 parts by weight, and the preferred upper limit is 20 parts by weight.If height of the invention The content of molecular compound is less than 0.5 parts by weight, then the photo-curable of obtained Photocurable resin composition is deteriorated sometimes. When the content of high-molecular compound of the invention is greater than 20 parts by weight, obtained Photocurable resin composition is sometimes weather-proof Property, storage stability be deteriorated, or be used for sealing material for liquid crystal display device when generate liquid crystal pollution.Macromolecule of the invention The preferred lower limit of the content of compound is 2 parts by weight, the preferred upper limit is 10 parts by weight.
Photocurable resin composition of the invention, which preferably combines to contain, is originated from dialkyl amino yl benzoic acid system for above-mentioned It closes high-molecular compound of the invention obtained from the polymerizable monomer polymerization of object and (hereinafter also referred to " is originated from dialkyl amido benzene The high-molecular compound of formic acid based compound ") and will be obtained from the above-mentioned polymerizable monomer polymerization from thioxanthone derivates Both high-molecular compounds (hereinafter also referred to " high-molecular compound from thioxanthone derivates ") of the invention, more preferably The above-mentioned high-molecular compound from dialkyl amino yl benzoic acid based compound is used as Photoepolymerizationinitiater initiater and is used above-mentioned High-molecular compound from thioxanthone derivates is as sensitizer.
Combination is originated from dialkyl amino yl benzoic acid based compound containing above-mentioned in Photocurable resin composition of the invention High-molecular compound and above-mentioned high-molecular compound the two from thioxanthone derivates in the case where, it is above-mentioned be originated from dioxane The high-molecular compound of base aminobenzoic acid based compound contains with the above-mentioned high-molecular compound from thioxanthone derivates Ratio is preferably derived from the high-molecular compound of dialkyl amino yl benzoic acid based compound: being spread out from thioxanthones with weight ratio meter High-molecular compound=1 of biology: 1~5: 1.By making the high-molecular compound from dialkyl amino yl benzoic acid based compound Content ratio with the high-molecular compound for being originated from thioxanthone derivates is the range, to make obtained light-cured resin The photo-curable of the light using long wavelength of composition becomes especially excellent.
In Photocurable resin composition of the invention other than high-molecular compound of the invention, it to be used for liquid crystal Show in the range of not causing the adverse effects such as liquid crystal pollution when element sealant can also containing other Photoepolymerizationinitiater initiaters, its Its sensitizer.
As above-mentioned other Photoepolymerizationinitiater initiaters, such as can enumerate: benzophenone based compound, acetophenone based compound, Acylphosphine oxide compound, titanocenes based compound, oxime ester based compound, benzoin ether based compound, benzil, thioxanthene Ketone, following formula (9-1) compound represented, following formula (9-2) compound represented etc..
It as the commercially available product among above-mentioned other Photoepolymerizationinitiater initiaters, such as can enumerate: IRGACURE 184, IRGACURE 369、IRGACURE 379、IRGACURE 651、IRGACURE 819、IRGACURE 907、IRGACURE 2959、 IRGACURE OXE01, Lucirin TPO (being BASF AG's manufacture), benzoin methylether, benzoin ethyl ether, benzoin isopropyl Ether (being the manufacture of Tokyo chemical conversion industry company), ADEKA OPTMERN-1414, ADEKA OPTMER N-1717, ADEKA OPTMER N-1919, ADEKA OPTMER NCI-839, ADEKA OPTMER NCI-930 etc. (being the manufacture of ADEKA company).
It as above-mentioned other sensitizers, such as can enumerate: anthracene derivant, anthraquinone derivative, coumarin derivative, thioxanthones Derivative, phthalocyanine derivates, following formula (10-1) compound represented, following formula (10-2) compound represented etc..
It as above-mentioned anthracene derivant, such as can enumerate: 9,10- dibutoxy anthracenes, 9,10- dipropoxy anthraquinone, 9,10- second Oxygroup anthraquinone etc..
It as above-mentioned anthraquinone derivative, such as can enumerate: 2- ethyl hydrazine, 1-methylanthracene quinone, Isosorbide-5-Nitrae-dihydroxy anthraquinone, 2- (2- hydroxyl-oxethyl)-anthraquinone etc..
As above-mentioned coumarin derivative, such as 7- lignocaine -4- methylcoumarin can be enumerated etc..
As above-mentioned thioxanthone derivates, such as 2,4- diethyl thioxanthone, 2-chlorothioxanthone, 4- isopropyl thiophene can be enumerated Ton ketone, the chloro- 4- propyl thioxanthones of 1- etc..
As above-mentioned phthalocyanine derivates, such as phthalocyanine can be enumerated etc..
Furthermore it is possible to by the benzophenone based compound enumerated as above-mentioned other Photoepolymerizationinitiater initiaters be used as it is above-mentioned its Its sensitizer.
Photocurable resin composition of the invention contains curable resin.
Above-mentioned curable resin preferably comprises (methyl) acrylic resin.
From aspect with high reactivity, above-mentioned (methyl) acrylic resin preferably has 2~3 (first in the molecule Base) acryloxy.
It as above-mentioned (methyl) acrylic resin, such as can enumerate: make the compound with hydroxyl and (methyl) propylene Acid reaction obtained from ester compounds, react (methyl) acrylic acid with epoxide obtained from epoxy (methyl) acrylic acid Ester, react (methyl) acrylic acid derivative with hydroxyl with isocyanate compound obtained from carbamate (methyl) Acrylate etc..Wherein, preferred epoxy (methyl) acrylate.
It should be noted that in the present specification, above-mentioned " (methyl) acrylic acid " refers to acrylic or methacrylic acid, on It states " (methyl) acrylic resin " and refers to the resin with (methyl) acryloxy.In addition, above-mentioned " (methyl) acrylic acid Ester " refers to acrylate or methacrylate.In addition, above-mentioned " epoxy (methyl) acrylate " expression makes in epoxy resin Compound obtained by whole epoxy groups are reacted with (methyl) acrylic acid.
