CN110325904A - 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 PDFInfo
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- CN110325904A CN110325904A CN201880014052.0A CN201880014052A CN110325904A CN 110325904 A CN110325904 A CN 110325904A CN 201880014052 A CN201880014052 A CN 201880014052A CN 110325904 A CN110325904 A CN 110325904A
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- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- 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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Abstract
The object of the present invention is to provide coating, curability and the excellent sealing material for liquid crystal display device of low liquid crystal pollution.It is further an object that providing using the sealing material for liquid crystal display device and manufactured conductive material and liquid crystal display element up and down.The present invention is a kind of sealing material for liquid crystal display device, it is the sealing material for liquid crystal display device containing curable resin and polymerization initiator, wherein, above-mentioned curable resin contains part (methyl) acrylic acid modified phenol aldehyde type epoxy resin (A), partially (methyl) acrylic acid modified non-phenol aldehyde type epoxy resin (B) and non-phenolic epoxy (methyl) acrylate (C), the content of the acrylic acid modified phenol aldehyde type epoxy resin of above-mentioned part (methyl) (A) is in above-mentioned 100 parts by weight of curable resin for more than 3 parts by weight and below 9 parts by weight, the content of the above-mentioned acrylic acid modified non-phenol aldehyde type epoxy resin (B) of part (methyl) is in above-mentioned 100 parts by weight of curable resin for below 25 parts by weight, and the above-mentioned acrylic acid modified non-phenol aldehyde type epoxy resin (B) of part (methyl) is relative to above-mentioned Partially the ratio of (methyl) acrylic acid modified phenol aldehyde type epoxy resin (A) is 1 or more, the content of above-mentioned non-phenolic epoxy (methyl) acrylate (C) is 10 parts by weight or more and 45 parts by weight in above-mentioned 100 parts by weight of curable resin hereinafter, the weight average molecular weight of above-mentioned part (methyl) acrylic acid modified phenol aldehyde type epoxy resin (A) is 700 or more and 2000 or less.
Description
Technical field
The present invention relates to coating, curability and the excellent sealing material for liquid crystal display device of low liquid crystal pollution.In addition,
The present invention relates to use the sealing material for liquid crystal display device and manufactured conductive material and liquid crystal display element up and down.
Background technique
In recent years, the manufacturing method as liquid crystal display elements such as liquid crystal displays, from shortening productive temp time, liquid
From the perspective of brilliant dosage optimizes, the open such technique of referred to as dripping of patent document 1, patent document 2 is used
Liquid crystal drop under type, the technique of dripping have used photo-thermal and the sealant with curing type.
In technique of dripping, firstly, forming oblong-shaped on one in two electroded substrates by distributing
Seal pattern.Then, the tiny droplets of liquid crystal are dripped in the sealing frame of substrate in the state that sealant is uncured, true
Sky is lower to be overlapped another substrate, and irradiates the light such as ultraviolet light to sealing to carry out precuring.Thereafter, it heats main solid to carry out
Change, makes liquid crystal display element.Now, which becomes the mainstream of the manufacturing method of liquid crystal display element.
However, in the modern times that the various mobile devices for being attached to liquid crystal display panels such as mobile phone, portable game become increasingly popular,
The miniaturization of device is most highly desirable project.As the method for miniaturization, the narrow architrave of liquid crystal display part, example can be enumerated
As configure the position of sealing the operation under black matrix (hereinafter also referred to narrow architrave design).
Designed along with such narrow architrave, in liquid crystal display element, from pixel region until sealant away from
It is close from change, there is a problem of becoming easy generation display unevenness because liquid crystal is polluted by sealant.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-133794 bulletin
Patent document 2: International Publication No. 02/092718
Summary of the invention
Problems to be solved by the invention
The object of the present invention is to provide coating, curability and excellent used for liquid crystal display element of low liquid crystal pollution
Sealant.It is further an object that providing using the sealing material for liquid crystal display device and manufactured conductive material up and down
Material and liquid crystal display element.
The method used for solving the problem
The present invention is a kind of sealing material for liquid crystal display device, is the liquid crystal containing curable resin and polymerization initiator
Display element sealant, wherein above-mentioned curable resin contains part (methyl) acrylic acid modified phenol aldehyde type epoxy resin
(A), part (methyl) acrylic acid modified non-phenol aldehyde type epoxy resin (B) and non-phenolic epoxy (methyl) acrylate (C), on
The content for stating part (methyl) acrylic acid modified phenol aldehyde type epoxy resin (A) is 3 weights in above-mentioned 100 parts by weight of curable resin
Part or more is measured and 9 parts by weight hereinafter, the content of above-mentioned part (methyl) acrylic acid modified non-phenol aldehyde type epoxy resin (B) is above-mentioned
It is 25 parts by weight in 100 parts by weight of curable resin hereinafter, and above-mentioned part (methyl) acrylic acid modified non-phenolic epoxy tree
Rouge (B) is 1 or more relative to the ratio of above-mentioned part (methyl) acrylic acid modified phenol aldehyde type epoxy resin (A), above-mentioned non-phenolic aldehyde
The content of type ring oxygen (methyl) acrylate (C) is 10 parts by weight or more and 45 weights in above-mentioned 100 parts by weight of curable resin
Part is measured hereinafter, the weight average molecular weight of above-mentioned part (methyl) acrylic acid modified phenol aldehyde type epoxy resin (A) is 700 or more and 2000
Below.
The present invention described below.
The present inventor has studied to improve the low liquid crystal pollution of sealing material for liquid crystal display device using molecular weight
Higher part (methyl) acrylic modified epoxy resin is as curable resin.However, using this curable resin
In the case of, the coating of gained sealing material for liquid crystal display device, curability are deteriorated sometimes.Thus, present inventors studied will
Partially (methyl) acrylic acid modified phenol aldehyde type epoxy resin, part (methyl) acrylic acid modified non-phenol aldehyde type epoxy resin and non-phenol
Aldehyde type ring oxygen (methyl) acrylate is applied in combination in a manner of respectively reaching specific content ratio.The result found that can
Coating, curability and the excellent sealing material for liquid crystal display device of low liquid crystal pollution are obtained, so as to complete the present invention.
Sealing material for liquid crystal display device of the invention contains curable resin.
Above-mentioned curable resin contains part (methyl) acrylic acid modified phenol aldehyde type epoxy resin (A) (hereinafter also referred to
" (A) ingredient "), part (methyl) acrylic acid modified non-phenol aldehyde type epoxy resin (B) (hereinafter also referred to " (B) ingredient ") and non-phenol
Aldehyde type ring oxygen (methyl) acrylate (C) (hereinafter also referred to " (C) ingredient ").By respectively reaching aftermentioned range with content ratio
Mode contain above-mentioned (A) ingredient, above-mentioned (B) ingredient and above-mentioned (C) ingredient, thus sealing used for liquid crystal display element of the invention
Coating, curability and the low liquid crystal pollution of agent become excellent.
It should be noted that above-mentioned " part (methyl) acrylic acid modified phenol aldehyde type epoxy resin " refers in this specification:
A part of epoxy group and (methyl) acrylic acid of phenol aldehyde type epoxy resin react and have imported the tree of (methyl) acryloyl group
Rouge.
