CN105359034A - Sealant for liquid crystal dropping method, vertical-conduction material, liquid crystal display element, and light-shielding flexible silicone particles - Google Patents

Sealant for liquid crystal dropping method, vertical-conduction material, liquid crystal display element, and light-shielding flexible silicone particles Download PDF

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Publication number
CN105359034A
CN105359034A CN201480037955.2A CN201480037955A CN105359034A CN 105359034 A CN105359034 A CN 105359034A CN 201480037955 A CN201480037955 A CN 201480037955A CN 105359034 A CN105359034 A CN 105359034A
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Prior art keywords
particle
liquid crystal
light
proofness
mentioned
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CN201480037955.2A
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松田正则
永井康彦
尾山雄一
长原悠
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • 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
    • G02F1/1341—Filling or closing of cells

Abstract

The purpose of the present invention is to provide a sealant for a liquid crystal dropping method, the sealant having excellent adhesion, causing almost no liquid crystal contamination, and being capable of preventing light leakage in a liquid crystal display element. The purpose of the present invention is also to provide light-shielding flexible silicone particles suitable for incorporation into the sealant. The sealant for a liquid crystal dropping method pertaining to the present invention contains a curable resin, a polymerization initiator and/or a thermosetting agent, and light-shielding flexible particles. In the light-shielding flexible silicone particles pertaining to the present invention, a light-shielding agent is incorporated into silicone-based particles.

Description

Sealant for liquid crystal dripping process, up and down conductive material, liquid crystal display cells and light-proofness soft silicone particle
Technical field
The present invention relates to a kind of excellent in adhesion and the sealant for liquid crystal dripping process of the light leak of liquid crystal display cells can be prevented when substantially not causing liquid crystal pollution.In addition, the present invention relates to and use conductive material up and down manufactured by this sealant for liquid crystal dripping process and liquid crystal display cells.In addition, the present invention relates to light-proofness soft silicone particle.
Background technology
In recent years, the manufacture method of the liquid crystal display cells such as liquid crystal display from the view point of the shortening of productive temp time, use the optimization of amount of liquid crystal such, progressively from vacuum injection mode in the past to such as disclosed in patent documentation 1, patent documentation 2 employ light containing light-cured resin, Photoepolymerizationinitiater initiater, heat-curing resin and thermal curing agents, heat and with curing type sealant, the liquid crystal drop under type transformation that is called as technique of dripping.
Drip in technique, first, one in 2 electroded transparency carriers forms rectangular seal pattern by divider.Then, in the frame fine droplet of liquid crystal being dripped to transparency carrier under the state that sealant is uncured whole, another transparency carrier overlapping, solidifies light such as sealing irradiation ultraviolet radiations temporarily immediately.Then, carry out heating at liquid crystal Tui Huo Time and carry out main solidification, making liquid crystal display cells.As long as under reduced pressure carry out the laminating of substrate, just can with high efficiency system liquid making crystal display element, at present, this technique of dripping has become the main flow of the manufacture method of liquid crystal display cells.
In addition, in the modern times that portable phone, portable game etc. have been popularized with the mobile device of various liquid crystal panel, the miniaturization of device is problem the most urgent.As the gimmick of miniaturization, the narrow edge of liquid crystal display part can be enumerated, such as, carry out the operation (following, also referred to as narrow edge design) be configured at the position of sealing under black matrix".
But, the liquid crystal display cells that the manufacture technics narrow edge that drips if utilize designs, then there is light because of black matrix" at sealing to be beyond one's reach position, therefore, the part of the light-cured resin be not cured is produced because fully not carrying out illumination to penetrate, after interim curing process, thus there is liquid crystal and be subject to polluting such problem in uncured light-cured resin stripping.
In addition, sealant is in the past transparent or milky, therefore, originally should suppress the black matrix" of light leak, also cannot block the light through sealant, thus exists and reduces the such problem of contrast.
Therefore, have studied the method for carrying out to give sealant light-proofness by adding opacifier.Such as, disclose in patent documentation 3 ~ 5: the sealant containing the opacifiers such as the black based material of titanium, carbon black based material as light-proofness composition.
But for such opacifier, make it be dispersed in easily cohesion after in resin, stably dispersing, cementability go wrong.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2001-133794 publication
Patent documentation 2: No. 02/092718th, International Publication
Patent documentation 3: Japanese Unexamined Patent Publication 2006-099027 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-292801 publication
Patent documentation 5: No. 2009/128470th, International Publication
Summary of the invention
Invent problem to be solved
The object of the invention is to, providing a kind of excellent in adhesion and the sealant for liquid crystal dripping process of the light leak of liquid crystal display cells can be prevented when substantially not causing liquid crystal pollution.In addition, the object of the invention is to, provide a kind of and use conductive material up and down manufactured by this sealant for liquid crystal dripping process and liquid crystal display cells.In addition, the object of the invention is to, a kind of light-proofness soft silicone particle is provided.
For solving the means of problem
The present invention 1 is a kind of sealant for liquid crystal dripping process used in the manufacture of the liquid crystal display cells based on liquid crystal dripping process, and described sealant for liquid crystal dripping process contains curable resin, polymerization initiator and/or thermal curing agents and the soft particle of light-proofness.
In addition, the present invention 2 makes the light-proofness soft silicone particle containing opacifier in silicone-based particle.
First, the present invention 1 is described in detail.
The present inventor finds, by coordinating the soft particle of light-proofness in the encapsulant, thus when making the baseplate-laminating of liquid crystal display cells, the soft particle of this light-proofness becomes the barrier between other sealant composition and liquid crystal, sealant can be prevented to liquid crystal stripping, and the light leak of liquid crystal display cells can be prevented, so far complete the present invention 1.
The sealant for liquid crystal dripping process of the present invention 1 contains the soft particle of light-proofness.The soft particle of above-mentioned light-proofness has: give light-proofness to sealant and prevent the effect of the light leak of liquid crystal display cells; And when manufacturing liquid crystal display cells, becoming the barrier between other sealant composition and liquid crystal and preventing sealant to the effect of liquid crystal stripping.In addition, by coordinating the soft particle of above-mentioned light-proofness, thus after making baseplate-laminating, departing from of the substrate to sealant cures can be prevented, therefore, the sealant for liquid crystal dripping process of the present invention 1 excellent in adhesion.
As the soft particle of above-mentioned light-proofness, preferably make in soft particle containing opacifier.
As the method made containing opacifier in above-mentioned soft particle, such as following method etc. can be enumerated: in the production phase of soft particle, medium by making the colorant such as pigment or dyestuff be dispersed in the raw material of soft particle as above-mentioned opacifier, thus make the method containing colorant in soft particle; After making does not have the soft particle of light-proofness, in the method for the surface coverage colorant of this soft particle; After making does not have the soft particle of light-proofness, make the method etc. of this soft particle absorption colorant.
As above-mentioned soft particle, such as silicone-based particle, ethene base system particle, carbamate system particle, fluorine system particle, nitrile system particle etc. can be enumerated.Wherein, preferred silicone-based particle, ethene base system particle.
Above-mentioned silicone-based particle preferably has two diorganosiloxane units that represented by following formula (1) as repetitive and has a silicone cure thing of caoutchouc elasticity.
[changing 1]
-(R 1 2SiO) a-(1)
In formula (1), R 1can enumerate: the alkyl such as methyl, ethyl, propyl group, butyl; The aryl such as phenyl, tolyl; The thiazolinyl such as vinyl, allyl; The aralkyl such as β-phenethyl, β-phenylpropyl; Part or all of the hydrogen atom of these alkyl is substituted by the alkyl after the halogen atom such as chlorine, fluorine; Epoxy radicals, amino, sulfydryl, acryloxy, methacryloxy etc. are containing the organic group etc. of reactive group.A is preferably 5 ~ 5000, is more preferably 10 ~ 1000.
For the reaction mechanism of the curing reaction of the above-mentioned silicone-based particle of formation, can enumerate based on methoxysilyl (≡ SiOCH 3) with the condensation reaction of hydroxyl silicyl (≡ SiOH) etc., sulfydryl silicyl (≡ SiSH) and vinyl silyl groups (≡ SiCH=CH 2) free radical reaction, vinyl silyl groups (≡ SiCH=CH 2) with the reaction mechanism etc. of the addition reaction of ≡ SiH base, from reactive, reaction process aspect, be preferably based on the reaction mechanism of (hydrosilylation (ヒ De ロ シ リ Le)) addition reaction.That is, in the present invention, preferably make and make (a) under the existence of (c) platinum group catalyst, carry out addition reaction containing the organopolysiloxane of vinyl and (b) organic hydrogen polysiloxanes, the composition of solidification occurs.
As (a) composition as above, the compound etc. such as represented by following formula (2) can be enumerated specifically.
In formula (2), R 1with the R in above-mentioned formula (1) 1identical, but preferably not there is the group of aliphatics unsaturated link.B and c is 0,1,2 or 3, and b+c=3, d are positive number, and e is 0 or positive number, and 2b+e >=2.
As the organic hydrogen polysiloxanes of above-mentioned (b) composition, the compound etc. such as represented by following formula (3) can be enumerated.
[changing 3]
R 2 fII gSIO (4-f-g)/2(3)
In above-mentioned formula (3), R 2for except aliphatics unsaturated link, usually carbon number be 1 ~ 20, preferably carbon number be the monovalent hydrocarbon not replacing or replace being bonded to silicon atom of 1 ~ 12, as this R 2the described monovalent hydrocarbon not replacing or replace, can enumerate such as: the alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, amyl group, neopentyl, hexyl, cyclohexyl, octyl group, nonyl, decyl, the aryl such as phenyl, tolyl, xylyl, naphthyl; The aralkyl such as benzyl, phenethyl, phenylpropyl; Part or all of the hydrogen atom of these groups is by group, the such as chloromethyl, chloropropyl, bromoethyl, trifluoro propyl etc. after the halogen atom replacements such as fluorine, bromine, chlorine.As R 2the monovalent hydrocarbon not replacing or replace, be preferably alkyl, aryl, be more preferably methyl, phenyl.In addition, f is 0.7 ~ 2.1, g is 0.001 ~ 1.0, and f+g is the positive number of satisfied 0.8 ~ 3.0, and preferred f is 1.0 ~ 2.0, g be 0.01 ~ 1.0, f+g is 1.5 ~ 2.5.
As such (b) composition, specifically, the compound etc. such as represented by following formula (4) can be enumerated.
In formula (4), R 1with the R in above-mentioned formula (1) 1identical, preferably not there is the group of aliphatics unsaturated link.M be 0 or 1, n be 2 or 3, and m+n=3, p are 0 or positive number, and q is 0 or positive number, and 2m+q >=2.
The platinum group catalyst of above-mentioned (c) composition is the vinyl being bonded to silicon atom made in (a) composition, with the hydrogen atom (SiH yl) being bonded to silicon atom in (b) composition, the catalyzer of addition reaction occurs, and can enumerate such as: the carbon of Supported Pt Nanoparticles or silicon dioxide, chloroplatinic acid, platinum-alkene complex, platinum-ol complex compound, platinum-phosphorus complex, iridium-platinum complex etc.
Become to assign to make the method for silicone-based particle as using above-mentioned (a) ~ (c), as long as make (a) composition and (b) composition react under the existence of (c) composition, solidify, and be not particularly limited, can enumerate such as: make the method that (a) composition and (b) composition solidify in the spraying dry of high temperature; Make the method that it solidifies in organic solvent; The method etc. of solidifying is made it after being made into emulsion.In addition, in order to make the dispersiveness of silicone-based particle better, can as required at the surface coverage organic poly sesquisiloxane resin of silicone-based particle.
As mentioned above, the soft particle of above-mentioned light-proofness manufactures by following method: in the production phase of soft particle, medium by making the colorants such as the above-mentioned pigment as opacifier or dyestuff be dispersed in the raw material of soft particle, thus colorant is included in soft particle.Specifically, by making the colorant such as pigment or dyestuff disperse or dissolve in above-mentioned (a) ~ (c) composition in advance, be then cured reaction, thus obtain the silicone-based particle with light-proofness.When colorant being disperseed in above-mentioned (a) ~ (c) composition, preferably in both silicone composition and colorant, add surfactant, the spreading agent with compatibility.By giving the colorant as opacifier before curing reaction, thus the situation of colorant stripping or stripping from particle tails off, and can suppress liquid crystal pollution.
In addition, as mentioned above, the soft particle of above-mentioned light-proofness also makes by following method: after producing the soft particle without light-proofness, in the method for the surface coverage colorant of this soft particle; After producing the soft particle without light-proofness, make the method for this soft particle absorption colorant.Specifically, by not there is the silicone-based particle dispersion of light-proofness in the medium being dissolved with colorant, stir certain hour and make colorant be bonded to this silicone-based particle, thus giving light-proofness; In addition, use HYBRIDIZER (Ha イ Block リ ダ イ ザ ー), THETACOMPOSER (シ ー タ コ ン ポ ー ザ ー) such Composite device, make colorant immobilization in the surface of silicone-based particle without light-proofness, give light-proofness thus.
