CN107533261B - 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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CN107533261B
CN107533261B CN201680022135.5A CN201680022135A CN107533261B CN 107533261 B CN107533261 B CN 107533261B CN 201680022135 A CN201680022135 A CN 201680022135A CN 107533261 B CN107533261 B CN 107533261B
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liquid crystal
crystal display
methyl
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display device
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CN107533261A (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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Priority to CN201910136802.8A priority Critical patent/CN109897599B/en
Priority to CN201910136803.2A priority patent/CN110041887B/en
Priority to CN201910136804.7A priority patent/CN110079259B/en
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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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The sealing material for liquid crystal display device of the present invention offer cementability and anti-excellent moisture permeability.It is further an object that providing using upper and lower conductive material and liquid crystal display element made of the sealing material for liquid crystal display device.The present invention is a kind of sealing material for liquid crystal display device, and containing curable resin and polymerization initiator and/or thermal curing agents, the solidfied material of the sealing material for liquid crystal display device is 0.8~3.0GPa in 25 DEG C of storage modulus.

Description

Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element
Technical field
The present invention relates to the sealing material for liquid crystal display device of cementability and anti-excellent moisture permeability.In addition, the present invention relates to Use upper and lower conductive material and liquid crystal display element made of the sealing material for liquid crystal display device.
Background technique
In recent years, as the manufacturing method of liquid crystal display element, from shortening pitch time, the optimized of amount of liquid crystal is used Viewpoint is set out, using such as patent document 1, patent document 2 is open such, liquid crystal drop add mode of referred to as dripping method, described Dripping method has used the photo-thermal containing curable resin, Photoepolymerizationinitiater initiater and thermal curing agents to share curing type sealant.
In dripping method, firstly, being formed by distribution to one of electroded transparent substrate of two panels rectangular close Seal pattern.Then, the fine droplet of liquid crystal is added dropwise to entire surface in the frame of transparent substrate in the state that sealant is uncured, It is overlapped another transparent substrate immediately, precuring is carried out to light such as sealing irradiation ultraviolet lights.Thereafter it heats main solid to carry out Change, makes liquid crystal display element.By carrying out the fitting of substrate under reduced pressure, liquid crystal display member can be made with high efficiency system Part, the dripping method become the mainstream of the manufacturing method of liquid crystal display element now.
With tablet terminal, portable terminal it is universal, liquid crystal display element is increasingly required for impact test, whereabouts The durability of test etc., increasingly requires the cementability of itself and substrate bonding.In addition, with the narrow architrave of panel, it is desirable that The moisture-proof reliability of driving under hot and humid environment etc., the performance for preventing water from immersing from outside sealant further requirement. In order to improve impact resistance, the moisture-proof reliability of liquid crystal display element, needing to improve the cementability of sealant and substrate etc. and drop The penetrability of the solidfied material of low sealant.However, it is difficult to make cementability and the excellent sealant of anti-penetrability both of which.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-133794 bulletin
Patent document 2: Japanese Unexamined Patent Publication 5-295087 bulletin
Summary of the invention
Problems to be solved by the invention
The present invention relates to the sealing material for liquid crystal display device of cementability and anti-excellent moisture permeability.In addition, mesh of the invention Be, provide using conductive material and liquid crystal display element up and down made of the sealing material for liquid crystal display device.
The means used to solve the problem
The present invention is used for liquid crystal display element close containing curable resin and polymerization initiator and/or thermal curing agents Agent is sealed, the solidfied material of the sealing material for liquid crystal display device is 0.8~3.0GPa in 25 DEG C of storage modulus.
The present invention described below.
Present inventor have discovered that can be bonded by making solidfied material reach specific range in 25 DEG C of storage modulus The excellent sealing material for liquid crystal display device of both property and anti-penetrability, so as to complete the present invention.
The solidfied material of sealing material for liquid crystal display device of the invention 25 DEG C of storage modulus lower limit be 0.8GPa, on It is limited to 3.0GPa.By making above-mentioned solidfied material in 25 DEG C of the storage modulus range, of the invention is used for liquid crystal display element close Cementability and the anti-penetrability both of which for sealing agent are excellent.Above-mentioned solidfied material is in the preferred lower limit of 25 DEG C of storage modulus 1.0GPa, preferred upper limit 2.8GPa, more preferable lower limit is 1.2GPa, the more preferable upper limit is 2.6GPa.
It should be noted that as the solidfied material for measuring above-mentioned 25 DEG C of storage modulus and aftermentioned 60 DEG C of storage modulus, The 100mW/cm irradiated using metal halide lamp to sealant 30 seconds can be used2After ultraviolet light (wavelength 365nm), with 120 Product obtained from DEG C heating solidifies it.
In addition, the usable measurement of dynamic viscoelasticity device of above-mentioned storage modulus (for example, IT measurement control Co. Ltd. system, " DVA-200 " etc.), it is 5mm, with a thickness of 0.35mm, gripping width 25mm, liter in test film width under each measuring temperature Warm speed is 10 DEG C/min, frequency is measured under conditions of being 10Hz.
The solidfied material of sealing material for liquid crystal display device of the invention is in the preferred lower limit of 60 DEG C of storage modulus 0.04GPa.By making storage modulus 0.04GPa or more of the above-mentioned solidfied material at 60 DEG C, of the invention is used for liquid crystal display element The anti-penetrability of sealant is more excellent.Above-mentioned solidfied material is 0.1GPa in the more preferable lower limit of 60 DEG C of storage modulus.
In addition, above-mentioned solidfied material is 2.5GPa in the preferred upper limit of 60 DEG C of storage modulus from the viewpoint of cementability.
Sealing material for liquid crystal display device of the invention contains curable resin and polymerization initiator and/or heat cure Agent.
For sealing material for liquid crystal display device of the invention, as make above-mentioned solidfied material 25 DEG C storage modulus at For the method for 0.8~3.0GPa, it is preferable to use contain following polymerizable compound (hereinafter also referred to " polymerizable compounds (a) " method of the substance) as above-mentioned curable resin: the polymerizable compound has 1 or more in 1 molecule and polymerize Property functional group and 1 or more the open loop structure of lactone and/or 1 or more acrylonitrile-butadiene structure, more preferably use Also containing the (hereinafter also referred to " polymerization of following simple function polymerizable compounds on the basis of containing above-mentioned polymerizable compound (a) Property compound (b) ") substance method: the simple function polymerizable compound in 1 molecule have 1 polymerizable functional group And do not have the open loop structure and acrylonitrile-butadiene structure of lactone.
As polymerizable functional group possessed by above-mentioned polymerizable compound (a), such as (methyl) acryloyl can be enumerated Base, epoxy group etc..Wherein, preferably (methyl) acryloyl group.
It should be noted that above-mentioned " (methyl) acryloyl group " refers to acryloyl group or methacryl in this specification Base.
Above-mentioned polymerizable compound (a) is preferably to gather in 1 molecule with 2 or more the multifunctional of above-mentioned polymerizable functional group Conjunction property compound.
When above-mentioned polymerizable compound (a) has the open loop structure of lactone, as the lactone, such as γ-ten can be enumerated One lactone, 6-caprolactone, γ-decalactone, σ-dodecalactone, nonyl lactone (γ-nonalactone), nonyl lactone (γ- Nonanolactone), gamma-valerolactone, σ-valerolactone, beta-butyrolactone, gamma-butyrolacton, beta-propiolactone, σ-caprolactone, 7- fourth Base -2- oxa- Zhuo ketone etc..Wherein, preferably open loop when main framing linear fraction carbon number reach 5~7 lactone, more preferably For 6-caprolactone.Above-mentioned polymerizable compound (a) can have the open loop structure of a kind of lactone among these, it is possible to have 2 Kind or more lactone open loop structure.