Above-mentioned " part (methyl) acrylic acid modified non-phenol aldehyde type epoxy resin " refers to: the not epoxy resin of phenol aldehyde type
A part of epoxy group and (methyl) acrylic acid of (hereinafter also referred to " non-phenol aldehyde type epoxy resin ") react and have imported (first
Base) acryloyl group resin.
Above-mentioned " non-phenolic epoxy (methyl) acrylate " refers to: whole epoxy groups of non-phenol aldehyde type epoxy resin with
(methyl) acrylic acid reacts and has imported the substance of (methyl) acryloyl group.
Above-mentioned " (methyl) acrylic compounds " refer to acrylic compounds or methacrylic, and " (methyl) acrylate " refers to third
Olefin(e) acid ester or methacrylate, " (methyl) acryloyl group " refer to acryloyl group or methylacryloyl.
Above-mentioned (A) ingredient be phenol aldehyde type, therefore, from the viewpoint of low liquid crystal pollution, even if make molecular weight become compared with
Height, viscosity rising is also slow, is not easy to deteriorate coating.
The lower limit of the weight average molecular weight of above-mentioned (A) ingredient is 700, the upper limit 2000.By keeping the weight of above-mentioned (A) ingredient equal
Molecular weight is 700 or more, and the low liquid crystal pollution of gained sealing material for liquid crystal display device becomes excellent.By making above-mentioned (A)
The weight average molecular weight of ingredient is 2000 hereinafter, the coating of gained sealing material for liquid crystal display device becomes excellent.Above-mentioned (A) at
It is preferably 1500 that the lower limit for the weight average molecular weight divided, which is preferably the 750, upper limit, and lower limit is more preferably the 800, upper limit and is more preferably
1200。
It should be noted that above-mentioned weight average molecular weight is using gel permeation chromatography (GPC) and to use four in this specification
Hydrogen furans is measured as solvent, and the value found out using polystyrene conversion.It is based on gathering as measuring using GPC
The pillar when weight average molecular weight of styrene conversion, can enumerate such as Shodex LF-804 (Showa electrician corporation).
As above-mentioned (A) ingredient, such as acrylic acid modified phenol novolak type epoxy in part (methyl), portion can be enumerated
Divide (methyl) acrylic acid modified o-cresol phenol aldehyde type epoxy resin, part (methyl) acrylic acid modified dicyclopentadiene phenolic type ring
Oxygen resin, part (methyl) acrylic acid modified biphenyl phenol aldehyde type epoxy resin, part (methyl) acrylic acid modified naphthol novolac type
Epoxy resin etc..Wherein, preferably part (methyl) acrylic acid modified phenol novolak type epoxy.
Above-mentioned (A) ingredient can be by making a part of epoxy group of phenol aldehyde type epoxy resin conventionally in base catalysis
In the presence of agent with (methyl) acrylic acid react and in above-mentioned (A) ingredient, phenol aldehyde type epoxy resin and phenolic epoxy (first
Base) acrylate mixture in obtain.
It should be noted that above-mentioned " phenolic epoxy (methyl) acrylate " refers to: phenolic epoxy in this specification
The whole epoxy groups and (methyl) acrylic acid of resin react and have imported the substance of (methyl) acryloyl group.
As the phenol aldehyde type epoxy resin for the raw material for becoming above-mentioned (A) ingredient, such as phenol novolak type epoxy can be enumerated
Resin, o-cresol phenol aldehyde type epoxy resin, dicyclopentadiene phenolic type epoxy resin, biphenyl phenol aldehyde type epoxy resin, naphthols phenol
Aldehyde type epoxy resin etc..
Lower limit of the content of above-mentioned (A) ingredient in above-mentioned 100 parts by weight of curable resin is 3 parts by weight, the upper limit is 9 weights
Measure part.More than 3 parts by weight of content by making above-mentioned (A) ingredient, the low liquid crystal of gained sealing material for liquid crystal display device is dirty
Metachromia becomes excellent.As make above-mentioned (A) ingredient 9 parts by weight of content hereinafter, obtained by sealing material for liquid crystal display device
Coating becomes excellent.It is preferably 8 parts by weight that the lower limit of the content of above-mentioned (A) ingredient, which is preferably 4 parts by weight, the upper limit, and the upper limit is more
Preferably 7 parts by weight.
As above-mentioned (B) ingredient, such as part (methyl) Acryrylic acid modified bisphenol A epoxy resin, part can be enumerated
(methyl) acrylic acid modified bisphenol f type epoxy resin, part (methyl) acrylic acid modified bisphenol E-type epoxy resin, part (first
Base) acrylic acid modified bisphenol-s epoxy resin, part (methyl) acrylic acid modified 2,2 '-diallyl bisphenol type asphalt mixtures modified by epoxy resin
Rouge, part (methyl) acrylic acid modified A Hydrogenated Bisphenol A type epoxy resin, the addition of part (methyl) acrylated epoxy propane are double
Phenol A type epoxy resin, part (methyl) acrylic acid modified resorcinol type epoxy resin, part (methyl) acrylic acid modified biphenyl
Type epoxy resin, part (methyl) acrylic acid modified sulfide type epoxy resin, part (methyl) acrylic acid modified diphenyl ether
Type epoxy resin, part (methyl) acrylic acid modified dicyclopentadiene-type epoxy resin, part (methyl) acrylic acid modified naphthalene type
Epoxy resin, part (methyl) acrylic acid modified glycidyl amine type epoxy resin, part (methyl) acrylic acid modified alkyl are more
First alcohol type epoxy resin, part (methyl) acrylic acid modified modified rubber type epoxy resin etc..Wherein, preferably partially (methyl)
Acryrylic acid modified bisphenol A epoxy resin.
Above-mentioned (B) ingredient can be by urging a part of epoxy group of non-phenol aldehyde type epoxy resin conventionally in alkalinity
In the presence of agent with (methyl) acrylic acid react and in above-mentioned (B) ingredient, non-phenol aldehyde type epoxy resin and non-phenol aldehyde type
It is obtained in the mixture of epoxy (methyl) acrylate.
As the non-phenol aldehyde type epoxy resin for the raw material for becoming above-mentioned (B) ingredient, such as bisphenol type epoxy tree can be enumerated
Rouge, bisphenol f type epoxy resin, bisphenol E-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, sulfide type epoxy resin, diphenyl ether type epoxy, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin,
Glycidyl amine type epoxy resin, alkyl polyols type epoxy resin, modified rubber type epoxy resin etc..
The upper limit of the content of above-mentioned (B) ingredient in above-mentioned 100 parts by weight of curable resin is 25 parts by weight.On making
The content for stating above-mentioned (B) ingredient in 100 parts by weight of curable resin is 25 parts by weight hereinafter, gained is used for liquid crystal display element close
The low liquid crystal pollution of envelope agent becomes excellent.The upper limit of the content of above-mentioned (B) ingredient in above-mentioned 100 parts by weight of curable resin
Preferably 22 parts by weight, the upper limit are more preferably 20 parts by weight.
