CN101875832A - Liquid crystal sealing agent and use the liquid crystal display of this liquid crystal sealing agent - Google Patents

Liquid crystal sealing agent and use the liquid crystal display of this liquid crystal sealing agent Download PDF

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Publication number
CN101875832A
CN101875832A CN2010101714053A CN201010171405A CN101875832A CN 101875832 A CN101875832 A CN 101875832A CN 2010101714053 A CN2010101714053 A CN 2010101714053A CN 201010171405 A CN201010171405 A CN 201010171405A CN 101875832 A CN101875832 A CN 101875832A
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liquid crystal
sealing agent
crystal sealing
resin
methyl
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CN2010101714053A
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CN101875832B (en
Inventor
吉田早纪
落直之
三轮广明
木田昌博
太田英之
西原荣一
并木务
今澄贵公男
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/483Reactive adhesives, e.g. chemically curing adhesives
    • B29C65/4835Heat curing adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/483Reactive adhesives, e.g. chemically curing adhesives
    • B29C65/4845Radiation curing adhesives, e.g. UV light curing adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/483Reactive adhesives, e.g. chemically curing adhesives
    • B29C65/485Multi-component adhesives, i.e. chemically curing as a result of the mixing of said multi-components
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1339Gaskets; Spacers; Sealing of cells

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

Abstract

The invention provides a kind of sealing agent with excellent coating and solidified nature, moisture-proof reliability excellence.A kind of liquid crystal sealing agent, it contains (a) and has the resin particle of core shell structure and (b) light-cured resin, and, use viscosity under 25 ℃ of E type viscometer determining as below the 100Pas, pre-baked viscosity is more than the 100Pas and below the 400Pas.

Description

Liquid crystal sealing agent and use the liquid crystal display of this liquid crystal sealing agent
Technical field
The present invention relates to liquid crystal sealing agent and use the liquid crystal display (liquid crystal is represented the セ Le) of this liquid crystal sealing agent, described liquid crystal sealing agent is excellent for some glue coating (デ イ ス ペ ン ス Tu worker property), can tackle silk screen printing, viscosity is the following liquid crystal sealing agent of 100Pas, and do not embed sealing via drying process or preliminary drying (プ リ ベ イ Network) operation liquid crystal.
Background technology
In recent years, the application extension of liquid crystal display is to the large display screen curtain of televisor etc., and the demand to liquid crystal display in a lot of purposes becomes big.Therefore, about the manufacturing of liquid crystal panel,, require substrate maximization and production time per piece (time of each operation) to shorten in order further to improve production.
When making liquid crystal indicator, after being coated on liquid crystal sealing agent on the glass substrate by methods such as a glue coating or silk screen printings, seal and form the unit, in vacuum, liquid crystal is injected in the unit from the liquid crystal injecting port that is arranged on the unit part, use sealing agent or sealing compound to seal this liquid crystal injecting port, make thus (vacuum impregnation).
In addition, in the cofferdam that is formed from a resin (weir), fit behind the dispenser method and the liquid crystal drip-injection method (method under the liquid crystal drop) that makes resin solidification also just in practicability.In liquid crystal drip-injection method, at first, form the rectangular seal pattern that constitutes by uncured sealing agent by some glue (デ イ ス ペ Application ス) on the plate base in 2 belt electrode transparency carriers.Then, on under the uncured state of sealing agent, the fine droplet of liquid crystal being instiled and being coated in the frame of seal pattern of transparency carrier comprehensively, fit with another transparency carrier immediately then, make liquid crystal cells, to seal pattern part irradiation ultraviolet radiation, carry out Procuring (Provisional sclerosis).Thereafter, curing (this sclerosis) is led in heating as required, makes liquid crystal display.Under reduced pressure carry out if make the operation of liquid crystal cells by adhesive substrates, just can be with high efficiency system liquid making crystal display element, at present, this drip-injection method is the main manufacture method of liquid crystal display device.
When making liquid crystal display device by liquid crystal drip-injection method, the seal pattern of the liquid crystal display device that generation makes deforms, liquid crystal embeds phenomenon (the embedding (Cha Write body) phenomenon in the seal pattern), and have the problem of the orientation of upsetting near the liquid crystal the sealing pattern.As the method that addresses this problem, think the method for using the common high sealing agent of viscosity ratio to form seal pattern is for example arranged, but may make a colloidality (デ イ ス ペ Application ス) variation, the style of calligraphy characterized by hollow strokes (か The れ) when producing some glue, broken string problems such as (Line cut れ).In addition, be purpose with in recent years further shortening production time per piece etc., in order to improve a glue speed and can easily to utilize silk screen printing to form seal pattern, require viscosity lower and do not embed the sealing agent of phenomenon.