In addition, the method for the colorant of the adsorption polymerism of the silicone-based particle without light-proofness can be used in.That is, on the surface of silicone-based particle without light-proofness, the polymkeric substance of the skeleton or functional group with the light absorbing specific wavelength is separated out, can light-proofness be given thus.Specifically, by under the existence of silicone particle without light-proofness, make the monomer of the raw material being used as above-mentioned polymkeric substance carry out emulsion polymerization, soap-free polymerization, dispersin polymerization etc., thus above-mentioned polymkeric substance is separated out on the surface of silicone-based particle.
As the polymkeric substance of separating out on the surface of silicone-based particle, can enumerate such as by acetylene and derivant thereof, aniline and its derivatives, Furan and its derivatives, pyrroles and derivant thereof, thiophene and derivatives polymerization and the polymkeric substance etc. that obtains.Wherein, the polypyrrole of preferred black excellent color reproducing performance.
As the above-mentioned silicone-based particle without light-proofness, commercially available silicone-based particle also can be used.
As above-mentioned commercially available silicone-based particle, such as KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (organosilicon Inc. of SHIN-ETSU HANTOTAI), TORAYFILE-506S, EP-9215 (Dong Li Dow Corning Corporation system) etc. can be enumerated, their classifications can be used.The above-mentioned silicone-based particle without light-proofness can be used alone, and also two or more kinds may be used.
As above-mentioned ethene base system particle, (methyl) acrylic particles can be used aptly.
Above-mentioned (methyl) acrylic particles is obtained by making the monomer as raw material be polymerized by known method.Specifically, can enumerate such as: the method making monomer suspension polymerizing under the existence of radical polymerization initiator; Under the existence of radical polymerization initiator, make noncrosslinking seed particles absorb monomer, thus make seed particles swelling and carry out the method etc. of seeding polymerization.
It should be noted that, in this manual, above-mentioned " (methyl) acrylic compounds " refers to acrylic compounds or methacrylic.
As the monomer of the raw material become for the formation of above-mentioned (methyl) acrylic particles, can enumerate such as: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) hexyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylic acid cetyl, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) alkyl-acrylates such as (methyl) isobornyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid glycerine ester, polyoxyethylene (methyl) acrylate, (methyl) glycidyl acrylate etc. are containing (methyl) esters of acrylic acid of oxygen atom, (methyl) vinyl cyanide etc. are containing the monomer of nitrile, the monofunctional monomers such as (methyl) esters of acrylic acid that (methyl) acrylic acid trifluoro methyl esters, (methyl) acrylic acid five fluorine ethyl ester etc. are fluorine-containing.Wherein, low from the Tg of homopolymer, the large aspect of distortion quantitative change during applying 1g load can be made to set out, preferably (methyl) alkyl-acrylates.
It should be noted that, in this manual, above-mentioned " (methyl) acrylate " refers to acrylate or methacrylate.
In addition, in order to have cross-linked structure, tetramethylol methane four (methyl) acrylate can be used, tetramethylol methane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine three (methyl) acrylate, glycerine two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, (gathering) tetramethylene glycol two (methyl) acrylate, 1, 4-butylene glycol two (methyl) acrylate, 1, 6-hexanediol two (methyl) acrylate, the polyfunctional monomers such as isocyanuric acid skeleton three (methyl) acrylate.Wherein, large from molecular weight between crosslinking points, the large aspect of distortion quantitative change during applying 1g load can be made to set out, be preferably (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, (gathering) tetramethylene glycol two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate.
Use amount preferred lower limit in monomer is overall of above-mentioned cross-linkable monomer is 1 % by weight, the preferred upper limit is 90 % by weight.By making the use amount of above-mentioned cross-linkable monomer be more than 1 % by weight, thus solvent resistance improves, and does not cause the problems such as swelling, be easy to disperse equably when mixing with various sealant raw material.By making the use amount of above-mentioned cross-linkable monomer be less than 90 % by weight, thus recovery rate can be made to reduce, becoming and not easily causing the problems such as resilience.The preferred lower limit of the use amount of above-mentioned cross-linkable monomer is 3 % by weight, the preferred upper limit is 80 % by weight.
In addition, except the monomer of aforesaid propylene acid system, can also use: the styrenic monomers such as styrene, α-methyl styrene; The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; The vinyl acetate classes such as vinyl acetate, vinyl butyrate, vinyl laurate, stearic acid vinyl ester; The unsaturated hydrocarbon such as ethene, propylene, isoprene, butadiene; The halogen-containing monomers such as vinyl chloride, fluorothene, chlorostyrene; The monomers such as (different) triallyl cyanurate, triallyltrimelitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ-(methyl) acryloxypropyl trimethoxy silane, trimethoxysilyl styrene, vinyltrimethoxy silane.
In addition, as above-mentioned ethene system particle, such as polydivinylbenezene particle, polychlorobutadiene particle, butadiene rubber particle etc. can be used.
As the commercially available product in above-mentioned carbamate system particle, such as ArtPearl (Gen Shang industrial group system), DAIMICBEAZ (industrial group's system of refining large day) etc. can be enumerated, their classifications can be used.
For above-mentioned ethene base system particle and above-mentioned carbamate system particle, also give light-proofness by the method identical with above-mentioned silicone particle.
The preferred lower limit of the hardness of the soft particle of above-mentioned light-proofness is 10, the preferred upper limit is 50.If the hardness of the soft particle of above-mentioned light-proofness is more than 50, then the cementability of the sealant for liquid crystal dripping process of gained is deteriorated sometimes, or in the liquid crystal display cells of gained, produce gap bad.The preferred lower limit of the hardness of the soft particle of above-mentioned light-proofness is 20, the preferred upper limit is 40.
It should be noted that, in this manual, the hardness of the soft particle of above-mentioned light-proofness refers to, the Durometer A hardness recorded according to JISK6253 defined method.
As opacifier contained in above-mentioned soft particle, such as iron oxide can be enumerated, titanium is black, nigrosine, cyanine are black, fullerene, carbon black, resin-coated type carbon black, ?the dyestuff etc. of look.Wherein, preferred titanium is black.
Above-mentioned titanium is black is following material, that is, compared with the average transmittance of the light to wavelength 300 ~ 800nm, near ultraviolet range, material that particularly transmissivity of the light of wavelength 370 ~ 450nm is higher.That is, above-mentioned titanium is black is the opacifier with following character: by covering the light of the wavelength of visible region fully, thus gives light-proofness to the soft particle of light-proofness, on the other hand, makes the Transmission light of the wavelength near ultraviolet range.Thus, as polymerization initiator described later, by using the light of wavelength (370 ~ 450nm) and the polymerization initiator of initiation reaction that the black transmissivity of above-mentioned titanium can be utilized to uprise, thus the photo-curable of the sealant for liquid crystal dripping process of the present invention 1 can be made to increase further.In addition, on the other hand, as the opacifier contained in above-mentioned soft particle, the material that preferred insulativity is high, as the opacifier that insulativity is high, is also suitably titanium black.
Black for above-mentioned titanium, the optical concentration (OD value) of every 1 μm is preferably more than 3, is more preferably more than 4.The light-proofness that above-mentioned titanium is black is more high better, and the preferred upper limit of the OD value that above-mentioned titanium is black is not particularly limited, and is generally less than 5.
Black for above-mentioned titanium, even if be that not surface treated titanium is black, also give play to sufficient effect, but also can use: the titanium of surface after the organic principle process such as coupling agent is black; The titanium that the inorganic constituents such as surface oxidized silicon, titanium dioxide, germanium oxide, aluminium oxide, zirconia, magnesium oxide cover is black; Titanium after surface treatment is black.Wherein, from the aspect that can improve insulativity further, the titanium preferably after organic principle process is black.
In addition, the black sealant for liquid crystal dripping process as opacifier contained in above-mentioned soft particle of titanium is used to have sufficient light-proofness, therefore, the liquid crystal display cells of gained does not have the leakage of light and has high-contrast, for having the display element of excellent display quality of image.
Commercially available product in black as above-mentioned titanium, can enumerate such as 12S, 13M, 13M-C, 13R-N (being Mitsubishi Materials Corp's system), TilackD (red fringe changes into Inc.) etc.
The preferred lower limit of the specific surface area that above-mentioned titanium is black is 13m 2/ g, the preferred upper limit are 30m 2/ g, preferred lower limit are 15m 2/ g, the preferred upper limit are 25m 2/ g.
In addition, the preferred lower limit of the specific insulation that above-mentioned titanium is black is 0.5 Ω cm, the preferred upper limit is 3 Ω cm, preferred lower limit is 1 Ω cm, the preferred upper limit is 2.5 Ω cm.
The preferred lower limit of the primary particle size of opacifier contained in above-mentioned soft particle is 50nm, the preferred upper limit is 500nm.If the primary particle size of opacifier contained in above-mentioned soft particle is lower than 50nm, then viscosity or thixotropic ratio uprise sometimes, or secondary aggregation occurs, and significantly reduce to the dispersiveness in particle.If the primary particle size of opacifier contained in above-mentioned soft particle is more than 500nm, then sometimes reduce to the dispersiveness in particle, or particle self is hardening and easily break.The preferred lower limit of the primary particle size of opacifier contained in above-mentioned soft particle is 70nm, the preferred upper limit is 300nm.
The content of opacifier contained in above-mentioned soft particle is relative to the soft overall particle of light-proofness, and preferred lower limit is 2 % by weight, the preferred upper limit is 30 % by weight.If the content of opacifier contained in above-mentioned soft particle lower than 2 % by weight, then cannot obtain sufficient light-proofness sometimes.If the content of opacifier contained in above-mentioned soft particle is more than 30 % by weight, then particle self is hardening and become and easily break sometimes.The preferred lower limit of the content of opacifier contained in above-mentioned soft particle is 5 % by weight, the preferred upper limit is 20 % by weight.
The sealant for liquid crystal dripping process of the present invention 1 can be used for the manufacture of the liquid crystal display cells utilizing liquid crystal dripping process.
The preferred maximum particle diameter of the soft particle of above-mentioned light-proofness is more than 100% of the cel-gap of liquid crystal display cells.If the maximum particle diameter of the soft particle of above-mentioned light-proofness lower than liquid crystal display cells cel-gap 100%, then sometimes become and cannot suppress sealing fracture, liquid crystal pollution fully.The maximum particle diameter of the soft particle of above-mentioned light-proofness is more preferably more than 100% of the cel-gap of liquid crystal display cells and is more than 5 μm.
In addition, the preferred upper limit of the maximum particle diameter of the soft particle of above-mentioned light-proofness is 20 μm.If the maximum particle diameter of the soft particle of above-mentioned light-proofness more than 20 μm, then causes resilience sometimes, the cementability of the sealant for liquid crystal dripping process of gained is deteriorated, or the liquid crystal display cells generation gap of gained is bad.The preferred upper limit of the maximum particle diameter of the soft particle of above-mentioned light-proofness is 15 μm.
In addition, the maximum particle diameter of the soft particle of above-mentioned light-proofness is preferably less than 2.6 times of cel-gap.If the maximum particle diameter of the soft particle of above-mentioned light-proofness exceedes 2.6 times of cel-gap, then sometimes cause resilience, the cementability of the sealant for liquid crystal dripping process of gained is deteriorated, or the liquid crystal display cells generation gap of gained is bad.The preferred upper limit of the maximum particle diameter of the soft particle of above-mentioned light-proofness is 2.2 times of cel-gap, further the preferred upper limit be 1.7 times of cel-gap.
It should be noted that, in this manual, maximum particle diameter and the mean grain size described later of the soft particle of above-mentioned light-proofness refer to, the value obtained by using laser diffraction formula particle size distribution device to measure the particle before being matched with sealant.As above-mentioned laser diffraction formula distribution measurement device, Mastersizer2000 (Malvern Inc.) etc. can be used.In addition, the cel-gap of liquid crystal display cells is different according to display element, is not therefore limited, but the cel-gap of general liquid crystal display cells is 2 μm ~ 10 μm.
For the soft particle of above-mentioned light-proofness, in the size-grade distribution of the soft particle of the light-proofness recorded by above-mentioned laser diffraction formula distribution measurement device, the particle of the particle diameter of more than 5 μm containing proportional in volume frequency preferably more than 60%.If the particle of the particle diameter of more than 5 μm containing proportional in volume frequency lower than 60%, then sometimes become cannot suppress fully sealing fracture or liquid crystal pollution.The particle of the particle diameter of more than 5 μm be more preferably more than 80% containing proportional.
