CN107250220A - Silicone particles, the manufacture method of Silicone particles, sealant for liquid crystal dripping process and liquid crystal display cells - Google Patents

Silicone particles, the manufacture method of Silicone particles, sealant for liquid crystal dripping process and liquid crystal display cells Download PDF

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CN107250220A
CN107250220A CN201680010161.6A CN201680010161A CN107250220A CN 107250220 A CN107250220 A CN 107250220A CN 201680010161 A CN201680010161 A CN 201680010161A CN 107250220 A CN107250220 A CN 107250220A
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silicone particles
mentioned
liquid crystal
silane compound
free
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上田沙织
山田恭幸
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Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Silicon Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a kind of raising resistance to chemical reagents and can reduce the Silicone particles of penetrability.The Silicone particles of the present invention have more than 0.1 μm, less than 500 μm of particle diameter, and, the Silicone particles are with siloxanes key, free-radical polymerised group and carbon number are the Silicone particles of more than 5 hydrophobic grouping, either make the silane compound with free-radical polymerised group and reacted with carbon number for the silane compound of more than 5 hydrophobic grouping and form siloxanes key Silicone particles obtained from, either make with free-radical polymerised group and reacted with carbon number for the silane compound of more than 5 hydrophobic grouping and form siloxanes key Silicone particles obtained from.

Description

Silicone particles, the manufacture method of Silicone particles, liquid crystal dripping process are with close Seal agent and liquid crystal display cells
Technical field
The present invention relates to the manufacture method of a kind of Silicone particles and Silicone particles.Moreover, it relates to one Kind above-mentioned sealant for liquid crystal dripping process and liquid crystal display cells for having used Silicone particles.
Background technology
The anisotropic conductive material such as anisotropic conductive cream and anisotropic conductive film is well-known.For it is above-mentioned it is each to For different in nature conductive material, electroconductive particle is dispersed with adhesive resin.Above-mentioned anisotropic conductive material is used to scratch Enter between the electrodes of various connecting object parts such as property printed base plate (FPC), glass substrate, glass epoxy substrate and semiconductor chip Row electrical connection, obtains connection structural bodies.In addition, as above-mentioned electroconductive particle, sometimes using with substrate particle and being configured at The electroconductive particle of conductive layer on the surface of the substrate particle.
In addition, liquid crystal display cells configure liquid crystal between 2 glass substrates and constituted.In the liquid crystal display cells, it is Make the interval (gap) of 2 glass substrates uniform and keep certain, distance piece can be used to be used as gap control material.
Recorded in following patent documents 1：As above-mentioned distance piece used for liquid crystal display element, polysiloxane rubber powder is used The rubber powders such as end.
In addition, following, Patent Document 2 discloses contain the poly organo of more than two kinds with different organic groups Alkane, composition stage or the particle continuously changed from particle centre portion to surface direction.
It is following that Patent Document 3 discloses make the multi-functional silane compound with polymerism unsaturated group on surface It is hydrolyzed in the presence of activating agent and polycondensation particle obtained from.In patent document 3, above-mentioned multi-functional silane compound At least one selected in being the compound and its derivative represented from specific chemical formula contains the 1st of free-radical polymerised group Silicon compound.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2009-139922 publications；
Patent document 2:Japanese Unexamined Patent Publication 2010-229303 publications；
Patent document 3:Japanese Unexamined Patent Publication 2000-204119 publications.
The content of the invention
Invent problem to be solved
In patent document 1~3 in described particle, resistance to chemical reagents is low sometimes, and penetrability is high.
For example, general polysiloxane rubber powder as described in Patent Document 1 is used as used for liquid crystal display element During distance piece, sometimes due to polysiloxane rubber powder, liquid crystal is contaminated.In addition, in the characteristic of the material of polysiloxanes, Sometimes penetrability is raised, and is produced in liquid crystal display uneven.
On the other hand, passed for the pressure sensor, acceleration transducer, CMOS that are configured in ceramic package in recent years The electronic component such as sensor component and ccd sensor element, high temperature, high pressure it is harsh under conditions of, also require that high-precision sense Survey ability.Therefore, the improvement of the penetrability at the junction surface between 2 ceramic components in above-mentioned electronic component turns into important class Topic.
It is an object of the present invention to provide a kind of improve resistance to chemical reagents and can reduce the Silicone particles of penetrability And the manufacture method of Silicone particles.In addition, it is an object of the present invention to provide one kind is above-mentioned to have used Silicone particles Sealant for liquid crystal dripping process and liquid crystal display cells.
The technical scheme solved the problems, such as
According to the broad aspect of the present invention there is provided a kind of Silicone particles, it has more than 0.1 μm, less than 500 μm Particle diameter, also, the Silicone particles be with siloxanes key, free-radical polymerised group and carbon number be more than 5 The Silicone particles (the 1st Silicone particles) of hydrophobic grouping, or make the silanization with free-radical polymerised group Compound and react with carbon number for the silane compound of more than 5 hydrophobic grouping and to form siloxanes key poly- obtained from Silicone particles (the 2nd Silicone particles), or make with free-radical polymerised group and there is carbon number to be more than 5 Hydrophobic grouping silane compound react and formed siloxanes key obtained from Silicone particles (the 3rd polysiloxanes grain Son).
At some specific aspect of the Silicone particles of the present invention, the Silicone particles are with siloxanes Key, there is in the end of the siloxanes key free-radical polymerised group and have carbon former on the side chain of the siloxanes key Subnumber is the Silicone particles (the 1st Silicone particles) of more than 5 hydrophobic grouping, or makes with free-radical polymerised The silane compound of group and silane compound with carbon number for more than 5 hydrophobic grouping react and form siloxanes key Silicone particles (the 2nd Silicone particles) obtained from, or make with free-radical polymerised group and with carbon Atomicity is reacted for the silane compound of more than 5 hydrophobic grouping and forms siloxanes key Silicone particles obtained from (the 3rd Silicone particles).
At some specific aspect of the Silicone particles of the present invention, the Silicone particles are with siloxanes Key, have in the end of the siloxanes key and be bonded to free-radical polymerised group on silicon atom and in the siloxanes There is Silicone particles (the 1st poly- silicon for the hydrophobic grouping that the carbon number being bonded on silicon atom is more than 5 on the side chain of key Oxygen alkane particle), or make with the silane compound for being bonded to free-radical polymerised group on silicon atom and with bonding Reacted in the carbon number on silicon atom for the silane compound of more than 5 hydrophobic grouping and form siloxanes key obtained from Silicone particles (the 2nd Silicone particles), or make be bonded to free-radical polymerised group on silicon atom and With the carbon number being bonded on silicon atom for more than 5 hydrophobic grouping silane compound react and formed siloxanes key from Obtained from Silicone particles (the 3rd Silicone particles).
At some specific aspect of the Silicone particles of the present invention, the Silicone particles are that have in 1 silicon The Silicone particles of the dimethylsiloxane skeleton of 2 methyl are bonded with atom.
At some specific aspect of the Silicone particles of the present invention, the Silicone particles are when have compressed 30% Modulus of elasticity in comperssion be 500N/mm2Following Silicone particles.
At some specific aspect of the Silicone particles of the present invention, the Silicone particles have been free from metal and urged The Silicone particles of agent or metallic catalyst containing below 100ppm.
At some specific aspect of the Silicone particles of the present invention, the Silicone particles are containing opacifier Silicone particles.
At some specific aspect of the Silicone particles of the present invention, the Silicone particles are used under liquid crystal drop The Silicone particles of technique sealant.
The Silicone particles of the present invention are preferably that there is siloxanes key, free-radical polymerised group and carbon number to be 5 The Silicone particles (the 1st Silicone particles) of hydrophobic grouping above.
The Silicone particles of the present invention, which are preferably also, to be made silane compound with free-radical polymerised group and has Carbon number reacts for the silane compound of more than 5 hydrophobic grouping and forms Silicone particles obtained from siloxanes key (the 2nd Silicone particles), or make with free-radical polymerised group and with the hydrophobic grouping that carbon number is more than 5 Silane compound react and form siloxanes key obtained from Silicone particles (the 3rd Silicone particles).
At some specific aspect of the Silicone particles of the present invention, the Silicone particles are to utilize radical polymerization Closing initiator makes the silane compound with free-radical polymerised group and the silicon with the hydrophobic grouping that carbon number is more than 5 Silicone particles (the 2nd Silicone particles) obtained from hydride compounds reaction, or utilize radical polymerization initiator Make with free-radical polymerised group and with carbon number obtained from the silane compound reaction of more than 5 hydrophobic grouping Silicone particles (the 3rd Silicone particles).
According to the broad aspect of the present invention there is provided a kind of manufacture method of Silicone particles, it is above-mentioned polysiloxanes The manufacture method of particle, this method includes following process：Make silane compound with free-radical polymerised group and with carbon Atomicity is reacted for the silane compound of more than 5 hydrophobic grouping, so as to obtain Silicone particles (the 2nd polysiloxanes grain Son), or, make with free-radical polymerised group and anti-for the silane compound of more than 5 hydrophobic grouping with carbon number Should, so as to obtain Silicone particles (the 3rd Silicone particles).
At some specific aspect of the manufacture method of the Silicone particles of the present invention, radical polymerization initiator is utilized Make the silane compound with free-radical polymerised group and the silane compound with the hydrophobic grouping that carbon number is more than 5 Reaction, so that Silicone particles (the 2nd Silicone particles) are obtained, or, make to have certainly using radical polymerization initiator By base polymerizable group and with silane compound reaction of the carbon number for more than 5 hydrophobic grouping, so as to obtain poly- silica Alkane particle (the 3rd Silicone particles).
According to the broad aspect of the present invention there is provided a kind of sealant for liquid crystal dripping process, it contains Thermocurable composition With above-mentioned Silicone particles.
According to the broad aspect of the present invention there is provided a kind of liquid crystal display cells, it includes：1st portion used for liquid crystal display element Part, the 2nd part used for liquid crystal display element, in the 1st part used for liquid crystal display element and the 2nd portion used for liquid crystal display element The periphery of 1st part used for liquid crystal display element and the 2nd part used for liquid crystal display element is entered in the state of part is opposed Gone sealed sealing, positioned at the inner side of the sealing and be configured at the 1st part used for liquid crystal display element and described Liquid crystal between 2nd part used for liquid crystal display element, the sealing is by making sealant for liquid crystal dripping process carry out thermosetting Change and formed, the sealant for liquid crystal dripping process contains Thermocurable composition and above-mentioned Silicone particles.
The effect of invention
The Silicone particles of the present invention have more than 0.1 μm, less than 500 μm of particle diameter, also, above-mentioned polysiloxanes grain Son is the Silicone particles for more than 5 hydrophobic grouping with siloxanes key, free-radical polymerised group and carbon number, or Person is to make the silane compound with free-radical polymerised group and the silanization with the hydrophobic grouping that carbon number is more than 5 Compound reacts and forms siloxanes key Silicone particles obtained from, or makes with free-radical polymerised group and tool The silane compound for having the hydrophobic grouping that carbon number is more than 5 reacts and forms siloxanes key polysiloxanes grain obtained from Son, therefore, it is possible to improve resistance to chemical reagents, and reduces penetrability.
Brief description of the drawings
Fig. 1 is the sectional view for an example for schematically showing the liquid crystal display cells for having used Silicone particles.
Fig. 2 is the main view sectional view for an example for schematically showing the connection structural bodies for having used electroconductive particle.
Fig. 3 is the sectional view for an example for schematically showing the electronic accessory device for having used Silicone particles.
Fig. 4 is by the sectional view of the junction surface part enlarged representation in the electronic accessory device shown in Fig. 3.