When above-mentioned polymerizable compound (a) has the open loop structure of lactone, the open loop structure of the lactone can be in 1 molecule Only 1, repetitive structure can also be formed.When the open loop structure of lactone forms repetitive structure, the preferred upper limit of repeat number is 5.
The preferred lower limit of the molecular weight of above-mentioned polymerizable compound (a) is 800, preferred upper limit 4000.It is above-mentioned by making The molecular weight of polymerizable compound (a) is the range, and the flexibility of gained sealing material for liquid crystal display device and anti-penetrability are more It is excellent.The more preferable upper limit of the molecular weight of above-mentioned polymerizable compound (a) is 2000.
It should be noted that being for above-mentioned " molecular weight " compound fixed for molecular structure in this specification The molecular weight found out by structural formula, but the wide in range compound of distribution and the modified uncertain compound in position for the degree of polymerization and Speech is indicated using weight average molecular weight sometimes.In addition, above-mentioned " weight average molecular weight " is surveyed by gel permeation chromatography (GPC) Value that is fixed, and being found out based on polystyrene conversion.Make when as the weight average molecular weight to be converted by GPC measurement based on polystyrene Column can be enumerated such as Shodex LF-804 (Showa Denko K. K's system).
Among above-mentioned polymerizable compound (a), as the polymerizable compound of the open loop structure with lactone, preferably to Polymerizable compound obtained from the open loop structure of lactone is imported in the skeleton of aftermentioned epoxy (methyl) acrylate.As upward Polymerizable compound obtained from the open loop structure for importing lactone in the skeleton of epoxy (methyl) acrylate is stated, example can be enumerated Such as following formula (1) compound represented.
In formula (1), R1Indicate hydrogen atom or methyl；R2Indicate group shown in following formula (2-1) or (2-2)；R3It indicates to come Derived from the structure of acid anhydrides；R4Indicate the structure from epoxide；The open loop structure of X expression lactone；N indicate 1~5 it is whole Number；A indicates 1~4 integer.
In formula (2-2), b indicates 0~8 integer；C indicates 0~3 integer；D indicates 0~8 integer；E indicates 0~8 Integer；B, any of c, d are 1 or more.
As above-mentioned polymerizable compound (a), specific enumerable such as caprolactone modification bisphenol type epoxy (methyl) third out Olefin(e) acid ester, Polybutadiene-acrylonitrile (CTBN) modified epoxy (methyl) acrylate, glycol-modified A containing terminal carboxyl group Type ring oxygen (methyl) acrylate etc..Above-mentioned polymerizable compound (a) may be used alone, can also be used in combination two kinds with On.
The preferred lower limit of the content of above-mentioned polymerizable compound (a) in whole 100 parts by weight of above-mentioned curable resin is 5 Parts by weight, preferred upper limit are 80 parts by weight.By making the content of above-mentioned polymerizable compound (a) range, being easy will solidification Object is set as above range in 25 DEG C of storage modulus.The more preferable lower limit of the content of above-mentioned polymerizable compound (a) is 10 weight Part, the more preferable upper limit are 60 parts by weight.
As polymerizable functional group possessed by above-mentioned polymerizable compound (b), can enumerate and above-mentioned polymerism chemical combination The identical polymerizable functional group of object (a), preferably (methyl) acryloyl group.
From the viewpoint of inhibiting liquid crystal pollution, above-mentioned polymerizable compound (b) preferably has hydrogen bond functional group.
As above-mentioned hydrogen bond functional group, such as-OH base ,-NH can be enumerated2(R indicates aromatic series or rouge for base ,-NHR base Fat race hydrocarbon and their derivative) ,-COOH base ,-CONH2Base ,-NHOH Ji Deng functional group；- NHCO- existing for intramolecular Key ,-NH- key ,-CONHCO- key ,-NH-NH- key etc..It is wherein preferably-OH base.
The preferred lower limit of the molecular weight of above-mentioned polymerizable compound (b) is 100, preferred upper limit 2000.It is above-mentioned by making The molecular weight of polymerizable compound (b) is 100 or more, is not easy dissolution into liquid crystal.By making above-mentioned polymerizable compound (b) Molecular weight be 2000 hereinafter, the coating of gained sealing material for liquid crystal display device is more excellent.Above-mentioned polymerizable compound (b) Molecular weight more preferable lower limit be 150, the more preferable upper limit is 1000.
As above-mentioned polymerizable compound (b), specific enumerable such as (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) out Acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- Hydroxyl -3- phenoxy-propyl, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloyl-oxyethyl hexahydro neighbour's benzene Dioctyl phthalate, (methyl) acrylic acid 2- (((butylamino) carbonyl) oxygroup) ethyl ester, aliphatic epoxy (methyl) acrylate (such as EBECRYL112 (DAICEL-ALLNEX LTD. system)), caprolactone (methyl) acrylate (such as SR495 (SARTOMER company System)), (methyl) acrylic acid 2- hydroxy methacrylates (such as SR604 (SARTOMER corporation)), caprolactone modification carbamate (methyl) acrylate (such as KUA-C2I (KSM Co., Ltd. system)), polycarbonate modified carbamate (methyl) propylene Acid esters (such as KUA-PC2I (KSM Co., Ltd. system)), polyether modified amino formic acid esters (methyl) acrylate (such as KUA- PEA2I, KUA-PEB2I, KUA-PEC2I (being KSM Co., Ltd. system)), (methyl) P-carboxy ethyl acrylates (such as β- CEA (DAICEL-ALLNEX LTD. system)), carboxyl (methyl) acrylate (such as EBECRYL770 (DAICEL-ALLNEX LTD. make)), (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, the positive fourth of (methyl) acrylic acid Ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid N-octyl, (methyl) Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) acrylic acid Lauryl, the different myristin of (methyl) acrylic acid, (methyl) stearyl acrylate, (methyl) cyclohexyl acrylate, (methyl) third Olefin(e) acid isobornyl thiocyanoacetate, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2- methoxyl group second Ester, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- butoxyethyl, (methyl) acrylic acid 2- phenoxy group second Ester, methoxy ethyl glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, phenoxy group diethylene glycol (first Base) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, ethyl carbitol (first Base) acrylate, (methyl) acrylic acid 2,2,2- trifluoro ethyl ester, 2,2,3,3- tetrafluoro propyl ester of (methyl) acrylic acid, (methyl) third Olefin(e) acid 1H, 1H, 5H- octafluoro pentyl ester, (methyl) acrylate, (methyl) acrylic acid diethylamino ethyl ester Deng.Wherein, epoxy (methyl) acrylate of preferably simple function, more preferably (methyl) acrylic acid 2- hydroxyl -3- phenoxy group Propyl ester.Above-mentioned polymerizable compound (b) may be used alone, can also be used in combination two or more.
It should be noted that above-mentioned " (methyl) acrylate " refers to acrylate or methacrylic acid in this specification Ester, above-mentioned " epoxy (methyl) acrylate " is that all epoxy groups in epoxide is instigated to be reacted with (methyl) acrylic acid The compound arrived.