For the soft particle of above-mentioned light-proofness, from the view point of the effect having given play to the generation suppressing sealing fracture or liquid crystal pollution further, preferably contain the particle of more than 100% of the cel-gap of liquid crystal display cells with more than 70% of the size-grade distribution in the soft overall particle of light-proofness, more preferably only by liquid crystal display cells cel-gap more than 100% particle form.
The preferred lower limit of the mean grain size of the soft particle of above-mentioned light-proofness is 2 μm, the preferred upper limit is 15 μm.If the mean grain size of the soft particle of above-mentioned light-proofness lower than 2 μm, then cannot prevent sealant to the stripping in liquid crystal sometimes fully.If the mean grain size of the soft particle of above-mentioned light-proofness is more than 15 μm, then the cementability of the sealant for liquid crystal dripping process of gained is deteriorated sometimes, or the liquid crystal display cells generation gap of gained is bad.The preferred lower limit of the mean grain size of the soft particle of above-mentioned light-proofness is 4 μm, the preferred upper limit is 12 μm.
As the soft particle of above-mentioned light-proofness, can the different soft particle of light-proofness of more than two kinds of maximum particle diameter used in combination.That is, can maximum particle diameter used in combination lower than liquid crystal display cells cel-gap 100% the soft particle of light-proofness and maximum particle diameter be the soft particle of light-proofness of more than 100% of the cel-gap of liquid crystal display cells.
The coefficient of variation (below also referred to as " CV value ") of the particle diameter of the soft particle of above-mentioned light-proofness is preferably less than 30%.If the CV value of the particle diameter of the soft particle of above-mentioned light-proofness more than 30%, then causes cel-gap bad sometimes.The CV value of the particle diameter of the soft particle of above-mentioned light-proofness is more preferably less than 28%.
It should be noted that, in this manual, the CV value of particle diameter refers to, by the numerical value calculated by following formula.
CV value (%)=(standard deviation/mean grain size of particle diameter) × 100 of particle diameter
Even if the soft particle maximum particle diameter of above-mentioned light-proofness or mean grain size or CV value are in beyond above-mentioned scope, maximum particle diameter or mean grain size or CV value is also made to reach in above-mentioned scope by classification.In addition, particle diameter lower than liquid crystal display cells cel-gap 100% the soft particle of light-proofness be sometimes helpless to the generation suppressing sealing fracture or liquid crystal pollution, if be matched with sealant, make thixotroping value increase, be therefore preferably removed by classification in advance.
As the method by soft for above-mentioned light-proofness particle classification, the such as method such as wet classification, dry classification can be enumerated.Wherein, preferred wet classification, more preferably wet screening level.
For the soft particle of above-mentioned light-proofness, by from apply load time initial point load value to reach reversion load value compression displacement be set to L1, by when being set to L2 to the unloading displacement reached initial point load value from reversion load value when discharging, represent that the recovery rate of L2/L1 is preferably less than 80% with percent.If the recovery rate of the soft particle of above-mentioned light-proofness more than 80%, then sometimes becomes obstacle, prevents sealant from reducing to the function of liquid crystal stripping.The preferred upper limit of the recovery rate of the soft particle of above-mentioned light-proofness is 70%, preferably the upper limit is 60% further.
It should be noted that, for the recovery rate of the soft particle of above-mentioned light-proofness, use micro-compression tester to apply certain load (1g) to 1 particle, resolve the recovery behavior after being removed by this load, derive recovery rate thus.
For the soft particle of above-mentioned light-proofness, compression displacement when applying the load of 1g is set to L3, when particle diameter is set to Dn, represents that the 1g strain of L3/Dn is preferably more than 30% with percent.If the 1g strain of the soft particle of above-mentioned light-proofness lower than 30%, then sometimes becomes obstacle, prevents sealant from reducing to the function of liquid crystal stripping.The preferred lower limit of the 1g strain of the soft particle of above-mentioned light-proofness is 40%.
It should be noted that, the 1g strain of the soft particle of above-mentioned light-proofness can use micro-compression tester to apply the load of 1g to 1 particle, is recorded by the displacement measured now.
For the soft particle of above-mentioned light-proofness, the compression displacement that particle is occurred damaged time point is set to L4, when particle diameter is set to Dn, represent that the breakage strain of L4/Dn is preferably more than 50% with percent.If the breakage strain of the soft particle of above-mentioned light-proofness lower than 50%, then sometimes becomes obstacle, prevents sealant from reducing to the function of liquid crystal stripping.The preferred lower limit of the breakage strain of the soft particle of above-mentioned light-proofness is 60%.
It should be noted that, the breakage strain of the soft particle of above-mentioned light-proofness can use micro-compression tester to apply load to 1 particle, measures displacement when this particle occurs damaged and records.For above-mentioned compression displacement L4, time point large for the discontinuous change of displacement for load loading is set to particle and damaged time point occurs, thus calculate.Think: even if in the loading of increase load, when also only deforming and breakage does not occur, damaged strain is more than 100%.
The preferred lower limit of the glass transition temperature of the soft particle of above-mentioned light-proofness is-200 DEG C, the preferred upper limit is 40 DEG C.If the glass transition temperature of the soft particle of above-mentioned light-proofness is more than-200 DEG C, then lower, suppress the effect of sealing fracture or liquid crystal pollution better, if lower than-200 DEG C, then sometimes have problems in the disposal of particle, or sealant becomes and easily caves in heating way, the sealant in solidification way contacts with liquid crystal and produces liquid crystal pollution.If the glass transition temperature of the soft particle of above-mentioned light-proofness is more than 40 DEG C, then sometimes there is gap bad.The preferred lower limit of the glass transition temperature of the soft particle of above-mentioned light-proofness is-150 DEG C, the preferred upper limit is 35 DEG C.
It should be noted that, the glass transition temperature of the soft particle of above-mentioned light-proofness represents the value recorded by means of differential scanning calorimetry mensuration (DSC) of " the transition temperature assay methods of plastics " based on JISK7121.
The melanism degree of the soft particle of above-mentioned light-proofness is preferably less than 10%, is more preferably less than 5%.The light-proofness of the soft particle of above-mentioned light-proofness is more low better, and for the degree of blackness of the soft particle of above-mentioned light-proofness, preferred lower limit is not particularly limited, but is generally more than 0.05%.
It should be noted that, the melanism degree of the soft particle of above-mentioned light-proofness can utilize the maximal value of the long spectral transmission of the visible region all-wave of 400 ~ 700nm to evaluate.Specifically, the laminar polymkeric substance that preparation has the thick 1mm of the composition identical with the particle for evaluating is used as melanism degree measurement sample, for this sample, obtains by using the long spectral transmission of spectrophotometric determination visible region all-wave.
The content of the soft particle of above-mentioned light-proofness is relative to curable resin 100 weight portion, and preferred lower limit is 3 weight portions, the preferred upper limit is 70 weight portions.If the content of the soft particle of above-mentioned light-proofness lower than 3 weight portions, then sometimes becomes and sealant cannot be prevented fully to the stripping of liquid crystal.If the content of the soft particle of above-mentioned light-proofness is more than 70 weight portions, then the cementability of the sealant for liquid crystal dripping process of gained is deteriorated sometimes.The preferred lower limit of the content of the soft particle of above-mentioned light-proofness is 5 weight portions, the preferred upper limit is 60 weight portions, preferred lower limit is 10 weight portions, the further preferred upper limit is further 50 weight portions.
The sealant for liquid crystal dripping process of the present invention 1 contains curable resin.
Above-mentioned curable resin is preferably containing (methyl) acrylic resin.
Promptly solidify in order to the sealant for liquid crystal dripping process of the present invention 1 can be made, preferably containing (methyl) acrylic resin as curable resin, and containing the radical polymerization initiator described later as polymerization initiator, in order to the sealant for liquid crystal dripping process of the present invention 1 just be made promptly to solidify by means of only heating, even and if be the liquid crystal display cells of narrow frame design, also the generation of liquid crystal pollution can be suppressed fully, more preferably containing (methyl) acrylic resin and hot radical polymerization initiator described later.
Above-mentioned curable resin is more preferably containing epoxy (methyl) acrylate.
It should be noted that, in this manual, above-mentioned " (methyl) acrylic resin " refers to the resin with (methyl) acryloyl group, and above-mentioned " (methyl) acryloyl group " refers to acryloyl group or methacryl.In addition, above-mentioned " epoxy (methyl) acrylate " is the compound of instigating the whole epoxy radicals in epoxy resin and (methyl) acrylic acid to react and obtaining.
As the epoxy resin of the raw material become for the synthesis of above-mentioned epoxy (methyl) acrylate, can enumerate such as: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2, 2 '-diallyl bisphenol type epoxy resin, A Hydrogenated Bisphenol A type epoxy resin, epoxypropane addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether-type epoxy resin, diphenyl ether type epoxy, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy, orthoresol phenol aldehyde type epoxy resin, dicyclopentadiene phenolic type epoxy resin, biphenyl phenol aldehyde type epoxy resin, naphthalene phenol novolak type epoxy, glycidyl amine type epoxy resin, alkyl polyols type epoxy resin, modified rubber type epoxy resin, epihydric alcohol ester compound, bisphenol A-type episulfide resin etc.
As the commercially available product in above-mentioned bisphenol A type epoxy resin, such as jER828EL, jER1001, jER1004 (being Mitsubishi Chemical Ind's system), EPICLON850-S (DIC Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned bisphenol f type epoxy resin, such as jER806, jER4004 (being Mitsubishi Chemical Ind's system) etc. can be enumerated.
As the commercially available product in above-mentioned bisphenol-s epoxy resin, such as EPICLONEXA1514 (DIC Inc.) etc. can be enumerated.
As above-mentioned 2, the commercially available product in 2 '-diallyl bisphenol type epoxy resin, can enumerate such as RE-810NM (Japanese chemical drug Inc.) etc.
As the commercially available product in above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as EPICLONEXA7015 (DIC Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned epoxypropane addition bisphenol A type epoxy resin, such as EP-4000S (ADEKA Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned resorcinol type epoxy resin, can enumerate such as EX-201 (NagasechemteXCorporation system).
As the commercially available product in above-mentioned biphenyl type epoxy resin, such as jERYX-4000H (Mitsubishi Chemical Ind's system) etc. can be enumerated.
As the commercially available product in above-mentioned thioether-type epoxy resin, such as YSLV-50TE (aurification Inc. is lived by Nippon Steel) etc. can be enumerated.
As the commercially available product in above-mentioned diphenyl ether type epoxy, such as YSLV-80DE (aurification Inc. is lived by Nippon Steel) etc. can be enumerated.
As the commercially available product in above-mentioned dicyclopentadiene-type epoxy resin, such as EP-4088S (ADEKA Inc.) etc. can be enumerated.
As the commercially available product of above-mentioned naphthalene type epoxy resin, such as EPICLONHP4032, EPICLONEXA-4700 (being DIC Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned phenol novolak type epoxy, such as EPICLONN-770 (DIC Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned orthoresol phenol aldehyde type epoxy resin, such as EPICLONN-670-EXP-S (DIC Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned dicyclopentadiene phenolic type epoxy resin, such as EPICLONHP7200 (DIC Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned biphenyl phenol aldehyde type epoxy resin, such as NC-3000P (Japanese chemical drug Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned naphthol novolac type epoxy resin, such as ESN-165S (aurification Inc. is lived by Nippon Steel) etc. can be enumerated.
As the commercially available product in above-mentioned glycidyl amine type epoxy resin, such as jER630 (Mitsubishi Chemical Ind's system), EPICLON430 (DIC Inc.), TETRAD-X (gas chemical company of Mitsubishi system) etc. can be enumerated.
As the commercially available product in abovementioned alkyl polyol type epoxy resin, such as ZX-1542 (aurification Inc. is lived by Nippon Steel), EPICLON726 (DIC Inc.), EPOLIGHT80MFA (chemical company of common prosperity society system), DENACOLEX-611 (NagasechemteXCorporation system) etc. can be enumerated.
As the commercially available product in above-mentioned modified rubber type epoxy resin, such as YR-450, YR-207 (be Nippon Steel and live aurification Inc.), EPOLEADPB (Daicel Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned epihydric alcohol ester compound, such as DENACOLEX-147 (NagasechemteXCorporation system) etc. can be enumerated.
As the commercially available product in above-mentioned bisphenol A-type episulfide resin, such as jERYL-7000 (Mitsubishi Chemical Ind's system) etc. can be enumerated.
As other commercially available products in above-mentioned epoxy resin, such as YDC-1312, YSLV-80XY, YSLV-90CR (be Nippon Steel and live aurification Inc.), XAC4151 (Asahi Kasei Corporation's system), jER1031, jER1032 (being Mitsubishi Chemical Ind's system), EXA-7120 (DIC Inc.), TEPIC (Nissan Chemical Inc.) etc. can be enumerated.