Description of reference numerals
1 ... liquid crystal display cells；
2 ... transparent glass substrates；
3 ... transparency electrodes；
4 ... alignment films；
5 ... liquid crystal；
6 ... sealings；
6A ... Silicone particles；
7 ... spacer particles；
51 ... connection structural bodies；
52 ... the 1st connecting object parts；
The electrodes of 52a ... the 1st；
53 ... the 2nd connecting object parts；
The electrodes of 53a ... the 2nd；
54 ... connecting portions；
54A ... electroconductive particles；
71 ... electronic accessory devices；
72 ... the 1st ceramic components；
73 ... the 2nd ceramic components；
74 ... junction surfaces；
74A ... Silicone particles；
74B ... glass；
75 ... electronic components；
76 ... lead frames；
R ... inner spaces.
Embodiment
Below, the present invention is explained.
(Silicone particles)
The Silicone particles of the present invention are that have more than 0.1 μm, the Silicone particles of less than 500 μm of particle diameter.
In with more than 0.1 μm, the Silicone particles of less than 500 μm of particle diameter, the present invention has following composition. The Silicone particles of the present invention are that (constituting 1) there is siloxanes key, free-radical polymerised group and carbon number to be more than 5 The Silicone particles (the 1st Silicone particles) of hydrophobic grouping, either (constituting 2) makes with free-radical polymerised group Silane compound and with carbon number for more than 5 hydrophobic grouping silane compound react and formed siloxanes key so as to must The Silicone particles (the 2nd Silicone particles) arrived, either (constituting 3) makes with free-radical polymerised group and with carbon Atomicity is reacted for the silane compound of more than 5 hydrophobic grouping and forms siloxanes key Silicone particles obtained from (the 3rd Silicone particles).
Above-mentioned 2nd Silicone particles are silane compounds with free-radical polymerised group and with carbon number are The reactant of the silane compound of more than 5 hydrophobic grouping, is the Silicone particles with siloxanes key.Above-mentioned 3rd poly- silicon Oxygen alkane particle is with free-radical polymerised group and is the anti-of the silane compound of more than 5 hydrophobic grouping with carbon number Thing is answered, is the Silicone particles with siloxanes key.
In the present invention, using above-mentioned composition, it is thus possible to improve the resistance to chemical reagents of the Silicone particles of the present invention, and And reduction penetrability, improve moisture-proof.
In addition, forming conductive part on the surface of the Silicone particles of the present invention and obtaining electroconductive particle and using containing Connection structural bodies that the conductive material of obtained electroconductive particle is conductively connected, the polysiloxanes containing the present invention is used The liquid crystal display cells of the sealant for liquid crystal dripping process of particle, by the present invention Silicone particles be used as gap adjust material In the electronic accessory device (electronic equipment etc.) of material 2 ceramic components of engagement, resistance to chemical reagents can be improved, and reduce moisture-inhibiting Property, the reliability under super-humid conditions can be improved.
For example, in above-mentioned connection structural bodies, the penetrability of the connecting portion of 2 connecting object parts of connection can be reduced, As a result, it is possible to lower keep connection resistance.For example, in above-mentioned liquid crystal display cells, the penetrability of sealing can be reduced, Immersed as a result, it is possible to suppress moisture into liquid crystal, the inequality of liquid crystal display can be prevented.For example, in above-mentioned electronic component member In part, the penetrability at the junction surface between 2 ceramic components can be reduced, the pressure sensing being configured in ceramic package can be suppressed The deterioration of the electronic components such as device, acceleration transducer, cmos sensor element and ccd sensor element, improves electronic component Reliability.
Siloxanes key, free-radical polymerised group and carbon number can pass through NMR for the presence of more than 5 hydrophobic grouping Etc. being measured.
Due to resistance to chemical reagents can be effectively improved, and penetrability is effectively reduced, therefore, polysiloxanes grain of the invention Son is preferably that (constituting 1 ') has siloxanes key, has free-radical polymerised group in the end of above-mentioned siloxanes key and upper State Silicone particles (the 1st polysiloxanes grain that there is carbon number for more than 5 hydrophobic grouping on the side chain of siloxanes key Son), either (constitute 2) makes silane compound with free-radical polymerised group and dredged with carbon number for more than 5 The silane compound of water base group reacts and forms siloxanes key Silicone particles (the 2nd Silicone particles) obtained from, Either (constituting 3) makes with free-radical polymerised group and with silane chemical combination of the carbon number for more than 5 hydrophobic grouping Thing reacts and forms siloxanes key Silicone particles (the 3rd Silicone particles) obtained from.
The free-radical polymerised group of the end of siloxanes key has the molecular weight ratio for the polymer for making silicone compounds Larger effect, due to free-radical polymerised group, can easily realize the desired of Silicone particles of the invention Particle diameter, can further improve resistance to chemical reagents.As above-mentioned free-radical polymerised group, vinyl, (methyl) propylene can be enumerated Acyl group and styryl etc..From the viewpoint of flexibility is improved, preferred vinyl.
Carbon number on the side chain of siloxanes key is effectively reduced silicone compounds for more than 5 hydrophobic grouping Polymer penetrability effect, resistance to chemical reagents can be improved., can as the hydrophobic grouping that above-mentioned carbon number is more than 5 Enumerate：The cyclic alkyl and carbon number that straight chained alkyl that carbon number is 5~30, carbon number are 5~30 are 5~30 Aromatic series base etc..From the viewpoint of moisture-proof is improved, preferably carbon number is 5~30 aromatic series base, even more preferably Phenyl.The hydrophobic grouping that above-mentioned carbon number is more than 5 is preferably the alkyl that carbon number is more than 5.Above-mentioned hydrophobic grouping Carbon number is preferably more than 6.
In above-mentioned composition 1, above-mentioned composition 1 ', above-mentioned composition 2 and above-mentioned composition 3, the free-radical polymerised preferred key of group Together in silicon atom.
Due to resistance to chemical reagents can be effectively improved, and penetrability is effectively reduced, therefore, in above-mentioned composition 1, above-mentioned structure Into in 1 ', above-mentioned composition 1 ", above-mentioned composition 2 and above-mentioned composition 3, above-mentioned carbon number is preferably bonded for more than 5 hydrophobic grouping In silicon atom.
As the preferred mode of the Silicone particles of the present invention, the Silicone particles are that (constituting 1 ") has silica Alkane key, have in the end of above-mentioned siloxanes key and be bonded to vinyl on silicon atom and in the side chain of above-mentioned siloxanes key The upper Silicone particles (the 1st Silicone particles) with the phenyl being bonded on silicon atom, either (constituting 2 ') makes End has the silane compound for the vinyl being bonded on silicon atom and has the phenyl being bonded on silicon atom on side chain Silane compound react and form siloxanes key Silicone particles (the 2nd Silicone particles) obtained from, either (constituting 3 ') makes to have the vinyl being bonded on silicon atom in end and has the phenyl being bonded on silicon atom on side chain Silane compound react and form siloxanes key Silicone particles (the 3rd Silicone particles) obtained from.
The Silicone particles of the present invention preferably have above-mentioned composition 1, more preferably with above-mentioned composition 1 ', further preferably With above-mentioned composition 1 ".The Silicone particles of the present invention preferably have above-mentioned composition 2, more preferably with above-mentioned composition 2 '.This The Silicone particles of invention preferably have above-mentioned composition 3, more preferably with above-mentioned composition 3 '.The Silicone particles of the present invention It is preferred that with above-mentioned composition 2 or above-mentioned composition 3, more preferably with above-mentioned composition 2 ' or above-mentioned composition 3 '.The poly- silica of the present invention Alkane particle preferably has above-mentioned composition 1 and above-mentioned composition 2 or with above-mentioned composition 1 and above-mentioned composition 3, more preferably with above-mentioned Constitute 1 ' and above-mentioned composition 2 or with above-mentioned composition 1 ' and above-mentioned composition 3, further preferably with above-mentioned composition 1 " with it is above-mentioned Constitute 2 ' or with above-mentioned composition 1 " and above-mentioned composition 3 '.
From the viewpoint for improving clearance control effect, effectively further improving resistance to chemical reagents and being effectively reduced penetrability Set out, the modulus of elasticity in comperssion (30%K values) when Silicone particles have compressed into 30% is preferably 1000N/mm2Hereinafter, more Preferably 500N/mm2Hereinafter, more preferably 300N/mm2Below.Above-mentioned 30%K values can exceed 1N/mm2, can also surpass Cross 50N/mm2, 100N/mm can also be exceeded2。
The above-mentioned modulus of elasticity in comperssion (30%K values) of above-mentioned Silicone particles can be determined as follows.
Using micro-compression tester, smooth tabletting end face in cylinder (100 μm of diameter, Buddha's warrior attendant are made of stones), in 25 DEG C, pressure 1 Silicone particles is compressed under conditions of contracting speed 0.3mN/ seconds and maximum testing load 20mN.Determine now Loading value (N) and compression displacement (mm).Can by obtain measured value, using following formula obtain above-mentioned modulus of elasticity in comperssion.Make For above-mentioned micro-compression tester, it can be used such as the manufacture of FISCHER companies " FISCHERSCOPE H-100 ".
30%K values (N/mm2)=(3/21/2)·F·S-3/2·R-1/2
F：Silicone particles carry out the loading value (N) during 30% compression
S：Silicone particles carry out the compression displacement (mm) during 30% compression
R：The radius (mm) of Silicone particles
The particle diameter of above-mentioned Silicone particles is more than 0.1 μm, less than 500 μm.The particle diameter of Silicone particles is above-mentioned When more than lower limit and below the above-mentioned upper limit, Silicone particles can be suitably used for sealant for liquid crystal dripping process etc.. The particle diameter of above-mentioned Silicone particles is preferably more than 1 μm, more preferably more than 5 μm, and preferably less than 300 μm, more preferably For less than 200 μm, more preferably less than 100 μm, particularly preferably less than 50 μm.The particle diameter of above-mentioned Silicone particles is When more than above-mentioned lower limit and below the above-mentioned upper limit, the interval between liquid crystal display cells part becomes appropriate, impact absorbency rise, It is not easily formed the Silicone particles of aggegation.In addition, by using the silane compound of above-mentioned composition 2 and above-mentioned composition 2 ', It is the Silicone particles more than above-mentioned lower limit and below the above-mentioned upper limit to be readily obtained particle diameter.
Above-mentioned particle diameter represents maximum diameter.Therefore, it is just spherical situation in Silicone particles for above-mentioned particle diameter Under, diameter is represented, in the case where Silicone particles is beyond just spherical, maximum diameter is represented.
From the viewpoint of the interval for accurately controlling 2 parts used for liquid crystal display element etc., above-mentioned polysiloxanes grain The CV values of the particle diameter of son are preferably less than 40%.
The length-width ratio of above-mentioned Silicone particles is preferably less than 2, more preferably less than 1.5, more preferably 1.2 with Under.Above-mentioned length-width ratio represents major diameter/minor axis.
Above-mentioned Silicone particles preferably do not contain metallic catalyst, or the metallic catalyst containing below 100ppm.On It is the catalyst containing metallic atom to state metallic catalyst.In the case of using metallic catalyst, the content of metallic catalyst It is more few better.When the content of metallic catalyst is more, there is the tendency of anti fouling performance reduction.The content of metallic catalyst is more preferably Below 80ppm, is still more preferably below 60ppm, more preferably below 50ppm, even more preferably for 40ppm with Under, particularly preferably below 30ppm, in addition, particularly preferably below 20ppm, most preferably below 10ppm.
In general, Silicone particles polymerize monomer by using metallic catalyst mostly and obtained.This poly- silicon Even if oxygen alkane particle is cleaned, also internally contain metallic catalyst, the content of metallic catalyst is sometimes more than 100ppm.With This is relative, and metallic catalyst is not contained typically without using Silicone particles obtained from metallic catalyst.Above-mentioned metal catalytic Agent represents the curing catalysts such as platinum, tin.
For making the method that above-mentioned metallic catalyst is below 100ppm, it is not particularly limited, can enumerates for example by adding Plus bridging property silane compound and be condensed method, in polysiloxane compound import polymerizable functional group and with polymerize Method that initiator is polymerize etc..
The content of above-mentioned metallic catalyst such as can using inductively coupled plasma apparatus for analyzing luminosity surveyed It is fixed.