About this problem, in patent documentation 1, reported before the operation of making liquid crystal cells, by uncured seal pattern thickening (tackify) is prevented to embed phenomenon.But, be low viscosity below the 100Pas and viscosity can not rise terrifically in the preliminary drying operation and after the preliminary drying operation the liquid crystal sealing agent that is used for liquid crystal drip-injection method about the initial viscosity after the firm preparation, also beyond example.
In addition, in patent documentation 2 and 3, reported the liquid crystal sealing agent that comprises the rubbery polymer particulate.In two documents, below all non-100Pas of initial viscosity.In patent documentation 4, reported the liquid crystal sealing agent of the cross-linked rubber that comprises core shell structure and specific maleimide compound, but initial viscosity surpasses 100Pas.In patent documentation 5, reported the liquid crystal sealing agent of the cross-linked rubber that comprises core shell structure, but initial viscosity surpasses 100Pas.And then, the rubbery polymer particulate be difficult for the shading light part that shone by UV when being used for being suppressed at photocuring the sealing agent composition when thermofixation stripping to the composition of liquid crystal, the effect of the thickening composition when not reporting it as preliminary drying.
Patent documentation 1: TOHKEMY 2008-275670 communique
Patent documentation 2: TOHKEMY 2007-219039 communique
Patent documentation 3: TOHKEMY 2007-262253 communique
Patent documentation 4: TOHKEMY 2005-2015 communique
Patent documentation 5: the international brochure that discloses No. 2004/41900
Summary of the invention
Liquid crystal embeds the phenomenon in the sealing agent when the objective of the invention is to suppress liquid crystal drip-injection method, provides to reduce liquid crystal sealing agent that embeds phenomenon and the liquid crystal display that uses this liquid crystal sealing agent.
The inventor etc. have carried out wholwe-hearted research, found that a kind of use has the curable resin composition of the resin particle of core shell structure, its initial viscosity is below the 100Pas, the coating that be coated with at a glue, silk screen printing all has excellence in being coated with, and via also keeping certain following viscosity, while generation unit gap (セ Le ギ ヤ Star プ) after the thickening.Find in addition, by using this curable resin composition, the embedding phenomenon in the time of can preventing liquid crystal drip-injection method, and finished the present invention.That is, the present invention relates to following (1)~(11).
(1) a kind of liquid crystal sealing agent, it contains the resin particle that (a) has core shell structure, and uses viscosity under 25 ℃ that E type viscometer records as below the 100Pas.
(2) as above-mentioned (1) described liquid crystal sealing agent, wherein, further comprise (b) light-cured resin.
(3) as above-mentioned (2) described liquid crystal sealing agent, wherein, (b) light-cured resin is epoxy (methyl) acrylate resin.
(4), wherein, in epoxy (methyl) acrylate resin, comprise 50 quality % above dihydroxy-benzene diglycidylether and acrylic acid reaction product as above-mentioned (3) described liquid crystal sealing agent.
(5) as each described liquid crystal sealing agent in above-mentioned (1)~(4), wherein, further comprise (c) silane coupling agent.
(6), wherein, comprise N-2-(amino-ethyl)-3-TSL 8330 as (c) silane coupling agent as above-mentioned (5) described liquid crystal sealing agent.
(7), wherein, further contain (d) optical free radical polymerization starter (light ラ ジ カ Le heavily closes Open beginning drug) as each described liquid crystal sealing agent in above-mentioned (1)~(6).
(8), wherein, further contain (e) heat reactive resin and/or (f) thermal curing agents as each described liquid crystal sealing agent in above-mentioned (1)~(7).
(9) as above-mentioned (8) described liquid crystal sealing agent, wherein, (e) heat reactive resin is a Resins, epoxy, and (f) thermal curing agents is the organic acid hydrazides.
(10) as each described liquid crystal sealing agent in above-mentioned (1)~(9), wherein, further containing (g) median size is the following mineral fillers of 3 μ m.
(11) a kind of liquid crystal display, the cured article sealing that it obtains by each described liquid crystal sealing agent in above-mentioned (1)~(10) is solidified.