Epoxy (methyl) acrylate of above-mentioned simple function is by making the epoxide of simple function and (methyl) acrylic acid Reaction etc. obtains, have the epoxide from the simple function structure and from should (methyl) acrylic acid knot Structure.
As the epoxide of above-mentioned simple function, can enumerate such as butyl glycidyl ether (such as DY-BP (four days City synthesizes Co. Ltd. system)), (such as (Yokkaichi synthesizes Co., Ltd. to Epogose 2EH to 2- hexyl glycidyl ether System)), allyl glycidyl ether (such as EX-101 (Nagase ChemteX Corporation system)), 2- ethylhexyl contracting Water glycerin ether (such as EX-121 (Nagase ChemteX Corporation system)), EO modified phenol glycidol ether (such as EX-145 (Nagase ChemteX Corporation system)), the modified laruyl alcohol glycidol ether of EO (such as EX-171 (Nagase ChemteX Corporation system)), phenyl glycidyl ether (such as EX-141 (Nagase ChemteX Corporation system)), to tert-butyl-phenyl glycidol ether (such as EX-146 (Nagase ChemteX Corporation System)), dibromo phenyl glycidol ether (such as EX-147 (Nagase ChemteX Corporation system)) etc..
In addition, such as Epoxy can be enumerated as the commercially available product in epoxy (methyl) acrylate of above-mentioned simple function Ester M-600A (Kyoeisha Chemical Co., Ltd.'s system) etc..
The preferred lower limit of the content of above-mentioned polymerizable compound (b) in whole 100 parts by weight of above-mentioned curable resin is 1 Parts by weight, preferred upper limit are 30 parts by weight.By making the content of above-mentioned polymerizable compound (b) range, being easy will solidification Object is set as above range in 25 DEG C of storage modulus.The more preferable lower limit of the content of above-mentioned polymerizable compound (b) is 5 weight Part, the more preferable upper limit are 25 parts by weight.
In sealing material for liquid crystal display device of the invention, as above-mentioned curable resin, preferably containing above-mentioned polymerization Property compound (a) and above-mentioned polymerizable compound (b) on the basis of, also containing poly- with (methyl) acryloyl group and epoxy group Conjunction property compound (hereinafter also referred to " polymerizable compound (c) ").It is of the invention by containing above-mentioned polymerizable compound (c) The cementability of sealing material for liquid crystal display device is more excellent.
As above-mentioned polymerizable compound (c), can enumerate for example by making the epoxy compound with 2 or more epoxy groups Part (methyl) acryl-modified epoxy resin obtained from a part of epoxy group and (methyl) acrylic acid of object react Deng.
It should be noted that above-mentioned " (methyl) acryloyl group " refers to acryloyl group or methacryl in this specification Base.
As the epoxide for the raw material for becoming above-mentioned polymerizable compound (c), such as bisphenol type epoxy can be enumerated Compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2,2 '-diallyl bisphenol type ring oxygen compounds, hydrogen Change biphenol type epoxy compound, propylene oxide addition bisphenol A type epoxy compound, resorcinol type ring oxygen compound, biphenyl type Epoxide, thioether-type epoxide, diphenyl ether type epoxide, dicyclopentadiene type epoxy compound, naphthalene type ring Oxygen compound, phenol novolak-type epoxy compound, ortho cresol novolak type epoxide, dicyclopentadiene phenolic are clear Paint shaped epoxide, biphenyl novolak type epoxy compounds, naphthol novolac type epoxy compound, glycidic amine type Epoxide, alkyl polyols type ring oxygen compound, modified rubber type ring oxygen compound, epihydric alcohol ester compound etc..
As the commercially available product in above-mentioned polymerizable compound (c), such as KRM8287 (DAICEL-ALLNEX can be enumerated LTD. it makes).
The content of above-mentioned polymerizable compound (c) is 5 weights relative to whole 100 parts by weight of curable resin, preferred lower limit Measure part, preferred upper limit is 50 parts by weight.By making the content of above-mentioned polymerizable compound (c) range, can further send out Shoot the generation for inhibiting liquid crystal pollution and the effect for improving cementability.The content of above-mentioned polymerizable compound (c) it is more preferable under It is limited to 10 parts by weight, the more preferable upper limit is 40 parts by weight.
Sealing material for liquid crystal display device of the invention within the scope without prejudice to the object of the present invention, can further contain Other polymerizable compounds are as polymerizable compound.
Above-mentioned other polymerizable compounds are in addition to being covered by above-mentioned polymerizable compound (a), above-mentioned polymerizable compound (b) with the polymerizable compound except above-mentioned polymerizable compound (c), for example multifunctional (methyl) acrylic compounds can be enumerated Close object, multi-functional epoxy compound etc..
As multifunctional (methyl) acrylic compounds for belonging to above-mentioned other polymerizable compounds, can enumerate for example The multifunctional (methyl) acrylate compounds as obtained from reacting (methyl) acrylic acid with the compound with hydroxyl are led to Cross multi-functional epoxy (methyl) acrylate obtained from reacting (methyl) acrylic acid with epoxide, by making isocyanic acid Polyfunctional carbamate (methyl) propylene obtained from ester compounds are reacted with (methyl) acrylic acid derivative with hydroxyl Acid esters etc..
Object is closed as the difunctional in above-mentioned multifunctional (methyl) acrylate compounds, can be enumerated without lactone Open loop structure and acrylonitrile-butadiene structure compound, can enumerate such as 1,3-BDO two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, 1,9- nonanediol two (methyl) propylene Acid esters, 1,10- decanediol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) propylene Acid esters, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, 2- normal-butyl -2- ethyl -1,3- third Glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, poly- the third two Alcohol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethyleneoxide addition bisphenol-A two (methyl) acrylic acid Ester, propylene oxide addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxy first Base bicyclopentadiene two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two (methyl) acrylate, 2- hydroxyl -3- (methyl) acryloxypropyl (methyl) acrylate, carbonate diol two (methyl) acrylate, two (first of polyetherdiol Base) acrylate, polyester-diol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc..
In addition, can be enumerated as the compound more than trifunctional in above-mentioned multifunctional (methyl) acrylate compounds The compound of open loop structure without lactone and acrylonitrile-butadiene structure out can enumerate such as trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, propylene oxide addition trihydroxy methyl Propane three (methyl) acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, glycerol three (methyl) acrylic acid Ester, propylene oxide addition glycerol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, three (methyl) acryloyl-oxies Base ethyl phosphonic acid ester, double trimethylolpropane four (methyl) acrylate, pentaerythrite four (methyl) acrylate, two Ji Wusi Alcohol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..
As above-mentioned multi-functional epoxy (methyl) acrylate, two functions or more can be enumerated and do not have the open loop of lactone Multi-functional epoxy (methyl) acrylate of structure, acrylonitrile-butadiene structure, can enumerate for example conventionally makes ring Product obtained from oxygen compound and (methyl) acrylic acid react in the presence of basic catalyst etc..
As the epoxide become for synthesizing the raw material of above-mentioned multi-functional epoxy (methyl) acrylate, can enumerate Epoxide identical with the epoxide of raw material of above-mentioned polymerizable compound (c) is become out.
It, can be by making such as (methyl) third with hydroxyl as above-mentioned polyfunctional carbamate (methyl) acrylate 2 equivalent of gadoleic acid derivative relative to 2 isocyanate group 1 equivalent of isocyanate compound catalytic amount tin system It closes and reacts etc. to obtain in the presence of object.