In addition, above-mentioned (B) ingredient is 1 or more relative to the ratio of above-mentioned (A) ingredient.By keeping above-mentioned (B) ingredient opposite
It is 1 or more in the ratio of above-mentioned (A) ingredient, the coating of gained sealing material for liquid crystal display device becomes excellent.Above-mentioned (B) at
Split-phase is preferably that 1.2, lower limit is more preferably 1.5 for the lower limit of the ratio of above-mentioned (A) ingredient.
It should be noted that " ratio of above-mentioned (B) ingredient relative to above-mentioned (A) ingredient " refers to containing for above-mentioned (B) ingredient
Amount/above-mentioned (A) ingredient content.
As above-mentioned (C) ingredient, such as bisphenol type epoxy (methyl) acrylate, bisphenol F type epoxy (first can be enumerated
Base) acrylate, bisphenol E-type epoxy (methyl) acrylate, bisphenol S type epoxy (methyl) acrylate, 2,2 '-diallyls
Bisphenol type epoxy (methyl) acrylate, A Hydrogenated Bisphenol A type ring oxygen (methyl) acrylate, propylene oxide addition bisphenol-A type ring
Oxygen (methyl) acrylate, resorcinol type ring oxygen (methyl) acrylate, biphenyl type epoxy (methyl) acrylate, sulfide
Type ring oxygen (methyl) acrylate, diphenyl ether type ring oxygen (methyl) acrylate, dicyclopentadiene type epoxy (methyl) propylene
Acid esters, naphthalene type ring oxygen (methyl) acrylate, glycidyl amine epoxy (methyl) acrylate, alkyl polyols type ring oxygen
(methyl) acrylate, modified rubber type ring oxygen (methyl) acrylate etc..Wherein, preferably bisphenol type epoxy (methyl) third
Olefin(e) acid ester.
Above-mentioned (C) ingredient can be by making whole epoxy groups of non-phenol aldehyde type epoxy resin conventionally in base catalysis
It reacts in the presence of agent with (methyl) acrylic acid to obtain.
As the non-phenol aldehyde type epoxy resin for the raw material for becoming above-mentioned (C) ingredient, it can enumerate and become above-mentioned (B) ingredient
Raw material the identical resin of non-phenol aldehyde type epoxy resin.
Lower limit of the content of above-mentioned (C) ingredient in above-mentioned 100 parts by weight of curable resin is 10 parts by weight, the upper limit 45
Parts by weight.It is more than 10 parts by weight of content by making above-mentioned (C) ingredient in above-mentioned 100 parts by weight of curable resin, gained
The photo-curable of sealing material for liquid crystal display device becomes excellent.By make above-mentioned (C) ingredient 45 parts by weight of content hereinafter,
The cementability of gained sealing material for liquid crystal display device becomes excellent.Above-mentioned (C) in above-mentioned 100 parts by weight of curable resin at
Point the lower limit of content be preferably that 14 parts by weight, lower limit are more preferably 18 parts by weight.
In sealing material for liquid crystal display device of the invention, within the scope without prejudice to the object of the present invention, as above-mentioned solid
The property changed resin and can be further containing other polymerizable compounds.
As above-mentioned other polymerizable compounds, for example above-mentioned phenol aldehyde type epoxy resin, above-mentioned non-phenolic aldehyde can be enumerated
Type epoxy resin, above-mentioned phenolic epoxy (methyl) acrylate, others (methyl) acrylic compounds etc..
As above-mentioned other (methyl) acrylic compounds, the compound for example by making that there is hydroxyl can be enumerated
(methyl) acrylate compounds obtained from reacting with (methyl) acrylic acid make (methyl) acrylic acid with hydroxyl spread out
Carbamate (methyl) acrylate obtained from biology reacts with isocyanate compound etc..
From the viewpoint of reactivity, above-mentioned others (methyl) acrylic compounds have 2 preferably in 1 molecule
Above (methyl) acryloyl group.
As the monofunctional compound among above-mentioned (methyl) acrylate compounds, such as (methyl) propylene can be enumerated
Sour methyl esters, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) i-butyl
Ester, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) acrylic acid
Different monooctyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid
Different myristin, (methyl) stearyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester,
(methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) cyclohexyl acrylate, (methyl) acrylic acid
Isobornyl thiocyanoacetate, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2- methoxy acrylate, (first
Base) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- butoxyethyl, (methyl) acrylic acid 2- phenoxy ethyl, methoxy
Ethyl glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group diethylene glycol (methyl) propylene
Acid esters, phenoxy group polyethylene glycol (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, ethyl carbitol (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) dimethylaminoethyl acrylate, (methyl) acrylic acid diethylamino
Base ethyl ester, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-
(methyl) acryloyl-oxyethyl 2- hydroxypropyl phthalate, 2- (methyl) acryloyl-oxyethyl phosphate, (first
Base) glycidyl acrylate etc..
In addition, closing object as the difunctional among above-mentioned (methyl) acrylate compounds, such as 1,3- can be enumerated
Butanediol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate,
1,9- nonanediol two (methyl) acrylate, 1,10- decanediol two (methyl) acrylate, ethylene glycol two (methyl) acrylic acid
Ester, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylic acid
Ester, 2- normal-butyl -2- ethyl -1,3-PD two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, 3 the third two
Alcohol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene oxide
Addition bisphenol-A two (methyl) acrylate, propylene oxide addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F
Two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two
(methyl) acrylate, 2- hydroxyl -3- (methyl) acryloxypropyl (methyl) acrylate, carbonate diol two (methyl)
Acrylate, polyetherdiol two (methyl) acrylate, polyester-diol two (methyl) acrylate, two (first of polycaprolactone glycol
Base) acrylate, polybutadiene diol two (methyl) acrylate etc..
In addition, example can be enumerated as the compound more than trifunctional among above-mentioned (methyl) acrylate compounds
Such as trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, epoxy
Propane addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate,
Ethyleneoxide addition isocyanuric acid three (methyl) acrylate, glycerol three (methyl) acrylate, propylene oxide addition glycerol three
(methyl) acrylate, pentaerythrite three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphates, bis- (three hydroxyls
Methylpropane) four (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid
Ester, dipentaerythritol six (methyl) acrylate etc..
It, can be for example, by making (methyl) acrylic acid with hydroxyl spread out as above-mentioned carbamate (methyl) acrylate
Biology is reacted with isocyanate compound in the presence of the tin based compound of catalytic amount to obtain.
As above-mentioned isocyanate compound, such as isophorone diisocyanate, 2,4- toluene diisocyanate can be enumerated
Acid esters, 2,6- toluene di-isocyanate(TDI), hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenylmethyl
4,4 '-diisocyanate (MDI) of alkane-, hydrogenation MDI, polymeric MDI, 1,5- naphthalene diisocyanate, norbornene alkyl diisocyanate,
Tolidine diisocyanate, benzene dimethylene diisocyanate (XDI), hydrogenation XDI, lysine diisocyanate, triphenyl
Methane triisocyanate, three (isocyanate phenyl) thiophosphates, tetramethylxylylene diisocyanate, 1,6,11-
Hendecane triisocyanate etc..
In addition, also can be used as above-mentioned isocyanate compound through polyalcohol and excessive isocyanates chemical combination
Through the isocyanate compound of chain extension obtained from the reaction of object.