As the commercially available product in above-mentioned epoxy (methyl) acrylate, such as EBECRYL860 can be enumerated, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (being DaicelAllnex Inc.), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (being chemical industrial company of Xin Zhong village system), EPOXYESTERM-600A, EPOXYESTER40EM, EPOXYESTER70PA, EPOXYESTER200PA, EPOXYESTER80MFA, EPOXYESTER3002M, EPOXYESTER3002A, EPOXYESTER1600A, EPOXYESTER3000M, EPOXYESTER3000A, EPOXYESTER200EA, EPOXYESTER400EA (being chemical company of common prosperity society system), DENACOLACRYLATEDA-141, DENACOLACRYLATEDA-314, DENACOLACRYLATEDA-911 (being NagasechemteXCorporation system) etc.
As other (methyl) acrylic resins beyond above-mentioned epoxy (methyl) acrylate, can enumerate such as: carbamate (methyl) acrylate etc. that the ester compounds obtained by making (methyl) acrylic acid react with the compound with hydroxyl, (methyl) acrylic acid derivative making isocyanates and have a hydroxyl react and obtain.
(methyl) acrylic acid is reacted with the compound with hydroxyl and the compound of simple function in the carboxylate that obtains as above-mentioned, can enumerate such as: (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, (methyl) acrylic acid-2-hydroxy butyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-methoxy acrylate, methoxyl ethylene glycol (methyl) acrylate, (methyl) acrylic acid-2-ethoxy ethyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) benzyl acrylate, ethyl carbitol (methyl) acrylate, (methyl) acrylate, phenoxy group diethylene glycol (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, (methyl) acrylic acid 2,2,2-trifluoro ethyl ester, (methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester, (methyl) acrylic acid 1H, 1H, 5H-octafluoro pentyl ester, acid imide (methyl) acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) n-octyl, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, the different myristin of (methyl) acrylic acid, (methyl) acrylic acid-2-butoxyethyl, (methyl) acrylic acid-2-phenoxy ethyl, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylate, 2-(methyl) acryloyloxyethyl succinate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid ester, 2-(methyl) acryloyl-oxyethyl-2-hydroxypropylphthalate ester, (methyl) glycidyl acrylate, 2-(methyl) acryloyl-oxyethyl phosphate etc.
As the compound of 2 officials' energy in above-mentioned ester compounds, can enumerate such as: BDO two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, 2-normal-butyl-2-ethyl-1,3-PD two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyglycol two (methyl) acrylate, epoxypropane addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two (methyl) acrylate, 2-hydroxyl-3-(methyl) acryloxypropyl (methyl) acrylate, carbonate diol two (methyl) acrylate, PTMEG two (methyl) acrylate, polyester-diol two (methyl) acrylate, polycaprolactone glycol two (methyl) acrylate, polybutadiene diol two (methyl) acrylate etc.
Can above compound as 3 officials in above-mentioned ester compounds, can enumerate such as: pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, epoxypropane addition trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition isocyanuric acid three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, pentaerythrite four (methyl) acrylate, glycerine three (methyl) acrylate, epoxypropane addition glycerine three (methyl) acrylate, three (methyl) acryloyl-oxyethyl phosphate etc.
Under above-mentioned carbamate (methyl) acrylate can be existed by the tin based compound such as at catalytic amount, relative to compound 1 equivalent with 2 isocyanate group, and (methyl) acrylic acid derivative 2 equivalent with hydroxyl is made to react with it and obtain.
As the isocyanates of raw material becoming above-mentioned carbamate (methyl) acrylate, can enumerate such as: isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl methane-4, 4 '-diisocyanate (MDI), hydrogenation MDI, aggretion type MDI, 1, 5-naphthalene diisocyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, XDI (XDI), hydrogenation XDI, lysinediisocyanate, triphenylmethane triisocyanate, three (isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, 1, 6, 10-undecane triisocyanate etc.
In addition, as above-mentioned isocyanates, can also use such as: by the reaction of the polyvalent alcohols such as ethylene glycol, glycerine, D-sorbite, trimethylolpropane, (gathering) propylene glycol, carbonate diol, PTMEG, polyester-diol, polycaprolactone glycol and excessive isocyanates and the isocyanate compound of the chain elongation obtained.
As the raw material becoming above-mentioned carbamate (methyl) acrylate, there is (methyl) acrylic acid derivative of hydroxyl, can enumerate such as: (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, commercially available product or the ethylene glycol such as (methyl) acrylic acid-2-hydroxy butyl ester, propylene glycol, 1, ammediol, 1, 3-butylene glycol, 1, 4-butylene glycol, list (methyl) acrylate of the dibasic alcohol such as polyglycol, trimethylolethane, trimethylolpropane, list (methyl) acrylate of the trihydroxy alcohols such as glycerine or two (methyl) acrylate, the epoxies such as bisphenol-a epoxy acrylate (methyl) acrylate etc.
As the commercially available product in above-mentioned carbamate (methyl) acrylate, can enumerate such as: M-1100, M-1200, M-1210, M-1600 (being East Asia Synesis Company system), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (being DaicelAllnex Inc.), ArtresinUN-9000H, ArtresinUN-9000A, ArtresinUN-7100, ArtresinUN-1255, ArtresinUN-330, ArtresinUN-3320HB, ArtresinUN-1200TPK, ArtresinSH-500B (being Gen Shang industrial group system), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (being chemical industrial company of Xin Zhong village system), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (being chemical company of common prosperity society system) etc.
Suppress to liquid crystal dysgenic in, above-mentioned (methyl) acrylic resin preferably has-OH base ,-NH-base ,-NH 2the unit of the hydrogen bonds such as base.
In addition, above-mentioned (methyl) acrylic resin preferably has 2 ~ 3 (methyl) acryloyl groups in the molecule from the high aspect of reactivity.
For the object that the cementability of the sealant for liquid crystal dripping process making gained improves, above-mentioned curable resin can also contain epoxy resin further.
As above-mentioned epoxy resin, can enumerate such as: above-mentioned epoxy resin, partly (methyl) acrylic modified epoxy resin etc. becoming raw material for the synthesis of epoxy (methyl) acrylate.
It should be noted that; in this instructions; above-mentioned part (methyl) acrylic modified epoxy resin refers to; there is respectively the resin of more than 1 epoxy radicals and (methyl) acryloyl group in 1 molecule; such as, can obtain by making the epoxy radicals of a part for the resin of the epoxy radicals with more than 2 and (methyl) acrylic acid react.
As the commercially available product among above-mentioned part (methyl) acrylic modified epoxy resin, such as UVACURE1561 (DaicelAllnex Inc.) etc. can be enumerated.
When containing above-mentioned epoxy resin as above-mentioned curable resin, during above-mentioned curable resin is overall, epoxy radicals is 50 % by mole relative to the preferred upper limit of the ratio of the total amount of (methyl) acryloyl group and epoxy radicals.If the ratio of above-mentioned epoxy radicals is more than 50 % by mole, then the sealant for liquid crystal dripping process of gained uprises relative to the dissolubility of liquid crystal and causes liquid crystal pollution sometimes, and the display performance of the liquid crystal display cells obtained is deteriorated.The preferred upper limit of the ratio of above-mentioned epoxy radicals is 20 % by mole.
The sealant for liquid crystal dripping process of the present invention 1 contains polymerization initiator and/or thermal curing agents.
Wherein, as polymerization initiator, preferably containing radical polymerization initiator.Resilience not only by the impact of the maximum particle diameter of the soft particle of above-mentioned light-proofness, is also subject to the impact of the curing rate of sealant.Compared with thermal curing agents, the curing rate of above-mentioned radical polymerization initiator can be fast especially, therefore by using with above-mentioned light-proofness soft particle combinations, thus suppression can be made because of above-mentioned light-proofness softness particle and the effect of the generation of incidental resilience is more excellent.
As above-mentioned radical polymerization initiator, can enumerate and produce the hot radical polymerization initiator of free radical by heating, produced the optical free radical polymerization initiator etc. of free radical by illumination.
As mentioned above, compared with thermal curing agents, the curing rate of above-mentioned radical polymerization initiator is fast especially, therefore, by using radical polymerization initiator, the generation sealing fracture or liquid crystal pollution can be suppressed, and the incidental resilience because of the soft particle of above-mentioned light-proofness can also be suppressed.
Wherein, because the sealant for liquid crystal dripping process obtained can be made to solidify rapidly by heat, therefore above-mentioned radical polymerization initiator is preferably containing hot radical polymerization initiator.
As above-mentioned hot radical polymerization initiator, the material such as comprising azo-compound, organic peroxide etc. can be enumerated.Wherein, the polymeric azo initiating agent of polymeric azo compound is preferably comprised.
It should be noted that, in this instructions, polymeric azo initiating agent refers to, there is azo group and generated by heat the free radical that (methyl) acryloxy can be made to solidify, number-average molecular weight is the compound of more than 300.
The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiating agent is 1000, and the preferred upper limit is 300,000.If the number-average molecular weight of above-mentioned polymeric azo initiating agent is less than 1000, then polymeric azo initiating agent produces harmful effect to liquid crystal sometimes.If the number-average molecular weight of above-mentioned polymeric azo initiating agent is more than 300,000, then to becoming difficulty during being mixed with of curable resin.The preferred lower limit of the number-average molecular weight of above-mentioned polymeric azo initiating agent is 5000, and the preferred upper limit is 100,000, and preferred lower limit is 10,000 further, and the preferred upper limit is 90,000 further.
It should be noted that, in this instructions, above-mentioned number-average molecular weight utilizes gel permeation chromatography (GPC) to measure, and by value that polystyrene conversion is tried to achieve.As the pillar during number-average molecular weight measured by GPC based on polystyrene conversion, such as ShodexLF-804 (Showa electrician Inc.) etc. can be enumerated.
As above-mentioned polymeric azo initiating agent, can enumerate such as: have make the structure of the unit bondings such as multiple polyalkylene oxide, dimethyl silicone polymer by azo group, polymeric azo initiating agent.
As the above-mentioned polymeric azo initiating agent with the structure making the unit bondings such as multiple polyalkylene oxides by azo group, preferably there is the material of polyethylene oxide structure.As such polymeric azo initiating agent, such as 4 can be enumerated, the condensed polymer, 4 of 4 '-azo two (4-cyanopentanoic acid) and poly alkylene glycol, 4 '-azo two (4-cyanopentanoic acid) and the condensed polymer etc. of dimethyl silicone polymer with terminal amino group, can enumerate such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (being pure pharmaceutical worker's industry Inc. with light) etc. specifically
As above-mentioned organic peroxide, can enumerate such as: ketone peroxide, ketal peroxide, hydroperoxides, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate etc.
As above-mentioned optical free radical polymerization initiator, such as benzophenone based compound, acetophenone based compound, acylphosphine oxide based compound, two luxuriant titanium sub-group compounds, oxime ester based compound, benzoin ether based compound, thioxanthones etc. can be enumerated.
As the commercially available product in above-mentioned optical free radical polymerization initiator, such as IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACUREOXE01, DAROCURTPO (being BASFJapan Inc.), benzoin methylether, benzoin ethyl ether, benzoin iso-propylether (be Tokyo above and change into industrial group's system) etc. can be enumerated.
In addition, as above-mentioned polymerization initiator, also cationic polymerization initiators can be used.
As above-mentioned cationic polymerization initiators, can be suitable for making to use light cationic polymerization initiators.As long as above-mentioned smooth cationic polymerization initiators can be penetrated by illumination and produce Bronsted acid or lewis acidic material, being just not particularly limited, can be ionic photic product acids type, also can be nonionic photic product acids type.
As above-mentioned smooth cationic polymerization initiators, the metal-organic complex classes etc. such as the salts such as such as aromatic diazonium salt, aromatic halonium salts, aromatic series sulfonium salt, iron-allene complex thing, two titanocene complexes, aryl-silane alcohol-aluminium complex can be enumerated.
As the commercially available product in above-mentioned smooth cationic polymerization initiators, such as AdekaoptomerSP-150, AdekaoptomerSP-170 (being ADEKA Inc.) etc. can be enumerated.
The content of above-mentioned polymerization initiator is relative to above-mentioned curable resin 100 weight portion, and preferred lower limit is 0.1 weight portion, the preferred upper limit is 30 weight portions.If the content of above-mentioned polymerization initiator is lower than 0.1 weight portion, then the sealant for liquid crystal dripping process of gained sometimes cannot be made fully to solidify.If the content of above-mentioned polymerization initiator is more than 30 weight portions, then the storage-stable of the sealant for liquid crystal dripping process of gained reduces sometimes.The preferred lower limit of the content of above-mentioned polymerization initiator is 1 weight portion, the preferred upper limit is 10 weight portions, preferably the upper limit is 5 weight portions further.