As the isocyanate compound for the raw material for becoming above-mentioned polyfunctional carbamate (methyl) acrylate, can arrange It is different to enumerate such as isophorone diisocyanate, 2,4- toluene di-isocyanate(TDI), 2,6- toluene di-isocyanate(TDI), hexa-methylene two Cyanate, trimethyl hexamethylene diisocyanate, 4,4 '-diisocyanate (MDI) of diphenyl methane-, hydrogenation MDI, polymerization Property MDI, 1,5- naphthalene diisocyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, xyxylene diisocyanate Ester (XDI), hydrogenation XDI, lysine diisocyanate, triphenylmethane triisocyanate, three (isocyanate phenyl) thio phosphorus Acid esters, tetramethyl xylylene diisocyanate, 1,6,11- hendecane triisocyanates etc..
In addition, the isocyanates chemical combination as the raw material for becoming above-mentioned polyfunctional carbamate (methyl) acrylate Object also can be used for example through ethylene glycol, propylene glycol, glycerol, D-sorbite, trimethylolpropane, carbonate diol, polyethers The isocyanates chemical combination of chain elongation obtained from the reacting of the polyalcohols such as glycol, polyester-diol and excessive isocyanate compound Object.
As the raw material for becoming above-mentioned polyfunctional carbamate (methyl) acrylate, (methyl) third with hydroxyl Gadoleic acid derivative can enumerate such as (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) third Olefin(e) acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxybutyl etc.；Ethylene glycol, propylene glycol, 1,3-PD, 1,3-BDO, List (methyl) acrylate of the dihydric alcohols such as 1,4-butanediol, polyethylene glycol；Trimethylolethane, trimethylolpropane, glycerol List (methyl) acrylate or two (methyl) acrylate of equal trihydroxylic alcohols；The epoxies such as bisphenol type epoxy (methyl) acrylate (methyl) acrylate etc..
As the multi-functional epoxy compound for belonging to above-mentioned other polymerizable compounds, it can enumerate and polymerize with as above-mentioned The identical epoxide of epoxide of the raw material of property compound (c).
Sealing material for liquid crystal display device of the invention contains polymerization initiator and/or thermal curing agents.
As above-mentioned polymerization initiator, can enumerate such as radical polymerization initiator, cationic polymerization initiators.
As above-mentioned radical polymerization initiator, the hot radical polymerization generated free radicals by heating can be enumerated and drawn Hair agent, the optical free radical polymerization initiator generated free radicals by light irradiation etc..
As above-mentioned optical free radical polymerization initiator, such as benzophenone based compound, acetophenone system chemical combination can be enumerated Object, acylphosphine oxide compound, titanocenes based compound, oxime ester based compound, benzoin ether based compound, thioxanthones etc..
As the commercially available product in above-mentioned optical free radical polymerization initiator, can enumerate such as IRGACURE184, IRGACURE369、IRGACURE379、IRGACURE651、IRGACURE819、IRGACURE907、IRGACURE2959、 IRGACURE OXE01, Lucirin TPO (being BASF AG's system)；Benzoin methylether, benzoin ethyl ether, benzoin iso-propylether (being Tokyo Chemical Industry Co., Ltd's system) etc..
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 polymeric azo initiator of polymeric azo compound.
It should be noted that polymeric azo initiator refers in this specification: there is azo group and given birth to by heat At (methyl) acryloxy can be made to carry out cured free radical, 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.Pass through Make the number-average molecular weight of the above-mentioned polymeric azo initiator range, can prevent from causing liquid crystal adverse effect, and hold Easily mix into curable resin.The more preferable lower limit of the number-average molecular weight of above-mentioned polymeric azo initiator be 5000, it is more excellent It chooses and is limited to 100,000, further preferred lower limit is 10,000, the further preferred upper limit is 90,000.
It should be noted that above-mentioned number-average molecular weight is surveyed by gel permeation chromatography (GPC) in this specification Value that is fixed, and being found out based on polystyrene conversion.When as the number-average molecular weight to be converted by GPC measurement based on polystyrene Column, can enumerate such as Shodex LF-804 (Showa Denko K. K's system).
As above-mentioned polymeric azo initiator, can enumerate for example with being bonded with multiple polyalkylene oxides by azo group The polymeric azo initiator of the structure of the units such as hydrocarbon, 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.It, can as such polymeric azo initiator Such as 4 are enumerated, condensation polymer, bis- (the 4- cyano penta of 4,4 '-azos of 4 '-azos bis- (4- cyanopentanoic acids) and polyalkylene glycol Acid) with terminal amino group dimethyl silicone polymer condensation polymer etc., it is specific enumerable go out such as VPE-0201, VPE- 0401, VPE-0601, VPS-0501, VPS-1001 (being Wako Pure Chemical Industries, Ltd.'s system) etc..
In addition, the example of the azo-compound as on-macromolecular, can enumerate V-65, V-501 (is and the pure medicine work of light Industry Co. Ltd. system) etc..
As above-mentioned organic peroxide, such as ketone peroxide, ketal peroxide, hydrogen peroxide, peroxidating can be enumerated Dialkyl group, peroxyester, diacyl peroxides, peroxy dicarbonate etc..
As above-mentioned cationic polymerization initiators, light cationic polymerization initiator can be compatibly used.Above-mentioned light cation As long as polymerization initiator generates Bronsted acid or lewis acid by light irradiation, there is no particular limitation, can be ionic light Acid generates the polymerization initiator of type, is also possible to nonionic light acid and generates type.
As above-mentioned light cationic polymerization initiator, such as aromatic diazonium salt, aromatic halonium salts, fragrance can be enumerated The metal-organic complexs such as the salts such as race's sulfonium salt, iron-diene complexes, titanocenes complex compound, aryl-silane alcohol-aluminium complex Class etc..
As the commercially available product in above-mentioned light cationic polymerization initiator, such as Adeka Optomer SP- can be enumerated 150, Adeka Optomer SP-170 (being ADEKA corporation) etc..
The content of above-mentioned polymerization initiator is 0.1 weight relative to whole 100 parts by weight of curable resin, preferred lower limit Part, preferred upper limit are 30 parts by weight.It is more than 0.1 parts by weight of content by making above-mentioned polymerization initiator, gained liquid crystal display The curability of element sealant is more excellent.As make above-mentioned polymerization initiator 30 parts by weight of content hereinafter, obtained by liquid crystal The storage stability of display element sealant is more excellent.The more preferable lower limit of the content of above-mentioned polymerization initiator be 1 parts by weight, The more preferable upper limit is 10 parts by weight, and the further preferred upper limit is 5 parts by weight.
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.
As above-mentioned solid organic acid hydrazides, bis- (hydrazide group the carbonylethyl) -5- isopropyls of such as 1,3- can be enumerated Hydantoins, sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, acid dihydrazide etc., as commercially available Product can enumerate such as SDH, MDH, ADH (Otsuka Kagaku K.K.'s system)；Ajicure VDH,Ajicure VDH-J, Ajicure UDH (being Ajinomoto Fine Techno Co., Inc. system) etc..
For the content of above-mentioned thermal curing agents relative to whole 100 parts by weight of curable resin, preferred lower limit is 1 parts by weight, excellent It chooses and is limited to 50 parts by weight.It is more than 1 parts by weight of content by making above-mentioned thermal curing agents, gained sealing used for liquid crystal display element The Thermocurable of agent is more excellent.As make above-mentioned thermal curing agents 50 parts by weight of content hereinafter, obtained by it is used for liquid crystal display element The coating of sealant is more excellent.The more preferable upper limit of the content of above-mentioned thermal curing agents is 30 parts by weight.