As above-mentioned polyalcohol, can enumerate for example ethylene glycol, propylene glycol, glycerol, D-sorbite, trimethylolpropane,
Carbonate diol, polyetherdiol, polyester-diol, polycaprolactone glycol etc..
As above-mentioned (methyl) acrylic acid derivative with hydroxyl, for example single (methyl) dihydroxypropyl alkane can be enumerated
Base ester, list (methyl) acrylate of dihydric alcohol, list (methyl) acrylate of trihydroxylic alcohol or two (methyl) acrylate etc..
As above-mentioned list (methyl) hydroxyalkyl acrylates, can enumerate such as (methyl) acrylic acid 2- hydroxy methacrylate,
(methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl etc..
As above-mentioned dihydric alcohol, such as ethylene glycol, propylene glycol, 1,3-PD, 1,3-BDO, Isosorbide-5-Nitrae-fourth can be enumerated
Glycol, polyethylene glycol etc..
As above-mentioned trihydroxylic alcohol, can enumerate such as trimethylolethane, trimethylolpropane, glycerol.
From the viewpoint of inhibiting liquid crystal pollution, above-mentioned others (methyl) acrylic compounds preferably have-OH
Base ,-NH- base ,-NH2The unit of the hydrogen bonds such as base.
Sealing material for liquid crystal display device of the invention contains polymerization initiator.
As above-mentioned polymerization initiator, can enumerate such as radical polymerization initiator, cationic polymerization initiators.
As above-mentioned radical polymerization initiator, the optical free radical polymerization generated free radicals by light irradiation can be used
Initiator, the hot radical polymerization initiator generated free radicals by heating.
As above-mentioned optical free radical polymerization initiator, such as benzophenone cpd, acetophenone compound, acyl can be enumerated
Base phosphine oxide compound, titanocenes compound, oxime ester compound, benzoin ether compound, thioxanthone compounds etc..
As above-mentioned optical free radical polymerization initiator, specifically, such as 1- hydroxycyclohexylphenylketone, 2- can be enumerated
Benzyl -2- dimethylamino -1- (4- morphlinophenyl) butanone, 1,2- (dimethylamino) -2- ((4- aminomethyl phenyl) methyl) -
1- (4- (4- morpholinyl) phenyl) -1- butanone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, bis- (2,4,6- trimethyls
Benzoyl) phenyl phosphine oxide, 2- methyl-1-(4- methylsulfanylphenyl)-2- morpholino propane-1- ketone, 1- (4- (2- hydroxyl
Ethyoxyl)-phenyl) -2- hydroxy-2-methyl -1- propane -1- ketone, 1- (4- (phenylsulfartyl) phenyl) -1,2- acetyl caproyl 2- (O-
Benzoyl oximes), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin
Isopropyl ether etc..
Above-mentioned optical free radical polymerization initiator may be used singly or in combination of two or more.
As above-mentioned hot radical polymerization initiator, can enumerate such as comprising azo-compound, organic peroxide
Hot radical polymerization initiator.It wherein, preferably include the initiator (hereinafter also referred to " high score of polymeric azo compound
Sub- azo initiator ").
Above-mentioned hot radical polymerization initiator may be used singly or in combination of two or more.
It should be noted that polymeric azo compound refers in this specification: there is azo group and generated by heat
It can make the cured free radical of (methyl) acryloyl group, 300 or more number-average molecular weight compound.
The lower limit of the number-average molecular weight of above-mentioned polymeric azo compound is preferably that the 1000, upper limit is preferably 300,000.Pass through
Make the number-average molecular weight of the above-mentioned polymeric azo compound range, is able to suppress liquid crystal pollution and easy and curable resin
Mixing.The lower limit of the number-average molecular weight of above-mentioned polymeric azo compound is more preferably the 5000, upper limit and is more preferably 100,000, lower limit
Further preferably 10,000, the upper limit is more preferably 90,000.
It should be noted that above-mentioned number-average molecular weight is using gel permeation chromatography (GPC) and to use four in this specification
Hydrogen furans is measured as solvent, and the value found out using polystyrene conversion.It is based on gathering as measuring using GPC
The pillar when number-average molecular weight of styrene conversion, can enumerate such as Shodex LF-804 (Showa electrician corporation).
As above-mentioned polymeric azo compound, can enumerate for example with being bonded multiple polycyclic oxygen by azo group
The compound of structure obtained by the units such as alkane, dimethyl silicone polymer.
As the above-mentioned polymeric azo for having and being bonded structure obtained by the units such as multiple polyalkylene oxides by azo group
Compound preferably has polyethylene oxide structure.
As above-mentioned polymeric azo compound, specifically, such as 4 can be enumerated, 4 '-azos are bis- (4- cyanopentanoic acid)
With condensation polymer, 4, the 4 '-azos bis- (4- cyanopentanoic acids) of polyalkylene glycol and with the dimethyl silicone polymer of terminal amino group
Condensation polymer etc..
As the commercially available product among above-mentioned polymeric azo compound, can enumerate such as VPE-0201, VPE-0401,
VPE-0601, VPS-0501, VPS-1001 (being Fujiphoto and the pure medicine corporation of light) etc..
In addition, the commercially available product as not high molecular azo-compound, can enumerate such as V-65, V-501 (
For Fujiphoto and the pure medicine corporation of light) etc..
As above-mentioned organic peroxide, such as ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl group can be enumerated
Peroxide, peroxy esters, diacyl peroxide, peroxy dicarbonate etc..
As above-mentioned cationic polymerization initiators, can be suitble to using light cationic polymerization initiator.
As long as above-mentioned light cationic polymerization initiator generates Bronsted acid or lewis acid by light irradiation, without special
It limits, can be the light cationic polymerization initiator that ionic light produces acids, be also possible to the light sun that nonionic light produces acids
Cation polymerization initiator.
As above-mentioned light cationic polymerization initiator, such as aromatic diazonium salt, aromatic halonium salts, virtue can be enumerated
The salts such as fragrant race's sulfonium salt；The organic metal networks such as iron-allene complex object, titanocenes complex compound, aryl-silane alcohol-aluminium complex
Close species etc..
As commercially available product among above-mentioned light cationic polymerization initiator, such as ADEKAOPTOMER SP- can be enumerated
150, ADEKAOPTOMER SP-170 (being ADEKA corporation) etc..
The content of above-mentioned polymerization initiator lower limit for above-mentioned 100 parts by weight of curable resin is preferably 0.01 weight
Measure part, the upper limit is preferably 10 parts by weight.By making the content of the above-mentioned polymerization initiator range, thus gained liquid crystal display member
Part inhibits liquid crystal pollution with sealant, and storage stability, curability become more excellent.Under the content of above-mentioned polymerization initiator
Limit is more preferably 0.1 parts by weight, the upper limit is more preferably 5 parts by weight.
Sealing material for liquid crystal display device of the invention preferably comprises thermal curing agents.
As above-mentioned thermal curing agents, such as organic acid hydrazides, imdazole derivatives, amine compounds, polynary phenol system can be enumerated
Compound, acid anhydrides etc..Wherein, it is suitble to use solid organic acid hydrazides.
Above-mentioned thermal curing agents may be used singly or in combination of two or more.
As above-mentioned solid organic acid hydrazides, can enumerate in bis- (diazanyl the carbonyl ethyl) -5- isopropyl second of such as 1,3-
Uride, sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, acid dihydrazide etc..