For the purposes of above-mentioned Silicone particles, it is not particularly limited.Above-mentioned Silicone particles are preferred in table Conductive layer is formed on face and obtains the electroconductive particle with above-mentioned conductive layer and uses, or as interval used for liquid crystal display element Part.Above-mentioned Silicone particles are preferred to formation conductive layer on the surface and obtain the electroconductive particle with above-mentioned conductive layer And use.Above-mentioned Silicone particles are preferably used as distance piece used for liquid crystal display element.
In addition, above-mentioned Silicone particles can also be in order to engage 2 ceramic components and obtain electronic accessory device (electronics Equipment etc.) and suitably use.
In addition, above-mentioned Silicone particles also preferably act as packing material, shock absorbent or absorption of vibrations agent.For example, As substitutes such as rubber or springs, above-mentioned Silicone particles can be used.
Hereinafter, other detailed contents of Silicone particles are illustrated.
The detailed content of Silicone particles：
The material of above-mentioned Silicone particles is preferably to have the silane compound of free-radical polymerised group and with carbon Atomicity is the silane compound of more than 5 hydrophobic grouping, or is preferably with free-radical polymerised group and with carbon atom Number is the silane compound of more than 5 hydrophobic grouping.Above-mentioned Silicone particles can pass through anti-by above-mentioned silane compound Siloxanes key and should be formed and obtain the process of Silicone particles and obtain.In the case where reacting these materials, formed Siloxanes key.In obtained Silicone particles, general Trapped radicals polymerizable group and carbon number for more than 5 dredge Water base group.By using this material, the polysiloxanes of the particle diameter with more than 0.1 μm, less than 500 μm can be readily derived Particle, and the resistance to chemical reagents of Silicone particles can be improved, and reduce penetrability.
In the above-mentioned silane compound with free-radical polymerised group, free-radical polymerised group is preferably bonded directly to Silicon atom.The above-mentioned silane compound with free-radical polymerised group can use only a kind, and can also use two or more.
The above-mentioned silane compound with free-radical polymerised group is preferably alkoxysilane compound containing trialkylsilyl group in molecular structure.It is used as above-mentioned tool There is the silane compound of free-radical polymerised group, can enumerate：Vinyltrimethoxy silane, VTES, Dimethoxymethylvinylchlane, diethoxymethylvinylschane, divinyl methoxy-ethylene base silane, divinyl Base oxethyl vinyl silanes, divinyl dimethoxysilane, divinyl diethoxy silane and 1,3- divinyl four Tetramethyldisiloxane etc..
In the above-mentioned silane compound with carbon number for more than 5 hydrophobic grouping, preferably carbon number is more than 5 Hydrophobic grouping is bonded directly to silicon atom.The above-mentioned silane compound with carbon number for more than 5 hydrophobic grouping can make With only a kind, and two or more can also be used.
Above-mentioned is preferably alkoxysilane compound containing trialkylsilyl group in molecular structure for the silane compound of more than 5 hydrophobic grouping with carbon number. As above-mentioned with silane compound of the carbon number for more than 5 hydrophobic grouping, it can enumerate：Phenyltrimethoxysila,e, two Methoxymethylphenyl silane, diethoxymethyl phenyl silane, dimethyl methyl phenyl silane, dimethylethyloxy phenyl Silane, hexaphenyldisiloxane, 1,3,3,5- tetramethyl -1,1,5,5- tetraphenyls trisiloxanes, phenyl -1 of 1,1,3,5,5- five, 3,5- trimethyls trisiloxanes, hexaphenyl cyclotrisiloxane, (trimethylsiloxy) silane of phenyl three and octaphenyl ring four Siloxanes etc..
It is above-mentioned to there is free-radical polymerised group and with silane compound of the carbon number for more than 5 hydrophobic grouping In, free-radical polymerised group is preferably bonded directly to silicon atom, and carbon number is more than the 5 preferred Direct Bonding of hydrophobic grouping In silicon atom.It is above-mentioned to there is free-radical polymerised group and with silane compound of the carbon number for more than 5 hydrophobic grouping Only a kind can be used, and two or more can also be used.
As above-mentioned with free-radical polymerised group and with silane chemical combination of the carbon number for more than 5 hydrophobic grouping Thing, can be enumerated：Phenyl vinyl dimethoxysilane, phenyl vinyl diethoxy silane, phenyl methyl ethenylmethoxy Silane, phenyl methyl vinylethoxysilane, diphenylethlene methoxylsilane, diphenylacetylene Ethoxysilane, Diethylamino phenyl alkenyl methoxy silane, diethylamino phenyl alkenyl Ethoxysilane and 1,1,3,3- tetraphenyl -1,3- divinyl two Siloxanes etc..
In order to obtain Silicone particles, above-mentioned silane compound with free-radical polymerised group and above-mentioned is being used It is above-mentioned with free-radical polymerised group in the case of silane compound with carbon number for more than 5 hydrophobic grouping Silane compound and the above-mentioned silane compound with the hydrophobic grouping that carbon number is more than 5 are with weight ratio meter preferably with 1：1 ~1：20 use, more preferably with 1：5~1：15 use.In above-mentioned Silicone particles, there is radical polymerization from above-mentioned Property group silane compound skeleton and from above-mentioned with silane compound of the carbon number for more than 5 hydrophobic grouping Skeleton is preferably using weight ratio meter as 1：1~1：20, more preferably 1：5~1：15.
In being completely used for obtaining the silane compound of Silicone particles, the number and carbon atom of free-radical polymerised group Number is preferably 1 for the number of more than 5 hydrophobic grouping：0.5~1：20, more preferably 1：1~1：15.
From effectively improving resistance to chemical reagents, it is effectively reduced penetrability and 30%K values is controlled into the sight in suitable scope Point sets out, and above-mentioned Silicone particles preferably have the dimethylsiloxane skeleton that 2 methyl are bonded with 1 silicon atom, The material of above-mentioned Silicone particles preferably comprises the silane compound that 2 methyl are bonded with 1 silicon atom.
From effectively improving resistance to chemical reagents, it is effectively reduced penetrability and 30%K values is controlled into the sight in suitable scope Point sets out, and above-mentioned Silicone particles react above-mentioned silane compound preferably by radical polymerization initiator and form silica Alkane key.Above-mentioned Silicone particles are preferably the Raolical polymerizable thing of above-mentioned silane compound.Above-mentioned Silicone particles Can pass through makes above-mentioned silane compound react and form siloxanes key and obtains poly- silicon by using radical polymerization initiator The process of oxygen alkane particle and obtain.In general, being difficult to obtain that there is more than 0.1 μm, 500 μm using radical polymerization initiator The Silicone particles of following particle diameter, are particularly difficult to obtain the Silicone particles with less than 100 μm of particle diameter.With this phase It is right, in the case of using radical polymerization initiator, by using the silane compound of above-mentioned composition 2 and above-mentioned composition 2 ', It can obtain that there are more than 0.1 μm, the Silicone particles of less than 500 μm of particle diameter, can also obtain that there are less than 100 μm The Silicone particles of particle diameter.
, can be without using the silanization with the hydrogen atom being bonded on silicon atom in order to obtain above-mentioned Silicone particles Compound.In this case, using radical polymerization initiator can polymerize silane compound without using metallic catalyst.As a result It is that metallic catalyst can not be contained in Silicone particles, it is possible to reduce metallic catalyst in Silicone particles Content, can effectively further improve resistance to chemical reagents, be effectively reduced penetrability, by the control of 30%K values in suitable scope.
As the specific manufacture method of above-mentioned Silicone particles main body, have by suspension polymerization, dispersion copolymerization method, Mini-emulsion polymerization method or emulsion polymerization etc. carry out the polymerisation of silane compound, the method for making Silicone particles Deng.Can also carry out the polymerization of silane compound and after obtaining oligomer, by suspension polymerization, dispersion copolymerization method, micro- Grain emulsion polymerization or emulsion polymerization etc. carry out the polymerisation of the silane compound as polymer (oligomer etc.), system Make Silicone particles.For example, it polymerize the silane compound with vinyl, can be in the form of polymer (oligomer etc.) Obtain the silane compound that there is the vinyl being bonded on silicon atom in end.It polymerize the silane compound with phenyl, The silane compound on side chain with the phenyl being bonded on silicon atom can be obtained in the form of polymer (oligomer etc.). Make the silane compound with vinyl and the silane compound polymerization with phenyl, can be with the shape of polymer (oligomer etc.) Formula obtains having the vinyl being bonded on silicon atom in end and has the silicon for the phenyl being bonded on silicon atom on side chain Hydride compounds.
Silicone particles can have multiple particles in outer surface.In this case, Silicone particles have poly- silica Alkane particle main body and the multiple particles being configured on the surface of Silicone particles main body, above-mentioned Silicone particles main body have Above-mentioned composition 1, above-mentioned composition 1 ', above-mentioned composition 1 ", above-mentioned composition 2, above-mentioned composition 2 ', above-mentioned composition 3 or above-mentioned composition 3 '.Make For above-mentioned multiple particles, Silicone particles and spherical silicon dioxide etc. can be enumerated.By there is above-mentioned multiple particles, it can press down The aggegation of Silicone particles processed.
Above-mentioned Silicone particles can contain opacifier.By using above-mentioned opacifier, contain Silicone particles Sealing material for liquid crystal display device can suitably serve as shading sealant.
As above-mentioned opacifier, it can enumerate for example：Polypyrrole, iron oxide, titanium are black, nigrosine, black anthocyanin, fullerene, Carbon black and resin-coating type carbon black etc..It is preferred that titanium is black.Above-mentioned light screening material may reside in the inside of Silicone particles, It may reside in outer surface.
(sealing material for liquid crystal display device and sealant for liquid crystal dripping process)
Sealing material for liquid crystal display device is preferably sealant for liquid crystal dripping process.Above-mentioned Silicone particles can be closed It is used for sealant for liquid crystal dripping process suitablely.
Above-mentioned sealant for liquid crystal dripping process (below, sometimes referred to simply as sealant) is preferably by being heating and curing.It is above-mentioned Sealant preferably comprises Thermocurable composition and above-mentioned Silicone particles.Above-mentioned sealant can contain photo-curable composition, It can also not contain., can be to above-mentioned sealant irradiation light in order to solidify, can not also irradiation light.It should be noted that upper State in the case that sealant do not contain photocuring composition, can be preserved under the irradiation of light.
Above-mentioned Thermocurable composition preferably comprise Thermocurable compound and polymerization initiator or Thermocurable compound and Thermal curing agents.In this case, can also and with polymerization initiator and thermal curing agents.
Relative to the above-mentioned parts by weight of Thermocurable compound 100, the content of above-mentioned Silicone particles is preferably 3 parts by weight More than, more than more preferably 5 parts by weight, and below preferably 70 parts by weight, below more preferably 50 parts by weight.Above-mentioned poly- silica When the content of alkane particle is more than above-mentioned lower limit and below the above-mentioned upper limit, the cementability of obtained sealant for liquid crystal dripping process Further become good.
As above-mentioned Thermocurable compound, it can enumerate：Oxetane compound, epoxide, episulfide compounds, (methyl) acyclic compound, oxybenzene compound, amino-compound, unsaturated polyester compound, urethanes, poly- silica Hydride compounds and polyimide compound etc..Above-mentioned Thermocurable compound can use only a kind, and can also use two or more.
From the viewpoint of cementability and long-term reliability is further improved, above-mentioned Thermocurable compound is preferably comprised (methyl) acyclic compound, further preferably epoxy (methyl) acrylate.Above-mentioned " (methyl) acyclic compound " refers to Compound with (methyl) acryloyl group.Above-mentioned " epoxy (methyl) acrylate " is to instigate (methyl) acrylic acid and epoxidation Compound formed by whole epoxy reactions of compound.It should be noted that " (methyl) acrylic " refers to " acrylic " The one or both of " methylpropenyl ", " (methyl) acryloyl group " refers to the one of " acryloyl group " and " methylacryloyl " Individual or both, " (methyl) acrylate " refers to the one or both of " acrylate " and " methacrylate ".