It as the simple function ester compounds among above-mentioned ester compounds, such as can enumerate: (methyl) acrylic acid 2- hydroxyl second Ester, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxybutyl, (first Base) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate, (first Base) stearyl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- methoxyl group Ethyl ester, methoxy ethyl glycol (methyl) acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid tetrahydro chaff Ester, (methyl) benzyl acrylate, ethyl carbitol (methyl) acrylate, (methyl) phenoxyethyl acrylate, phenoxy group two Ethylene glycol (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylic acid Ester, (methyl) acrylic acid -2,2,2- trifluoro ethyl ester, 2,2,3,3- tetrafluoro propyl ester of (methyl) acrylic acid, (methyl) acrylic acid 1H, 1H, 5H- octafluoro pentyl ester, acid imide (methyl) acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) N-butyl acrylate, (methyl) propyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) n-octyl, (first Base) the different nonyl ester of acrylic acid, the different myristin of (methyl) acrylic acid, (methyl) acrylic acid 2- butoxyethyl, (methyl) acrylic acid 2- phenoxy ethyl, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid lignocaine second Ester, (methyl) dimethylaminoethyl acrylate, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloxy second Base hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl 2- hydroxypropyl phthalate, the contracting of (methyl) acrylic acid Water glyceride, 2- (methyl) acryloyl-oxyethyl phosphate etc..
In addition, as two function ester compounds among above-mentioned ester compounds, such as can enumerate: two (first of 1,4-butanediol Base) acrylate, 1,3-BDO two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, 1,9- nonanediol Two (methyl) acrylate, 1,10- decanediol two (methyl) acrylate, 2- normal-butyl -2- ethyl-two (first of 1,3-PD Base) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol (methyl) Acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) propylene Acid esters, polyethylene glycol two (methyl) acrylate, propylene oxide addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl Two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two (methyl) acrylic acid Ester, (methyl) acrylic acid 2- hydroxyl -3- (methyl) acryloxy propyl ester, carbonate diol two (methyl) acrylate, polyethers Glycol two (methyl) acrylate, polycaprolactone glycol two (methyl) acrylate, gathers polyester-diol two (methyl) acrylate Butadiene glycol two (methyl) acrylate etc..
In addition, as the ester compounds more than trifunctional among above-mentioned ester compounds, such as can enumerate: pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, propylene oxide addition trimethylolpropane tris (methyl) Acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (first Base) acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, pentaerythrite four (methyl) third Olefin(e) acid ester, glycerine three (methyl) acrylate, propylene oxide addition glycerine three (methyl) acrylate, three (methyl) propylene Acyloxyethyl phosphate etc..
It as above-mentioned epoxy (methyl) acrylate, such as can enumerate: according to conventional method by epoxy resin and (methyl) Epoxy obtained from acrylic acid is reacted in the presence of basic catalyst (methyl) acrylate etc..
For as the epoxy resin for the raw material for synthesizing above-mentioned epoxy (methyl) acrylate, such as it can arrange It lifts: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2,2 '-diallyl bisphenol type asphalt mixtures modified by epoxy resin Rouge, A Hydrogenated Bisphenol A type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type ring Oxygen resin, thioether-type epoxy resin, diphenyl ether type epoxy, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, benzene Phenol phenolic resin varnish type epoxy resin, o-cresol phenolic epoxy varnish, dicyclopentadiene novolaks type ring oxygen resin, connection Phenol aldehyde type epoxy resin, naphthol novolac type epoxy resin, glycidyl amine type epoxy resin, alkyl polyols type Epoxy resin, modified rubber type epoxy resin, epihydric alcohol ester compound etc..
As the commercially available product among above-mentioned bisphenol A type epoxy resin, such as can enumerate: jER828EL, jER1004 (are Mitsubishi Chemical Ind's manufacture), EPICLON850 (manufacture of DIC company) etc..
As the commercially available product among above-mentioned bisphenol f type epoxy resin, such as can enumerate: jER806, jER4004 (are three The manufacture of water chestnut chemical company) etc..
As the commercially available product among above-mentioned bisphenol-s epoxy resin, such as can enumerate: (DIC is public by EPICLON EXA1514 Department's manufacture) etc..
It as the commercially available product among above-mentioned 2,2 '-diallyl bisphenol type epoxy resin, such as can enumerate: RE-810NM (Japanese chemical drug corporation is made) etc..
As the commercially available product among above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as EPICLON EXA7015 (DIC can be enumerated Company's manufacture) etc..
As the commercially available product among above-mentioned propylene oxide addition bisphenol A type epoxy resin, such as EP-4000S can be enumerated (manufacture of ADEKA company) etc..
As the commercially available product among above-mentioned resorcinol type epoxy resin, such as EX-201 (Nagase can be enumerated The manufacture of Chemtex company) etc..
As the commercially available product among above-mentioned biphenyl type epoxy resin, such as jERYX-4000H (Mitsubishi Chemical Ind can be enumerated Manufacture) etc..
As the commercially available product among above-mentioned sulfide type epoxy resin, such as YSLV-50TE can be enumerated (aurification is lived by Nippon Steel Company manufacture) etc..
As the commercially available product among above-mentioned diphenyl ether type epoxy, for example, can enumerate YSLV-80DE (Nippon Steel live gold Chemical company's manufacture) etc..
As the commercially available product among above-mentioned dicyclopentadiene type epoxy resin, such as EP-4088S (ADEKA company can be enumerated Manufacture) etc..
It as the commercially available product among above-mentioned naphthalene type epoxy resin, such as can enumerate: EPICLON HP4032, EPICLON EXA-4700 (being the manufacture of DIC company) etc..
As the commercially available product among above-mentioned phenol novolak type epoxy resin, such as EPICLON N-770 can be enumerated (manufacture of DIC company) etc..
As the commercially available product among above-mentioned o-cresol phenolic epoxy varnish, such as EPICLON N-670- can be enumerated EXP-S (manufacture of DIC company) etc..
As the commercially available product among above-mentioned dicyclopentadiene novolaks type ring oxygen resin, such as EPICLON can be enumerated HP7200 (manufacture of DIC company) etc..
As the commercially available product among above-mentioned biphenyl phenolic resin varnish type epoxy resin, such as NC-3000P (Japanization can be enumerated The manufacture of medicine company) etc..
As the commercially available product among above-mentioned naphthol novolac type epoxy resin, such as ESN-165S (Nippon Steel can be enumerated Firmly aurification company manufactures) etc..
As the commercially available product among above-mentioned glycidyl amine type epoxy resin, such as can enumerate: (Mitsubishi Chemical is public by jER630 Department's manufacture), EPICLON 430 (manufacture of DIC company), TETRAD-X (manufacture of Mitsubishi Gas Chemical company) etc..