Even liquid crystal sealing agent of the present invention also can keep certain certain following viscosity via the preliminary drying operation, therefore, can the generation unit gap.And, the low such excellent effect of the embedding of liquid crystal in sealing agent when having liquid crystal drip-injection method.Therefore,, the time that a glue is coated with, the silk screen printing coating is spent can be shortened, display panels can be easily made by using the sealing agent.
Embodiment
Below, the present invention is described in detail.
The resin particle with core shell structure (a) that uses among the present invention is not particularly limited, for example, can use the resin particle with core particle and shell, described core particle comprises the resin with caoutchouc elasticity, and described shell comprises the resin that is formed at this core particle surface.Particularly, for the core segment and the shell of particle partly has polymer particulates of different nature, preferably have the core-shell-type particulate of grafting layer or the core-shell-type particulate that constitutes by the shell of the core of rubbery polymer and glassy polymers in the outside of particle shape rubber.Core segment for example can be enumerated: butadiene type rubber, acrylic rubber, siloxanes acrylic acid or the like compounded rubber or make core shell acrylic copolymer that the polymerizable monomer polymerization obtains etc.As the example of this polymerizable monomer, can enumerate: (methyl) acrylic ester monomers such as (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) ethyl acrylate, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems; Aromatic ethenyl compounds such as vinylbenzene, Vinyl toluene, alpha-methyl styrene; Vinyl cyanide such as vinyl cyanide, methacrylonitrile based compound; Inclined to one side dicyano ethene, (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-3-hydroxyl butyl ester, fumaric acid-2-hydroxy methacrylate, hydroxy butyl vinyl ether, butyl maleate, methacrylic acid butoxy ethyl ester etc.In addition, can also enumerate: ethylene glycol bisthioglycolate (methyl) acrylate, butyleneglycol two (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, hexylene glycol two (methyl) acrylate, hexylene glycol three (methyl) acrylate, oligomeric ethylene glycol two (methyl) acrylate, oligomeric ethylene glycol three (methyl) acrylate etc. have the cross-linkable monomer of 2 above reactive groups; Aromatic diethylene base monomers such as Vinylstyrene; Trimellitic acid triallyl, triallyl isocyanurate etc., can use in them more than a kind or 2 kinds.When using resin particle except that the resin particle with core shell structure or thickening material, thickening at short notice perhaps is difficult to keep certain viscosity.Have the resin particle of core shell structure by use, the initial viscosity that makes liquid crystal sealing agent is below the 100Pas, by the suitable thickening of preliminary drying operation, can suppress liquid crystal and embed in the sealing agent.Resin particle (a) with core shell structure can obtain from the market, and the outside that for example can be set forth in particle shape rubber has メ タ Block レ Application シ リ one ズ that Mitsubishi Rayon Co. Ltd. of grafting layer (レ イ ヨ Application Co., Ltd. of Mitsubishi) makes or changes into the system F-351 of Co., Ltd. etc. as the ガ Application Star of acrylate copolymer.Need to prove,, when the total amount of liquid crystal sealing agent of the present invention is set at 100 quality %, be preferably 5 quality %~30 quality %, be preferably 10 quality %~20 quality % especially as the content of the resin particle with core shell structure (a).
Initial viscosity after the firm preparation of liquid crystal sealing agent of the present invention is below the 100Pas.Initial viscosity is 100Pas when following, some glue coating excellence, and, can tackle silk screen printing.Even liquid crystal sealing agent of the present invention thickening by the preliminary drying operation is but also acutely rising of viscosity after the thickening.Liquid crystal sealing agent of the present invention thickening at short notice, and viscosity stability excellence.In addition, be more than the 100Pas and 400Pas when following by the viscosity after the preliminary drying thickening, the generation unit gap, can carry out applying thereafter no problemly, can make liquid crystal cells, therefore, liquid crystal sealing agent of the present invention is below the 400Pas with the viscosity after the preliminary drying thickening preferably.By pre-baked heating completely solidified.Thus, liquid crystal embeds in the sealing agent in the time of can preventing liquid crystal drip-injection method.