As the epoxide of the raw material for synthesizing above-mentioned epoxy (methyl) acrylate, it can enumerate for example：Bisphenol-A Type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, 2,2 '-diallyl bisphenol type epoxy resin, hydrogenation Bisphenol-type epoxy resin, expoxy propane addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, Sulfide type epoxy resin, diphenyl ether type epoxy, dicyclopentadiene-type epoxy resin, naphthalene type epoxy resin, phenol phenol Novolac type epoxy resin, o-cresol phenolic epoxy varnish, dicyclopentadiene novolac type epoxy resin, xenol Novolac type epoxy resin, naphthol novolac type epoxy resin, glycidyl amine type epoxy resin, alkyl polyols type epoxy Resin, modified rubber type epoxy resin, epihydric alcohol ester compound and bisphenol A-type episulfide resin etc..
As the commercially available product of above-mentioned bisphenol A type epoxy resin, it can enumerate for example：JER828EL, jER1001 and jER1004 (being Mitsubishi Chemical Ind's manufacture)；EPICLON 850-S (manufacture of DIC companies) etc..
As the commercially available product of above-mentioned bisphenol f type epoxy resin, it (is Mitsubishi that can enumerate such as jER806 and jER4004 Company manufactures) etc..
As the commercially available product of above-mentioned bisphenol-s epoxy resin, such as EPICLON EXA1514 (DIC company systems can be enumerated Make) etc..
As above-mentioned 2, the commercially available product of 2 '-diallyl bisphenol type epoxy resin can enumerate such as RE-810NM (Japan Chemical drug company manufactures) etc..
As the commercially available product of above-mentioned A Hydrogenated Bisphenol A type epoxy resin, such as EPICLON EXA7015 (DIC companies can be enumerated Manufacture) etc..
As the commercially available product of above-mentioned expoxy propane addition bisphenol A type epoxy resin, such as EP-4000S (ADEKA can be enumerated Company manufactures) etc..
As the commercially available product of above-mentioned resorcinol type epoxy resin, can enumerating such as EX-201, (Nagase ChemteX are public Department's manufacture) etc..
As the commercially available product of above-mentioned biphenyl type epoxy resin, such as jERYX-4000H (Mitsubishi Chemical Ind's systems can be enumerated Make) etc..
As the commercially available product of above-mentioned sulfide type epoxy resin, can enumerating such as YSLV-50TE, (it is public that aurification is lived by Nippon Steel Department's manufacture) etc..
As the commercially available product of above-mentioned diphenyl ether type epoxy, can enumerating such as YSLV-80DE, (aurification is lived by Nippon Steel Company manufactures) etc..
As the commercially available product of above-mentioned dicyclopentadiene-type epoxy resin, such as EP-4088S (ADEKA company systems can be enumerated Make) etc..
As the commercially available product of above-mentioned naphthalene type epoxy resin, such as EPICLON HP4032 and EPICLON EXA- can be enumerated 4700 (being the manufacture of DIC companies) etc..
As the commercially available product of above-mentioned phenol novolak type epoxy resin, can enumerating such as EPICLON N-770, (DIC is public Department's manufacture) etc..
As the commercially available product of above-mentioned o-cresol phenolic epoxy varnish, such as EPICLON N-670-EXP- can be enumerated S (manufacture of DIC companies) etc..
As the commercially available product of above-mentioned dicyclopentadiene novolac type epoxy resin, such as EPICLON HP7200 can be enumerated (manufacture of DIC companies) etc..
As the commercially available product of above-mentioned biphenyl phenolic resin varnish type epoxy resin, can enumerating such as NC-3000P, (Japanese chemical drug is public Department's manufacture) etc..
As the commercially available product of above-mentioned naphthol novolac type epoxy resin, can enumerating such as ESN-165S, (gold is lived by Nippon Steel Chemical company manufactures) etc..
As the commercially available product of above-mentioned glycidyl amine type epoxy resin, such as jER630 (Mitsubishi Chemical Ind's systems can be enumerated Make)；EPICLON 430 (manufacture of DIC companies)；TETRAD-X (manufacture of Mitsubishi Gas Chemical company) etc..
As the commercially available product of abovementioned alkyl polyol type epoxy resin, it can enumerate for example：(aurification is lived to ZX-1542 by Nippon Steel Company manufactures)；EPICLON 726 (manufacture of DIC companies)；Epolite 80MFA (manufacture of chemical company of common prosperity society)； Denacol EX-611 (manufacture of Nagase ChemteX companies) etc..
As the commercially available product of above-mentioned modified rubber type epoxy resin, it (is new day that can enumerate such as YR-450 and YR-207 Iron lives the manufacture of aurification company)；EPOLEAD PB (manufacture of Daicel company) etc..
As the commercially available product of above-mentioned epihydric alcohol ester compound, such as Denacol EX-147 (Nagase can be enumerated ChemteX companies manufacture) etc..
As the commercially available product of above-mentioned bisphenol A-type episulfide resin, such as jERYL-7000 (Mitsubishi Chemical Ind's systems can be enumerated Make) etc..
As other commercially available products of above-mentioned epoxy resin, it can enumerate for example：YDC-1312, YSLV-80XY and YSLV- 90CR (being that the manufacture of aurification company is lived by Nippon Steel)；XAC4151 (Asahi Kasei Corporation's manufacture)；JER1031 and jER1032 are ( Manufactured for Mitsubishi Chemical Ind)；EXA-7120 (manufacture of DIC companies)；TEPIC (manufacture of Nissan Chemical company) etc..
As the commercially available product of above-mentioned epoxy (methyl) acrylate, it can enumerate for example：EBECRYL860、EBECRYL3200、 EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、 EBECRYL3703, EBECRYL3800, EBECRYL6040 and EBECRYLRDX63182 (are DAICEL-ALLNEX company systems Make)；EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD and EMA-1020 (are chemical industrial company of Xin Zhong villages Manufacture)；Epoxy-ester M-600A, epoxy-ester 40EM, epoxy-ester 70PA, epoxy-ester 200PA, epoxy-ester 80MFA, epoxy-ester 3002M, Epoxy-ester 3002A, epoxy-ester 1600A, epoxy-ester 3000M, epoxy-ester 3000A, epoxy-ester 200EA and epoxy-ester 400EA are ( Manufactured for chemical company of common prosperity society)；Denacol Acrylate DA-141, Denacol Acrylate DA-314 and Denacol Acrylate DA-911 (being the manufacture of Nagase ChemteX companies) etc..
As other (methyl) acyclic compounds beyond above-mentioned epoxy (methyl) acrylate, can enumerate for example makes tool The ester compounds that have the compound of hydroxyl with (methyl) propylene acid reaction to obtain and make (methyl) acrylic acid with hydroxyl Derivative reacts polyurethane (methyl) acrylate etc. obtained from isocyanate compound.
It can make so as to obtained ester compounds with above-mentioned (methyl) propylene acid reaction as the compound made with hydroxyl With any of ester compounds more than ester compounds of simple function, the ester compounds of 2 functions and 3 functions.
As the ester compounds of above-mentioned simple function, it can enumerate for example：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) propylene Sour 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxybutyls, (methyl) i-butyl Ester, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) stearyl acrylate Base ester, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- methoxy acrylates, methoxyl group Ethylene glycol (methyl) acrylate, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) third Olefin(e) acid benzyl ester, ethyl carbitol (methyl) acrylate, (methyl) acrylate, phenoxy group diethylene glycol (methyl) Acrylate, phenoxy group polyethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, 2,2,2- trifluoros Ethyl (methyl) acrylate, the fluoropropyls of 2,2,3,3- tetra- (methyl) acrylate, 1H, 1H, 5H- octafluoros amyl group (methyl) propylene Acid esters, acid imide (methyl) acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, the different nonyl of (methyl) acrylic acid Ester, the different tetradecane base ester of (methyl) acrylic acid, (methyl) acrylic acid 2- butoxyethyls, (methyl) acrylic acid 2- phenoxy group second Ester, (methyl) acrylic acid double cyclopentenyl ester, (methyl) isodecyl acrylate, (methyl) acrylic acid diethylamino ethyl ester, (first Base) acrylate, 2- (methyl) acryloyl-oxyethyls butanedioic acid, 2- (methyl) acryloyl-oxyethyl six Hydrogen phthalic acid, 2- (methyl) acryloyl-oxyethyl 2- hydroxypropyl phthalates, (methyl) acrylic acid shrink sweet Grease and 2- (methyl) acryloyl-oxyethyl phosphate etc..
As the ester compounds of above-mentioned 2 function, it can enumerate for example：1,4- butanediols two (methyl) acrylate, 1,3- fourths Glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, 1, 10- decanediols two (methyl) acrylate, (methyl) acrylate of 2- normal-butyl -2- ethyl -1,3- propane diols two, DPG Two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, expoxy propane addition bisphenol-A two (methyl) acrylate, ethyleneoxide addition bisphenol-A two (methyl) third Olefin(e) acid ester, ethyleneoxide addition Bisphenol F two (methyl) acrylate, dihydroxymethyl dicyclopentadienyl two (methyl) acrylic acid Ester, 1,3 butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified isocyanuric acid two (methyl) acrylate, 2- hydroxyls -3- (methyl) acryloxypropyl (methyl) acrylate, carbonate diol two (methyl) Acrylate, PTMEG two (methyl) acrylate, polyester-diol two (methyl) acrylate, (first of polycaprolactone glycol two Base) acrylate and polybutadiene diol two (methyl) acrylate etc..
As ester compounds more than above-mentioned 3 function, it can enumerate for example：Pentaerythrite three (methyl) acrylate, three hydroxyls Methylpropane three (methyl) acrylate, expoxy propane addition trimethylolpropane tris (methyl) acrylate, oxirane add Into trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, epoxy second Alkane 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, (methyl) acrylate of expoxy propane addition glycerine three and three (methyl) acryloyl-oxyethyl phosphates etc..
Above-mentioned polyurethane (methyl) acrylate for example can be by making have 2 NCOs relative to 1 equivalent Isocyanate compound deposited for (methyl) acrylic acid derivatives with hydroxyl of 2 equivalents in the tin based compound of catalytic amount Obtained in lower reaction.Further, it is possible to use the isocyanate compound of the NCO with more than 2.
As the isocyanate compound of the raw material of above-mentioned polyurethane (methyl) acrylate, it can enumerate for example：Different Fo Er Ketone diisocyanate, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, hexamethylene diisocyanate, trimethyl Hexamethylene diisocyanate, diphenyl methane -4,4 '-diisocyanate (MDI), hydrogenation MDI, polymeric MDI, 1,5- naphthalenes two be different Cyanate, norbornene alkyl diisocyanate, tolidine diisocyanate, benzene methyl disulfide cyanate (XDI), hydrogenation XDI, rely Propylhomoserin diisocyanate, triphenylmethane triisocyanate, three (isocyanate phenyl) thiophosphates, tetramethyl xylene two Isocyanates and 1,6,10- hendecane triisocyanates etc..
As the isocyanate compound of the raw material of above-mentioned polyurethane (methyl) acrylate, for example, it can also use and pass through Ethylene glycol, glycerine, D-sorbite, trimethylolpropane, (poly-) propane diols, carbonate diol, PTMEG, polyester-diol or The isocyanate compound of chain elongation obtained from the reaction of the polyalcohols such as polycaprolactone glycol and excessive isocyanates.
As (methyl) acrylic acid derivative with hydroxyl of the raw material of above-mentioned polyurethane (methyl) acrylate, it can lift Go out for example：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, And the commercially available product such as (methyl) acrylic acid 2- hydroxybutyls；Ethylene glycol, propane diols, 1,3- propane diols, 1,3 butylene glycol, 1,4- fourths two List (methyl) acrylate of the dihydric alcohol such as alcohol and polyethylene glycol；Trimethylolethane, trimethylolpropane and glycerine etc. three List (methyl) acrylate of first alcohol and two (methyl) acrylate；The epoxies such as bisphenol A-type acrylic acid epoxy ester (methyl) propylene Acid esters etc..