As above-mentioned thermal curing agents, such as organic acid hydrazides, imdazole derivatives, amines, polyhydric phenol based compound, acid anhydrides etc. can be enumerated.Wherein, the organic acid hydrazides that suitable use is solid-state.
As above-mentioned solid-state organic acid hydrazides, such as 1 can be enumerated, two (diazanyl carbon the ethyl)-5-isopropyl hydantoins (1 of 3-, 3-PVC ス (ヒ De ラ ジ ノ カ Le ボ エ チ Le)-5-イ ソ プ ロ ピ Le ヒ ダ Application ト イ Application), sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, acid dihydrazide etc., as commercially available product, such as AmicureVDH can be enumerated, AmicureUDH (being AjinomotoFine-Techno Inc.), SDH, IDH, ADH (being great Zhong chemical company system), MDH (JapanFinechem Inc.) etc.
The content of above-mentioned thermal curing agents is relative to above-mentioned curable resin 100 weight portion, and preferred lower limit is 1 weight portion, the preferred upper limit is 50 weight portions.If the content of above-mentioned thermal curing agents is lower than 1 weight portion, then sometimes cannot make the abundant heat curing of the sealant for liquid crystal dripping process of gained.If the content of above-mentioned thermal curing agents is more than 50 weight portions, then the viscosity of the sealant for liquid crystal dripping process of gained becomes too high sometimes, and coating is deteriorated.The preferred upper limit of the content of above-mentioned thermal curing agents is 30 weight portions.
The sealant for liquid crystal dripping process of the present invention 1 is preferably containing curing accelerator.By using above-mentioned curing accelerator, even if thus at high temperature do not heat, sealant also can be made to solidify fully.
As above-mentioned curing accelerator, the polybasic carboxylic acid, Epoxy amine adducts etc. such as with isocyanuric acid ring skeleton can be enumerated, specifically can enumerate such as: three (2-ethyloic) isocyanuric acid ester, three (2-carboxyethyl) isocyanuric acid ester, three (3-carboxylic propyl group) isocyanuric acid ester, two (2-carboxyethyl) isocyanuric acid ester etc.
The content of above-mentioned curing accelerator is relative to above-mentioned curable resin 100 weight portion, and preferred lower limit is 0.1 weight portion, and the preferred upper limit is 10 weight portions.If the content of above-mentioned curing accelerator is lower than 0.1 weight portion, then the sealant for liquid crystal dripping process sometimes obtained fully does not solidify, or needs the heating under high temperature to be cured.If the content of above-mentioned curing accelerator is more than 10 weight portions, then the sealant for liquid crystal dripping process obtained is sometimes poor in cementability.
The objects such as the further raising of the raising for viscosity, the improvement based on the cementability of stress dispersion effect, the improvement of linear expansion coefficient, the moisture-proof of solidfied material, the sealant for liquid crystal dripping process of the present invention 1 is also preferably containing filling agent.
As above-mentioned filling agent, can enumerate such as: the inorganic fillers such as talcum, asbestos, silicon dioxide, zeyssatite, terre verte, bentonitic clay, calcium carbonate, magnesium carbonate, aluminium oxide, smectite, zinc paste, iron oxide, magnesium oxide, tin oxide, titanium dioxide, magnesium hydroxide, aluminium hydroxide, beaded glass, silicon nitride, barium sulphate, gypsum, calcium silicate, sericite atlapulgite, aluminium nitride; The organic fillers etc. such as polyester micropartical, polyurethane particulate, polyvinyl particulate, acrylic polymers particulate, core-shell acrylic-resin copolymer particle.These filling agents may be used singly or in combination of two or more.
The content of above-mentioned filling agent is overall relative to sealant for liquid crystal dripping process, and preferred lower limit is 5 % by weight, the preferred upper limit is 70 % by weight.If the content of above-mentioned filling agent is lower than 5 % by weight, then sometimes the effects such as the improvement of cementability cannot be given play to fully.If the content of above-mentioned filling agent is more than 70 % by weight, then the viscosity of the sealant for liquid crystal dripping process of gained uprises sometimes, and coating is deteriorated.The preferred lower limit of the content of above-mentioned filling agent is 10 % by weight, the preferred upper limit is 50 % by weight.
The sealant for liquid crystal dripping process of the present invention 1 is preferably containing silane coupling agent.Above-mentioned silane coupling agent mainly has as the effect by bonding auxiliary agent bonding well with substrate etc. for sealant.
As above-mentioned silane coupling agent, from improving the excellent effect with the cementability of substrate etc., by the aspect that curable resin flows out in liquid crystal being suppressed to set out with curable resin chemical bonding, suitable use is N-phenyl-3-TSL 8330,3-TSL 8330,3-mercaptopropyi trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-isocyanates propyl trimethoxy silicane etc. such as.These silane coupling agents may be used singly or in combination of two or more.
The content of above-mentioned silane coupling agent is overall relative to sealant for liquid crystal dripping process, and preferred lower limit is 0.1 % by weight, the preferred upper limit is 20 % by weight.If the content of above-mentioned silane coupling agent is lower than 0.1 % by weight, then sometimes cannot give play to the effect based on coordinating silane coupling agent to bring fully.If the content of above-mentioned silane coupling agent is more than 20 % by weight, then the sealant for liquid crystal dripping process of gained pollutes liquid crystal sometimes.The preferred lower limit of the content of above-mentioned silane coupling agent is 0.5 % by weight, the preferred upper limit is 10 % by weight.
The sealant for liquid crystal dripping process of the present invention 1 can also contain the opacifier of the state be not included in soft particle further on the basis of the soft particle of above-mentioned light-proofness.As above-mentioned opacifier, the opacifier identical with opacifier contained in soft particle can be used.
The content of above-mentioned opacifier is overall relative to sealant for liquid crystal dripping process, and preferred lower limit is 5 % by weight, the preferred upper limit is 80 % by weight.If the content of above-mentioned opacifier is lower than 5 % by weight, then sometimes cannot obtain sufficient light-proofness.If the content of above-mentioned opacifier is more than 80 % by weight, then the sealant for liquid crystal dripping process of gained declines for the cementability of substrate or the intensity after solidifying sometimes, or illustrative declines.The preferred lower limit of the content of above-mentioned opacifier is 10 % by weight, the preferred upper limit is 70 % by weight, preferred lower limit is 30 % by weight further, preferably the upper limit is 60 % by weight further.
The sealant for liquid crystal dripping process of the present invention 1 can further as required containing the reactive diluent for adjusting viscosity, polymeric beads thing, defoamer, levelling agent, polymerization inhibitor, other the adjuvant such as coupling agent at equal intervals for adjusting panel gap.
The method manufacturing the sealant for liquid crystal dripping process of the present invention 1 is not particularly limited, mixers such as such as using homo dispenser, homogeneous mixer, universal mixer, planetary-type mixer, kneader, three-roller can be enumerated, by the method etc. of the adjuvant mixing such as curable resin, polymerization initiator and/or thermal curing agents, the soft particle of light-proofness and the silane coupling agent that adds as required.
The sealant for liquid crystal dripping process of the present invention 1, use E type viscosity meter 25 DEG C, the preferred lower limit of viscosity that records of the condition of 1rpm is 50,000 Pas, the preferred upper limit is 500,000 Pas.If above-mentioned viscosity is lower than 50,000 Pas or more than 500,000 Pas, then operability when sometimes sealant for liquid crystal dripping process being coated substrate etc. is deteriorated.The preferred upper limit of above-mentioned viscosity is 400,000 Pas.
The OD value of the sealant for liquid crystal dripping process of the present invention 1 is preferably more than 2, is more preferably more than 3.The light-proofness of the sealant for liquid crystal dripping process of the present invention 1 is more high better, and the preferred upper limit of the OD value of the sealant for liquid crystal dripping process of the present invention 1 is not particularly limited, and is generally less than 6.
By coordinating electrically conductive microparticle in the sealant for liquid crystal dripping process of the present invention 1, thus upper and lower conductive material can be manufactured.As above is also one of the present invention containing the sealant for liquid crystal dripping process of the present invention 1 and the conductive material up and down of electrically conductive microparticle.
As above-mentioned electrically conductive microparticle, such as, can be used in Metal Ball, particulate etc. that the surface of resin particle is formed with conductive metal layer.Wherein, can carry out conducting electricity when not damaging transparency carrier etc. the angle connected from the elasticity of the excellence by resin particle, being preferably formed with the particulate of conductive metal layer on the surface of resin particle.
Use the sealant for liquid crystal dripping process of the present invention 1 or upper and lower conductive material of the present invention and the liquid crystal display cells made also is one of the present invention.
As the method manufacturing liquid crystal display cells of the present invention, the method etc. such as with following operation can be enumerated: prepare the transparency carriers 2 such as electroded glass substrate or PET substrate such as ito thin film, on one, the sealant for liquid crystal dripping process of the present invention 1 etc. is passed through the operation that serigraphy, divider coating etc. form rectangular seal pattern wherein; Under the state that the sealant for liquid crystal dripping process etc. of the present invention 1 is uncured, in the frame being coated on transparency carrier that the fine droplet of liquid crystal is dripped whole, the operation of another substrate overlapping immediately; And the operation sealant for liquid crystal dripping process of the present invention 1 being heated and makes it solidify.In addition, before the operation making it solidify heating the sealant for liquid crystal dripping process of the present invention 1, carry out operation sealant being solidified temporarily to light such as seal pattern partial illumination ultraviolets.
Next, the present invention 2 is described in detail in detail.
The light-proofness soft silicone particle of the present invention 2 makes silicone-based particle contain opacifier and make.The light-proofness soft silicone particle of the present invention 2 can be suitable for use as the soft particle of light-proofness contained in the sealant for liquid crystal dripping process of the present invention 1.Namely, the present inventor finds, by coordinating this light-proofness soft silicone particle in the encapsulant, thus when making the baseplate-laminating of liquid crystal display cells, this light-proofness soft silicone particle becomes the barrier before other sealant composition and liquid crystal, sealant can be prevented to stripping in liquid crystal, and the light leak of liquid crystal display cells can be prevented, so far complete the present invention 2.
As the method made containing opacifier in above-mentioned silicone-based particle, such as following method etc. can be listed: in the production phase of silicone-based particle, medium by making the colorant such as pigment or dyestuff be dispersed in the raw material of silicone-based particle as above-mentioned opacifier, thus make the method containing colorant in silicone-based particle; After making does not have the silicone-based particle of light-proofness, in the method for the surface coverage colorant of this silicone-based particle; After making does not have the silicone-based particle of light-proofness, make the method etc. of this silicone-based particle absorption colorant.
Above-mentioned silicone-based particle preferably has two diorganosiloxane units represented by following formula (1) as repetitive and has a silicone cure thing of caoutchouc elasticity.
[changing 5]
-(R 1 2SIO) a-(1)
In formula (1), R 1can enumerate: the alkyl such as methyl, ethyl, propyl group, butyl; The aryl such as phenyl, tolyl; The thiazolinyl such as vinyl, allyl; The aralkyl such as β-phenethyl, β-phenylpropyl; Part or all of the hydrogen atom of these alkyl is substituted by the alkyl after the halogen atom such as chlorine, fluorine; Epoxy radicals, amino, sulfydryl, acryloxy, methacryloxy etc. are containing the organic group etc. of reactive group.A is preferably 5 ~ 5000, is more preferably 10 ~ 1000.
For the curing mechanism of above-mentioned silicone-based particle, can enumerate based on methoxysilyl (≡ SiOCH 3) with the condensation reaction of hydroxyl silicyl (≡ SiOH) etc., sulfydryl silicyl (≡ SiSH) and vinyl silyl groups (≡ SiCH=CH 2) free radical reaction, vinyl silyl groups (≡ SiCH=CH 2) with the reaction mechanism etc. of the addition reaction of ≡ SiH base, from reactive, reaction process aspect, be preferably based on the reaction mechanism of (hydrosilylation) addition reaction.That is, in the present invention, preferably make and make (a) under the existence of (c) platinum group catalyst, carry out addition reaction containing organopolysiloxane and (b) organic hydrogen polysiloxanes of vinyl, the composition that solidifies occurs.
As such (a) composition, the such as compound etc. shown in following formula (2) can be enumerated specifically.
In formula (2), R 1with the R in above-mentioned formula (1) 1identical, but preferably not there is the group of aliphatics unsaturated link.B and c is 0,1,2 or 3, and b+c=3, d are positive number, and e is 0 or positive number, and 2b+e >=2.