The light-cured resin that uses among the present invention (b) just is not particularly limited as long as the stripping property in liquid crystal is low; can enumerate urethane acrylate; (methyl) acrylate (or salt); epoxy (methyl) acrylate etc. has the compound of acryl as functional group; specifically have: benzyl methacrylate; cyclohexyl methacrylate; the glycerine dimethacrylate; the glycerine trimethacrylate; the glycerol tri-acrylate of EO modification; pentaerythritol acrylate; Viscoat 295; isocyanuric acid three (acryloxy ethyl) ester; dipentaerythritol acrylate; the Phloroglucinol triacrylate; 1,6-hexylene glycol diglycidyl ether acrylate etc.In addition, consider preferred especially epoxy (methyl) acrylate resin from the viewpoint of liquid crystal pollution.This epoxy (methyl) acrylate resin can obtain by making the Resins, epoxy that has 2 above epoxy group(ing) in acrylic or methacrylic acid and the molecule carry out esterification at least.This building-up reactions can be carried out with common known method.For example, add catalyzer (for example benzyldimethylamine, triethylamine, benzyl trimethyl ammonium chloride, triphenylphosphine, triphenyl Deng) and stopper (for example hydroquinone monomethyl ether, Resorcinol, methyl hydroquinone, thiodiphenylamine, butylated hydroxytoluene etc.), the acrylic or methacrylic acid that makes predetermined equivalence ratio and Resins, epoxy are for example carrying out esterification under 80~110 ℃.In addition, as the Resins, epoxy that has at least 2 above epoxy group(ing) in the molecule, for example can enumerate: bisphenol A type epoxy resin, the bisphenol A type epoxy resin that alkyl replaces, the bisphenol A type epoxy resin of oxirane addition, bisphenol f type epoxy resin, the bisphenol f type epoxy resin that alkyl replaces, the bisphenol f type epoxy resin of oxirane addition, bisphenol-s epoxy resin, the bisphenol-s epoxy resin that alkyl replaces, the bisphenol-s epoxy resin of oxirane addition, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, naphthalene type Resins, epoxy, glycidyl amine type epoxy resin, dicyclopentadiene-type epoxy resin, the Resins, epoxy of siloxanes (silicone) modification, the Resins, epoxy of carbamate (urethane) modification, the Resins, epoxy of modified rubber etc., preferred bisphenol A type epoxy resin, the bisphenol A type epoxy resin that alkyl replaces, the bisphenol A type epoxy resin of oxirane addition, bisphenol f type epoxy resin, the bisphenol f type epoxy resin that alkyl replaces, the bisphenol f type epoxy resin of oxirane addition, bisphenol-s epoxy resin, the bisphenol-s epoxy resin that alkyl replaces, the bisphenol-s epoxy resin of oxirane addition.In the present invention, when the total amount of liquid crystal sealing agent of the present invention was set at 100 quality %, light-cured resin (b) shared content in liquid crystal sealing agent was about 20 quality %~about 80 quality %.
In the present invention, especially preferably comprise the above resorcinol diglycidyl ether of the 50 quality % that account for epoxy (methyl) acrylate resin total amount and acrylic acid reaction product as epoxy (methyl) acrylate resin.The liquid crystal pollution excellence of resorcinol diglycidyl ether and acrylic acid reaction product and be low viscosity, therefore, use its sealing agent of the present invention with liquid crystal pollution, and the relevant characteristic of viscosity further improve.
In order to improve bonding strength, liquid crystal sealing agent of the present invention preferably contains silane coupling agent (c).As silane coupling agent, for example can enumerate: the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-sulfydryl propyl trimethoxy silicane, vinyltrimethoxy silane, N-(2-(vinyl benzyl amino) ethyl)-3-TSL 8330 hydrochloride, the 3-methyl allyl acyloxypropyl trimethoxysilane, the 3-chloropropylmethyldimethoxysilane, silane coupling agents such as 3-r-chloropropyl trimethoxyl silane.These silane coupling agents can mix use more than 2 kinds.Wherein, in order to obtain better adhesive strength and thixotropy, 2 kinds of silane coupling agents of preferably combination use.Further preferred wherein a kind of silane coupling agent is to have amino silane coupling agent.Especially preferably comprise N-2-(amino-ethyl)-3-TSL 8330 as amino silicane coupling agent.N-2-(amino-ethyl)-3-TSL 8330 can obtain (for example, SHIN-ETSU HANTOTAI's chemical industry system KBM-603) from the market.By using silane coupling agent, the liquid crystal sealing agent that can obtain having strong tackiness and coating excellence.When the total amount of liquid crystal sealing agent of the present invention was set at 100 quality %, this silane coupling agent (c) shared content in liquid crystal sealing agent was preferably 0.05~3 quality %.