As the commercially available product of above-mentioned polyurethane (methyl) acrylate, it can enumerate for example：M-1100、M-1200、M-1210、 And M-1600 (being the manufacture of East Asia Synesis Company)；EBECRYL230、EBECRYL270、EBECRYL4858、EBECRYL8402、 EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL1290、EBECRYL5129、 EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220 and EBECRYL2220 (are DAICEL-ALLNEX companies manufacture)；ArtResin UN-9000H、ArtResin UN-9000A、ArtResin UN-7100、 ArtResin UN-1255, ArtResin UN-330, ArtResin UN-3320HB, ArtResin UN-1200TPK and ArtResin SH-500B (being the manufacture of Gen Shang industrial groups)；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- 4200th, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H and UA-4000 (being the manufacture of chemical industrial company of Xin Zhong villages)；AH-600、AT-600、UA-306H、AI-600、UA-101T、UA- 101I, UA-306T and UA-306I (being the manufacture of chemical company of common prosperity society) etc..
From the viewpoint of the harmful effect to liquid crystal is suppressed, above-mentioned (methyl) acyclic compound preferably has-OH Base ,-NH- bases ,-NH2The unit of the hydrogen bondings such as base.
From the viewpoint of reactivity is improved, above-mentioned (methyl) acyclic compound preferably has 2 or 3 (methyl) third Enoyl-.
From the viewpoint of the cementability for improving sealing material for liquid crystal display device, above-mentioned Thermocurable compound can contain There is epoxide.
As above-mentioned epoxide, it can enumerate for example as the raw material for synthesizing above-mentioned epoxy (methyl) acrylate Epoxide or part (methyl) acrylated epoxy compound etc..
Above-mentioned part (methyl) acrylated epoxy compound refers to epoxy radicals and (methyl) respectively with more than 1 The compound of acryloyl group.Above-mentioned part (methyl) acrylated epoxy compound for example can be by with more than 2 Epoxy radicals compound in make the part reaction of (methyl) acrylic acid and the epoxy radicals of more than 2 and obtain.
As the commercially available product of above-mentioned part (methyl) acrylated epoxy compound, such as KRM8287 can be enumerated (manufacture of DAICEL-ALLNEX companies) etc..
Use above-mentioned (methyl) acyclic compound, above-mentioned epoxide and the feelings as above-mentioned Thermocurable compound Under condition, in total 100 moles of % of (methyl) acryloyl group and epoxy radicals during above-mentioned Thermocurable compound is all, epoxy radicals Preferably 20 moles more than %, and preferably 50 moles below %.When above-mentioned epoxy radicals is below the above-mentioned upper limit, liquid crystal display member Part sealant is further difficult to produce liquid crystal pollution, the display performance of liquid crystal display cells to the dissolubility step-down of liquid crystal Become further good.
As above-mentioned polymerization initiator, radical polymerization initiator and cationic polymerization initiators etc. can be enumerated.It is above-mentioned poly- Can be used by closing initiator by only a kind, and can also use two or more.
As above-mentioned radical polymerization initiator, it can enumerate and the optical free radical polymerization of free radical is produced by light irradiation draw Send out agent and hot radical polymerization initiator of free radical etc. is produced by heating.
Above-mentioned radical polymerization initiator is compared with thermal curing agents, and curing rate is very fast.Therefore, by using free radical Polymerization initiator, can suppress sealing fracture, the generation of liquid crystal pollution, and also suppress easy due to above-mentioned Silicone particles The resilience of generation.
As above-mentioned optical free radical polymerization initiator, it can enumerate for example：Benzophenone based compound, acetophenone system chemical combination Thing, acylphosphine oxide based compound, titanocenes based compound, oxime ester based compound, benzoin ether based compound and thioxanthones Deng.
As the commercially available product of above-mentioned optical free radical polymerization initiator, it can enumerate for example：IRGACURE184、 IRGACURE369、IRGACURE379、IRGACURE651、IRGACURE819、IRGACURE907、IRGACURE2959、 IRGACUREOXE01 and Lucirin TPO (being the manufacture of BASF Japan companies)；Benzoin methylether, benzoin ethyl ether and Benzoin iso-propylether (being the manufacture of Tokyo chemical conversion industry company) etc..
As above-mentioned hot radical polymerization initiator, it can enumerate such as azo-compound and organic peroxide.It is preferred that Azo-compound, more preferably as the polymeric azo initiator of polymeric azo compound.
Polymeric azo compound refers to make what (methyl) acryloxy solidified with azo group, by heat generation The compound that free radical and number-average molecular weight are more than 300.
The number-average molecular weight of above-mentioned polymeric azo initiator is preferably more than 1000, and more preferably more than 5000, enter one Step is preferably more than 10,000, and preferably less than 300,000, more preferably less than 100,000, more preferably less than 90,000.Above-mentioned height When the number-average molecular weight of molecule azo initiator is more than above-mentioned lower limit, polymeric azo initiator is difficult to bad to liquid crystal generation Influence.When the number-average molecular weight of above-mentioned polymeric azo initiator is below the above-mentioned upper limit, the mixing with Thermocurable compound Become easy.
Above-mentioned number-average molecular weight is obtained to be measured with gel permeation chromatography (GPC), by polystyrene conversion Value.As the post determined for GPC, it can enumerate such as Shodex LF-804 (manufacture of Showa electrician company).
As above-mentioned polymeric azo initiator, it can enumerate for example with being bonded with the oxidation of multiple polycyclics by azo group Polymeric azo initiator of structure of the unit such as thing or dimethyl silicone polymer etc..
Polymeric azo with the structure for being bonded with the units such as multiple polyepoxides by above-mentioned azo group triggers Agent preferably has PEO structure.As this polymeric azo initiator, it can enumerate for example：Double (the 4- cyanogen of 4,4 '-azo Base valeric acid) and the condensation polymer and 4,4 '-azo double (4- cyanopentanoic acids) of PAG and the poly- diformazan with terminal amino group Condensation polymer of radical siloxane etc., specifically, can enumerate such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 and V-501 (being and the manufacture of Wako Pure Chemical Industries company) etc..
As above-mentioned organic peroxide, it can enumerate for example：Ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl group mistake Oxide, peroxyester, diacyl peroxide and peroxy dicarbonate etc..
As above-mentioned cationic polymerization initiators, light cationic polymerization initiator can be preferably suitably used.Above-mentioned light Cationic polymerization initiators produce Bronsted acid or lewis acid by light irradiation.For above-mentioned light cationic polymerization initiator Species, is not particularly limited, and can be ionic light acid generation type, or nonionic light acid generation type.
As above-mentioned light cationic polymerization initiator, it can enumerate for example：Aromatic diazonium salt, aromatic halonium salts, virtue The salts such as fragrant race's sulfosalt；Iron-allene complex thing；Titanocenes complex compound；The organic metal networks such as aryl-silane alcohol-aluminium complex Compound class etc..
As the commercially available product of above-mentioned light cationic polymerization initiator, can enumerate such as ADEKAOPTMER SP-150 and ADEKAOPTMER SP-170 (being the manufacture of ADEKA companies) etc..
Relative to the above-mentioned parts by weight of Thermocurable compound 100, the content of above-mentioned polymerization initiator is preferably 0.1 parts by weight More than, more than more preferably 1 parts by weight, and below preferably 30 parts by weight, below more preferably 10 parts by weight, further preferably Below 5 parts by weight.When the content of above-mentioned polymerization initiator is more than above-mentioned lower limit, sealing material for liquid crystal display device can be made Cure sufficiently.When the content of above-mentioned polymerization initiator is below the above-mentioned upper limit, the storage of sealing material for liquid crystal display device is steady Qualitative rise.
As above-mentioned thermal curing agents, such as organic acid hydrazides, imdazole derivatives, amines, polyhydric phenols system can be enumerated Compound and acid anhydrides etc..It is preferably used in the organic acid hydrazides for solid under the conditions of 23 DEG C.Above-mentioned thermal curing agents can use only 1 Kind, and two or more can also be used.
As the above-mentioned organic acid hydrazides under the conditions of 23 DEG C for solid, it can enumerate for example：Double (hydrazine the carbonyl ethyl) -5- of 1,3- Isopropyl hydantoins, sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide and acid dihydrazide etc..
As the commercially available product of the above-mentioned organic acid hydrazides under the conditions of 23 DEG C being solid, it can enumerate for example：Amicure VDH and Amicure UDH (being the manufacture of aginomoto FINE TECHNO companies)；SDH, IDH, ADH and MDH (are great mound Company manufactures) etc..
Relative to the above-mentioned parts by weight of Thermocurable compound 100, the contents of above-mentioned thermal curing agents be preferably 1 parts by weight with On, and below preferably 50 parts by weight, below more preferably 30 parts by weight.The content of above-mentioned thermal curing agents is more than above-mentioned lower limit When, the abundant heat-cure of sealing material for liquid crystal display device can be made.When the content of above-mentioned thermal curing agents is below the above-mentioned upper limit, The viscosity of sealing material for liquid crystal display device will not be too high, and coating becomes good.
Above-mentioned sealing material for liquid crystal display device preferably comprises curing accelerator.By using above-mentioned curing accelerator, i.e., Make not heated under the high temperature conditions, sealant can also be cured sufficiently.
As above-mentioned curing accelerator, the polybasic carboxylic acid or epoxy amine for example with isocyanide urea groups ring skeleton can be enumerated Adduct etc., specifically, can be enumerated for example：Three (2- carboxymethyl groups) isocyanates, three (2- carboxy ethyls) isocyanates, three (3- carboxypropyls) isocyanates and double (2- carboxy ethyls) isocyanates etc..
Relative to the above-mentioned parts by weight of Thermocurable compound 100, the content of above-mentioned curing accelerator is preferably 0.1 parts by weight More than, and below preferably 10 parts by weight.It is used for liquid crystal display element when the content of above-mentioned curing accelerator is more than above-mentioned lower limit Sealant is cured sufficiently, it is not necessary in order that it solidifies and heated under the high temperature conditions.The content of above-mentioned curing accelerator is When below the above-mentioned upper limit, the cementability rise of sealing material for liquid crystal display device.
Above-mentioned sealing material for liquid crystal display device is preferably for cementability caused by the raising of viscosity, stress dispersion effect Contain filler for the purpose of improvement, the improvement of linear expansivity, raising of the moisture-proof of solidfied material etc..
As above-mentioned filler, it can enumerate for example：Talcum, asbestos, silica, diatomite, montmorillonite, bentonite, carbon Sour calcium, magnesium carbonate, aluminum oxide, montmorillonite, zinc oxide, iron oxide, magnesia, tin oxide, titanium oxide, magnesium hydroxide, hydroxide The inorganic fillers such as aluminium, bead, silicon nitride, barium sulfate, gypsum, calcium silicates, sericite, atlapulgite and aluminium nitride are poly- Ester particle, polyurethane particles, polyvinyl particle, particles of acrylic polymer and core shell acrylate copolymer particle Deng organic filler etc..Above-mentioned filler can use only a kind, and can also use two or more.
In the above-mentioned weight % of sealing material for liquid crystal display device 100, the content of above-mentioned filler be preferably 10 weight % with On, more preferably more than 20 weight %, and preferably below 70 weight %, more preferably below 60 weight %.Above-mentioned filler Content to be more than above-mentioned lower limit when, fully play improvement of cementability and other effects.The content of above-mentioned filler is on above-mentioned When limit is following, the viscosity of sealing material for liquid crystal display device will not be too high, and coating becomes good.
Above-mentioned sealing material for liquid crystal display device preferably comprises silane coupler.Above-mentioned silane coupler mainly has conduct Effect for the bonding additives of adhesive sealant well and substrate etc..Silane coupler can use only a kind, can also be simultaneously Use two or more.
On above-mentioned silane coupler, from improve with the excellent effect of the cementability of substrate etc., can by with curability Resin is chemically bonded and suppressed from the aspect of curable resin flowed out in liquid crystal, such as preferred N- phenyl -3- amino Propyl trimethoxy silicane, 3- TSL 8330s, 3-mercaptopropyi trimethoxy silane, 3- glycidoxies third Base trimethoxy silane or 3- isocyanates propyl trimethoxy silicanes etc..