As the commercially available product among abovementioned alkyl polyol type epoxy resin, such as can enumerate: ZX-1542 (live by Nippon Steel Aurification company manufacture), EPICLON726 (manufacture of DIC company), EPOLIGHT80MFA (manufacture of chemical company, common prosperity society), Denacol EX-611 (manufacture of Nagase Chemtex company) etc..
Commercially available product among modified version epoxy resin as above-mentioned rubber, such as can enumerate: YR-450, YR-207 (are The manufacture of aurification company is lived by Nippon Steel), EPOLEAD PB (manufacture of Daicel company) etc..
As the commercially available product among above-mentioned epihydric alcohol ester compound, such as Denacol EX-147 (Nagase can be enumerated The manufacture of Chemtex company) etc..
It as other commercially available products among above-mentioned epoxy resin, such as can enumerate: YDC-1312, YSLV-80XY, YSLV- 90CR (being that the manufacture of aurification company is lived by Nippon Steel), XAC4151 (Asahi Kasei Corporation's manufacture), jER1031, jER1032 (are Mitsubishi Chemical Ind's manufacture), EXA-7120 (manufacture of DIC company), TEPIC (manufacture of Nissan Chemical company) etc..
It is specific to be, for example: by resorcinol type epoxy resin as the method for manufacturing above-mentioned epoxy (methyl) acrylate (Nagase Chemtex corporation, " EX-201 ") 360 parts by weight, as 2 parts by weight of p methoxy phenol of polymerization inhibitor, conduct 2 parts by weight of triethylamine and 210 parts by weight of acrylic acid of catalysts are sent into air on one side and carry out return stirring, on one side 90 DEG C reaction 5 hours, it is hereby achieved that resorcinol type epoxy acrylate.
As the commercially available product among above-mentioned epoxy (methyl) acrylate, such as can enumerate: EBEC RYL860, EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、 EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (are Daicel- The manufacture of Allnex company), EA-1010, EA-1020, EA-5323, EA-5520, E A-CHD, EMA-1020 (be the village Xin Zhong Learn industrial group manufacture), EPOXY EST ER M-600A, EPOXY ESTER 40EM, EPOXY ESTER 70PA, EPOXY ESTER 200PA、EPOXY ESTER 80MFA、EPOXY ESTER 3002M、E POXY ESTER3002A、EPOXY ESTER1600A、EPOXY ESTER3000M、EPOXY ESTER3000A、EPOXY ESTER 200EA、EPOXY ESTER 400EA (being the manufacture of chemical company, common prosperity society), Denacol Acrylate DA-141, Dena col Acrylate DA- 314, Denacol Acrylate DA-911 (being the manufacture of Nagase Chemt ex company) etc..
As it is above-mentioned react (methyl) acrylic acid derivative with hydroxyl with isocyanate compound obtained from ammonia Carbamate (methyl) acrylate, such as can obtain as follows: relative to tool, there are two the isocyanates of isocyanate group 1 equivalent of compound, make 2 equivalent of (methyl) acrylic acid derivative with hydroxyl in the presence of the tin based compound of catalytic amount with Reaction and obtain.
For the isocyanate compound as the raw material of above-mentioned carbamate (methyl) acrylate, such as it can arrange It lifts: isophorone diisocyanate, 2,4- toluene di-isocyanate(TDI), 2,6- toluene di-isocyanate(TDI), hexa-methylene diisocyanate Ester, trimethyl hexamethylene diisocyanate, 4,4 '-diisocyanate (MDI) of diphenyl methane-, hydrogenation MDI, polymeric MDI, 1,5- naphthalene diisocyanate, norbornene alkyl diisocyanate, ditolyl diisocyanate, benzene dimethylene diisocyanate (XDI), hydrogenate XDI, lysine diisocyanate, triphenylmethane triisocyanate, three (isocyanate phenyl) thiophosphates, Tetramethylxylene diisocyanate, 1,6,11- hendecane triisocyanates etc..
In addition, for the isocyanate compound as the raw material of above-mentioned carbamate (methyl) acrylate, example As also can be used through ethylene glycol, glycerine, D-sorbite, trimethylolpropane, (poly-) propylene glycol, carbonate diol, gathering Chain obtained from the reacting of the polyalcohols such as ether glycol, polyester-diol, polycaprolactone glycol and excessive isocyanate compound increases The isocyanate compound grown.
It is derivative with regard to (methyl) acrylic acid with hydroxyl of the raw material as above-mentioned carbamate (methyl) acrylate It for object, such as can enumerate: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid (methyl) acrylic acid hydroxy alkyl esters such as 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxybutyl；Ethylene glycol, propylene glycol, 1,3- third List (methyl) acrylate of the dihydric alcohols such as glycol, 1,3-BDO, 1,4-butanediol, polyethylene glycol；Trimethylolethane, three List (methyl) acrylate of the trihydroxylic alcohols such as hydroxymethyl-propane, glycerine or two (methyl) acrylate；Bisphenol type epoxy propylene The epoxies such as acid esters (methyl) acrylate etc..
Above-mentioned carbamate (methyl) acrylate specifically can for example obtain as follows: trimethylolpropane 134 is added It is parts by weight, the BHT0.2 parts by weight as polymerization inhibitor, 0.01 parts by weight of dibutyl tin dilaurate as catalysts, different 666 parts by weight of isophorone diisocyanate, Bian react on 60 DEG C of return stirring sides 2 hours, then, acrylic acid -2- hydroxyl are added Air and return stirring are sent into 51 parts by weight of ethyl ester, side, and 90 DEG C of Bian are reacted 2 hours, thus obtain.
It as the commercially available product among above-mentioned carbamate (methyl) acrylate, such as can enumerate: M-1100, M- 1200, M-1210, M-1600 (be East Asia Synesis Company manufacture), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL1290、 EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、 EBECRYL2220 (be Daicel-Allnex company manufacture), Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100、Artresin UN-1255、Artresin UN-330、Artresin UN-3320HB、Artresin UN-1200TPK, Artresin SH-500B (be Gen Shang industrial group manufacture), U-122P, U-108A, U-340P, U-4HA, U-6HA、U-324A、U-15HA、UA-5201P、UA-W2A、U-1084A、U-6LPA、U-2HA、U-2PHA、UA-4100、UA- 7100、UA-4200、UA-4400、UA-340P、U-3HA、UA-7200、U-2061BA、U-10H、U-122A、U-340A、U- 108, U-6H, UA-4000 (being the manufacture of chemical industrial company, the village Xin Zhong), AH-600, AT-600, UA-306H, AI-600, UA- 101T, UA-101I, UA-306T, UA-306I (being the manufacture of chemical company, common prosperity society) etc..