In addition; the optical free radical polymerization starter (d) that uses among the present invention so long as the radical-type polymerization initiator just be not particularly limited; for example can enumerate: benzil dimethyl ketal, 1-hydroxycyclohexylphenylketone, diethyl thioxanthone, benzophenone, 2-ethyl-anthraquinone, 2-hydroxy-2-methyl Propiophenone, 2-methyl-[4-(methylthio group) phenyl]-2-morpholinyl-1-propane, 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide etc.In addition, can also use 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone or methacrylic acid-2-isocyanato ethyl ester and 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-reaction product of 2-methylpropane-1-ketone.
In the liquid crystal sealing agent of the present invention, about the proportioning of composition (d) optical free radical polymerization starter with respect to composition (b), with respect to composition (b) 100 mass parts, composition (d) is 0.01~20 mass parts, is preferably 5~15 mass parts.The content of free-radical generating type optical free radical polymerization starter is during less than 0.01 mass parts, and photocuring reaction is insufficient, and during greater than 20 mass parts, the content of initiator is too much, exists initiator to pollute the problem that liquid crystal or cured resin characteristic reduce.
Can also contain heat reactive resin (e) and thermal curing agents (f) in the liquid crystal sealing agent of the present invention.By using heat reactive resin (e) and thermal curing agents (f), the liquid crystal pollution change is good, and the reliability of adhesive strength and hot resistance test improves.
As operable heat reactive resin (e) among the present invention, be not particularly limited, the above Resins, epoxy of preferred 2 officials energy for example can be enumerated: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, bisphenol-A phenolic varnish type Resins, epoxy, bisphenol F phenolic varnish type Resins, epoxy, alicyclic epoxy resin, aliphatics chain Resins, epoxy, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glycolylurea type Resins, epoxy, the isocyanuric acid ester type epoxy resin, phenol novolak type epoxy resin with triphenol methylmethane skeleton, and the 2-glycidyl etherificate thing of two sense phenols, the 2-glycidyl etherificate thing of two sense alcohols, and their halogenide, hydride etc.Wherein, consider preferred bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin from the viewpoint of liquid crystal pollution.
In addition, the water-disintegrable cl content as the Resins, epoxy of the heat reactive resin that uses among the present invention is preferably below the 600ppm.Water-disintegrable cl content is during greater than 600ppm, and liquid crystal sealing agent may become problem to the contaminative of liquid crystal.Water-disintegrable cl content for example can be by being dissolved in about 0.5g Resins, epoxy in the 20ml dioxane, after carrying out refluxing in 30 minutes with the KOH/ ethanolic soln 5ml of 1N, carries out titration with the 0.01N silver nitrate solution, and is quantitative thus.When the total amount of liquid crystal sealing agent of the present invention was set at 100 quality %, this Resins, epoxy shared content in liquid crystal sealing agent of the present invention was about 0~about 50 quality %.
In addition, operable in the liquid crystal sealing agent of the present invention (f) composition is not particularly limited, and can preferably use solid-state organic acid hydrazides.For example can enumerate: as Whitfield's ointment hydrazides, phenylformic acid hydrazides, naphthalene-1-formic acid hydrazides, terephthaldehyde's acid dihydrazide, isophthalic dihydrazide, the naphthalene-2 of aromatic series hydrazides, 6-diformazan acid dihydrazide, pyridine-2,6-diformazan acid dihydrazide, benzene-1,2,4-tricarboxylic acid three hydrazides, naphthalene-1,4,5,8-tetracarboxylic acid four hydrazides, Pyromellitic Acid four hydrazides etc.In addition, when this organic acid hydrazides is the aliphatics hydrazide compound, for example can enumerate: formyl hydrazine, acethydrazide, the propionyl hydrazine, oxalic acid two hydrazides, propanedioic acid two hydrazides, the amber acid dihydrazide, pentanedioic acid two hydrazides, adipic dihydrazide, pimelic acid two hydrazides, hexanaphthene-1,4-diformazan acid dihydrazide, the winestone acid dihydrazide, the apple acid dihydrazide, iminodiethanoic acid two hydrazides, N, the two Urea,amino-of N '-hexa-methylene, citric acid three hydrazides, nitrilotriacetic acid(NTA) three hydrazides, hexanaphthene tricarboxylic acid three hydrazides, 1, two (diazanyl the carbonyl ethyl)-5-sec.-propyl glycolylurea of 3-etc. have two hydrazides classes of Xie Ansuan glycolylurea skeleton etc.Consider from the viewpoint of the balance of solidification reactivity and potentiality, be preferably two functional two hydrazides, especially preferably enumerate a diformazan acid dihydrazide.