As commercially available product among above-mentioned solid organic acid hydrazides, having for such as great Zhong chemical company can be enumerated
Machine acid hydrazides, organic acid hydrazides of the fine scientific & technical corporation of organic acid hydrazides, aginomoto of Japanese fine chemistry corporation etc..
As the organic acid hydrazides of above-mentioned great Zhong chemical company, can enumerate such as SDH, ADH.
As the organic acid hydrazides of above-mentioned Japanese fine chemistry corporation, can enumerate such as MDH.
As the organic acid hydrazides of the fine scientific & technical corporation of above-mentioned aginomoto, can enumerate such as AMICURE VDH,
AMICURE VDH-J, AMICURE UDH etc..
The content of above-mentioned thermal curing agents lower limit for whole 100 parts by weight of curable resin be preferably 1 parts by weight,
The upper limit is preferably 50 parts by weight.By making the content of the above-mentioned thermal curing agents range, so that gained is used for liquid crystal display element close
Coating, the storage stability that agent remains excellent are sealed, and curability becomes more excellent.The upper limit of the content of above-mentioned thermal curing agents
More preferably 30 parts by weight.
In sealing material for liquid crystal display device of the invention, for raising viscosity, further increases and disperse to imitate based on stress
The purpose of the cementability of fruit, the moisture-proof for improving linear expansivity, raising solidfied material etc., preferably comprises filler.
As above-mentioned filler, inorganic filler, organic filler can be used.
As above-mentioned inorganic filler, can enumerate for example silica, talcum, bead, asbestos, gypsum, diatomite,
Terre verte, bentonite, montmorillonite, sericite, atlapulgite, aluminium oxide, zinc oxide, iron oxide, magnesia, tin oxide, titanium oxide,
Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminium hydroxide, aluminium nitride, silicon nitride, barium sulfate, calcium silicates etc..
As above-mentioned organic filler, can enumerate for example polyester micropartical, polyurethane particulate, polyvinyl particle,
Acrylic polymer particle etc..
Above-mentioned filler may be used singly or in combination of two or more.
The lower limit of the content of above-mentioned filler in 100 parts by weight of sealing material for liquid crystal display device of the invention is preferably
10 parts by weight, the upper limit are preferably 70 parts by weight.By making the content of the above-mentioned filler range, it is able to suppress coating etc.
Deteriorate and further plays the effect for improving cementability etc..The lower limit of the content of above-mentioned filler be more preferably 20 parts by weight,
The upper limit is more preferably 60 parts by weight.
In sealing material for liquid crystal display device of the invention, from flexibility, cementability for improving solidfied material etc. or inhibit
The viewpoints such as insertion, dissolution from sealant to liquid crystal of the liquid crystal into sealant are set out, and soft particle is preferably comprised.
As above-mentioned soft particle, such as silicone-based particle, ethylene base system particle, carbamate system grain can be enumerated
Son, fluorine system particle, nitrile system particle etc..Wherein, preferably silicone-based particle, ethylene base system particle.
Above-mentioned softness particle may be used singly or in combination of two or more.
As above-mentioned silicone-based particle, dispersibility from the viewpoint of in resin, preferably silicone rubber particle.
As above-mentioned ethylene base system particle, use (methyl) acrylic particles can be suitble to.
Above-mentioned (methyl) acrylic particles can be obtained by being become the monomer generation polymerization of raw material using known method
?.Monomer is for example subjected to the method for suspension polymerisation in the presence of radical polymerization initiator, is led to specifically, can enumerate
Cross makes noncrosslinking seed particles absorb monomer and seed particles is made to be swollen and carry out in the presence of radical polymerization initiator
The method etc. of seeding polymerization.
As the monomer for being used to form the raw material of above-mentioned (methyl) acrylic particles is become, such as (methyl) can be enumerated
Alkyl-acrylates, (methyl) esters of acrylic acid containing oxygen atom, the monomer containing nitrile, fluorine-containing (methyl) esters of acrylic acid etc.
Monofunctional monomer.
As above-mentioned (methyl) alkyl-acrylates, such as (methyl) methyl acrylate, (methyl) propylene can be enumerated
Acetoacetic ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate,
(methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylic acid cetyl, (methyl) stearyl acrylate
Ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc..
As above-mentioned (methyl) esters of acrylic acid containing oxygen atom, such as (methyl) acrylic acid 2- hydroxyl second can be enumerated
Ester, (methyl) glycerol acrylate, polyoxyethylene (methyl) acrylate, (methyl) glycidyl acrylate etc..
As the above-mentioned monomer containing nitrile, such as (methyl) acrylonitrile etc. can be enumerated.
As above-mentioned fluorine-containing (methyl) esters of acrylic acid, such as (methyl) acrylic acid trifluoromethyl ester, (first can be enumerated
Base) five fluorine ethyl ester etc. of acrylic acid.
Wherein, low from the Tg of homopolymer, it sets out in terms of being capable of increasing deflection when applying 1g load, preferably (first
Base) alkyl-acrylates.
In addition, in order to make it have cross-linked structure, as the original for being used to form above-mentioned (methyl) acrylic particles
The monomer of material, and polyfunctional monomer can be used.
As above-mentioned polyfunctional monomer, such as tetramethylol methane four (methyl) acrylate, tetra methylol can be enumerated
Methane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid
Ester, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerol three (methyl) acrylic acid
Ester, glycerol two (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propylene glycol two (methyl) acrylic acid
Ester, (poly-) tetramethylene two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycol two (methyl)
Acrylate, isocyanuric acid skeleton three (methyl) acrylate etc..Wherein, big from molecular weight between crosslinking points, it is capable of increasing application
It sets out in terms of deflection when 1g load, preferably (poly-) ethylene glycol two (methyl) acrylate, two (first of (poly-) propylene glycol
Base) acrylate, (poly-) tetramethylene two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6- oneself two
Alcohol two (methyl) acrylate.
The dosage of above-mentioned cross-linkable monomer is used to form the monomer of the raw material of above-mentioned (methyl) acrylic particles becoming
It is preferably 90 weight % that whole lower limit, which is preferably 1 weight %, the upper limit,.By 1 weight of dosage for making above-mentioned cross-linkable monomer
% or more is measured, so that solvent resistance improves, the problems such as swelling when being kneaded with other sealant ingredients, is become easy
It is evenly dispersed.By making the 90 weight % of dosage of above-mentioned cross-linkable monomer hereinafter, so as to reduce recovery rate.Above-mentioned crosslinking
The lower limit of the dosage of property monomer is more preferably 3 weight %, the upper limit is more preferably 80 weight %.
In turn, on the basis of these acrylic monomers, styrenic monomers, vinyl ethers, carboxylic can also be used
Vinyl acetate esters, unsaturated hydrocarbons, halogen-containing monomer, triallyl cyanurate, triallyl isocyanurate, tri trimellitate
Allyl ester, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ-(methyl) third
The monomers such as alkene acryloxypropylethoxysilane trimethoxy silane, vinyltrimethoxysilane.
As above-mentioned styrenic monomers, such as styrene, α-methylstyrene, trimethoxysilyl can be enumerated
Styrene etc..