Sealing material for liquid crystal display device of the invention preferably comprises soft particle.Above-mentioned softness particle is in manufacture liquid crystal As the barrier between other sealant ingredients and liquid crystal when showing element, having prevents liquid crystal from entering sealant and sealant dissolution Effect into liquid crystal.
The maximum particle diameter of above-mentioned softness particle be preferably 100% or more of the unit interval of liquid crystal display element and for 5~ 20μm.Above-mentioned softness particle is 100% or more particle of unit interval by using maximum particle diameter, can be sprung back, and is led to Crossing makes 20 μm of the maximum particle diameter of above-mentioned soft particle hereinafter, liquid crystal display element can be made without as caused by springing back It is spaced bad.
It should be noted that the unit interval of liquid crystal display element is different because of display element, do not limit, common liquid crystal The unit interval of display element is 2~10 μm.
The preferred lower limit of the maximum particle diameter of above-mentioned softness particle is the 100% of the unit interval of liquid crystal display element and is 5 μ m.That is, the preferred lower limit of the maximum particle diameter of above-mentioned softness particle is 5 μm when the unit interval of liquid crystal display element is 5 μm or less, When the unit interval of liquid crystal display element is more than 5 μm, the preferred lower limit of the maximum particle diameter of above-mentioned softness particle reaches liquid crystal display The 100% of the unit interval of element.By make 5 μm of maximum particle diameter of above-mentioned soft particle between the unit of liquid crystal display element Every 100% among the value for reaching above-mentioned preferred lower limit person more than, inhibit sealing rupture, the effect of liquid crystal pollution it is more excellent.
In addition, from the viewpoint of reducing cementability, the interval of liquid crystal display element is bad caused by inhibiting because of rebound, on The preferred upper limit for stating the maximum particle diameter of soft particle is 20 μm.The more preferable upper limit of the maximum particle diameter of above-mentioned softness particle is 15 μ m。
In turn, from the viewpoint of reducing cementability, the interval of liquid crystal display element is bad caused by inhibiting because of rebound, on The maximum particle diameter for stating soft particle is preferably 2.6 times of unit interval or less.It is above-mentioned softness particle maximum particle diameter it is more preferable The upper limit is 2.2 times of unit interval, the further preferred upper limit is unit interval 1.7 times.
It should be noted that in this specification, for the particle before being engaged to sealant, above-mentioned softness particle Maximum particle diameter and aftermentioned average grain diameter refer to be measured by using laser diffraction formula particle size distribution device obtained from Value.As above-mentioned laser diffraction formula distribution measurement device, 2000 (Malvern of MASTERSIZER can be used Instruments. make) etc..
The size distribution for the soft particle of above-mentioned softness particle measured by above-mentioned laser diffraction formula distribution measurement device Among, the content ratio for the particle that partial size is 5 μm or more is preferably 60% or more with volume frequency meter.By making 5 μm of partial size The content ratio of above particle is calculated as 60% or more with volume frequency, inhibits sealing rupture, the effect of liquid crystal pollution more excellent. The content ratio for the particle that partial size is 5 μm or more is more preferably 80% or more.
From the viewpoint of further playing the effect for inhibiting sealing rupture, liquid crystal pollution to occur, above-mentioned softness particle It is preferred that contain the unit interval of liquid crystal display element in the way of 70% or more of the size distribution in soft particle entirety 100% or more particle is more preferably only made of 100% or more particle of the unit interval of liquid crystal display element.
The preferred lower limit of the average grain diameter of above-mentioned softness particle is 2 μm.By the average grain diameter 2 for making above-mentioned soft particle μm or more, inhibit sealing rupture, the effect of liquid crystal pollution more excellent.The more preferable lower limit of average grain diameter of above-mentioned softness particle is 4μm。
In addition, from the viewpoint of reducing cementability, the interval of liquid crystal display element is bad caused by inhibiting because of rebound, on The preferred upper limit for stating the average grain diameter of soft particle is 15 μm.The more preferable upper limit of the average grain diameter of above-mentioned softness particle is 12 μ m。
As above-mentioned soft particle, the different two or more soft particles of maximum particle diameter can be used in mixed way.I.e., it is possible to Maximum particle diameter is lower than 100% soft particle of the unit interval of liquid crystal display element and maximum particle diameter is liquid crystal display element 100% or more soft particle of unit interval be used in mixed way.
From the viewpoint of inhibiting unit interval bad, the coefficient of variation of the partial size of above-mentioned softness particle is (hereinafter also referred to CV value) it is preferably 30% or less.The CV value of the partial size of above-mentioned softness particle is more preferably 28% or less.
It should be noted that the CV value of partial size refers to the numerical value found out by following formula in this specification.
The CV value (%) of partial size=(standard deviation/average grain diameter of partial size) × 100
Even above-mentioned softness particle maximum particle diameter, average grain diameter, CV value are in the particle outside above range, can also lead to It crosses classification and becomes maximum particle diameter, average grain diameter, CV value in above range.In addition, partial size is lower than the list of liquid crystal display element The 100% soft particle at member interval is helpless to inhibit sealing rupture, the generation of liquid crystal pollution, when being engaged to sealant sometimes Increase thixotroping value, it is therefore preferable that removing in advance by being classified.
As the method being classified to above-mentioned soft particle, such as the methods of wet classification, dry classification can be enumerated. Wherein, preferably wet classification, more preferably wet screening grade.
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.
From the viewpoint of the dispersibility being dispersed in resin, above-mentioned silicone-based particle is preferably silicone rubber particle.
As the commercially available product in above-mentioned silicone-based particle, such as KMP-594, KMP-597, KMP-598, KMP- can be enumerated 600, KMP-601, KMP-602 (Shin-Etsu Chemial Co., Ltd's system)；Trefil E-506S,EP-9215(Dow Corning Toray Co., Ltd. system) etc., they can be classified and be used.Above-mentioned silicone-based particle can be used alone, can also group It closes using two or more.
As above-mentioned ethylene base system particle, it is suitble to use (methyl) acrylic particles.
Above-mentioned (methyl) acrylic particles can be polymerize by the monomer for becoming raw material using well known method come It obtains.The specific enumerable method that monomer is for example subjected to suspension polymerisation in the presence of radical polymerization initiator out；Pass through So that noncrosslinking seed particles is absorbed monomer in the presence of radical polymerization initiator, makes seed particles swelling to carry out crystal seed The method etc. of 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 Methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid oneself Ester, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylic acid whale (methyl) acrylic acid such as wax ester, (methyl) stearyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate Alkyl esters；(methyl) acrylic acid 2- hydroxy methacrylate, (methyl) glycerol acrylate, polyoxyethylene (methyl) acrylate, (first Base) (methyl) esters of acrylic acid containing oxygen atom such as glycidyl acrylate；The monomers containing nitrile such as (methyl) acrylonitrile； The simple functions lists such as fluorine-containing (methyl) esters of acrylic acid such as (methyl) acrylic acid trifluoromethyl ester, five fluorine ethyl ester of (methyl) acrylic acid Body.Wherein, preferably (methyl) alkyl-acrylates, this is because the Tg of homopolymer is low, is capable of increasing and is applying 1g load-carrying When deflection.