For the purpose for the cementability for improving obtained Photocurable resin composition, above-mentioned curable resin is preferably also Contain epoxy resin.It as above-mentioned epoxy resin, such as can enumerate: as synthesizing above-mentioned epoxy (methyl) acrylate Epoxy resin, part (methyl) acrylic modified epoxy resin of raw material etc..
It should be noted that in the present specification, above-mentioned part (methyl) acrylic modified epoxy resin refers in 1 molecule Resin with epoxy group and each 1 of (methyl) acryloyl group or more, for example, can be by making 2 or more epoxy resin The epoxy group of a part is reacted with (methyl) acrylic acid to be obtained.
Contain above-mentioned (methyl) acrylic resin and above-mentioned epoxy resin in Photocurable resin composition of the invention In the case where, preferably cooperate above-mentioned (methyl) in such a way that (methyl) the ratio between acryloxy and epoxy group are 50:50~95:5 Acrylic resin and above-mentioned epoxy resin.If the ratio of (methyl) acryloxy is less than 50%, even if polymerization terminates, still Largely there is uncured epoxy resin ingredient, therefore generates liquid crystal dirt sometimes when being used for sealing material for liquid crystal display device Dye.If the ratio of (methyl) acryloxy is greater than 95%, cementability is deteriorated obtained Photocurable resin composition sometimes.
From the viewpoint of liquid crystal pollution when inhibiting for sealing material for liquid crystal display device, above-mentioned curable resin is excellent Choosing has-OH base ,-NH- base ,-NH2The unit of the hydrogen bonds such as base.
Photocurable resin composition of the invention can also contain hot radical polymerization initiator.
As above-mentioned hot radical polymerization initiator, such as it can enumerate and be made of azo-compound, organic peroxide etc. Hot radical polymerization initiator.Wherein, the initiator being preferably made of polymeric azo compound is (hereinafter also referred to " high Molecule azo initiator ").
It should be noted that in the present specification, polymeric azo initiator refers to, there is azo group and produced by heat Life can make the cured free radical of (methyl) acryloxy, 300 or more number-average molecular weight compound.
The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiator is 1000, preferred upper limit is 300,000.On if The number-average molecular weight of polymeric azo initiator is stated less than 1000, then macromolecule is even when being used for sealing material for liquid crystal display device Nitrogen initiator causes adverse effect to liquid crystal sometimes.If the number-average molecular weight of above-mentioned polymeric azo initiator is greater than 300,000, Sometimes it is difficult to mix into curable resin.The more preferable lower limit of the number-average molecular weight of above-mentioned polymeric azo initiator is 5000, the more preferable upper limit is 100,000, and further preferred lower limit is 10,000, and the further preferred upper limit is 90,000.
It as above-mentioned polymeric azo initiator, such as can enumerate: have and be bonded with multiple polycyclic oxygen by azo group The polymeric azo initiator of the structure of the units such as alkane, dimethyl silicone polymer.
Draw as the above-mentioned polymeric azo with the structure for being bonded with the units such as multiple polyalkylene oxides by azo group Send out agent, it is however preferred to have the polymeric azo initiator of polyethylene oxide structure.As such polymeric azo initiator, example Can such as enumerate: condensation polymer, 4, the 4 '-azos of 4,4 '-azos bis- (4- cyanopentanoic acids) and ployalkylene glycol are bis- (4- cyanopentanoic acid) With the condensation polymer of the dimethyl silicone polymer with terminal amino group etc., specifically, can for example enumerate: VPE-0201, VPE- 0401, VPE-0601, VPS-0501, VPS-1001 (being to be manufactured with Wako Pure Chemical Industries company) etc..
In addition, the azo-compound as on-macromolecular, such as can enumerate: V-65, V-501 (are and Wako Pure Chemical Industries Company's manufacture) etc..
It as above-mentioned organic peroxide, such as can enumerate: ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl group mistake Oxide, peroxyester, peroxidating two acyl, peroxy dicarbonate etc..
About the content of above-mentioned hot radical polymerization initiator, relative to 100 parts by weight of curable resin, preferred lower limit For 0.1 parts by weight, the preferred upper limit is 30 parts by weight.If the content of above-mentioned hot radical polymerization initiator less than 0.1 parts by weight, Then the thermal polymerization of obtained Photocurable resin composition sometimes cannot be carried out sufficiently.If above-mentioned hot radical polymerization initiator Content be greater than 30 parts by weight, then be used for sealing material for liquid crystal display device when sometimes because unreacted hot radical polymerization draw It sends out agent and generates liquid crystal pollution.The more preferable lower limit of the content of above-mentioned hot radical polymerization initiator is 0.5 parts by weight, more preferably The upper limit is 10 parts by weight.
Photocurable resin composition of the invention can also contain thermal curing agents.
It as above-mentioned thermal curing agents, such as can enumerate: organic acid hydrazides, imdazole derivatives, amine compounds, polynary phenol system Close object, acid anhydrides etc..Wherein, it is preferable to use organic acid hydrazides.
It as above-mentioned organic acid hydrazides, such as can enumerate: decanedioyl hydrazine, isopthalic dihydrazide, adipic dihydrazide, malonyl hydrazine Deng.
As the commercially available product among above-mentioned organic acid hydrazides, such as can enumerate: SDH, ADH (are great Zhong chemical company system Make), AMICURE VDH, AMICURE VDH-J, AMICURE UDH (be Ajinomoto Fine-Techno company manufacture) etc..
About the content of above-mentioned thermal curing agents, relative to above-mentioned 100 parts by weight of curable resin, preferred lower limit is 1 weight Part, preferred upper limit are 50 parts by weight.If the content of above-mentioned thermal curing agents less than 1 parts by weight, can not make obtained light sometimes The abundant heat-cure of hardening resin composition.If the content of above-mentioned thermal curing agents is greater than 50 parts by weight, obtained light is solid The viscosity of the property changed resin combination becomes excessively high, and coating is deteriorated sometimes.The preferred upper limit of the content of above-mentioned thermal curing agents For 30 parts by weight.
The improvement of cementability, the improvement of linear expansivity, solidfied material for the raising of viscosity, based on stress dispersion effect The purpose of raising of moisture-proof, Photocurable resin composition of the invention preferably comprise filler.