As above-mentioned vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether can be enumerated
Deng.
As above-mentioned vinyl carboxylates esters, such as vinyl acetate, vinyl butyrate, vinyl laurate can be enumerated
Ester, stearic acid vinyl ester etc..
As above-mentioned unsaturated hydrocarbons, can enumerate such as ethylene, propylene, isoprene, butadiene.
As above-mentioned halogen-containing monomer, can enumerate such as vinyl chloride, vinyl fluoride, chloro styrene.
As above-mentioned (methyl) acrylic particles, can also be suitble to using core shell (methyl) acrylate copolymer particle.
As commercially available product among above-mentioned core shell (methyl) acrylate copolymer particle, such as F351 can be enumerated
(AICA industrial group system) etc..
In addition, such as polydivinylbenezene particle, polychlorobutadiene grain can be used as above-mentioned ethylene base system particle
Son, butadiene rubber particle etc..
The lower limit of the average grain diameter of above-mentioned softness particle is preferably 0.01 μm, the upper limit is preferably 10 μm.It is above-mentioned soft by making
The average grain diameter of soft particle is the range, to make the flexibility of the solidfied material of gained sealing material for liquid crystal display device, bonding
Property improve effect become more excellent.The lower limit of the average grain diameter of above-mentioned softness particle is more preferably 0.1 μm, the upper limit is more preferably
8μm。
It should be noted that the average grain diameter of above-mentioned softness particle refers to: by using laser diffraction formula in this specification
Value obtained from particle size distribution device is measured.As above-mentioned laser diffraction formula particle size distribution device, can make
With MASTERSIZER 2000 (Malvern Instruments Ltd. system) etc..
It is preferably 50 that the lower limit of the hardness of above-mentioned softness particle, which is preferably the 10, upper limit,.By making the hard of above-mentioned soft particle
Degree is the range, thus the effect for improving the flexibility of the solidfied material of resulting sealing material for liquid crystal display device, cementability
Become more excellent.The lower limit of the hardness of above-mentioned softness particle is more preferably the 20, upper limit and is more preferably 40.
It should be noted that the hardness of above-mentioned softness particle refers to: utilizing the side based on JIS K 6253 in this specification
Method and the Durometer A hardness measured.
The lower limit of the content of above-mentioned soft particle in 100 parts by weight of sealing material for liquid crystal display device of the invention is preferred
It is preferably 50 parts by weight for 5 parts by weight, the upper limit.By making the content of the above-mentioned soft particle range, to make resulting liquid
The effect that the flexibility of the solidfied material of crystal display element sealant, cementability improve becomes more excellent.Above-mentioned softness particle
The lower limit of content is more preferably 10 parts by weight, the upper limit is more preferably 30 parts by weight.
In sealing material for liquid crystal display device of the invention, for the purpose for further increasing cementability, silicon is preferably comprised
Alkane coupling agent.Above-mentioned silane coupling agent mainly has as by the work of the bonding additives of the good bondings such as sealant and substrate
With.
As above-mentioned silane coupling agent, can be suitble to using such as 3- TSL 8330,3- mercaptopropyi three
Methoxy silane, 3- glycidoxypropyltrime,hoxysilane etc..
Above-mentioned silane coupling agent may be used singly or in combination of two or more.
The lower limit of the content of above-mentioned silane coupling agent in 100 parts by weight of sealing material for liquid crystal display device of the invention is excellent
It is selected as 0.1 parts by weight, the upper limit is preferably 10 parts by weight.By making the content of the above-mentioned silane coupling agent range, so as to
Inhibit the generation of liquid crystal pollution and further plays the effect for improving cementability.The lower limit of the content of above-mentioned silane coupling agent is more
Preferably 0.3 parts by weight, the upper limit are more preferably 5 parts by weight.
Sealing material for liquid crystal display device of the invention can contain opacifier.By containing above-mentioned opacifier, thus this
The sealing material for liquid crystal display device of invention can be suitable as shading sealant.
As above-mentioned opacifier, black such as iron oxide, titanium, nigrosine, Cyanine Black, fullerene, carbon black, resin can be enumerated
Cover type carbon black etc..Wherein, preferably titanium is black.
Above-mentioned opacifier may be used singly or in combination of two or more.
Above-mentioned titanium is black be near ultraviolet range, the transmission of especially wavelength 370nm or more and 450nm light below
Rate is higher than the substance of the average transmittance for wavelength 300nm or more and 800nm light below.That is, it is under having that above-mentioned titanium is black
State the opacifier of property: to sealing used for liquid crystal display element of the invention and sufficiently covering the light of wavelength of visible light region
On the other hand agent, which assigns light-proofness, transmits the light of the wavelength near ultraviolet range.As liquid crystal display of the invention
The high substance of the opacifier contained in element sealant, preferably insulating properties, the opacifier high as insulating properties, is also suitably for
Titanium is black.
Above-mentioned titanium is black to play sufficient effect non-surface treated, but surface also can be used and be coupled agent
Treated that titanium is black for equal organic principles；It is oxidized the inorganic constituents such as silicon, titanium oxide, germanium oxide, aluminium oxide, zirconium oxide, magnesia
The surface treated titaniums such as titanium after covering is black are black.Wherein, from the viewpoint of it can further increase insulating properties, preferably had
Treated that titanium is black for machine ingredient.
In addition, using containing the black sealing material for liquid crystal display device of the invention as opacifier of above-mentioned titanium and manufacturing
Liquid crystal display element has sufficient light-proofness, therefore can be realized with high contrast without light leakage and with excellent image
The liquid crystal display element of display quality.
As above-mentioned titanium it is black among commercially available product, the titanium that can enumerate such as Mitsubishi General Materials corporation is black, red fringe
The titanium for being melted into corporation is black etc..
Titanium as above-mentioned Mitsubishi General Materials corporation is black, can enumerate such as 12S, 13M, 13M-C, 13R-N, 14M-
C etc..
Titanium as above-mentioned red fringe chemical conversion corporation is black, can enumerate such as Tilack D.
The preferred lower limit of the black specific surface area of above-mentioned titanium is 13m2/ g, preferred upper limit 30m2/ g, more preferable lower limit are
15m2/ g, the more preferable 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, preferred upper limit is 3 Ω cm, more preferably
Lower limit is 1 Ω cm, the more preferable upper limit is 2.5 Ω cm.
The primary particle size of above-mentioned opacifier as long as liquid crystal display element substrate between distance hereinafter, as long as do not limit especially
Fixed, it is preferably 5 μm that lower limit, which is preferably 1nm, the upper limit,.By making the primary particle size of the above-mentioned opacifier range, so as to make
Coating becomes more excellent without increasing the viscosity of resulting sealing material for liquid crystal display device, thixotropy substantially.Above-mentioned screening
The lower limit of the primary particle size of photo etching is more preferably 5nm, the upper limit is more preferably 200nm, lower limit be more preferably 10nm, the upper limit into
One step is preferably 100nm.
It should be noted that particle size distribution meter (such as PARTICLE can be used in the primary particle size of above-mentioned opacifier
SIZING SYSTEMS corporation, " NICOMP 380ZLS ") and above-mentioned opacifier is made to be scattered in solvent (water, organic solvent etc.)