In the above-mentioned weight % of sealing material for liquid crystal display device 100, the content of above-mentioned silane coupler is preferably 0.1 weight Measure more than %, more preferably more than 0.5 weight %, and preferably below 20 weight %, more preferably below 10 weight %.It is above-mentioned When the content of silane coupler is more than above-mentioned lower limit, the effect caused by silane coupler with is fully played.Above-mentioned silicon When the content of alkane coupling agent is below the above-mentioned upper limit, further suppress the liquid crystal caused by sealing material for liquid crystal display device Pollution.
Above-mentioned sealing material for liquid crystal display device can contain opacifier.Pass through the use of above-mentioned opacifier, liquid crystal display Element sealant can suitably serve as shading sealant.
As above-mentioned opacifier, it can enumerate for example：Iron oxide, titanium are black, nigrosine, black anthocyanin, fullerene, carbon black and Resin-coating type carbon black etc..It is preferred that titanium is black.
Because the liquid crystal display cells manufactured using the sealing material for liquid crystal display device containing opacifier are had sufficiently Light-proofness, it is thereby achieved that no spilling for light and with high contrast, the liquid crystal with excellent display quality of image Display element.
Black above-mentioned titanium is with compared with the mean transmissivity of 300~800nm of wavelength light, relative to ultraviolet range Nearby, it is particularly the higher material of the transmitance of 370~450nm of wavelength light.Above-mentioned titanium is black to be had by the way that fully masking can See the light of the wavelength in light region and the property of light-proofness is assigned to sealing material for liquid crystal display device, on the other hand, with making purple The property that the light of the wavelength of outside line areas adjacent is passed through.The insulating properties of contained opacifier is excellent in sealing material for liquid crystal display device Choosing is high, and as the high opacifier of insulating properties, preferably titanium is black.
The black optical concentration (OD values) of every 1 μm of above-mentioned titanium is preferably more than 3, and more preferably more than 4.The black shading of above-mentioned titanium Property the higher the better, for the upper limit preferred in the black OD values of above-mentioned titanium, be not particularly limited, OD values be usually less than 5.
Even if above-mentioned titanium is black and carbon black is without surface treatment, sufficient effect is also played.Surface can also be used even Titanium that the connection organic principle such as agent is handled is black, by silica, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide and magnesia etc. The titanium surface-treated titanium such as black of inorganic constituents cladding is black.Due to insulating properties can be improved, it is therefore preferable that being entered with organic principle The titanium of row processing is black.
As the black commercially available product of above-mentioned titanium, it can enumerate for example：12S, 13M, 13M-C, 13R-N and 14M-C (are Mitsubishi Materials Co., Ltd manufactures)；Tilak D (red fringe chemical conversion company manufacture) etc..
The black specific surface area of above-mentioned titanium is preferably 13m2/ more than g, more preferably 15m2/ more than g, and preferably 30m2/ g with Under, more preferably 25m2/ below g.
The black volume resistance of above-mentioned titanium is preferably more than 0.5 Ω cm more preferably more than 1 Ω cm, and preferably 3 Below Ω cm, more preferably below 2.5 Ω cm.
The primary particle size of above-mentioned opacifier produces influence to the interval of 2 parts used for liquid crystal display element.Above-mentioned opacifier Primary particle size be preferably more than 1nm, more preferably more than 5nm, more preferably more than 10nm, and preferably less than 5 μm, More preferably below 200nm, more preferably below 100nm.When the primary particle size of above-mentioned opacifier is more than above-mentioned lower limit, The viscosity or thixotropy of sealing material for liquid crystal display device are difficult to significantly increase, and operability becomes good.The one of above-mentioned opacifier When secondary particle diameter is below the above-mentioned upper limit, the coating of sealing material for liquid crystal display device becomes good.
It is preferably more than 5 weight % relative to the above-mentioned parts by weight of Thermocurable compound 100, the content of above-mentioned opacifier, More preferably more than 10 weight %, more preferably more than 30 weight %, and preferably below 80 weight %, more preferably 70 Below weight %, more preferably below 60 weight %.When the content of above-mentioned opacifier is more than above-mentioned lower limit, it can be filled The light-proofness divided.When the content of above-mentioned opacifier is below the above-mentioned upper limit, the adaptation of sealing material for liquid crystal display device, solidification Intensity rise afterwards, and then illustrative rise.
Above-mentioned sealing material for liquid crystal display device can contain stress moderator, reactive diluent, thixotroping as needed Agent, distance piece, curing accelerator, defoamer, levelling agent, polymerization inhibitor, other additives etc..
As the method for manufacturing above-mentioned sealing material for liquid crystal display device, it is not particularly limited, can enumerates for example using equal Being thermally cured property of the mixer such as matter disperser, mixer for well-distribution, universal mixer, planetary-type mixer, kneader and three-roller The additive such as compound, polymerization initiator or thermal curing agents, Silicone particles and the silane coupler that is added as needed on enters Method of row mixing etc..
Viscosity under 25 DEG C of above-mentioned sealing material for liquid crystal display device and 1rpm is preferably 50,000 more than Pas, is preferably 500000 below Pas, more preferably 400,000 below Pas.When above-mentioned viscosity is more than above-mentioned lower limit and below the above-mentioned upper limit, liquid The coating of crystal display element sealant becomes good.Above-mentioned viscosity is measured using E type viscosimeters.
(liquid crystal display cells)
Above-mentioned sealing material for liquid crystal display device can be used to obtain liquid crystal display cells.Liquid crystal display cells include：1st Part used for liquid crystal display element, the 2nd part used for liquid crystal display element, in above-mentioned 1st part used for liquid crystal display element and the above-mentioned 2nd By above-mentioned 1st part used for liquid crystal display element and above-mentioned 2nd liquid crystal display member in the state of part used for liquid crystal display element is opposed Part has carried out sealed sealing with the periphery of part and positioned at the inner side of above-mentioned sealing and has been configured at above-mentioned 1st liquid crystal Show the liquid crystal between element part and above-mentioned 2nd part used for liquid crystal display element.The liquid crystal display cells are applicable under liquid crystal drop Technique, and above-mentioned sealing by make sealant for liquid crystal dripping process carry out heat cure and formed.Above-mentioned sealing is liquid crystal The thermosetting compound of technique of dripping sealant.
Fig. 1 is the sectional view for an example for schematically showing the liquid crystal display cells for having used Silicone particles.
Liquid crystal display cells 1 shown in Fig. 1 have a pair of transparent glass substrates 2.Transparent glass substrate 2 is on opposed face With dielectric film (not shown).As the material of dielectric film, such as SiO can be enumerated2Deng.Insulation in transparent glass substrate 2 Transparency electrode 3 is formed on film.As the material of transparency electrode 3, ITO etc. can be enumerated.Transparency electrode 3 can for example be entered by photoetching Row is patterned and formed.Alignment films 4 are formed in transparency electrode 3 on the surface of transparent glass substrate 2.It is used as alignment films 4 Material, can enumerate polyimides etc..
Liquid crystal 5 is enclosed between a pair of transparent glass substrates 2.Multiple intervals are configured between a pair of transparent glass substrates 2 Part particle 7.By multiple spacer particles 7, the interval of a pair of transparent glass substrates 2 is controlled.In a pair of transparent glass substrates 2 Sealing 6 is configured between the edge part of periphery.By sealing 6, prevent from flowing out to the outside of liquid crystal 5.Containing poly- in sealing 6 Silicone particles 6A.For liquid crystal display cells 1, the part positioned at the upside of liquid crystal 5 is the 1st portion used for liquid crystal display element Part, the part positioned at the downside of liquid crystal is the 2nd part used for liquid crystal display element.
It should be noted that the liquid crystal display cells shown in Fig. 1 are an example, the structure of liquid crystal display cells can be fitted Work as change.
(connection structural bodies)
Above-mentioned Silicone particles in order to formed on the surface conductive layer and obtain with above-mentioned conductive layer electric conductivity grain Son and use.By using the conduction material of above-mentioned electroconductive particle or use containing above-mentioned electroconductive particle and adhesive resin Material, is attached to connecting object part, can obtain connection structural bodies.
Above-mentioned connection structural bodies includes the 1st connecting object part, the 2nd connecting object part, the 1st connecting object part of connection With the connecting portion of the 2nd connecting object part, the connecting portion is preferably to be formed by above-mentioned electroconductive particle or by being led containing above-mentioned The connection structural bodies of the conductive material formation of conductive particles and adhesive resin.In the case where electroconductive particle is used alone, Connecting portion is from as electroconductive particle.That is, the 1st, the 2nd connecting object part is attached by electroconductive particle.In order to obtain Above-mentioned connection structural bodies and the above-mentioned conductive material preferably anisotropic conductive material used.
Above-mentioned 1st connecting object part preferably has the 1st electrode on surface.Above-mentioned 2nd connecting object part is preferably in table Face has the 2nd electrode.Above-mentioned 1st electrode and above-mentioned 2nd electrode are preferably electrically connected by above-mentioned electroconductive particle.
Fig. 2 is the main view sectional view for an example for schematically showing the connection structural bodies for having used electroconductive particle.
Connection structural bodies 51 shown in Fig. 2 includes：1st connecting object part 52, the 2nd connecting object part 53, connection the 1st The connecting portion 54 of the connecting object part 53 of connecting object part 52 and the 2nd.Connecting portion 54 is by containing electroconductive particle 54A and bonding The conductive material of agent resin is formed.Connecting portion 54 contains electroconductive particle 54A.Electroconductive particle 54A includes Silicone particles With the conductive layer being configured on the surface of Silicone particles.In Fig. 2, illustrate for convenience, electroconductive particle 54A sketch earth's surfaces Show.
1st connecting object part 52 surface (above) have multiple 1st electrode 52a.2nd connecting object part 53 is in table Face is (following) to have multiple 2nd electrode 53a.1st electrode 52a and the 2nd electrode 53a are carried out by one or more electroconductive particles 1 Electrical connection.Therefore, the 1st, the 2nd connecting object part 52,53 is electrically connected by electroconductive particle 1.
For the manufacture method of above-mentioned connection structural bodies, it is not particularly limited.It is used as the manufacture method of connection structural bodies One example, can enumerate and configure above-mentioned conductive material between the 1st connecting object part and the 2nd connecting object part and folded After layer body, method that the laminated body is heated and pressurizeed etc..The pressure of above-mentioned pressurization is 9.8 × 104~4.9 × 106Pa Left and right.The temperature of above-mentioned heating is 120~220 DEG C or so.For connecting the electrode of flexible printing substrate, being configured at resin film Electrode and touch panel electrode above-mentioned pressurization pressure be 9.8 × 104~1.0 × 106Pa or so.
As above-mentioned connecting object part, specifically, it can enumerate：The electronics such as semiconductor chip, capacitor and diode Electronic components such as the loop substrate such as part and printed base plate, flexible printing substrate, glass epoxy substrate and glass substrate etc.. Above-mentioned conductive material is preferably used for connecting the conductive material of electronic component.Above-mentioned conductive paste is the conductive material of paste, preferably It is coated in the state of paste on connecting object part.
Above-mentioned electroconductive particle and above-mentioned conductive material are also suitably used for touch panel.Therefore, above-mentioned connecting object portion Part is preferably also flexible substrate, or is configured with the surface of resin film the connecting object part of electrode.Above-mentioned connection pair It is preferably the connecting object part that electrode is configured with the surface of resin film as part is preferably flexible substrate.Scratched above-mentioned Property substrate be flexible printing substrate etc. in the case of, flexible substrate typically has electrode on surface.