As the organic hydrogen polysiloxanes of above-mentioned (b) composition, the compound etc. such as represented by following formula (3) can be enumerated.
[changing 7]
R 2 fH gSiO (4-f-g)/2(3)
In above-mentioned formula (3), R 2for except aliphatics unsaturated link, usually carbon number be 1 ~ 20, preferably carbon number be the monovalent hydrocarbon not replacing or replace being bonded to silicon atom of 1 ~ 12, as this R 2the described monovalent hydrocarbon not replacing or replace, can enumerate such as: the alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, amyl group, neopentyl, hexyl, cyclohexyl, octyl group, nonyl, decyl, the aryl such as phenyl, tolyl, xylyl, naphthyl; The aralkyl such as benzyl, phenethyl, phenylpropyl; Part or all of the hydrogen atom of these groups is by group, the such as chloromethyl, chloropropyl, bromoethyl, trifluoro propyl etc. after the halogen atom replacements such as fluorine, bromine, chlorine.As R 2the monovalent hydrocarbon not replacing or replace, be preferably alkyl, aryl, be more preferably methyl, phenyl.In addition, f is 0.7 ~ 2.1, g is 0.001 ~ 1.0, and f+g is the positive number of satisfied 0.8 ~ 3.0, and preferred f is 1.0 ~ 2.0, g be 0.01 ~ 1.0, f+g is 1.5 ~ 2.5.
As such (b) composition, specifically, the compound etc. such as represented by following formula (4) can be enumerated.
In formula (4), R 1with the R in above-mentioned formula (1) 1identical, preferably not there is the group of aliphatics unsaturated link.M be 0 or 1, n be 2 or 3, and m+n=3, p are 0 or positive number, and q is 0 or positive number, and 2m+q >=2.
The platinum group catalyst of above-mentioned (c) composition is the vinyl being bonded to silicon atom made in (a) composition, with the hydrogen atom (SiH yl) being bonded to silicon atom in (b) composition, the catalyzer of addition reaction occurs, and can enumerate such as: the carbon of Supported Pt Nanoparticles or silicon dioxide, chloroplatinic acid, platinum-alkene complex, platinum-ol complex compound, platinum-phosphorus complex, iridium-platinum complex etc.
Become to assign to make the method for silicone-based particle as using above-mentioned (a) ~ (c), as long as make (a) composition and (b) composition react under the existence of (c) composition, solidify, and be not particularly limited, can enumerate such as: make the method that (a) composition and (b) composition solidify in the spraying dry of high temperature; Make the method that it solidifies in organic solvent; The method etc. of solidifying is made it after being made into emulsion.In addition, in order to make the dispersiveness of silicone-based particle better, can as required at the surface coverage organic poly sesquisiloxane resin of silicone-based particle.
As mentioned above, above-mentioned light-proofness soft silicone particle manufactures by following method: medium by making the colorant such as pigment or dyestuff as above-mentioned opacifier be dispersed in the raw material of silicone-based particle, thus colorant is included in silicone-based particle.Specifically, by making the colorant such as pigment or dyestuff disperse or dissolve in above-mentioned (a) ~ (c) composition in advance, be then cured reaction, thus obtain the silicone-based particle with light-proofness.When colorant being disperseed in above-mentioned (a) ~ (c) composition, preferably in both silicone composition and colorant, add surfactant, the spreading agent with compatibility.By giving the colorant as opacifier before curing reaction, thus the situation of colorant stripping or stripping from particle tails off, and can suppress liquid crystal pollution.
In addition, as mentioned above, above-mentioned light-proofness soft silicone particle also makes by following method: after producing the silicone-based particle without light-proofness, in the method for the surface coverage colorant of this silicone-based particle; After producing the silicone-based particle without light-proofness, make the method for this silicone-based particle absorption colorant.Specifically, by not there is the silicone-based particle dispersion of light-proofness in the medium being dissolved with colorant, stir certain hour and make colorant be bonded to this silicone-based particle, thus giving light-proofness; In addition, use the such Composite device of HYBRIDIZER, THETACOMPOSER, make colorant immobilization in the surface of silicone-based particle without light-proofness, give light-proofness thus.
In addition, the method for the colorant of the adsorption polymerism of the silicone-based particle without light-proofness can be used in.That is, on the surface of silicone-based particle without light-proofness, the polymkeric substance of the skeleton or functional group with the light absorbing specific wavelength is separated out, can light-proofness be given thus.Specifically, by under the existence of silicone particle without light-proofness, make the monomer of the raw material being used as above-mentioned polymkeric substance carry out emulsion polymerization, soap-free polymerization, dispersin polymerization etc., thus above-mentioned polymkeric substance is separated out on the surface of silicone-based particle.
As the polymkeric substance of separating out on the surface of silicone-based particle, can enumerate such as by acetylene and derivant thereof, aniline and its derivatives, Furan and its derivatives, pyrroles and derivant thereof, thiophene and derivatives polymerization and the polymkeric substance etc. that obtains.Wherein, the polypyrrole of preferred black excellent color reproducing performance.
As the above-mentioned silicone-based particle without light-proofness, commercially available silicone-based particle also can be used.
As above-mentioned commercially available silicone-based particle, such as KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (organosilicon Inc. of SHIN-ETSU HANTOTAI), TORAYFILE-506S, EP-9215 (Dong Li Dow Corning Corporation system) etc. can be enumerated, their classifications can be used.The above-mentioned silicone-based particle without light-proofness can be used alone, and also two or more kinds may be used.
As opacifier contained in above-mentioned silicone-based particle, can enumerate such as iron oxide, titanium is black, nigrosine, cyanine are black, fullerene, carbon black, resin-coated type carbon black etc.Wherein, preferred titanium is black.
Above-mentioned titanium is black is following material, that is, compared with the average transmittance of the light to wavelength 300 ~ 800nm, near ultraviolet range, material that particularly transmissivity of the light of wavelength 370 ~ 450nm is higher.That is, above-mentioned titanium is black is the opacifier with following character: by covering the light of the wavelength of visible region fully, thus gives light-proofness to light-proofness soft silicone particle, on the other hand, makes the Transmission light of the wavelength near ultraviolet range.Thus, such as, as the polymerization initiator used in sealant for liquid crystal dripping process, by using the light of wavelength (370 ~ 450nm) and the polymerization initiator of initiation reaction that the black transmissivity of above-mentioned titanium can be utilized to uprise, thus the photo-curable of this sealant for liquid crystal dripping process can be made to increase further.In addition, on the other hand, when for sealant for liquid crystal dripping process etc., as the opacifier contained in above-mentioned silicone-based particle, the material that preferred insulativity is high, as the opacifier that insulativity is high, also preferably titanium is black.
Black for above-mentioned titanium, the optical concentration (OD value) of every 1 μm is preferably more than 3, is more preferably more than 4.The light-proofness that above-mentioned titanium is black is more high better, and the preferred upper limit of the OD value that above-mentioned titanium is black is not particularly limited, and is generally less than 5.
Black for above-mentioned titanium, even if be that not surface treated titanium is black, also give play to sufficient effect, but also can use: the titanium of surface after the organic principle process such as coupling agent is black; The titanium that the inorganic constituents such as surface oxidized silicon, titanium dioxide, germanium oxide, aluminium oxide, zirconia, magnesium oxide cover is black; Titanium after surface treatment is black.Wherein, from the aspect that can improve insulativity further, the titanium preferably after organic principle process is black.
In addition, be contained in as the titanium black-envelope of opacifier the light-proofness soft silicone particle obtained in above-mentioned silicone-based particle using making, when such as sealant for liquid crystal dripping process, this sealant for liquid crystal dripping process has sufficient light-proofness, the liquid crystal display cells of gained does not have the leakage of light and has high-contrast, has excellent display quality of image.
Commercially available product in black as above-mentioned titanium, can enumerate such as 12S, 13M, 13M-C, 13R-N (being Mitsubishi Materials Corp's system), TilackD (red fringe changes into Inc.) etc.
The preferred lower limit of the specific surface area that above-mentioned titanium is black is 13m 2/ g, the preferred upper limit are 30m 2/ g, preferred lower limit are 15m 2/ g, the preferred upper limit are 25m 2/ g.
In addition, the preferred lower limit of the specific insulation that above-mentioned titanium is black is 0.5 Ω cm, the preferred upper limit is 3 Ω cm, preferred lower limit is 1 Ω cm, the preferred upper limit is 2.5 Ω cm.
The preferred lower limit of the primary particle size of opacifier contained in above-mentioned silicone-based particle is 50nm, the excellent upper limit is 500nm.If the primary particle size of opacifier contained in above-mentioned silicone-based particle is lower than 50nm, then secondary aggregation is fierce, sometimes significantly reduces to the dispersiveness in silicone particle.If the primary particle size of opacifier contained in above-mentioned silicone-based particle is more than 500nm, then silicone particle is hard and become and easily break sometimes.The preferred lower limit of the primary particle size of opacifier contained in above-mentioned silicone-based particle is 70nm, the preferred upper limit is 300nm.
The content of opacifier contained in above-mentioned silicone-based particle is relative to light-proofness soft silicone overall particle, and preferred lower limit is 2 % by weight, the preferred upper limit is 30 % by weight.If the content of opacifier contained in above-mentioned silicone-based particle lower than 2 % by weight, then cannot obtain sufficient light-proofness sometimes.If the content of opacifier contained in above-mentioned silicone-based particle is more than 30 % by weight, then silicone particle is hard and become and easily break sometimes.The preferred lower limit of the content of opacifier contained in above-mentioned silicone-based particle is 5 % by weight, the preferred upper limit is 20 % by weight.
When above-mentioned light-proofness soft silicone system particle is used for sealant for liquid crystal dripping process, maximum particle diameter is preferably more than 100% of the cel-gap of liquid crystal display cells.If the maximum particle diameter of above-mentioned light-proofness soft silicone system particle lower than liquid crystal display cells cel-gap 100%, then sometimes become cannot suppress fully sealing fracture or liquid crystal pollution.The maximum particle diameter of above-mentioned light-proofness soft silicone system particle is more preferably more than 100% of the cel-gap of liquid crystal display cells and is more than 5 μm.
In addition, the preferred upper limit of the maximum particle diameter of above-mentioned light-proofness soft silicone system particle is 20 μm.If the maximum particle diameter of above-mentioned light-proofness soft silicone system particle is more than 20 μm, then sometimes when causing resilience for when sealant for liquid crystal dripping process, the cementability of the sealant for liquid crystal dripping process of gained is deteriorated, or the liquid crystal display cells generation gap of gained is bad.The preferred upper limit of the maximum particle diameter of above-mentioned light-proofness soft silicone system particle is 15 μm.
In addition, the maximum particle diameter of above-mentioned light-proofness soft silicone system particle is less than 2.6 times of cel-gap.If the maximum particle diameter of above-mentioned light-proofness soft silicone system particle exceedes 2.6 times of cel-gap, then sometimes when causing resilience for when sealant for liquid crystal dripping process, the cementability of the sealant for liquid crystal dripping process of gained is deteriorated, or the liquid crystal display cells generation gap of gained is bad.The preferred upper limit of the maximum particle diameter of above-mentioned light-proofness soft silicone system particle is 2.2 times of cel-gap, further the preferred upper limit be 1.7 times of cel-gap.
It should be noted that, in this manual, maximum particle diameter and the mean grain size described later of above-mentioned light-proofness soft silicone system particle refer to, the value obtained by using laser diffraction formula particle size distribution device to measure the particle before being matched with sealant.As above-mentioned laser diffraction formula distribution measurement device, Mastersizer2000 (Malvern Inc.) etc. can be used.In addition, the cel-gap of liquid crystal display cells is different according to display element, is not therefore limited, but the cel-gap of general liquid crystal display cells is 2 μm ~ 10 μm.
For above-mentioned light-proofness soft silicone system particle, in the size-grade distribution of the light-proofness soft silicone system particle recorded by above-mentioned laser diffraction formula distribution measurement device, the particle of the particle diameter of more than 5 μm be preferably more than 60% containing proportional in volume frequency.If the particle of the particle diameter of more than 5 μm containing proportional in volume frequency lower than 60%, then when for sealant for liquid crystal dripping process, sometimes cannot suppress fully sealing fracture or liquid crystal pollution.The particle of the particle diameter of more than 5 μm be more preferably more than 80% containing proportional.
For above-mentioned light-proofness soft silicone system particle, when for sealant for liquid crystal dripping process, from the view point of the effect playing the generation suppressing sealing fracture or liquid crystal pollution further, preferably contain the particle of more than 100% of the cel-gap of liquid crystal display cells with more than 70% of the size-grade distribution in light-proofness soft silicone system overall particle, more preferably only by liquid crystal display cells cel-gap more than 100% particle form.