As above-mentioned filler, it such as can enumerate: talcum, asbestos, silica, diatomite, terre verte, bentonite, carbonic acid Calcium, magnesium carbonate, aluminium oxide, montmorillonite, zinc oxide, acidification iron, magnesia, tin oxide, titanium dioxide, magnesium hydroxide, hydroxide The inorganic fillers such as aluminium, glass microballoon, silicon nitride, barium sulfate, gypsum, calcium silicates, sericite, atlapulgite, aluminium nitride, polyester The organic fillers such as particle, polyurethane particulate, polyvinyl particle, acrylic acid series polymeric compounds particle.These fillers can To be used alone, also can be used together two or more.
The preferred lower limit of the content of above-mentioned filler in 100 parts by weight of Photocurable resin composition of the invention is 10 Parts by weight, preferred upper limit are 70 parts by weight.If the content of above-mentioned filler less than 10 parts by weight, is unable to give full play viscous sometimes Improvement of connecing property and other effects.If the content of above-mentioned filler is greater than 70 parts by weight, obtained Photocurable resin composition Viscosity become excessively high, sometimes coating be deteriorated.The preferred lower limit of the content of above-mentioned filler is 20 parts by weight, more preferably The upper limit be 60 parts by weight.
Photocurable resin composition of the invention preferably comprises silane coupling agent.Above-mentioned silane coupling agent mainly has work For for by the effect of the bonding additives of the good bondings such as Photocurable resin composition and substrate of the invention.
As above-mentioned silane coupling agent, from raising with the excellent effect of the cementability of substrate etc., as liquid crystal display member From the perspective of inhibiting outflow of the curable resin into liquid crystal when part sealant, such as it is preferable to use 3- aminopropyl front threes Oxysilane, 3-mercaptopropyi trimethoxy silane, 3- glycidoxypropyltrime,hoxysilane, 3- isocyanates propyl three Methoxy silane etc..These silane coupling agents can be used alone, and also can be used together two or more.
The preferred lower limit of the content of above-mentioned silane coupling agent in 100 parts by weight of Photocurable resin composition of the invention For 0.1 parts by weight, preferred upper limit is 20 parts by weight.If the content of above-mentioned silane coupling agent sometimes can not less than 0.1 parts by weight Give full play to effect caused by cooperation silane coupling agent.If the content of above-mentioned silane coupling agent is greater than 20 parts by weight, inciting somebody to action Obtained Photocurable resin composition is used to cause liquid crystal pollution sometimes when sealing material for liquid crystal display device.Above-mentioned silane The preferred lower limit of the content of coupling agent is 0.5 parts by weight, and the preferred upper limit is 10 parts by weight.
Photocurable resin composition of the invention can also contain opacifier.By containing above-mentioned opacifier, the present invention Photocurable resin composition can suitably be used as shading sealant.
As above-mentioned opacifier, such as can enumerate: iron oxide, titanium be black, nigrosine, Cyanine Black, fullerene, carbon black, resin Incrusting type carbon black etc..Wherein, preferably titanium is black.
Above-mentioned titanium is black to be, attached for ultraviolet range compared with the average transmittance of the light for 300~800nm of wavelength The higher substance of transmissivity of close, particularly 370~450nm of wavelength light.That is, it is the shading with following property that above-mentioned titanium is black Agent: the light by fully covering the wavelength of visible light region, and shading is assigned to Photocurable resin composition of the invention Property, on the other hand, make the light transmission of the wavelength near ultraviolet range.As contained by Photocurable resin composition of the invention The high substance of some opacifiers, preferably insulating properties, the opacifier high as insulating properties, it is also preferred that titanium is black.
Black every 1 μm of the optical concentration (OD value) of above-mentioned titanium is preferably 3 or more, and more preferably 4 or more.The black screening of above-mentioned titanium The higher the better for photosensitiveness, the OD value black for above-mentioned titanium, without the preferred upper limit, but usually 5 or less.
For black for above-mentioned titanium, even not surface treated titanium is black, can also play sufficient effect, but can also be with Using surface through the processed titanium of the organic principles such as coupling agent it is black or be oxidized silicon, titanium dioxide, acidification germanium, aluminium oxide, oxygen Change zirconium, titanium that the inorganic constituents such as magnesia cover is black etc., and surface treated titanium is black.Wherein, from further increasing insulating properties From the aspect of, it is preferably black through the processed titanium of organic principle.
In addition, using containing the black Photocurable resin composition of the invention as opacifier of above-mentioned titanium as liquid crystal Show element sealant and the liquid crystal display element that manufactures has sufficient light-proofness, therefore, not the leakage of light and there is height Contrast can be realized the liquid crystal display element with excellent display quality of image.
As above-mentioned titanium it is black among commercially available product, such as can enumerate: 12S, 13M, 13M-C, 13R-N, 14M-C (are The manufacture of Mitsubishi Materials company), Tilack D (red fringe chemical conversion company manufacture) etc..
The preferred lower limit of the black specific surface area of above-mentioned titanium is 13m2/ g, the preferred upper limit are 30m2/ g, preferred lower limit For 15m2/ g, the preferred upper limit are 25m2/g。
In addition, the preferred lower limit of the black volume resistance of above-mentioned titanium is 0.5 Ω cm, the preferred upper limit is 3 Ω cm, more Preferred lower limit is 1 Ω cm, and the preferred upper limit is 2.5 Ω cm.
The primary particle size of above-mentioned opacifier is if the distance between the substrate of liquid crystal display element etc. hereinafter, not limiting especially then Fixed, preferred lower limit is 1nm, and the preferred upper limit is 5 μm.If the primary particle size of above-mentioned opacifier is lower than 1nm, obtained light Viscosity, the thixotropy of hardening resin composition substantially increase, and operability is deteriorated sometimes.If the primary particle size of above-mentioned opacifier is big In 5 μm, then the coating of obtained Photocurable resin composition is deteriorated sometimes.The primary particle size of above-mentioned opacifier it is more excellent The lower limit of choosing is 5nm, and the preferred upper limit is 200nm, and further preferred lower limit is 10nm, and the further preferred upper limit is 100nm。
The preferred lower limit of the content of above-mentioned opacifier in 100 parts by weight of Photocurable resin composition of the invention is 5 Parts by weight, preferred upper limit are 80 parts by weight.If the content of above-mentioned opacifier less than 5 parts by weight, is unable to get adequately sometimes Light-proofness.If the content of above-mentioned opacifier be greater than 80 parts by weight, sometimes obtained Photocurable resin composition to base Intensity decline or illustrative decline after the adaptation of plate, solidification.The preferred lower limit of the content of above-mentioned opacifier is 10 Parts by weight, the preferred upper limit are 70 parts by weight, and further preferred lower limit is 30 parts by weight, and the further preferred upper limit is 60 Parts by weight.