When the median size of these hydrazide compounds is excessive, can become the major cause of problems such as the gap that is created in the time of will going up the lower glass substrate applying in the liquid crystal cells process of making narrow gap can not form smoothly, therefore, be preferably below the 3 μ m, more preferably below the 2 μ m.In addition, same, maximum particle diameter is preferably below the 8 μ m, more preferably below the 5 μ m.This particle diameter is by laser diffraction and scattering formula particle size distribution device (dry type) (セ イ シ Application enterprise of Co., Ltd. system; LMS-30) measure.
In the liquid crystal sealing agent of the present invention, the epoxy equivalent (weight) of the epoxy group(ing) of the Resins, epoxy of composition (e) is set at 1 o'clock, the containing ratio of the aromatic series hydrazide compound of composition (f) is 0.2~0.8, is preferably 0.4~0.6.
In addition, as operable mineral filler (g) in the liquid crystal sealing agent of the present invention, can enumerate: fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, lime carbonate, magnesiumcarbonate, barium sulfate, calcium sulfate, mica, talcum, clay, aluminum oxide, magnesium oxide, zirconium white, aluminium hydroxide, magnesium hydroxide, Calucium Silicate powder, pure aluminium silicate, lithium aluminium silicate, zirconium silicate, barium titanate, glass fibre, carbon fiber, molybdenumdisulphide, asbestos etc., preferred molten silicon-dioxide, crystalline silica, silicon nitride, boron nitride, lime carbonate, barium sulfate, calcium sulfate, mica, talcum, clay, aluminum oxide, aluminium hydroxide, Calucium Silicate powder, pure aluminium silicate, more preferably fused silica, crystalline silica, aluminum oxide, talcum.These mineral fillers can mix more than 2 kinds to be used.When its median size is excessive, can become the major cause of problems such as the gap that is created in the time of will going up the lower glass substrate applying in the liquid crystal cells process of making narrow gap can not form smoothly, therefore, median size is preferably below the 3 μ m, more preferably below the 2 μ m.Particle diameter is by laser diffraction and scattering formula particle size distribution device (dry type) (セ イ シ Application enterprise of Co., Ltd. system; LMS-30) measure.
When the total amount of liquid crystal sealing agent of the present invention was set at 100 quality %, the content of operable mineral filler (g) in liquid crystal sealing agent was generally 5~40 quality % in the liquid crystal sealing agent of the present invention, is preferably 15~30 quality %.The content of mineral filler is during less than 5 quality %, the adhesive strength of glass substrate is reduced, and the moisture-proof reliability is also poor, and therefore, the decline of the adhesive strength after the moisture absorption sometimes also becomes big.In addition, the content of mineral filler is during greater than 40 quality %, and filler content is too much, therefore, is difficult for crushing sometimes and can not forms the gap of liquid crystal cells.
Liquid crystal sealing agent of the present invention can further cooperate additives such as organic filler and pigment, flow agent, defoamer, solvent as required.As operable solvent among the present invention, be not particularly limited, for example can enumerate: polyol ethers acetate esters such as the ethers of polyvalent alcohols such as the diacetate esters class of polyvalent alcohols such as propylene-glycol diacetate, diethylene glycol monoethyl ether, dipropylene glycol dme, diethylene glycol monoethyl ether acetic ester etc.
In order to obtain liquid crystal sealing agent of the present invention, at first, dissolving mixes (d) composition, (e) composition in (b) composition as required.Then, in this mixture, mix (c) composition, add (a) composition, thermal curing agents (f), (g) composition and add organic filler, defoamer, flow agent and solvent etc. as required, for example three-roll mill (3 ロ one Le ミ Le), sand mill, ball mill etc. carry out uniform mixing to use known mixing device, filter with wire netting, thus, can make liquid crystal sealing agent of the present invention.