As the electrode for being arranged at above-mentioned connecting object part, it can enumerate：Gold electrode, nickel electrode, tin electrode, aluminium electrode, The metal electrodes such as copper electrode, silver electrode, molybdenum electrode and tungsten electrode.In the case where above-mentioned connecting object part is flexible substrate, Above-mentioned electrode is preferably gold electrode, nickel electrode, tin electrode or copper electrode.In the situation that above-mentioned connecting object part is glass substrate Under, above-mentioned electrode is preferably aluminium electrode, copper electrode, molybdenum electrode or tungsten electrode.It should be noted that being aluminium electrode in above-mentioned electrode In the case of, can be the electrode only formed by aluminium, or have the electrode of aluminium lamination in the surface stack of metal oxide layer. As the material of above-mentioned metal oxide layer, the indium oxide doped with the metallic element of trivalent and the metal doped with trivalent can be enumerated Zinc oxide of element etc..As the metallic element of above-mentioned trivalent, Sn, Al and Ga etc. can be enumerated.
(electronic accessory device)
Above-mentioned Silicone particles the peripheral part of the 1st ceramic component and the 2nd ceramic component be configured at the 1st ceramic component and Between 2nd ceramic component, gap control material is also used as.
Fig. 3 is the sectional view for an example for schematically showing the electronic accessory device for having used Silicone particles. Fig. 4 is to represent junction surface part (by position of Fig. 3 dotted line) amplification in the electronic accessory device shown in Fig. 3 Sectional view.
Fig. 3, the electronic accessory device 71 shown in 4 include：1st ceramic component 72, the 2nd ceramic component 73, junction surface 74, electricity Sub- part 75, lead frame 76.
1st, the 2nd ceramic component 72,73 is formed by ceramic material respectively.1st, the 2nd ceramic component 72,73 is, for example, respectively Basket.1st ceramic component 72 is, for example, substrate.2nd ceramic component 73 is, for example, to cover.1st ceramic component 72 has in peripheral part Protrude from the convex portion of the side of the 2nd ceramic component 73 (upside).1st ceramic component 72 has shape in the side of the 2nd ceramic component 73 (upside) Into the recess of the inner space R for housing electronic part 75.It should be noted that the 1st ceramic component 72 can not have it is convex Portion.2nd ceramic component 73 has the convex portion for protruding from the side of the 1st ceramic component 72 (downside) in peripheral part.2nd ceramic component 73 exists The side of 1st ceramic component 72 (downside) has the recess for forming the inner space R for housing electronic part 75.Need explanation It is that the 2nd ceramic component 73 can not have convex portion.
The peripheral part of 74 pair the 1st of junction surface ceramic component 72 and the peripheral part of the 2nd ceramic component 73 are engaged.It is specific and The convex portion of speech, the convex portion of the peripheral part of 74 pair of the 1st ceramic component 72 in junction surface and the peripheral part of the 2nd ceramic component 73 connects Close.
Encapsulation is formed by the 1st, the 2nd ceramic component 72,73 engaged by junction surface 74.Inner space is formed by encapsulation R.Junction surface 74 seals inner space R in liquid-tight manner and airtightly.Junction surface 74 is sealing.
Electronic component 75 is configured in the inner space R of above-mentioned encapsulation.Specifically, configured on the 1st ceramic component 72 There is electronic component 75.In present embodiment, 2 electronic components 75 are used.
Contain multiple Silicone particles 74A and glass 74B in junction surface 74.Junction surface 74, which is used, to be contained with glass particle not With multiple particle 74A and glass 74B grafting material and formed.The grafting material is ceramic package grafting material.
Grafting material can contain solvent, can also contain resin.In junction surface 74, the glass such as glass particle 74B is molten Melt and solidified after being bonded.
As electronic component, sensor element, MEMS and bare chip etc. can be enumerated.As the sensor element, it can lift Go out pressure sensor component, acceleration sensor element, cmos sensor element and ccd sensor element etc..
Lead frame 76 is configured between the peripheral part of the 1st ceramic component 72 and the peripheral part of the 2nd ceramic component 73.Lead Framework 76 is extended in the inner space R sides of encapsulation and exterior space side.The terminal and lead frame 76 of electronic component 75 lead to Electric wire is crossed to be electrically connected.
Junction surface 74 partly directly engages the peripheral part of the peripheral part of the 1st ceramic component 72 and the 2nd ceramic component 73, And partly engagement indirectly.Specifically, junction surface 74 the 1st ceramic component 72 peripheral part and the 2nd ceramic component 73 it is outer The part with lead frame 76 between all portions, by the peripheral part of the 1st ceramic component 72 and the peripheral part of the 2nd ceramic component 73 Engaged indirectly by lead frame 76.Tool between the peripheral part of the 1st ceramic component 72 and the peripheral part of the 2nd ceramic component 73 The part of leaded framework 76, the 1st ceramic component 72 is connected with lead frame 76, the ceramic component 72 of lead frame 76 and the 1st and Junction surface 74 is connected, and junction surface 74 is connected with the ceramic component 73 of lead frame 76 and the 2nd, the 2nd ceramic component 73 and junction surface 74 Connection.Junction surface 74 between the peripheral part of the 1st ceramic component 72 and the peripheral part of the 2nd ceramic component 73 without lead frame 76 part, the peripheral part of the peripheral part of the 1st ceramic component 72 and the 2nd ceramic component 73 is directly engaged.In the 1st ceramic component The part without lead frame 76 between the peripheral part of 72 peripheral part and the 2nd ceramic component 73, the ceramics of junction surface 74 and the 1st The ceramic component 73 of part 72 and the 2nd is connected.
There is lead frame 76 between the peripheral part of the 1st ceramic component 72 and the peripheral part of the 2nd ceramic component 73 The distance in the gap of part, the peripheral part of the 1st ceramic component 72 and the peripheral part of the 2nd ceramic component 73 is as contained by junction surface 74 Multiple particle 74A controls.
Junction surface directly or indirectly engages the peripheral part of the peripheral part of the 1st ceramic component and the 2nd ceramic component.Need It is noted that the electrically connected method beyond lead frame can be used.
As electronic accessory device 71, electronic accessory device for example including：The 1st ceramic part formed by ceramic material Part, the 2nd ceramic component, junction surface and the electronic component formed by ceramic material, above-mentioned junction surface is by above-mentioned 1st ceramic component The peripheral part of peripheral part and above-mentioned 2nd ceramic component is directly or indirectly engaged, by engaged by above-mentioned junction surface the above-mentioned 1st, 2nd ceramic component formation encapsulation, above-mentioned electronic component is configured in the inner space of above-mentioned encapsulation, and above-mentioned junction surface is contained multiple Silicone particles and glass.
In addition, as the grafting material used in electronic accessory device 71, above-mentioned ceramic package grafting material is upper State is used to form above-mentioned junction surface in electronic accessory device, contains Silicone particles and glass.
Hereinafter, embodiment and comparative example are enumerated, the present invention is specifically described.The present invention is not limited to following implementation Example.
(embodiment 1)
(1) making of polysiloxane oligomers
1,3- divinyl tetramethyl disiloxanes 1 are added in the removable flask for the 100ml being arranged in warm bath groove Parts by weight and the parts by weight of the 0.5 weight % p-methyl benzenesulfonic acid aqueous solution 20.After being stirred 1 hour under the conditions of 40 DEG C, bicarbonate is added The parts by weight of sodium 0.05.Then, addition dimethoxymethylphenylsilane 10 parts by weight, the weight of dimethyldimethoxysil,ne 49 Part, the parts by weight of trimethylmethoxysilane 0.6 and the parts by weight of MTMS 3.6, are stirred 1 hour.Then, add The parts by weight of 10 weight % potassium hydroxide aqueous solutions 1.9, are warming up to 85 DEG C, while being depressurized with aspirator, while stirring 10 is small When, reacted.After reaction terminates, normal pressure is returned to, 40 DEG C are cooled to, the parts by weight of acetic acid 0.2 are added, it is quiet in separatory funnel Put more than 12 hours.The lower floor after two separate is taken out, is purified with evaporator, thus obtains polysiloxane oligomers.
(2) making of Silicone particles (containing organic polymer)
Preparation is dissolved with t butyl 2 ethyl peroxyhexanoate in the obtained parts by weight of polysiloxane oligomers 30, and (polymerization is drawn Send out agent, You companies manufacture " Perbutyl O ") 0.5 parts by weight lysate A.In addition, in the parts by weight of ion exchange water 150 In, by the parts by weight of polyoxyethylene alkyl phenyl ether (emulsifying agent) 0.8 and the polyvinyl alcohol (degree of polymerization：About 2000, saponification degree：86.5 ~89 moles of %, Japan synthesis chemical company manufacture " GOHSENOL GH-20 ") the parts by weight of the 5 weight % aqueous solution 80 mixed Close, prepare aqueous solution B.
Added in the removable flask being arranged in warm bath groove after above-mentioned lysate A, add above-mentioned aqueous solution B.So Afterwards, by using Shirasu Porous Glass (SPG) film (about 5 μm of pore average diameter), emulsified.Then, heat up To 85 DEG C, polymerization 9 hours is carried out.The total amount of the particle after polymerization is entered after water-filling cleaning by centrifuging, makes particle again It is secondary to be scattered in the parts by weight of ion exchange water 100, obtain dispersion liquid.Then, cataloid (daily output is added in dispersion liquid Chemical industrial company manufactures " MP-2040 ") carry out after 0.7 parts by weight freeze-dried, thus obtain substrate particle.By what is obtained Substrate particle carries out progressive operation, thus obtains the Silicone particles of 6.8 μm of average grain diameter.
(embodiment 2)
The parts by weight of dimethyldimethoxysil,ne 49 are changed to the carbinol-modified reactive silicone oil in two ends (SHIN-ETSU HANTOTAI's chemistry work Industry company manufactures " KF-6001 ") 49 parts by weight, in addition, operate similarly to Example 1, obtain Silicone particles.
(embodiment 3)
The parts by weight of MTMS 3.6 are changed to the parts by weight of tetraethoxysilane 3.6, in addition, with reality Apply example 1 similarly to operate, obtain Silicone particles.
(embodiment 4)
The parts by weight of MTMS 3.6 are changed to the parts by weight of phenyltrimethoxysila,e 3.6, in addition, Operate similarly to Example 1, obtain Silicone particles.
(embodiment 5)
The parts by weight of 1,3- divinyl tetramethyl disiloxanes 1 are changed to 1,1,3,3- tetraphenyl -1,3- divinyl The parts by weight of disiloxane 1.2, in addition, operate, obtain Silicone particles similarly to Example 1.
(embodiment 6)
Shirasu Porous Glass (SPG) film (about 5 μm of pore average diameter) is changed to 1 μm of pore average diameter Film, in addition, operate similarly to Example 1, obtain Silicone particles.
(embodiment 7)
Prepare to dissolve in the sour parts by weight of silicone oil 20 of two terminal acrylics and to the parts by weight of styryl trimethoxy silane 10 Have t butyl 2 ethyl peroxyhexanoate (polymerization initiator, You companies manufacture " Perbutyl O ") 0.5 parts by weight lysate A.In addition, in the parts by weight of ion exchange water 150, by the weight % aqueous solution (emulsifying agent) of lauryl sulfate triethanolamine salt 40 0.8 parts by weight and the polyvinyl alcohol (degree of polymerization：About 2000, saponification degree：86.5~89 moles of %, the manufacture of synthesis chemical company of Japan " GOHSENOL GH-20 ") the parts by weight of the 5 weight % aqueous solution 80 mixed, prepare aqueous solution B.In warm bath groove is arranged at Removable flask in add after above-mentioned lysate A, add above-mentioned aqueous solution B.Then, by using Shirasu Porous Glass (SPG) film (about 20 μm of pore average diameter), is emulsified.Then, 85 DEG C are warming up to, is polymerize 9 hours.Pass through centrifugation Separation enters the total amount of the particle after polymerization after water-filling cleaning, carries out progressive operation, obtains Silicone particles A.