The preferred lower limit of the mean grain size of above-mentioned light-proofness soft silicone system particle is 2 μm, the preferred upper limit is 50 μm.If the mean grain size of above-mentioned light-proofness soft silicone system particle is lower than 2 μm, then when for sealant for liquid crystal dripping process, sealant sometimes cannot be suppressed fully to the stripping of liquid crystal.If the mean grain size of above-mentioned light-proofness soft silicone system particle is more than 50 μm, then when for sealant for liquid crystal dripping process, sometimes the cementability of the sealant for liquid crystal dripping process of gained is deteriorated, or the liquid crystal display cells generation gap of gained is bad.The preferred lower limit of the mean grain size of above-mentioned light-proofness soft silicone system particle is 4 μm, the preferred upper limit is 15 μm, preferably the upper limit is 12 μm further.
As above-mentioned light-proofness soft silicone system particle, can the different light-proofness soft silicone system of more than two kinds particle of maximum particle diameter used in combination.Namely, when for sealant for liquid crystal dripping process, can maximum particle diameter used in combination lower than liquid crystal display cells cel-gap 100% light-proofness soft silicone system particle, be the light-proofness soft silicone system particle of more than 100% of the cel-gap of liquid crystal display cells with maximum particle diameter.
The coefficient of variation (following, also referred to as " CV value ") of the particle diameter of above-mentioned light-proofness soft silicone system particle is preferably less than 30%.If the CV value of the particle diameter of above-mentioned light-proofness soft silicone system particle more than 30%, then, when for sealant for liquid crystal dripping process, causes cel-gap bad sometimes.The CV value of the particle diameter of above-mentioned light-proofness soft silicone system particle is more preferably less than 28%.
It should be noted that, in this manual, the CV value of particle diameter refers to, by the numerical value calculated by following formula.
CV value (%)=(standard deviation/mean grain size of particle diameter) × 100 of particle diameter
Even if above-mentioned light-proofness soft silicone system particle maximum particle diameter or mean grain size or CV value are in beyond above-mentioned scope, maximum particle diameter or mean grain size or CV value is also made to reach in above-mentioned scope by classification.In addition, when for sealant for liquid crystal dripping process, particle diameter lower than liquid crystal display cells cel-gap 100% light-proofness soft silicone system particle be sometimes helpless to suppress sealing fracture or the generation of liquid crystal pollution, if be matched with sealant, make thixotroping value increase, be therefore preferably removed by classification in advance.
As the method to the particle classification of above-mentioned light-proofness soft silicone system, the such as method such as wet classification, dry classification can be enumerated.Wherein, preferred wet classification, more preferably wet screening level.
For above-mentioned light-proofness soft silicone system particle, by from apply load time initial point load value to reach reversion load value compression displacement be set to L1, by when being set to L2 to the unloading displacement reached initial point load value from reversion load value when discharging, represent that the recovery rate of L2/L1 is preferably less than 80% with percent.If the recovery rate of above-mentioned light-proofness soft silicone system particle more than 80%, then when for sealant for liquid crystal dripping process, sometimes becomes obstacle, prevents sealant to the function reduction of liquid crystal stripping.The preferred upper limit of the recovery rate of above-mentioned light-proofness soft silicone system particle is 70%, preferably the upper limit is 60% further.
It should be noted that, for the recovery rate of above-mentioned light-proofness soft silicone system particle, use micro-compression tester to apply certain load (1g) to 1 particle, resolve the recovery behavior after being removed by this load, derive recovery rate thus.
For above-mentioned light-proofness soft silicone system particle, compression displacement when applying the load of 1g is set to L3, when particle diameter is set to Dn, represents that the 1g strain of L3/Dn is preferably more than 30% with percent.If the 1g strain of above-mentioned light-proofness soft silicone system particle is lower than 30%, then when for sealant for liquid crystal dripping process, sometimes becomes obstacle, prevent sealant to the function reduction of liquid crystal stripping.The preferred lower limit of the 1g strain of above-mentioned light-proofness soft silicone system particle is 40%.
It should be noted that, the 1g strain of above-mentioned light-proofness soft silicone system particle can use micro-compression tester to apply the load of 1g to 1 particle, is recorded by the displacement measured now.
For above-mentioned light-proofness soft silicone system particle, the compression displacement that particle is occurred damaged time point is set to L4, when particle diameter is set to Dn, represent that the breakage strain of L4/Dn is preferably more than 50% with percent.If the breakage strain of above-mentioned light-proofness soft silicone system particle is lower than 50%, then when for sealant for liquid crystal dripping process, sometimes becomes obstacle, prevent sealant from reducing to the function of liquid crystal stripping.The preferred lower limit of the breakage strain of above-mentioned light-proofness soft silicone system particle is 60%.
It should be noted that, the breakage strain of above-mentioned light-proofness soft silicone system particle can use micro-compression tester to apply load to 1 particle, measures displacement when this particle occurs damaged and records.For above-mentioned compression displacement L4, time point large for the discontinuous change of displacement for load loading is set to particle and damaged time point occurs, thus calculate.Think: even if in the loading of increase load, when also only deforming and breakage does not occur, damaged strain is more than 100%.
The preferred lower limit of the glass transition temperature of above-mentioned light-proofness soft silicone system particle is-200 DEG C, the preferred upper limit is 40 DEG C.If the glass transition temperature of above-mentioned light-proofness soft silicone particle is more than-200 DEG C, then lower, suppress the effect of sealing fracture or liquid crystal pollution better, if lower than-200 DEG C, then sometimes have problems in the disposal of particle, or sealant becomes and easily caves in heating way, the sealant in solidification way contacts with liquid crystal and produces liquid crystal pollution.If the glass transition temperature of above-mentioned light-proofness soft silicone particle is more than 40 DEG C, then sometimes there is gap bad.The preferred lower limit of the glass transition temperature of above-mentioned light-proofness soft silicone system particle is-150 DEG C, the preferred upper limit is 35 DEG C.It should be noted that, the glass transition temperature of above-mentioned light-proofness soft silicone system particle represents the value recorded by means of differential scanning calorimetry mensuration (DSC) of " the transition temperature assay methods of plastics " based on JISK7121.
The effect of invention
According to the present invention, can provide a kind of excellent in adhesion, substantially do not cause liquid crystal pollution and the sealant for liquid crystal dripping process of the light leak of liquid crystal display cells can be prevented.In addition, according to the present invention, can provide and use this sealant for liquid crystal dripping process and the conductive material up and down that manufactures and liquid crystal display cells.In addition, according to the present invention, light-proofness soft silicone particle can be provided.
Embodiment
Below enumerate embodiment to illustrate in greater detail the present invention, but the present invention is not limited in these embodiments.
(making of the soft particle A of light-proofness)
Methylhydrogenpolysi,oxane (compound represented by following formula (the 6)) 20g that the methyl vinyl silicone being 600cP by viscosity (compound represented by following formula (5)) 500g, viscosity are 30cP and titanium black (Mitsubishi Materials Corp's system, " 13M ") 26g drops in the glass beaker of 1 liter capacity, uses homogeneous mixer to be uniformly mixed with 2000rpm.
Then, add polyoxyethylene (addition molal quantity=9 mole) octyl phenyl ether 1g, water 150g, proceed to stir with 6000rpm, result causes phase inversion, observes thickening, further, directly stir with 3000rpm, add water 329g simultaneously, result obtains O/W type emulsion.
Then, this emulsion is moved to the glass flask with the stirring apparatus utilizing anchor type paddle, toluene solution (platinum content 0.05%) 1g of chloroplatinic acid-alkene complex and the potpourri of polyoxyethylene (addition molal quantity=9 mole) octyl phenyl ether 1g is under agitation added under room temperature (25 DEG C), carry out reaction in 12 hours, result obtains dispersion liquid (hereinafter also referred to " silicone rubber spheroidal particle aqueous dispersions-1 "), Coulter-counter (CoulterElectronics Inc.) is used to measure the mean grain size of the particle in this dispersion liquid, result is 10 μm, at room temperature drying is carried out to this dispersion liquid number g, result obtains resilient rubber powder.
In the glass flask of 3 liters, drop into silicone rubber spheroidal particle aqueous dispersions-1 and ammoniacal liquor (the concentration 28 % by weight) 60g of water 2290g, 580g, water temperature is set to 10 DEG C, under the condition of oar rotating speed 200rpm, utilizes anchor type paddle to stir.The pH of liquid is now 11.2, methyltrimethoxy silane 65g was dripped with 20 minutes in this liquid, during this period liquid temperature is being remained on 5 ~ 15 DEG C, after carrying out stirring in 4 hours further, be heated to 55 ~ 60 DEG C, then carry out stirring for 1 hour, utilized by the liquid of gained pressure filter to make the pie of water about 30%.
Then, this pie is carried out drying with the temperature of 105 DEG C in hot air circular drying machine, utilize jet mill to pulverize the dry thing of gained.Then, by particle diameter, the maximum particle diameter of progressive operation adjustment regulation, obtain the light-proofness soft silicone particle containing opacifier and the soft particle A of light-proofness.
Methylhydrogenpolysi,oxane (compound shown in following formula (the 6)) 20g that the base vinylsiloxane being 600cP by viscosity (compound shown in following formula (5)) 500g, viscosity are 30cP, titanium black (Mitsubishi Materials Corp's system, " 13M ") 26g drop in the glass beaker of 1 liter capacity, homogeneous mixer is used to be uniformly mixed with 2000rpm, in the liquid of gained thus, add toluene solution (platinum content 0.05%) 1g of chloroplatinic acid-alkene complex, produce therefrom mixed liquor.
Injected by the mixed liquor of gained and implement on groove that Teflon (registered trademark) is coated with in advance, the mode reaching 1mm with the thickness after solidifying adjusts height, room temperature reaction 24 hours, obtains sheet material thus.Cut the sheet material of gained, obtain the laminar melanism degree measurement sample of the thickness 1mm with the identical composition of particle A soft with light-proofness.
Shown in table 1: " maximum particle diameter " of the soft particle A of light-proofness of gained, " mean grain size ", " the CV value of particle diameter ", " glass transition temperature ", use " the melanism degree " of the melanism degree measurement sample measured by UV-3600 (Inc. of Shimadzu Seisakusho Ltd.), and use slight compression exerciser (Inc. of Shimadzu Seisakusho Ltd., " PCT-200 ") and utilize the cylinder flat surface of adamantine diameter 50 μm at compression speed 0.28mN/sec, initial point load value 1.0mN, under the condition of reversion load value 10mN, particulate is measured and " recovery rate " that obtain, " 1g strain ", and " damaged strain ".
(making of the soft particle B of light-proofness)
The use amount of black for titanium (Mitsubishi Materials Corp's system, " 13M ") is set to 52g, in addition, carry out the reaction that A soft with light-proofness is identical, produce as the soft particle containing opacifier, the soft particle B of light-proofness soft silicone particle and light-proofness, and produce the laminar melanism degree measurement sample of the thickness 1mm with the identical composition of particle B soft with light-proofness.
The soft particle of light-proofness for gained, illustrates in Table 1: carry out measured by identical operation, " maximum particle diameter ", " mean grain size ", " the CV value of particle diameter ", " glass transition temperature ", " melanism degree ", " recovery rate ", " 1g strains " and " breakage strains " with the soft particle A of light-proofness.
(making of the soft particle C of light-proofness)
When not adding titanium and being black, only use methyl vinyl silicone and methylhydrogenpolysi,oxane, carry out the reaction identical with above-mentioned " making of the soft particle A of light-proofness ", obtain silicone-based particle.
The silicone-based particle 20g of gained and water 210g is dropped into the detachable flask of 1 liter, carry out stirring, making it disperse.In addition, additionally, make and make polyvinyl pyrrolidone 3g be dissolved in the solution obtained in water 50g, and the solution of gained to be joined in above-mentioned detachable flask and to stir 30 minutes.
Then, add pyrroles 10g, hydrogen peroxide (original text: Over acidifying water) (15 % by weight) 5.3g and sulfuric acid (5 % by weight) 24.4g and stir 30 minutes.Then, iron sulfate 7 hydrate 0.08g is dissolved in water 1g, is added in above-mentioned detachable flask.Then, at room temperature continue stirring 12 hours, then particle is washed with water for several times.After the at room temperature drying of this dispersion liquid, adjusted particle diameter, the maximum particle diameter of regulation by progressive operation, obtain light-proofness soft silicone particle and the soft particle C of light-proofness.
The soft particle C of light-proofness for gained, illustrates in Table 1: carry out operating in the same manner as the soft particle A of light-proofness record, " maximum particle diameter ", " mean grain size ", " the CV value of particle diameter ", " glass transition temperature ", " recovery rate ", " 1g strains " and " breakage strains ".
It should be noted that, for the soft particle C of light-proofness, melanism degree measurement sample cannot be produced, therefore do not carry out the mensuration of melanism degree.