Liquid crystal display of the present invention be will on substrate, be formed with a pair of substrate of predetermined electrode with predetermined interval subtend configuration, and the liquid crystal display that gets with enclosing liquid crystal in the crack around the liquid crystal sealing agent sealing of the present invention and betwixt.The kind of the liquid crystal of enclosing is not particularly limited.At this, substrate constitutes by comprising assembled substrate glass, quartz, plastics, silicon etc., that at least one has a light transmission.As its method for making, when for example being the liquid crystal drip-injection mode, after in liquid crystal sealing agent of the present invention, adding spacer (ス ペ one サ one) (gap control material) such as glass fibre, use this liquid crystal sealing agent of coating in this a pair of substrate one such as adhesive dispensing device (デ イ ス ペ Application サ one) or silk-screen printing device, thickening operation (preliminary drying) such as heat then.For example under 90 ℃, carry out 5~15 minutes preliminary drying operation.Then, the inboard dispenser method to the cofferdam of this liquid crystal sealing agent, superimposed with another glass substrate in a vacuum, carry out the gap and produce.After forming the gap, to sealing liquid crystal portion irradiation ultraviolet radiation, carry out photocuring by the uviolizing machine.Ultraviolet irradiation amount is preferably 500mJ/cm 2~6000mJ/cm 2, 1000mJ/cm more preferably 2~4000mJ/cm 2, as required, 90~130 ℃ under carry out 1~2 hour solidify, can obtain liquid crystal display of the present invention thus thereafter.The liquid crystal display of the present invention that obtains thus is not bad by the demonstration that liquid crystal pollution causes, and tackiness, moisture-proof reliability excellence.As spacer, for example can enumerate glass fibre, silicon-dioxide microballon, polymer bead etc.Its diameter is preferably 4~7 μ m according to purpose and difference is generally 2~8 μ m.About its usage quantity, be generally about 0.1~about 4 mass parts with respect to liquid crystal sealing agent 100 mass parts of the present invention, be preferably about 0.5~about 2 mass parts, more preferably about 0.9~about 1.5 mass parts.
Embodiment
The present invention will be described in more detail by the following examples.In an embodiment, part expression mass parts, % represents quality %.
(the liquid crystal drip-injection method preparation of sealing agent)
With each resinous principle of mixed shown in the following table 1 and after stirring, heating makes the Photoepolymerizationinitiater initiater dissolving.Suitably add filler, thickening material etc., and stir thereafter.Thereafter, make its dispersion with three-roll mill, use metal mesh filter, the preparation liquid crystal drip-injection method is used sealing agent embodiment (1)~(5), comparative example (1)~(5).
Figure GSA00000101245000121
Below represent each liquid crystal drip-injection method of preparation assessment item content and its result with sealing agent.
(liquid crystal pollution)
After each liquid crystal drip-injection method of the bottom of 10ml phial (バ イ ヤ Le bottle) coating 100mg is with sealing agent, add the liquid crystal (MLC-6866-100: メ Le Network Co., Ltd. system) of its 10 times of amounts.Heat after 1 hour, cooled off 30 minutes.After the cooling, get supernatant liquor, with digital ultra-high resistance meter (R8340: the ア of Co., Ltd. De バ Application テ ス ト system) measure, compare with the value of the liquid crystal that does not have sealing agent by the decant branch.Judge by following standard.
More than zero 1.0E+12
·△1.0E+11~1.0E+12
Below * the 1.0E+11
(some colloidality)
Be filled in syringe with sealing agent each liquid crystal drip-injection method that makes and after carrying out deaeration, with adhesive dispensing device (Wu KURA エ Application ジ ニ ア リ Application グ corporate system シ ヨ Star ト マ ス タ 1) on glass substrate with the speed coating sealing agent of 20mm/ second, the Visual Confirmation shape.To have average evaluation that the style of calligraphy characterized by hollow strokes, sealing interrupt etc. for *, be zero with the average evaluation that above-mentioned fault do not occur.
(embedding test)
The substrate of the sealing agent coating that as above operation is made is put in the hot-air oven that is set in 90 ℃, after 10 minutes, an amount of liquid crystal drip-injection in the sealing frame, is placed in the vacuum forming apparatus, under vacuum with another superimposed substrate.After being back to normal atmosphere, Visual Confirmation embeds.Observed 10 minutes, with the average evaluation of sealed penetration (シ one Le パ Application Network) be *, be zero with imperforated average evaluation.
(printing)
After each liquid crystal drip-injection method that makes carried out deaeration with sealing agent with EME deaeration machine, with screen process press (the accurate industry of ニ ユ one ロ Application グ (strain) system LS-150) printing coating sealing agent on glass substrate.The Visual Confirmation printing.To have average evaluation that the style of calligraphy characterized by hollow strokes, sealing interrupt etc. for *, be zero with the average evaluation that above-mentioned fault do not occur.
(viscosity after the thickening)
The liquid crystal drip-injection method that makes is coated on the glass substrate so that the thickness of about 40 μ m is planar with sealing agent, then on 90 ℃ hot plate, heated 5 minutes, 10 minutes, 15 minutes., each coated substrates be back to room temperature, 25 ℃ of viscosity of using E type viscometer determining sealing agent down thereafter.