Obtained Silicone particles A6.5 weight is added in the removable flask for the 500ml being arranged in warm bath groove Part, the parts by weight of cetyl trimethylammonium bromide 0.6, the parts by weight of distilled water 240, the parts by weight of methanol 120.Stirred under the conditions of 40 DEG C Mix after 1 hour, the addition parts by weight of divinylbenzene 3.0 and the parts by weight of styrene 0.5, be warming up to 75 DEG C and stir 0.5 hour.So Afterwards, 2 are added, the double parts by weight of (different butyric acid) dimethyl 0.4 of 2 '-azo are simultaneously stirred 8 hours, are reacted.Will by centrifuging The total amount of particle after polymerization enters water-filling cleaning, obtains Silicone particles.
(comparative example 1)
Without the parts by weight of methoxymethylphenyl silane 10, in addition, operate, gathered similarly to Example 1 Silicone particles.
(comparative example 2)
Without 1,3- divinyl tetramethyl disiloxanes, p-methyl benzenesulfonic acid, t butyl 2 ethyl peroxyhexanoate, except this Outside, operate similarly to Example 1, synthesize Silicone particles, obtained particle is gel.
(comparative example 3)
Prepare the parts by weight of polyoxyethylene alkyl phenyl ether 0.8 and polyvinyl alcohol (polymerization in the parts by weight of ion exchange water 150 Degree：About 2000, saponification degree：86.5~89 moles of %, Japan synthesis chemical company manufacture " GOHSENOL GH-20 ") 5 weights Measure the mixed liquor of the parts by weight of the % aqueous solution 80.
By the parts by weight of dimethyldimethoxysil,ne 40, the parts by weight of dimethyl benzene methoxylsilane 10 and methyl hydrogen two The parts by weight of alkene siloxanes 2 are mixed under normal temperature condition, add the total amount of above-mentioned mixed liquor.Then, by using Shirasu Porous Glass (SPG) film (about 5 μm of pore average diameter) and emulsified.Removable flask is moved it to, while carrying out Stirring, while being cooled to after 15 DEG C, the parts by weight of toluene solution 0.1 of addition chlorination platinic acid-alkene complex are simultaneously stirred 12 hours, thus obtain Silicone particles.
(evaluation)
(1) particle diameter of Silicone particles
To obtained Silicone particles, using laser diffraction formula particle size distribution device, (Malvern companies manufacture " Mastersizer2000 ") particle diameter is determined, calculate average value.
(2) modulus of elasticity in comperssion (30%K values) of Silicone particles
Under conditions of 23 DEG C by the above method, use micro-compression tester (FISCHER companies manufacture " FISCHERSCOPE H-100 ") the above-mentioned moduluss of elasticity in comperssion (30%K values) of Silicone particles to obtaining is measured.
(3) anti-liquid crystal contaminative
The preparation of sealant for liquid crystal dripping process：
By bisphenol A-type epoxymethacrylate (Thermocurable compound, the manufacture of DAICEL-ALLNEX companies " KRM7985 ") 50 parts by weight, caprolactone modification bisphenol A-type acrylic acid epoxy ester (Thermocurable compound, DAICEL-ALLNEX Company manufacture " EBECRYL3708 ") 20 parts by weight, part acrylic acid modified bisphenol E types epoxy resin (Thermocurable compound, DAICEL-ALLNEX companies manufacture " KRM8276 ") 30 parts by weight, 2,2- dimethoxy -2- phenyl acetophenones (optical free radical gather Close initiator, BASF Japan companies manufacture " IRGACURE651 ") 2 parts by weight, acid dihydrazide (thermal curing agents, big mound Company manufacture " MDH ") 10 parts by weight, the obtained parts by weight of Silicone particles 30, silica (filler, Admatechs Company manufacture " Admafine SO-C2 ") 20 parts by weight, 3- glycidoxypropyltrime,hoxysilanes (silane coupler, letter More chemical industrial company's manufacture " KBM-403 ") 2 parts by weight and core shell acrylate copolymer particulate (stress moderator, Zeonization Cheng companies manufacture " F351 ") coordinated, with planetary agitating device, (THINKY companies manufacture " de-soak stirring Taro (あ わ と り Practice Taros) ") be stirred after, equably mixed with ceramic three-roller, obtain sealing material for liquid crystal display device.
The making of liquid crystal display cells：
Relative to the obtained parts by weight of each sealing material for liquid crystal display device 100, made using planetary agitating device average The spacer particle that 5 μm of particle diameter (manufacture of ponding chemical industrial company " Micro Pearl SP-2050 ") 1 parts by weight are equably divided Dissipate, obtained sealant containing distance piece is filled in the syringe (Musashi engineering company manufactures " PSY-10E ") of distributor, entered Row deaeration is handled.Then, using distributor (Musashi engineering company manufactures " SHOTMASTER300 "), with the transparent of ito thin film On electrode base board sealant is coated with the way of describing rectangular frame.Then, TN liquid crystal is added dropwise with liquid crystal Dropping feeder The fine droplet of (Chisso companies manufacture " JC-5001LA ") and coating, are fitted using vacuum forming apparatus under 5Pa vacuum Another transparency carrier.100mW/cm is irradiated to the unit after laminating using metal halide lamp2Ultraviolet after 30 seconds, Heated 1 hour under the conditions of 120 DEG C and make sealant heat cure, obtain liquid crystal display cells (5 μm of cell gap).
The evaluation method of anti-liquid crystal contaminative：
To obtained liquid crystal display cells, observation by visual observation results from the liquid crystal (particularly corner) on sealing periphery Display is uneven.Judge anti-liquid crystal contaminative with following benchmark.
[determinating reference of anti-liquid crystal contaminative]
○○：Inequality is not shown completely
○：Seldom produce display uneven
△：Produce obvious display uneven
×：Produce serious display uneven
(4) low-moisture permeability (the irregular colour evaluations of the liquid crystal display cells driven after preserving under the conditions of hot and humid)
The liquid crystal display cells obtained in the evaluation for preparing above-mentioned (3).
The evaluation method of low-moisture permeability：
After obtained liquid crystal display cells are preserved 72 hours in the environment of 80 DEG C of temperature, humidity 90%RH, carry out AC3.5V voltage driving, observes the sealant periphery of middle tone by visual observation.Judge low-moisture permeability with following benchmark.
[determinating reference of low-moisture permeability]
○○：On sealing periphery completely without irregular colour
○：Seldom produce irregular colour
△：Produce obvious irregular colour
×：Produce serious irregular colour
(5) resistance to chemical reagents
Fallen into a trap the parts by weight of Silicone particles 10 that measure in vial, to this various parts by weight of solvent 100 of addition, Vibrated 24 hours in 30 DEG C of bath.After 24 hours, filtered, take out Silicone particles, carry out 72 hours it is freeze-dried. The weight of dried sample is determined, weight decrement is evaluated.
Show the result in table 1 below.
Table 1

Claims (15)

1. a kind of Silicone particles, it has more than 0.1 μm, less than 500 μm of particle diameter, also,
The Silicone particles are with the hydrophobic group that siloxanes key, free-radical polymerised group and carbon number are more than 5 The Silicone particles of group,
Either make silane compound with free-radical polymerised group and be more than 5 hydrophobic grouping with carbon number Silane compound reacts and forms siloxanes key Silicone particles obtained from,
Either make with free-radical polymerised group and anti-for the silane compound of more than 5 hydrophobic grouping with carbon number Siloxanes key Silicone particles obtained from and should be formed.
2. Silicone particles as claimed in claim 1, it is that have with siloxanes key, in the end of the siloxanes key Free-radical polymerised group and the poly- silicon on the side chain of the siloxanes key with the hydrophobic grouping that carbon number is more than 5 Oxygen alkane particle,
Either make silane compound with free-radical polymerised group and be more than 5 hydrophobic grouping with carbon number Silane compound reacts and forms siloxanes key Silicone particles obtained from,
Either make with free-radical polymerised group and anti-for the silane compound of more than 5 hydrophobic grouping with carbon number Siloxanes key Silicone particles obtained from and should be formed.
3. Silicone particles as claimed in claim 2, it is that have with siloxanes key, in the end of the siloxanes key The free-radical polymerised group that is bonded on silicon atom and having on the side chain of the siloxanes key is bonded on silicon atom Carbon number for more than 5 hydrophobic grouping Silicone particles,
Either make the silane compound with the free-radical polymerised group being bonded on silicon atom and former with silicon is bonded to Carbon number on son reacts for the silane compound of more than 5 hydrophobic grouping and forms siloxanes key poly- silica obtained from Alkane particle,
Either make with the free-radical polymerised group being bonded on silicon atom and with the carbon atom being bonded on silicon atom Number reacts for the silane compound of more than 5 hydrophobic grouping and forms siloxanes key Silicone particles obtained from.
4. such as Silicone particles according to any one of claims 1 to 3, it is that have to be bonded with 2 on 1 silicon atom The Silicone particles of the dimethylsiloxane skeleton of methyl.
5. such as Silicone particles according to any one of claims 1 to 4, it is modulus of elasticity in comperssion when have compressed 30% For 500N/mm2Following Silicone particles.
6. such as Silicone particles according to any one of claims 1 to 5, it has been free from metallic catalyst or contained The Silicone particles of below 100ppm metallic catalyst.
7. such as Silicone particles according to any one of claims 1 to 6, it is the Silicone particles containing opacifier.
8. such as Silicone particles according to any one of claims 1 to 7, it is for sealant for liquid crystal dripping process Silicone particles.
9. such as Silicone particles according to any one of claims 1 to 8, it is with siloxanes key, free-radical polymerised Group and carbon number for more than 5 hydrophobic grouping Silicone particles.
10. such as Silicone particles according to any one of claims 1 to 8, it makes with free-radical polymerised group Silane compound and reacted with carbon number for the silane compound of more than 5 hydrophobic grouping and form siloxanes key and obtain Silicone particles,
Either make with free-radical polymerised group and anti-for the silane compound of more than 5 hydrophobic grouping with carbon number Silicone particles obtained from siloxanes key and should be formed.
11. Silicone particles as claimed in claim 10, it is to be made using radical polymerization initiator with radical polymerization Close property group silane compound and with carbon number for more than 5 hydrophobic grouping silane compound reaction obtained from gather Silicone particles, or made using radical polymerization initiator with free-radical polymerised group and there is carbon number to be 5 Silicone particles obtained from the silane compound reaction of hydrophobic grouping above.
12. a kind of manufacture method of Silicone particles, it is the manufacture method of the Silicone particles described in claim 10, This method includes following process：
Make the silane compound with free-radical polymerised group and the silanization with the hydrophobic grouping that carbon number is more than 5 Compound reacts and forms siloxanes key, so that Silicone particles are obtained,
Or, make with free-radical polymerised group and anti-for the silane compound of more than 5 hydrophobic grouping with carbon number Siloxanes key and should be formed, so as to obtain Silicone particles.
13. the manufacture method of Silicone particles as claimed in claim 12, wherein, make tool using radical polymerization initiator There is the silane compound of free-radical polymerised group and anti-for the silane compound of more than 5 hydrophobic grouping with carbon number Should, so that Silicone particles are obtained,
Or, using radical polymerization initiator make with free-radical polymerised group and with carbon number for more than 5 dredge The silane compound reaction of water base group, so as to obtain Silicone particles.
14. a kind of sealant for liquid crystal dripping process, its contain Thermocurable composition and
Silicone particles any one of claim 1~11.
15. a kind of liquid crystal display cells, it includes：
1st part used for liquid crystal display element,
2nd part used for liquid crystal display element,
, will be described in the state of the 1st part used for liquid crystal display element and the 2nd part used for liquid crystal display element are opposed The periphery of 1st part used for liquid crystal display element and the 2nd part used for liquid crystal display element carried out sealed sealing,
Positioned at the inner side of the sealing and be configured at the 1st part used for liquid crystal display element and the 2nd liquid crystal display member Liquid crystal between part part,
The sealing is formed by making sealant for liquid crystal dripping process carry out heat cure,
The sealant for liquid crystal dripping process contains Thermocurable composition and the poly- silicon any one of claim 1~11 Oxygen alkane particle.
CN201680010161.6A 2015-05-08 2016-04-28 Silicone particles, the manufacture method of Silicone particles, sealant for liquid crystal dripping process and liquid crystal display cells Pending CN107250220A (en)

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