In addition, tetramethylol methane four (methyl) acrylate, tetra methylol also can be used in order to have cross-linked structure 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) The polyfunctional monomers such as acrylate, isocyanuric acid skeleton three (methyl) acrylate.Wherein, preferably two (first of (poly-) ethylene glycol Base) acrylate, (poly-) propylene glycol two (methyl) acrylate, (poly-) tetramethylene two (methyl) acrylate, Isosorbide-5-Nitrae-fourth two Alcohol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, this is because molecular weight is big between crosslinking points, Neng Gouzeng Deflection greatly when applying 1g load-carrying.
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 Preferred lower limit in entirety is 1 weight %, preferred upper limit is 90 weight %.By 1 weight of dosage for making above-mentioned cross-linkable monomer % or more is measured, solvent resistance rises, and the problems such as will not being swollen when with the mixing of various sealant raw materials, is easy evenly dispersed. The problems such as by making the 90 weight % of dosage of above-mentioned cross-linkable monomer hereinafter, can reduce recovery rate, being not susceptible to rebound.On The more preferable lower limit for stating the dosage of cross-linkable monomer is 3 weight %, the more preferable upper limit is 80 weight %.
It in turn, can be on the basis of using these acrylic monomers, also using benzene such as styrene, α-methylstyrenes Vinyl monomer；The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether；Vinyl acetate, butyric acid The vinyl acetates class such as vinyl acetate, vinyl laurate, stearic acid vinyl ester；The insatiable hungers such as ethylene, propylene, isoprene, butadiene And hydrocarbon；The halogen-containing monomer such as vinyl chloride, vinyl fluoride, chlorostyrene；(different) triallyl cyanurate, tri trimellitate allyl Ester, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ-(methyl) acryloyl The monomers such as oxygroup propyl trimethoxy silicane, trimethoxysilyl styrene, vinyltrimethoxysilane.
In addition, such as polydivinylbenezene particle, polychlorobutadiene grain can be used as above-mentioned ethylene base system particle Son, butadiene rubber particle etc..
As the commercially available product in above-mentioned carbamate system particle, such as Art Pearl (Negami can be enumerated Chemical Industrial Co., Ltd system), Dimic Beads (Dainichiseika Color Chem's system) etc., can be by it Be classified and use.
It is bad from the cementability reduction of inhibition gained sealing material for liquid crystal display device, the interval of gained liquid crystal display element From the perspective of, it is above-mentioned softness particle hardness preferred lower limit be 10, preferred upper limit 50.The hardness of above-mentioned softness particle More preferable lower limit is 20, the more preferable upper limit is 40.
It should be noted that the hardness of above-mentioned softness particle refers to through the side according to JIS K 6253 in this specification The Durometer A hardness of method measurement.
For the content of above-mentioned softness particle relative to sealing material for liquid crystal display device entirety, preferred lower limit is 15 weight %. By making the 15 weight % of content or more of above-mentioned soft particle, the effect for inhibiting sealing rupture, liquid crystal pollution to occur is more excellent. The more preferable lower limit of the content of above-mentioned softness particle is 20 weight %.
In addition, from the viewpoint of reducing cementability, the interval of liquid crystal display element is bad caused by inhibiting because of rebound, on The content of soft particle is stated relative to sealing material for liquid crystal display device entirety, preferred upper limit is 50 weight %.Above-mentioned softness grain The more preferable upper limit of the content of son is 40 weight %.
Sealing material for liquid crystal display device of the invention is preferably for raising viscosity, by stress dispersion effect come further It improves the purpose of cementability, the moisture-proof for improving linear expansivity, raising solidfied material etc. and contains filler.
As above-mentioned filler, it is de- that such as silica, talcum, bead, asbestos, gypsum, diatomite, illiteracy can be enumerated Soil, bentonite, montmorillonite, sericite, atlapulgite, aluminium oxide, zinc oxide, iron oxide, magnesia, tin oxide, titanium oxide, carbonic acid The inorganic fillers such as calcium, magnesium carbonate, magnesium hydroxide, aluminium hydroxide, aluminium nitride, silicon nitride, barium sulfate, calcium silicates；Polyester micropartical, The organic fillers such as polyurethane particulate, polyvinyl particle, acrylic polymer particle.
For the content of above-mentioned filler relative to whole 100 parts by weight of curable resin, preferred lower limit is 10 parts by weight, preferably The upper limit is 70 parts by weight.By making the content of the above-mentioned filler range, it can further play and coating etc. is inhibited to dislike The effect of change and raising cementability etc..The more preferable lower limit of the content of above-mentioned filler is 20 parts by weight, the more preferable upper limit is 60 Parts by weight.
Sealing material for liquid crystal display device of the invention preferably contains silane for the purpose for further increasing cementability Coupling agent.Above-mentioned silane coupling agent mainly has as the work for making the bonding additives of the good bondings such as sealant and substrate With.
As above-mentioned silane coupling agent, such as 3- TSL 8330,3- mercaptopropyi can be compatibly used Trimethoxy silane, 3- glycidoxy-propyltrimethoxy silane etc..
The content of above-mentioned silane coupling agent is 0.1 weight relative to whole 100 parts by weight of curable resin, preferred lower limit Part, preferred upper limit are 20 parts by weight.By making the content of the above-mentioned silane coupling agent range, inhibition can be further played Liquid crystal pollution occurs and improves the effect of cementability.The more preferable lower limit of the content of above-mentioned silane coupling agent is 0.5 parts by weight, more Preferred upper limit is 10 parts by weight.
Sealing material for liquid crystal display device of the invention can contain opacifier.By containing above-mentioned opacifier, the present invention Sealing material for liquid crystal display device can be suitably used as shading sealant.
As above-mentioned opacifier, it can enumerate that black such as iron oxide, titanium, nigrosine, phthalocyanine be black, fullerene, carbon black, resin Cover type carbon black etc..Wherein, preferably titanium is black.
It is near ultraviolet range, especially wavelength is that the transmissivity of the light of 370~450nm is higher than pair that above-mentioned titanium is black In the substance of the average transmittance for the light that wavelength is 300~800nm.That is, it is the opacifier having the following properties that above-mentioned titanium is black: logical It crosses the sufficiently light of the wavelength of masking visible light region and assigns light-proofness to sealing material for liquid crystal display device of the invention, it is another Aspect makes the light transmission of the wavelength near ultraviolet range.As what is contained in sealing material for liquid crystal display device of the invention The high substance of opacifier, preferably insulating properties, the opacifier high as insulating properties, it is black to be also suitably for titanium.
Above-mentioned titanium is black to play sufficient effect non-surface treated, and surface also can be used and be coupled agent etc. Titanium obtained from organic principle processing is black；Be oxidized silicon, titanium oxide, germanium oxide, aluminium oxide, zirconium oxide, magnesia etc. it is inorganic at Point covering titanium is black etc. that surface treated titanium is black.Wherein, from the viewpoint of it can further increase insulating properties, preferably with having The titanium that machine ingredient is handled is black.
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, thus can be realized not light leakage, with high contrast, it is aobvious with excellent image Show the liquid crystal display element of quality.
As above-mentioned titanium it is black in commercially available product, can enumerate such as 12S, 13M, 13M-C, 13R-N, 14M-C (is Mitsubishi Materials Corporation system), Tilak D (Ako Kasei Co., Ltd.'s system) etc..
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, preferred lower limit 1nm, preferred upper limit are 5 μm.By making the primary particle size of the above-mentioned opacifier range, gained liquid crystal Show that the viscosity of element sealant, thixotropy not will increase dramatically, coating is more excellent.The primary particle size of above-mentioned opacifier is more Preferred lower limit is 5nm, the more preferable upper limit is 200nm, further preferred lower limit is 10nm, the further preferred upper limit is 100nm.