As the method for manufacturing Photocurable resin composition of the invention, such as method can be listed below etc.: using equal The mixing machines such as even disperser, homogeneous mixer, universal mixer, planetary-type mixer, kneader, three-roller, by curability tree Rouge, polymerizable monomer of the invention and/or high-molecular compound of the invention and the other photopolymerization being added as needed are drawn Send out the mixing of the additives such as agent, other sensitizers, silane coupling agent.
Photocurable resin composition of the invention is preferably used as sealing material for liquid crystal display device.
Using Photocurable resin composition of the invention, manufactured sealing material for liquid crystal display device is also the present invention One of.
By cooperating electrically conductive microparticle in sealing material for liquid crystal display device of the invention, conductive material up and down can be manufactured. Such conductive material up and down containing sealing material for liquid crystal display device and electrically conductive microparticle of the invention is also one of present invention.
As above-mentioned electrically conductive microparticle, metal ball can be used, be formed with conductive metal layer on the surface of resin particle Particle etc..Wherein, conduction can be carried out in the case where not damaging transparent substrate etc. from the excellent resilience by resin particle From the perspective of connection, the particle of conductive metal layer is preferably formed on the surface of resin particle.
The liquid crystal display manufactured using sealing material for liquid crystal display device of the invention or conductive material up and down of the invention Element is also one of present invention.
As the method for manufacturing liquid crystal display element of the invention, such as the method etc. with following process can be enumerated: An on piece in 2 transparent substrates such as glass substrate or PET substrate with electrodes such as ito thin films, Sealing material for liquid crystal display device of the invention etc. is set to form rectangular seal pattern by silk-screen printing, distributor coating etc. Process；The tiny droplets of liquid crystal are dripped in the state that sealing material for liquid crystal display device of the invention etc. is uncured and are applied to In the frame of transparent substrate in entire surface, it is overlapped the process of another substrate immediately；With to sealing used for liquid crystal display element of the invention The light such as the seal pattern partial illumination ultraviolet light of agent etc., thus the process for keeping sealant temporary fixing；And to temporary fixing Sealant is heated and is allowed to lead cured process.
The effect of invention
According to the present invention it is possible to provide the high sensitivity of light low to the pollution of liquid crystal, to long wavelength, sensitization effect Excellent polymerizable monomer and by high-molecular compound obtained from polymerizable monomer polymerization.In addition, according to the present invention, The Photocurable resin composition containing the polymerizable monomer and/or the high-molecular compound can be provided, using the photocuring It property resin combination and manufactured sealing material for liquid crystal display device and is manufactured using the sealing material for liquid crystal display device Conductive material up and down and liquid crystal display element.
Detailed description of the invention
Fig. 1 be schematically show using each sealing material for liquid crystal display device for obtaining in embodiment and comparative example and With the sectional view of liquid crystal display element made by the state of no light shielding part.
Fig. 2 be schematically show using each sealing material for liquid crystal display device for obtaining in embodiment and comparative example and To there is the sectional view of liquid crystal display element made by the state of light shielding part.
Specific embodiment
Embodiment is enumerated below, is further elaborated with the present invention, but the present invention is not limited to these embodiments.
(production of polymerizable monomer A)
By R shown in 16.5 parts by weight of formula (2-1) compound represented and formula (6-1)1For 6.4 weight of compound of hydrogen Part, in the PS-PPH3 as basic catalyst, (Biotage Japan corporation has supported triphenyl in polystyrene (PS) The basic catalyst of phosphine) in the presence of 0.7 parts by weight, is reacted in 110 DEG C when stirring 48 hours, thus obtain formula (7- 1) R shown in1For the compound (polymerizable monomer A) of hydrogen.
It should be noted that R shown in formula (2-1) compound represented and formula (6-1)1For the match ratio of the compound of hydrogen Example is using molar ratio computing as formula (2-1) compound represented: R shown in formula (6-1)1For compound=2:1 of hydrogen.
(production of high-molecular compound A)
By obtained 10 parts by weight of polymerizable monomer A in 0.5 parts by weight of azodiisobutyronitrile as polymerization initiator In the presence of stirred 7 hours when carrying out nitrogen displacement at 70 DEG C, while being reacted, thus obtain high-molecular compound A.Gained The number-average molecular weight of the high-molecular compound A arrived is 14200 (degree of polymerization 50).
(production of polymerizable monomer B)
By R shown in 16.5 parts by weight of formula (2-2) compound represented and formula (6-1)1For 5.5 weight of compound of hydrogen Part, in the PS-PPH3 as basic catalyst, (Biotage Japan corporation has supported triphenyl in polystyrene (PS) The basic catalyst of phosphine) in the presence of 0.7 parts by weight, is reacted in 110 DEG C when stirring 48 hours, thus obtain formula (7-2) institute The R shown1For the compound (polymerizable monomer B) of hydrogen.
It should be noted that R shown in formula (2-2) compound represented and formula (6-1)1For the match ratio of the compound of hydrogen Example is using molar ratio computing as formula (2-2) compound represented: R shown in formula (6-1)1For compound=85.3 of hydrogen: 42.9.
(production of high-molecular compound B)
By obtained 10 parts by weight of polymerizable monomer B in 0.5 parts by weight of azodiisobutyronitrile as polymerization initiator In the presence of stirred 7 hours when carrying out nitrogen displacement at 70 DEG C, while being reacted, thus obtain high-molecular compound B.Gained The number-average molecular weight of the high-molecular compound B arrived is 12900 (degree of polymerization 40).
(production of polymerizable monomer C)
By R shown in 16.5 parts by weight of formula (2-3) compound represented and formula (6-1)1For 4.1 weight of compound of hydrogen Part, in the PS-PPH3 as basic catalyst, (Biotage Japan corporation has supported triphenyl in polystyrene (PS) The basic catalyst of phosphine) in the presence of 0.7 parts by weight, is reacted in 110 DEG C when stirring 48 hours, thus obtain formula (7- 3) R shown in1For the compound (polymerizable monomer C) of hydrogen.