(cell gap)
At the spacer (PF-50S: Nippon Electric Glass Co., Ltd system) after of each liquid crystal drip-injection method that makes with mixing 5 μ m in the sealing agent, be filled in the syringe and after carrying out deaeration, (military KURA エ Application ジ ニ ア リ Application グ corporate system シ ヨ Star ト マ ス タ 1) is coated with sealing agent on glass substrate with adhesive dispensing device.Then, dispenser method on coated substrates, opposition side fit be coated with spacer in the face (Na ト コ ス ペ one サ one KSEB-525F: glass Na ト コ Co., Ltd. system), via UV irradiation, heating process production unit.(the system OMS-NK3 of Central Motor Wheel Co., Ltd.) measures the unitary cell gap that makes with the liquid crystal characteristic evaluating apparatus.
Table 2
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Liquid crystal pollution ??○ ??○ ?○ ?△ ?○ ??○ ??○ ??○ ?△ ?○
The point colloidality ??○ ??○ ?○ ?○ ?○ ??○ ??○ ??○ ?○
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Embed test ??○ ??○ ?○ ?○ ?△ ??○ ??○ ??○ ?○
Silk screen printing ??○ ??△ ?△ ?△ ?○ ??○ ??○ ??○ ?○
Viscosity after the thickening (5rpm/5 minute) ??128 ??296 ?199 ?118 ?93 ??(*) ??(*) ??(*) ?61 ?486
Viscosity after the thickening (5rpm/10 minute) ??169 ??375 ?269 ?173 ?108 ??(*) ??(*) ??(*) ?75 ?534
Viscosity after the thickening (5rpm/15 minute) ??208 ??(*) ?293 ?230 ?112 ??(*) ??(*) ??(*) ?80 ?577
Cell gap ??5.0 ??5.0 ?5.0 ?5.0 ?5.0 ??6.8 ??7.0 ??6.9 ?5.0 ?5.0
(*) expression viscosity is more than 6000, can not measure with E type viscometer
Industrial applicability
As mentioned above, liquid crystal sealing agent of the present invention except satisfy can tackle serigraphy liquid crystal drip-injection method with the desired initial viscosity of liquid crystal sealing agent, the thixotropy, the production method of liquid crystal pollution, serigraphy, cell gap, the liquid crystal characteristics such as embedding in sealant are also excellent. On the other hand as can be known, although the comparative example initial viscosity is low, excess stickiness increases and generation unit gap not during precuring, perhaps not thickening and liquid crystal pollution, some colloidality variation after the precuring. In addition we know, in the high comparative example of initial viscosity, some colloidality or serigraphy are poor. Therefore can say that by operation, the liquid crystal sealing agent of the present application contaminative to liquid crystal in whole operation is low, embeddability, operability during to the coating operability of substrate, liquid crystal drip-injection method are excellent, reliability is high.

Claims (10)

1. liquid crystal sealing agent, it contains (a) and has the resin particle of core shell structure and (b) light-cured resin, and, use viscosity under 25 ℃ of E type viscometer determining as below the 100Pas, pre-baked viscosity is more than the 100Pas and below the 400Pas.
2. liquid crystal sealing agent as claimed in claim 1, wherein, (b) light-cured resin is epoxy (methyl) acrylate resin.
3. liquid crystal sealing agent as claimed in claim 2 wherein, in epoxy (methyl) acrylate resin, comprises 50 quality % above resorcinol diglycidyl ether and acrylic acid reaction product.
4. as each described liquid crystal sealing agent in the claim 1~3, wherein, further comprise (c) silane coupling agent.
5. liquid crystal sealing agent as claimed in claim 4 wherein, comprises N-2-(amino-ethyl)-3-TSL 8330 as (c) silane coupling agent.
6. liquid crystal sealing agent as claimed in claim 4 wherein, further contains (d) optical free radical polymerization starter.
7. liquid crystal sealing agent as claimed in claim 6 wherein, further contains (e) heat reactive resin and/or (f) thermal curing agents.
8. liquid crystal sealing agent as claimed in claim 7, wherein, (e) heat reactive resin is a Resins, epoxy, (f) thermal curing agents is the organic acid hydrazides.
9. liquid crystal sealing agent as claimed in claim 8, wherein, further containing (g) median size is the following mineral fillers of 3 μ m.
10. liquid crystal display, cured article sealing that it obtains by the described liquid crystal sealing agent of claim 9 is solidified.
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