It should be noted that the primary particle size of above-mentioned opacifier can be used particle size distribution meter (for example, PARTICLE SIZING SYSTEMS corporation, " NICOMP 380ZLS ") it is measured.
The preferred 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 5 parts by weight, preferred upper limit are 80 parts by weight.By making the content of the above-mentioned opacifier range, gained is used for liquid crystal display element Intensity and drafting property after the cementability of sealant, solidification will not reduce, and can further play the effect for improving light-proofness. The more preferable lower limit of the content of above-mentioned opacifier is 10 parts by weight, the more preferable upper limit is 70 parts by weight, and further preferred lower limit is 30 parts by weight, the further preferred upper limit are 60 parts by weight.
Sealing material for liquid crystal display device of the invention further can contain stress moderator, reactivity as needed The additives such as diluent, thixotropic 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, it can enumerate and for example be distributed using homogeneous The mixing machines such as device, mixer for well-distribution, omnipotent mixer, epicyclic mixer, kneader, triple-roller mill, by curable resin with polymerize The method etc. that initiator and/or thermal curing agents are mixed with additives such as the silane coupling agents that is added as needed.
The preferred upper limit of the glass transition temperature of the solidfied material of sealing material for liquid crystal display device of the invention is 100 ℃.By make 100 DEG C of above-mentioned glass transition temperature hereinafter, the cementability of sealing material for liquid crystal display device of the invention more It is excellent.The more preferable upper limit of above-mentioned glass transition temperature is 80 DEG C, the further preferred upper limit is 60 DEG C.
In addition, the preferred lower limit of the glass transition temperature of above-mentioned solidfied material is 40 from the viewpoint of anti-penetrability etc. DEG C, more preferable lower limit be 46 DEG C.
It should be noted that above-mentioned " glass transition temperature " refers to: being obtained by Measurement of Dynamic Viscoelasticity in this specification Among the maximum of the loss angle tangent (tan δ) arrived, there is the temperature of the maximum as caused by micro Brownian motion.Above-mentioned glass Changing transition temperature can be measured by using the conventionally known method of determination of viscoelasticity device etc..
In addition, can be used as the solidfied material for measuring above-mentioned glass transition temperature and measure above-mentioned storage modulus Solidfied material similarly makes product obtained from sealant cures.
By cooperating electrically conductive microparticle into sealing material for liquid crystal display device of the invention, conductive material up and down can be manufactured Material.Such conductive material up and down containing sealing material for liquid crystal display device and electrically conductive microparticle of the invention is also the present invention One of.
As above-mentioned electrically conductive microparticle, metal ball can be used, be formed with conductive metal layer on the surface of resin particle Electrically conductive microparticle etc..Wherein, the electrically conductive microparticle that conductive metal layer is formed on the surface of resin particle passes through resin particle Excellent resilience and the ground such as transparent substrate can not be damaged and be conductively connected, so be suitble to.
Use liquid crystal display made of 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.
Sealing material for liquid crystal display device of the invention is applicable to manufacture liquid crystal display element by liquid crystal dripping method.
It is specific enumerable to go out for example to have as the method for manufacturing liquid crystal display element of the invention by liquid crystal dripping method There is the method etc. of following processes: by silk-screen printing, distribution coating etc., sealing material for liquid crystal display device of the invention etc. being made to exist The process of rectangular seal pattern is formed on substrate；In the uncured state such as sealing material for liquid crystal display device of the invention Under, the fine droplet dropwise addition of liquid crystal is applied to entire surface in the frame of transparent substrate, is overlapped the process of other substrates immediately；With And and keep sealant pre- solid the light such as the seal pattern partial illumination ultraviolet light of sealing material for liquid crystal display device of the invention etc. The process of change；And the sealant of precuring is heated and carries out leading cured process.
As aforesaid substrate, it is suitably for flexible base board.
As above-mentioned flexible base board, it can enumerate and for example use polyethylene terephthalate, polyester, poly- (methyl) The plastics substrate of acrylate, polycarbonate, polyether sulfone etc..In addition, sealing material for liquid crystal display device of the invention can also To be used when being bonded common glass substrate.
Aforesaid substrate is usually formed the transparent electrode comprising indium oxide etc., the alignment films comprising polyimides etc., inanimate matter Ion shielding film etc..
Invention effect
In accordance with the invention it is possible to provide the sealing material for liquid crystal display device of cementability and anti-excellent moisture permeability.In addition, root According to the present invention, it is capable of providing using upper and lower conductive material and liquid crystal display element made of the sealing material for liquid crystal display device.
Specific embodiment
The present invention is described in more detail in embodiment described below, but the present invention is not limited to these embodiments.
(embodiment 1)
Use planetary stirring machine (THINKY CORPORATION system, " あ わ と りTaro "), polymerism will be used as Close the caprolactone modification bisphenol-a epoxy acrylate (DAICEL-ALLNEX LTD. system, " EBECRYL3708 ") 75 of object (a) Parts by weight, as polymerizable compound (b) acrylic acid 2- hydroxyl -3- phenoxy-propyl (Kyoeisha Chemical Co., Ltd.'s system, " Epoxy Ester M-600A ") 10 parts by weight, the acyl modified bisphenol E-type ring of part propylene as polymerizable compound (c) Oxygen resin (DAICEL-ALLNEX LTD. system, " KRM8287 ") 15 parts by weight, the 1- (4- as optical free radical polymerization initiator (phenylsulfartyl) phenyl) -1,2- octadione- 2- (O- benzoyl oxime) (BASF AG's system, " IRGACURE OXE01 ") 1 weight Part, as acid dihydrazide (Otsuka Kagaku K.K.'s system, " MDH ") 1 parts by weight of thermal curing agents, as the two of filler Silica (ADMATECHS CO., LTD. system, " Admafine SO-C2 ") 50 parts by weight, the 3- epoxy as silane coupling agent Third oxygen propyl trimethoxy silicane (Shin-Etsu Chemial Co., Ltd's system, " KBM-403 ") 1 parts by weight and slow as stress After being mixed with core-shell acrylic-resin copolymer particle (ZEON KASEI CO., LTD system, " F351 ") 10 parts by weight of agent, It further uses triple-roller mill to be mixed, to prepare sealing material for liquid crystal display device.
For the 100mW/cm for using metal halide lamp to irradiate to gained sealing material for liquid crystal display device 30 seconds2It is ultraviolet After line (wavelength 365nm), with 120 DEG C are heated 1 hour and make its cured solidfied material, measurement of dynamic viscoelasticity device is used (IT measurement control Co. Ltd. system, " DVA-200 "), with 25 DEG C test film width be 5mm, it is wide with a thickness of 0.35mm, clamping Degree is 25mm, the storage modulus that heating rate is 10 DEG C/min, frequency measures under conditions of being 10HZ is 1.0GPa, identical Under conditions of with 60 DEG C measure storage modulus be 0.04GPa.
(embodiment 2~10 and Comparative Examples 1 and 2)
By the way that each material of match ratio described in table 1 is stirred mixing similarly to Example 1, to prepare embodiment 2~10 and Comparative Examples 1 and 2 sealing material for liquid crystal display device.
For resulting each sealing material for liquid crystal display device, solidfied material is made similarly to Example 1, for resulting Each solidfied material, 25 DEG C measured similarly to Example 1 and 60 DEG C of storage modulus are shown in table 1.