It should be noted that R shown in formula (2-3) compound represented and formula (6-1)1For the match ratio of the compound of hydrogen Example is using molar ratio computing as formula (2-3) compound represented: R shown in formula (6-1)1For compound=63.2 of hydrogen: 32.0.
(production of high-molecular compound C)
By obtained 10 parts by weight of polymerizable monomer C in 0.5 parts by weight of azodiisobutyronitrile as polymerization initiator In the presence of stirred 7 hours when carrying out nitrogen displacement at 70 DEG C, while being reacted, thus obtain high-molecular compound C.Gained The number-average molecular weight of the high-molecular compound C arrived is 10200 (degree of polymerization 26).
(production of polymerizable monomer D)
By all R shown in 16.5 parts by weight of formula (2-1) compound represented and formula (6-2)2For the compound of methoxyl group 11.8 parts by weight, in the PS-PPH3 as basic catalyst, (Biotage Japan corporation supports in polystyrene (PS) The basic catalyst of triphenylphosphine) in the presence of 0.7 parts by weight, reacted in 110 DEG C when stirring 48 hours, thus To formula (7-4) compound represented (polymerizable monomer D).
It should be noted that all R shown in formula (2-1) compound represented and formula (6-2)2Match for the compound of methoxyl group Composition and division in a proportion example is using molar ratio computing as formula (2-1) compound represented: all R shown in formula (6-2)2For compound=2 of methoxyl group: 1.
(production of high-molecular compound D)
By obtained polymerizable monomer D10 parts by weight in 0.5 parts by weight of azodiisobutyronitrile as polymerization initiator In the presence of stirred 7 hours when carrying out nitrogen displacement at 70 DEG C, while being reacted, thus obtain high-molecular compound D.Gained The number-average molecular weight of the high-molecular compound D arrived is 8900 (degree of polymerization 22).
(production of polymerizable monomer E)
By R shown in 16.5 parts by weight of formula (5-1) compound represented and formula (6-1)1For 3.7 parts by weight of compound of hydrogen In the PS-PPH3 as basic catalyst, (Biotage Japan corporation has supported triphenylphosphine in polystyrene (PS) Basic catalyst) reacted in 110 DEG C when stirring 48 hours in the presence of 0.7 parts by weight, thus obtain formula (8-1) institute The R shown1For the compound (polymerizable monomer E) of hydrogen.
It should be noted that R shown in formula (5-1) compound represented and formula (6-1)1For the match ratio of the compound of hydrogen Example is using molar ratio computing as formula (5-1) compound represented: R shown in formula (6-1)1For compound=57.63:28.9 of hydrogen.
(production of high-molecular compound E)
By obtained polymerizable monomer E10 parts by weight in ethyl alcohol 20.0g, water 0.5g and as the 6N- salt of acid catalyst It stirs 4 hours, while being reacted at 70 DEG C when carrying out nitrogen circulation in the presence of sour 0.6 parts by weight, thus obtain macromolecule Compound E.The number-average molecular weight of obtained high-molecular compound E is 15200 (degree of polymerization 37).
(production of polymerizable monomer F)
By R shown in 16.5 parts by weight of formula (5-2) compound represented and formula (6-1)1For 4.7 weight of compound of hydrogen Part, in the PS-PPH3 as basic catalyst, (Biotage Japan corporation has supported triphenyl in polystyrene (PS) The basic catalyst of phosphine) in the presence of 0.7 parts by weight, is reacted in 110 DEG C when stirring 48 hours, thus obtain formula (8- 2) R shown in1For the compound (polymerizable monomer F) of hydrogen.
It should be noted that R shown in formula (5-2) compound represented and formula (6-1)1For the match ratio of the compound of hydrogen Example is using molar ratio computing as formula (5-2) compound represented: R shown in formula (6-1)1For compound=72.3 of hydrogen: 36.7.
(production of high-molecular compound F)
By obtained 10 parts by weight of polymerizable monomer F in ethyl alcohol 20.0g, water 0.5g and as the 6N- salt of acid catalyst It stirs 4 hours, while being reacted at 70 DEG C when carrying out nitrogen circulation in the presence of sour 0.6 parts by weight, thus obtain macromolecule Compound F.The number-average molecular weight of obtained high-molecular compound F is 16500 (degree of polymerization 46).
(production of polymerizable monomer G)
By all R shown in 16.5 parts by weight of formula (5-1) compound represented and formula (6-2)2For the compound of methoxyl group In the PS-PPH3 as basic catalyst, (Biotage Japan corporation supports 6.8 parts by weight in polystyrene (PS) The basic catalyst of triphenylphosphine) 0.7 parts by weight in 110 DEG C while stir 48 hours while reacted, thus obtain formula (8-3) institute The compound (polymerizable monomer G) shown.
It should be noted that all R shown in formula (5-1) compound represented and formula (6-2)2For the compound of methoxyl group Mixing ratio using molar ratio computing as formula (5-1) compound represented: all R shown in formula (6-2)2For the compound of methoxyl group =57.6:28.8.
(production of high-molecular compound G)
By obtained polymerizable monomer G10 parts by weight in ethyl alcohol 20.0g, water 0.5g and as the 6N- salt of acid catalyst It stirs 4 hours, while being reacted in 70 DEG C when carrying out nitrogen circulation in the presence of sour 0.6 parts by weight, thus obtain macromolecule Compound G.The number-average molecular weight of obtained high-molecular compound G is 7600 (degree of polymerization 15).
(embodiment 1~17, comparative example 1)
According to documented match ratio in table 1,2, planetary stirring machine (Thinky corporation, " あ わ と り are usedToo Youth ") by after the mixing of each material, it further uses three-roller and is mixed, thus prepare each liquid of embodiment 1~17, comparative example 1 Crystal display element sealant.
<evaluation>
Each sealing material for liquid crystal display device obtained in embodiment and comparative example is conducted the following evaluation.It will knot Fruit is shown in table 1,2.