In be measured.
The lower limit of the content of above-mentioned opacifier in 100 parts by weight of sealing material for liquid crystal display device of the invention is preferably
5 parts by weight, the upper limit are preferably 80 parts by weight.By making the content of the above-mentioned opacifier range, so as to further play
The effect of light-proofness is improved out without the intensity and description after making the cementability of resulting sealing material for liquid crystal display device, solidification
Property is greatly reduced.The lower limit of the content of above-mentioned opacifier is more preferably 10 parts by weight, the upper limit is more preferably 70 parts by weight, lower limit into
It is more preferably 60 parts by weight that one step, which is preferably 30 parts by weight, the upper limit,.
Sealing material for liquid crystal display device of the invention further can contain stress relaxation agent, reactivity as needed
Diluent shakes the additives such as change agent, spacer, curing accelerator, defoaming agent, levelling agent, polymerization inhibitor.
As the method for manufacturing sealing material for liquid crystal display device of the invention, can enumerate for example using homogenous disperse
The mixing machines such as device, mixer for well-distribution, omnipotent mixer, epicyclic mixer, kneader, triple-roller mill draw curable resin, polymerization
Hair agent and thermal curing agents, as needed method that the additives such as silane coupling agent that add are mixed etc..
Sealing material for liquid crystal display device of the invention is measured under conditions of 25 DEG C, 1rpm using E type viscosimeter
It is preferably 800Pas that the lower limit of viscosity, which is preferably 100Pas, the upper limit,.By making the above-mentioned viscosity range, thus resulting
The coating of sealing material for liquid crystal display device becomes excellent.It is more excellent that the lower limit of above-mentioned viscosity is more preferably 200Pas, the upper limit
It is selected as 700Pas.
By cooperating electrically conductive microparticle into sealing material for liquid crystal display device of the invention, led up and down so as to manufacture
Logical material.In addition, the conductive material up and down containing sealing material for liquid crystal display device and electrically conductive microparticle of the invention is also this
One of 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, the particle that conductive metal layer is formed on the surface of resin particle passes through the excellent resilience energy of resin particle
Enough the ground such as transparent substrate are not damaged to be conductively connected, so it is preferred that.
In addition, the manufactured liquid using sealing material for liquid crystal display device of the invention or conductive material up and down of the invention
Crystal display element is also one of present invention.
As the method for manufacturing liquid crystal display element of the invention, it is suitble to use liquid crystal dripping process, specifically, can arrange
It enumerates such as the method with following each process.
Liquid crystal display element can be obtained by following methods, the method carries out following process first: thin in subsidiary ITO
One in two substrates such as glass substrate, PET substrate of the electrodes such as film it is upper by silk-screen printing,
The coating sealing material for liquid crystal display device of the invention such as distributor coating and the seal pattern for forming frame-shaped；Then it carries out as follows
Process: the tiny droplets of liquid crystal are dripped in the state that sealing material for liquid crystal display device of the invention is uncured and are applied to substrate
Seal pattern frame in, be overlapped another substrate under vacuum；Thereafter, it carries out to sealing used for liquid crystal display element of the invention
The light such as the seal pattern partial illumination ultraviolet light of agent and make sealant precuring process and to the sealant through precuring into
Row heats and its is made to lead cured process.
The effect of invention
In accordance with the invention it is possible to provide coating, curability and excellent used for liquid crystal display element close of low liquid crystal pollution
Seal agent.In addition, in accordance with the invention it is possible to provide using the sealing material for liquid crystal display device and manufactured conductive material up and down and
Liquid crystal display element.
Specific embodiment
Hereinafter, showing embodiment the present invention is described in more detail, but the present invention is not merely defined in these embodiments.
(production of phenol aldehyde type curable resin mixture (A1))
Phenol novolak type epoxy (DIC corporation, " EPICLON N-740 ") 557 parts by weight are made to be dissolved in toluene
After 900mL, triphenylphosphine 0.3g is added, uniform solution is made.Time-consuming 2 hours by 122 parts by weight of acrylic acid in return stirring
Under be added dropwise to acquired solution after, 6 hours return stirrings of further progress.Then, phenolic aldehyde is obtained by decompression removal toluene
Type curable resin mixture (A1).
Pass through1H-NMR、13C-NMR and FT-IR and confirm: phenol aldehyde type curable resin mixture (A1) is containing part
Acrylic acid modified 11.8 weight % of phenol novolak type epoxy, 68.6 weight % of phenol novolak type epoxy, phenol novolac
The mixture of 19.6 weight % of type epoxy acrylate.
In addition, the weight average molecular weight of resulting part acrylic acid modified phenol phenol aldehyde type epoxy resin is 1200.
(production of phenol aldehyde type curable resin mixture (A2))
Phenol novolak type epoxy (DIC corporation, " EPICLON N-730S ") 395 parts by weight are made to be dissolved in toluene
After 900mL, triphenylphosphine 0.3g is added, uniform solution is made.Time-consuming 2 hours by 94 parts by weight of acrylic acid under return stirring
After being added dropwise to acquired solution, 6 hours return stirrings of further progress.Then, phenol aldehyde type is obtained by decompression removal toluene
Curable resin mixture (A2).
Pass through1H-NMR、13C-NMR and FT-IR and confirm: phenol aldehyde type curable resin mixture (A2) is containing part
Acrylic acid modified 11.8 weight % of phenol novolak type epoxy, 68.6 weight % of phenol novolak type epoxy, phenol novolac
The mixture of 19.6 weight % of type epoxy acrylate.
In addition, the weight average molecular weight of resulting part acrylic acid modified phenol phenol aldehyde type epoxy resin is 800.
(production of phenol aldehyde type curable resin mixture (A3))
Phenol novolak type epoxy (DIC corporation, " EPICLON N-770 ") 965 parts by weight are made to be dissolved in toluene
After 1800mL, triphenylphosphine 0.3g is added, uniform solution is made.Time-consuming 2 hours by 216 parts by weight of acrylic acid in return stirring
Under be added dropwise to acquired solution after, 6 hours return stirrings of further progress.Then, phenolic aldehyde is obtained by decompression removal toluene
Type curable resin mixture (A3).
Pass through1H-NMR、13C-NMR and FT-IR and confirm: phenol aldehyde type curable resin mixture (A3) is containing part
Acrylic acid modified 11.8 weight % of phenol novolak type epoxy, 68.6 weight % of phenol novolak type epoxy, phenol novolac
The mixture of 19.6 weight % of type epoxy acrylate.
In addition, the weight average molecular weight of resulting part acrylic acid modified phenol phenol aldehyde type epoxy resin is 2500.
(production of non-phenol aldehyde type curable resin mixture (B1))
Bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system, " jER 828EL ") 326 parts by weight are made to be dissolved in toluene 900mL
Afterwards, triphenylphosphine 0.3g is added, uniform solution is made.Time-consuming 72 parts by weight of acrylic acid was added dropwise under return stirring in 2 hours
To acquired solution, 6 hours return stirrings of further progress.Then, non-phenol aldehyde type is obtained by decompression removal toluene to consolidate
The property changed resin compound (B1).