(making of the soft particle D of light-proofness)
Black to polytetramethylene glycol diacrylate 50g, ethylhexyl methacrylate 950g and titanium (Mitsubishi Materials Corp's system, " 13M ") 50g is dropped in the glass beaker of 3 liters, uses homogeneous mixer to be uniformly mixed with 2000rpm.Further, in this mixed liquor, add benzoyl peroxide 40g, till utilizing agitator to carry out being mixed to dissolving equably (following, to be also called " monomer mixed solution " by the mixed liquor of gained).
In the reactor of polyvinyl alcohol (PVA) 1 % by weight aqueous solution having dropped into 5kg, drop into above-mentioned monomer mixed solution, stir 2 ~ 4 hours, carry out particle diameter adjustment thus, with the particle diameter making the drop of monomer reach regulation.Then, under the nitrogen atmosphere of 85 DEG C, carry out reaction in 9 hours, obtain polymer particle.Utilized by the polymer particle of gained hot wash for several times, then carry out progressive operation, adjustment particle diameter and maximum particle diameter.Further, utilize methyl alcohol to carry out the displacement of several solvent, then utilize vacuum drier at 30 DEG C, under reduced pressure carry out drying in 12 hours, thus obtain the soft particle D of light-proofness.
A part for above-mentioned monomer mixed solution injected and implement on groove that Teflon (registered trademark) is coated with in advance, the mode reaching 1mm with the thickness after solidifying adjusts height, makes it react 20 hours, obtain sheet material thus at 85 DEG C.Cut the sheet material of gained, obtain the laminar melanism degree measurement sample of the thickness 1mm with the identical composition of particle D soft with light-proofness.
The soft particle D of light-proofness for gained, illustrates in Table 1: carry out measured by identical operation, " maximum particle diameter ", " mean grain size ", " the CV value of particle diameter ", " glass transition temperature ", " melanism degree ", " recovery rate ", " 1g strains " and " breakage strains " with the soft particle A of light-proofness.
(making of the soft particle E of light-proofness)
Replace polytetramethylene glycol diacrylate 50g and ethylhexyl methacrylate 950g, and use polytetramethylene glycol diacrylate 400g and styrene 600g, in addition, carry out the operation that particle D soft with light-proofness is identical, produce the soft particle E of light-proofness and there is the laminar melanism degree measurement sample of thickness 1mm of the identical composition of particle E soft with light-proofness.
The soft particle E of light-proofness for gained, illustrates in Table 1: carry out measured by identical operation, " maximum particle diameter ", " mean grain size ", " the CV value of particle diameter ", " glass transition temperature ", " melanism degree ", " recovery rate ", " 1g strains " and " breakage strains " with the soft particle A of light-proofness.
(making of the soft particle F of light-proofness)
Replace polytetramethylene glycol diacrylate 50g and ethylhexyl methacrylate 950g, and use polytetramethylene glycol diacrylate 750g and styrene 250g, in addition, carry out the operation that particle D soft with light-proofness is identical, make the soft particle F of light-proofness and there is the laminar melanism degree measurement sample of thickness 1mm of the identical composition of particle F soft with light-proofness.
The soft particle F of light-proofness for gained, illustrates in Table 1: carry out measured by identical operation, " maximum particle diameter ", " mean grain size ", " the CV value of particle diameter ", " glass transition temperature ", " melanism degree ", " recovery rate ", " 1g strains " and " breakage strains " with the soft particle A of light-proofness.
(making of the soft particle G of light-proofness)
When classification, the mode reaching less than 5 μm with maximum particle diameter adjusts, and in addition, carries out the operation that particle A soft with light-proofness is identical, obtains the soft particle G of light-proofness.
The soft particle F of light-proofness for gained, illustrates in Table 1: carry out measured by identical operation, " maximum particle diameter ", " mean grain size ", " the CV value of particle diameter ", " glass transition temperature ", " melanism degree ", " recovery rate ", " 1g strains " and " breakage strains " with the soft particle A of light-proofness.
It should be noted that, because particle composition is identical with the soft particle A of light-proofness, so the utilization of melanism degree measurement sample is the sample identical with the sample of gained in the soft particle A of light-proofness.
(making of the soft particle A of non-light-proofness)
Except do not add titanium black except, carry out the reaction that particle A soft with light-proofness is identical, produce as the soft particle A of non-light-proofness not containing the soft particle of opacifier, and produce the laminar melanism degree measurement sample of the thick 1mm with the identical composition of particle A soft with non-light-proofness.
The soft particle A of non-light-proofness for gained, illustrates in Table 1: carry out measured by identical operation, " maximum particle diameter ", " mean grain size ", " the CV value of particle diameter ", " glass transition temperature ", " melanism degree ", " recovery rate ", " 1g strains " and " breakage strains " with the soft particle A of light-proofness.
[table 1]
(embodiment 1)
Coordinate bisphenol-a epoxy acrylate (the DaicelAllnex Inc. as curable resin, " EBECRYL3700 ") 70 weight portions and bisphenol f type epoxy resin (Mitsubishi Chemical Ind's system, " jER806 ") 30 weight portions, as the polymeric azo initiating agent of hot radical polymerization initiator (with light pure pharmaceutical worker's industry Inc., " VPE-0201 ") 7 weight portions, as sebacic dihydrazide (the great Zhong chemical company system of thermal curing agents, " SDH ") 8 weight portions, light-proofness soft particle A30 weight portion, as silicon dioxide (the Admatechs Inc. of filling agent, " ADMAFINESO-C2 ") 10 weight portions, with 3-glycidoxypropyltrime,hoxysilane (the organosilicon Inc. of SHIN-ETSU HANTOTAI as silane coupling agent, " KBM-403 ") 1 weight portion, utilize planetary stirring apparatus (TINKY Inc., " あ わ と り Practice Taro ") stir, then utilize ceramic 3 roller machines to make it mix equably, thus obtain sealant for liquid crystal dripping process.
(embodiment 2 ~ 14, comparative example 1 ~ 3)
Match ratio described in table 2, identical operation is carried out with embodiment 1, planetary for each materials'use stirring apparatus (TINKY Inc. " あ わ と り Practice Taro ") is mixed, then use 3 roller machines to mix further, prepare the sealant for liquid crystal dripping process of embodiment 2 ~ 14, comparative example 1 ~ 3.
< evaluates >
For each sealant for liquid crystal dripping process obtained in embodiment and comparative example, carry out following evaluation.Show the result in table 2.
(cementability)
Utilize planetary stirring apparatus, relative to each sealant for liquid crystal dripping process 100 weight portion of gained in embodiment and comparative example, the sept particle of mean grain size 5 μm (ponding chemical industrial company system, " Micro-PearlSP-2050 ") 1 weight portion is disperseed equably, get the central portion that denier is placed in corning glass 1737 (20mm × 50mm × thick 0.7mm), thereon overlapping homotype glass and sealant for liquid crystal dripping process is expanded, heat 1 hour at 120 DEG C and make sealant heat curing, obtaining adhesive test sheet.
For the adhesive test sheet of gained, tensiometer is used to measure bonding strength.Be 270N/cm by bonding strength 2above average evaluation is "○", be 250N/cm by bonding strength 2above and lower than 270N/cm 2average evaluation be " △ ", by bonding strength lower than 250N/cm 2average evaluation be "×", thus have rated cementability.
(light-proofness)
Utilize planetary stirring apparatus, relative to each sealant for liquid crystal dripping process 100 weight portion obtained in embodiment and comparative example, the sept particle of mean grain size 5 μm (ponding chemical industrial company system, " Micro-PearlSP-2050 ") 1 weight portion is disperseed equably, be coated on the glass substrate of 50mm × 50mm, thereon the glass substrate of overlapping homotype.Then, heat 1 hour at 120 DEG C and make sealant heat curing, obtaining OD pH-value determination pH test film.For the OD pH-value determination pH test film of gained, PDA-100 (KONICA Inc.) is used to measure OD value, by OD value be more than 3 average evaluation be " 00 ", will be "○" for more than 2.5 and lower than the average evaluation of 3, will be " △ " for more than 2 and lower than the average evaluation of 2.5, be "×" by the average evaluation lower than 2, thus have rated light-proofness.
(liquid crystal pollution)
Utilize planetary stirring apparatus, relative to each sealant for liquid crystal dripping process 100 weight portion obtained in embodiment and comparative example, make sept particle (the ponding chemical industrial company system of mean grain size 5 μm, " Micro-PearlSP-2050 ") 1 weight portion disperses equably, the sealant of gained is filled to syringe (the Musashi high-tech company system of point adapted, " PSY-10E ") in, carry out deaeration process, then divider (Musashi high-tech company system is utilized, " SHOTMASTER300 ") on the transparent electrode substrate of band ito thin film, be coated with sealant in the mode describing rectangular frame.Then, utilize liquid crystal dripping device to drip the fine droplet of coating TN liquid crystal (CHISSO Inc., " JC-5001LA "), utilize vacuum forming apparatus to fit under the vacuum of 5Pa another transparency carrier.Unit after laminating heated 1 hour at 120 DEG C and makes sealant heat curing, obtaining liquid crystal display cells (cel-gap 5 μm).
For the liquid crystal display cells of gained, the display utilizing visualization to produce in the liquid crystal (particularly corner portion) of sealing periphery is uneven, be " 00 " by not showing uneven average evaluation completely, be "○" by substantially not showing uneven average evaluation, be " △ " by slightly there is to show uneven average evaluation, be "×" by confirming the average evaluation seriously showing inequality, thus have rated liquid crystal pollution.
[table 2]
Utilizability in industry
According to the present invention, can provide a kind of excellent in adhesion, substantially can not cause liquid crystal pollution and the sealant for liquid crystal dripping process of the light leak of liquid crystal display cells can be prevented.In addition, according to the present invention, can provide and use this sealant for liquid crystal dripping process and the conductive material up and down that manufactures and liquid crystal display cells.In addition, according to the present invention, light-proofness soft silicone particle can be provided.

Claims (12)

1. a sealant for liquid crystal dripping process, is characterized in that, is the sealant for liquid crystal dripping process used in the manufacture of the liquid crystal display cells based on liquid crystal dripping process,
Described sealant for liquid crystal dripping process contains curable resin, polymerization initiator and/or thermal curing agents and the soft particle of light-proofness.
2. sealant for liquid crystal dripping process according to claim 1, is characterized in that, the maximum particle diameter of the soft particle of light-proofness is more than 100% of the cel-gap of liquid crystal display cells.
3. sealant for liquid crystal dripping process according to claim 1 and 2, it is characterized in that, about the soft particle of light-proofness, by from apply load time initial point load value to reach reversion load value compression displacement be set to L1, by when being set to L2 to the unloading displacement reached initial point load value from reversion load value when discharging, represent that the recovery rate of L2/L1 is less than 80% with percent.
4. the sealant for liquid crystal dripping process according to any one of claims 1 to 3, it is characterized in that, about the soft particle of light-proofness, when the compression displacement during load of applying 1g is set to L3 and particle diameter is set to Dn, represent that with percent the 1g strain of L3/Dn is more than 30%.
5. the sealant for liquid crystal dripping process according to any one of Claims 1 to 4, is characterized in that, the glass transition temperature of the soft particle of light-proofness is-200 ~ 40 DEG C.
6. the sealant for liquid crystal dripping process according to any one of Claims 1 to 5, it is characterized in that, about the soft particle of light-proofness, when the compression displacement that particle be there occurs damaged time point is set to L4 and particle diameter is set to Dn, represent that with percent the breakage strain of L4/Dn is more than 50%.
7. the sealant for liquid crystal dripping process according to any one of claim 1 ~ 6, is characterized in that, the coefficient of variation of the particle diameter of the soft particle of light-proofness is less than 30%.
8. the sealant for liquid crystal dripping process according to any one of claim 1 ~ 7, is characterized in that, on the basis of the soft particle of light-proofness, also containing opacifier.
9. a conductive material about, is characterized in that, containing the sealant for liquid crystal dripping process according to any one of claim 1 ~ 8 and electrically conductive microparticle.
10. a liquid crystal display cells, is characterized in that, uses the sealant for liquid crystal dripping process according to any one of claim 1 ~ 8 or upper and lower conductive material according to claim 9 to manufacture.
11. 1 kinds of light-proofness soft silicone particles, is characterized in that, make to form containing opacifier in silicone-based particle.
12. light-proofness soft silicone particles according to claim 11, it is characterized in that, mean grain size is 2 ~ 50 μm.
CN201480037955.2A 2013-07-03 2014-06-26 Sealant for liquid crystal dropping method, vertical-conduction material, liquid crystal display element, and light-shielding flexible silicone particles Pending CN105359034A (en)

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