(photo-curable)
It is coated in embodiment and comparative example in such a way that the gap after glass adhering substrate is about 5 μm on the glass substrate Obtained each sealing material for liquid crystal display device, is overlapped the glass substrate of identical size on the substrate, then, uses metal halogen Compound light irradiation 100mW/cm2Ultraviolet light (wavelength 365nm) 10 seconds.Using infrared spectroscopy device (BIORAD corporation, " FTS3000 "), measurement is originated from variable quantity of the peak of (methyl) acryloyl group before and after light irradiation, thus carries out photo-curable Evaluation.Opisthogenesis will be irradiated in light and be used as " ◎ " from the situation that the peak of (methyl) acryloyl group reduces 93% or more, will irradiate in light The case where opisthogenesis reduces 85% more than and less than 93% from the peak of (methyl) acryloyl group will irradiate opisthogenesis certainly in light as "○" The case where peak of (methyl) acryloyl group reduces 75% more than and less than 85% is used as " △ ", will irradiate opisthogenesis from (methyl) in light The case where reduction at the peak of acryloyl group is less than 75% is as "×", to have rated photo-curable.
(liquid crystal pollution)
It is micro- to disperse spacer in 100 parts by weight of each sealing material for liquid crystal display device obtained in embodiment and comparative example Grain (ponding chemical industrial company system, " Micropearl SI-H050 ") 1 parts by weight and sealing material for liquid crystal display device is made, An on piece in 2 substrates with alignment films and transparent electrode after grinding is in a manner of the line width 1mm for making sealant It is coated using distributor.
Then the tiny droplets of liquid crystal (Chisso corporation, " JC-5004LA ") are dripped and is applied to transparent electrode In the frame of the sealant of substrate in entire surface, it is bonded another colour filtering chip basic board with transparent electrode immediately, uses metal halide Object lamp is to sealant partial illumination 100mW/cmm2Ultraviolet light (wavelength 365nm) 30 seconds and be allowed to solidify, further with 120 DEG C It heats 1 hour and obtains liquid crystal display element.
It has made the following two kinds liquid crystal display element: having used the application place of distributor control sealant and make sealant The liquid crystal display element (no light shielding part) arrived completely by illumination；And it is taken with the 50% of line width with the black matrix" of colour filtering chip basic board The mode connect is coated with liquid crystal display element obtained by sealant (having light shielding part).Fig. 1 is to schematically show use in embodiment With each sealing material for liquid crystal display device obtained in comparative example and with liquid crystal display element made by the state of no light shielding part Sectional view, Fig. 2 is to schematically show to use each sealing material for liquid crystal display device for obtaining in embodiment and comparative example And the sectional view to there is liquid crystal display element made by the state of light shielding part.As shown in Figure 1, without light shielding part on sealant 1 Liquid crystal display element is the state that sealant 1 is arrived by illumination completely, on the other hand, there is the liquid crystal display of light shielding part on sealant 1 Element is as shown in Fig. 2, the sealant 1 of the part contacted with liquid crystal 3 is covered by black matrix" 2 and completely according to less than light.
100 hours operation tests are carried out to obtained liquid crystal display element, then by visual observation to reaching at 80 DEG C The liquid crystal aligning disorder near sealant after the lower state for applying 1000 hours voltage is confirmed.
Orientation disorder judged by the irregular colour of display unit, will absolutely not face according to the degree of irregular colour The situation of color unevenness is evaluated as " ◎ ", comments the situation for slightly having the case where irregular colour to be evaluated as "○", lacking irregular colour Valence is " △ ", the considerable situation of irregular colour is evaluated as "×", to have rated liquid crystal pollution.
It should be noted that being evaluated as " ◎ ", the grade that the liquid crystal display element of "○" is absolutely not problem on practical.
[table 1]
[table 2]
Industrial availability
According to the present invention it is possible to provide the high sensitivity of light low to the pollution of liquid crystal, to long wavelength, sensitization effect Excellent polymerizable monomer and by high-molecular compound obtained from polymerizable monomer polymerization.In addition, according to the present invention, The Photocurable resin composition containing the polymerizable monomer and/or the high-molecular compound can be provided, using the photocuring Property resin combination and manufactured sealing material for liquid crystal display device and using manufactured by the sealing material for liquid crystal display device Conductive material up and down and liquid crystal display element.
Symbol description
1, sealant
2, black matrix"
3, liquid crystal

Claims (8)

1. a kind of sealing material for liquid crystal display device, which is characterized in that be using containing curable resin and polymerizable monomer And/or the Photocurable resin composition of high-molecular compound obtained from polymerizable monomer polymerization is manufactured, In,
The polymerizable monomer is to keep dialkyl amino yl benzoic acid based compound and epoxide with unsaturated double-bond anti- Polymerizable monomer obtained from answering makes dialkyl amino yl benzoic acid based compound and the epoxy compound with alkoxysilyl Polymerizable monomer obtained from object reaction or make with can with the thioxanthone derivates of the functional group of epoxy reaction with have Polymerizable monomer obtained from the epoxide reaction of alkoxysilyl,
It is described have can with the thioxanthone derivates of the functional group of epoxy reaction be following formula (3) compound represented,
In formula (3), X is hydrogen, group shown in hydroxyl or following formula (4), and each X can be the same or different, but at least one X For group shown in hydroxyl or following formula (4),
2. sealing material for liquid crystal display device according to claim 1, which is characterized in that dialkyl amino yl benzoic acid system Conjunction object be following formula (2-1) compound represented or formula (2-2) compound represented,
3. sealing material for liquid crystal display device according to claim 1, which is characterized in that thioxanthone derivates are following formula (5-1) or formula (5-2) compound represented,
4. sealing material for liquid crystal display device according to claim 1,2 or 3, which is characterized in that under epoxide is Formula (6-1) or formula (6-2) compound represented are stated,
In formula (6-1), R1Indicate hydrogen or methyl, in formula (6-2), R2The alkyl or carbon number that expression carbon number is 1~10 are 1~10 Alkoxy, each R2It can be the same or different, at least one R2It is the alkoxy that carbon number is 1~10.
5. sealing material for liquid crystal display device according to claim 1,2 or 3, which is characterized in that high-molecular compound The degree of polymerization is 3 or more.
6. sealing material for liquid crystal display device according to claim 1,2 or 3, which is characterized in that light-cured resin group It closes object and contains opacifier.
7. a kind of conductive material up and down, which is characterized in that contain liquid crystal display element described in claim 1,2,3,4,5 or 6 With sealant and electrically conductive microparticle.
8. a kind of liquid crystal display element, which is characterized in that be using the member of liquid crystal display described in claim 1,2,3,4,5 or 6 Part sealant or it is as claimed in claim 7 up and down conductive material and manufacture.
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