Pass through1H-NMR、13C-NMR and FT-IR and confirm: non-phenol aldehyde type curable resin mixture (B1) is containing portion
Divide 50 weight % of Acryrylic acid modified bisphenol A epoxy resin, 25 weight % of bisphenol A type epoxy resin, bisphenol type epoxy acrylic acid
The mixture of 25 weight % of ester.
(Examples 1 to 10, comparative example 1~8)
According to the match ratio recorded in table 1,2, using planetary agitating device, (THINKY corporation, " あ ゎ と り practices too
Youth ") each material is stirred after, uniformly mixed using ceramic triple-roller mill, obtain Examples 1 to 10, comparative example 1~8
Sealing material for liquid crystal display device.
<evaluation>
For each sealing material for liquid crystal display device obtained in embodiment and comparative example, conduct the following evaluation.It will knot
Fruit is shown in table 1,2.
(viscosity)
For each sealing material for liquid crystal display device obtained in embodiment and comparative example, E type viscosimeter is used
(BROOKFIELD corporation, " DV-III "), 25 DEG C of measurement, the viscosity under the conditions of 1rpm.
(coating)
Using distributor (Musashi Engineering corporation, " SHOTMASTER300 "), by embodiment and compare
Each sealing material for liquid crystal display device coating obtained in example is on the glass substrate.Distribution nozzle is fixed between 400 μm, nozzle
Gap is fixed on 30 μm, applies pressure fixing when 300kPa is coated, the feelings that will without the style of calligraphy characterized by hollow strokes, sagging be coated
Condition is denoted as "○", although coating, which is not disconnected the case where producing the style of calligraphy characterized by hollow strokes, sagging, is denoted as " △ ", coating will have occurred and disconnect
Or the case where can not being coated with completely, is denoted as "×", to evaluate coating.
(curability)
Each sealing material for liquid crystal display device obtained in embodiment and comparative example is coated with about 5 μm on the glass substrate
Afterwards, it is overlapped the glass substrate of identical size.Then, using metal halide lamp, 3000mJ/cm is irradiated2Wavelength 365nm purple
Outside line.Using infrared spectroscopy device (BIORAD corporation, " FTS3000 "), measurement is originated from the peak of (methyl) acryloyl group in light
Irradiate the variable quantity (slip) of front and back.
The situation that the slip at the peak from (methyl) acryloyl group after light is irradiated is 95% or more is denoted as " ◎ ", is
85% more than and less than 95% the case where be denoted as "○", for 75% more than and less than 85% the case where be denoted as " △ ", less than 75%
The case where be denoted as "×", to evaluate curability.
(low liquid crystal pollution)
Cooperate the titanium dioxide of 1 weight % into each sealing material for liquid crystal display device obtained by embodiment and comparative example
Silicon spacer (ponding chemical industrial company system, " SI-H055 "), carry out deaeration processing and after removing the bubble in sealant, filling
Into the syringe (Musashi Engineering corporation, " PSY-10E ") of distribution, deaeration processing is carried out again.It connects
, using distributor (Musashi Engineering corporation, " SHOTMASTER300 "), ito thin film is attached at two
Sealant is coated in a manner of describing frame on one among glass substrate.Then, using liquid crystal Dropping feeder by TN liquid crystal
The tiny droplets dropwise addition of (CHISSO corporation, " JC-5001LA ") is applied in the frame of sealant, and it is thin to be overlapped another subsidiary ITO
The glass substrate of film, and two substrates are bonded under the decompression of 5Pa using vacuum forming apparatus.Using metal halide lamp to patch
Unit after conjunction irradiates 3000mJ/cm2Ultraviolet light after, by 120 DEG C heat 60 minutes and make sealant heat cure, thus
Produce liquid crystal display element.Gained liquid crystal display element is taken care of 100 hours in the environment of 80 DEG C of temperature, humidity 90%RH
Afterwards, the voltage driving for carrying out AC3.5V, shows the presence or absence of uneven (irregular colour) by visual observation to observe.It will not observe completely
The uneven situation of display is denoted as "○", will there is a situation where that display unevenness is denoted as " △ " in the peripheral portion of liquid crystal display element, will
Display unevenness is not only present in the peripheral portion of liquid crystal display element but also is denoted as "×" the case where diffusing to central portion, to comment
The low liquid crystal pollution of valence.
[table 1]
[table 2]
Industrial availability
In accordance with the invention it is possible to provide coating, curability and excellent used for liquid crystal display element close of low liquid crystal pollution
Seal agent.In addition, in accordance with the invention it is possible to provide using the sealing material for liquid crystal display device and manufactured conductive material up and down and
Liquid crystal display element.
Claims (3)
1. a kind of sealing material for liquid crystal display device, which is characterized in that it is the liquid containing curable resin and polymerization initiator
Crystal display element sealant, wherein
The curable resin contains the acrylic acid modified phenol aldehyde type epoxy resin A in part (methyl), part (methyl) acrylic acid changes
Property non-phenol aldehyde type epoxy resin B and non-phenolic epoxy (methyl) acrylate C,
The content of the acrylic acid modified phenol aldehyde type epoxy resin A of part (methyl) is in 100 parts by weight of curable resin
For it is more than 3 parts by weight and 9 parts by weight hereinafter,
The content of the acrylic acid modified non-phenol aldehyde type epoxy resin B of part (methyl) is in 100 parts by weight of curable resin
In be 25 parts by weight hereinafter, and the part (methyl) acrylic acid modified non-phenol aldehyde type epoxy resin B relative to the part (first
Base) ratio of acrylic acid modified phenol aldehyde type epoxy resin A is 1 or more,
The content of non-phenolic epoxy (methyl) the acrylate C is 10 weight in 100 parts by weight of curable resin
Part or more and 45 parts by weight hereinafter,
The weight average molecular weight of the acrylic acid modified phenol aldehyde type epoxy resin A of part (methyl) is 700 or more and 2000 or less.
2. a kind of conductive material up and down, contains sealing material for liquid crystal display device described in claim 1 and electrically conductive microparticle.
3. a kind of liquid crystal display element is using sealing material for liquid crystal display device described in claim 1 or claim 2
The conductive material up and down and it is manufactured.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017138031 | 2017-07-14 | ||
| JP2017-138031 | 2017-07-14 | ||
| PCT/JP2018/025841 WO2019013154A1 (en) | 2017-07-14 | 2018-07-09 | Sealing agent for liquid crystal display elements, vertical conduction material, and liquid crystal display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110325904A true CN110325904A (en) | 2019-10-11 |
| CN110325904B CN110325904B (en) | 2022-11-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880014052.0A Active CN110325904B (en) | 2017-07-14 | 2018-07-09 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7053471B2 (en) |
| KR (1) | KR102549659B1 (en) |
| CN (1) | CN110325904B (en) |
| TW (1) | TWI785071B (en) |
| WO (1) | WO2019013154A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2019013154A1 (en) | 2020-05-07 |
| TWI785071B (en) | 2022-12-01 |
| TW201908453A (en) | 2019-03-01 |
| CN110325904B (en) | 2022-11-01 |
| KR102549659B1 (en) | 2023-06-29 |
| KR20200030493A (en) | 2020-03-20 |
| WO2019013154A1 (en) | 2019-01-17 |
| JP7053471B2 (en) | 2022-04-12 |
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