< evaluates >
For each sealing material for liquid crystal display device obtained by embodiment and comparative example, following evaluations are carried out.It will knot Fruit is shown in table 1.
(glass transition temperature)
Using metal halide lamp, each sealing material for liquid crystal display device obtained by embodiment and comparative example is irradiated 30 seconds 100mW/cm2It after ultraviolet light (wavelength 365nm), is heated 1 hour with 120 DEG C, makes the film with a thickness of 300 μm, system At test film.For gained test film, measurement of dynamic viscoelasticity device (IT measurement control Co. Ltd. system, " DVA- are used 200 ") dynamic viscoelastic, is measured at -80 DEG C~200 DEG C, 10Hz, the temperature of the maximum of loss angle tangent (tan δ) is made It is found out for glass transition temperature.
(cementability)
Take the sealing material for liquid crystal display device of denier respectively obtained by embodiment and comparative example be placed in 20mm × The central portion of polyethylene terephthalate (PET) film (LINTEC CO., LTD. system, " PET5011 ") of 50mm, on it It is overlapped the PET5011 of same size, sealing material for liquid crystal display device is sprawled in pressing.In this state, using metal halide Lamp, the 100mW/cm of irradiation 30 seconds2It after ultraviolet light (wavelength 365nm), is heated 1 hour with 120 DEG C, makes adhesive test piece. Use EZgraph (Shimadzu Corporation's system), the adhesive strength of measurement gained adhesive test piece.In addition, using glass Substrate replaces PET5011, similarly makes adhesive test piece, measures adhesive strength.
"○" is denoted as when adhesive strength is 1N/cm or more, adhesive strength be 0.5N/cm more than or lower than 1N/cm when be denoted as " △ ", adhesive strength are denoted as "×" when being lower than 0.5N/cm, evaluate it for the cementability of PET film.
(anti-penetrability)
Using coating machine, by each sealing material for liquid crystal display device obtained by embodiment and comparative example with 200~300 μm thickness coating be that smooth demoulding is membranaceous, use 30 seconds 100mW/cm of metal halide light irradiation2(wavelength is ultraviolet light After 365nm), heated 1 hour with 120 DEG C, to obtain moisture permeability measurement cured film.By based on the damp proof of JIS Z 0208 The method of the moisture permeability test method (agar diffusion method) of packaging material makes moisture permeability test cup, installs resulting moisture permeability measurement With cured film, investment to temperature 60 C, the constant temperature constant humidity baking oven of humidity 90%RH measures moisture permeability.The value of gained moisture permeability is low In 70g/m2"○" is denoted as when r for 24 hours, is 70g/m2R is more than or lower than 100g/m for 24 hours2" △ " is denoted as when r for 24 hours, is 100g/m2"×" is denoted as when r or more for 24 hours, evaluates anti-penetrability.
(low liquid crystal pollution)
Disperse spacer in 100 parts by weight of each sealing material for liquid crystal display device obtained by embodiment and comparative example Particle (Sekisui Chemical Co., Ltd's system, " MICRO PEARL SI-H050 ") 1 parts by weight, for two panels band brushing One of substrate (length 75mm, width 75mm, with a thickness of 0.7mm) of alignment films and transparent electrode, is reached with display unit Mode to 45mm × 55mm, the sealant line width with 1mm are allocated coating.
Then, the fine droplet dropwise addition of liquid crystal (CHISSO CORPORATION system, " JC-5004LA ") is applied to band thoroughly Entire surface in the frame of the sealant of the substrate of prescribed electrode is bonded another filter substrate with transparent electrode immediately, uses gold Belong to halide lamp to 30 seconds 100mW/cm of sealant partial illumination2It is small with 120 DEG C of heating 1 after ultraviolet light (wavelength 365nm) When, obtain liquid crystal display element.
After confirming and carrying out operating operation test in 100 hours to gained liquid crystal display element, become and applied with 80 DEG C by visual observation Liquid crystal aligning disorder near sealant after adding the state of 1000 hours voltage.
Orientation disorder judged by the irregular colour of display unit, not according to the degree of irregular colour, absolutely not color Equal Shi Jizuo " ◎ ", it is denoted as that "○", there are be denoted as " △ " when a small amount of irregular colour, be clearly present face when slightly there is irregular colour It is denoted as "×" when color unevenness, thinks poorly of liquid crystal pollution.
It should be noted that be evaluated as " ◎ ", the liquid crystal display element of "○" be practical aspect absolutely not problem water Flat, " △ " is to be designed according to the display of liquid crystal display element and be possible to the level to go wrong, and "×" is unsuitable for practical It is horizontal.
(impact resistance of liquid crystal display element)
For each sealing material for liquid crystal display device obtained by embodiment and comparative example, with above-mentioned " (low liquid crystal pollution Property) " 10 (10 units) liquid crystal display elements are similarly respectively made, it carries out carrying out each liquid crystal display element from the height of 2m The drop test of whereabouts.After drop test, all units are denoted as "○" when because of removing, breakage not leading to liquid crystal leakage, and 1 Unit more than or lower than 5 units liquid crystal display element there are being denoted as when liquid crystal leakage " △ ", liquid crystals more than 5 units Show that element there are "×" is denoted as when liquid crystal leakage, evaluates the impact resistance of liquid crystal display element.
[table 1]
Industrial availability
In accordance with the invention it is possible to provide the sealing material for liquid crystal display device of cementability and anti-excellent moisture permeability.In addition, root According to the present invention, it is capable of providing using upper and lower conductive material and liquid crystal display element made of the sealing material for liquid crystal display device.

Claims (8)

1. a kind of sealing material for liquid crystal display device, which is characterized in that containing curable resin and polymerization initiator and/or Thermal curing agents,
The solidfied material of the sealing material for liquid crystal display device is 0.8GPa~3.0GPa in 25 DEG C of storage modulus,
The solidfied material of the sealing material for liquid crystal display device is 0.04GPa or more in 60 DEG C of storage modulus.
2. sealing material for liquid crystal display device according to claim 1, which is characterized in that curable resin contains polymerism Compound, open loop of the polymerizable compound with 1 or more polymerizable functional group and 1 or more lactone in 1 molecule Structure and/or 1 or more acrylonitrile-butadiene structure.
3. sealing material for liquid crystal display device according to claim 2, which is characterized in that curable resin contains simple function Polymerizable compound, the simple function polymerizable compound with 1 polymerizable functional group and do not have lactone in 1 molecule Open loop structure and acrylonitrile-butadiene structure.
4. sealing material for liquid crystal display device according to claim 3, which is characterized in that whole 100 weights of curable resin It measures in part, with 1 polymerizable functional group and without the open loop structure and acrylonitrile-butadiene structure of lactone in 1 molecule Simple function polymerizable compound content be 1~30 parts by weight.
5. sealing material for liquid crystal display device according to claim 1,2,3 or 4, which is characterized in that contain soft particle.
6. sealing material for liquid crystal display device according to claim 1,2,3 or 4, which is characterized in that contain opacifier.
7. a kind of conductive material up and down, which is characterized in that containing described in electrically conductive microparticle and claim 1,2,3,4,5 or 6 Sealing material for liquid crystal display device.
8. a kind of liquid crystal display element, which is characterized in that it is using liquid crystal display described in claim 1,2,3,4,5 or 6 Obtained from element sealant or upper and lower conductive material as claimed in claim 7 are manufactured.
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