WO2016181860A1 - シリコーン粒子、シリコーン粒子の製造方法、液晶滴下工法用シール剤及び液晶表示素子 - Google Patents
シリコーン粒子、シリコーン粒子の製造方法、液晶滴下工法用シール剤及び液晶表示素子 Download PDFInfo
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- WO2016181860A1 WO2016181860A1 PCT/JP2016/063366 JP2016063366W WO2016181860A1 WO 2016181860 A1 WO2016181860 A1 WO 2016181860A1 JP 2016063366 W JP2016063366 W JP 2016063366W WO 2016181860 A1 WO2016181860 A1 WO 2016181860A1
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- 0 ***1CCCC1 Chemical compound ***1CCCC1 0.000 description 1
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
Definitions
- the present invention relates to silicone particles and a method for producing silicone particles. Moreover, this invention relates to the sealing compound for liquid crystal dropping methods, and a liquid crystal display element using the said silicone particle.
- Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
- anisotropic conductive material conductive particles are dispersed in a binder resin.
- the anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure.
- connection target members such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure.
- connection target members such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure.
- FPC flexible printed circuit
- conductive particles conductive particles having base particles and a conductive layer disposed on the surface of the base particles may be used.
- the liquid crystal display element is configured by arranging liquid crystal between two glass substrates.
- a spacer is used as a gap control material in order to keep the distance (gap) between two glass substrates uniform and constant.
- Patent Document 1 describes that rubber powder such as silicone rubber powder is used as the spacer for the liquid crystal display element.
- Patent Document 2 includes particles having two or more types of polyorganosiloxanes having different organic groups, the composition of which changes stepwise or continuously from the center of the particle toward the surface. It is disclosed.
- Patent Document 3 discloses particles obtained by hydrolyzing and polycondensing a polyfunctional silane compound having a polymerizable unsaturated group in the presence of a surfactant.
- the polyfunctional silane compound is a first silicon compound containing at least one radical polymerizable group selected from a compound represented by a specific formula and derivatives thereof.
- Patent Documents 1 to 3 may have low chemical resistance or high moisture permeability.
- the liquid crystal may be contaminated due to the silicone rubber powder.
- moisture permeability increases, and unevenness in liquid crystal display may occur.
- An object of the present invention is to provide a silicone particle capable of increasing chemical resistance and decreasing moisture permeability and a method of producing the silicone particle. Moreover, the objective of this invention is providing the sealing compound for liquid crystal dropping methods, and a liquid crystal display element using the said silicone particle.
- the silicone particles have a particle diameter of 0.1 ⁇ m or more and 500 ⁇ m or less, and the silicone particles include a siloxane bond, a radical polymerizable group, and a hydrophobic group having 5 or more carbon atoms. Or a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond. Silicone particles (second silicone particles) or silicone particles obtained by reacting a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms to form a siloxane bond ( A third silicone particle) is provided.
- the silicone particle includes a siloxane bond, a radical polymerizable group at a terminal of the siloxane bond, and a hydrophobic group having 5 or more carbon atoms in a side chain of the siloxane bond.
- silicone particle or a silicone particle obtained by reacting a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms to form a siloxane bond (third Silicone particles).
- the silicone particle is bonded to a silicon atom in a siloxane bond, a radical polymerizable group bonded to a silicon atom at a terminal of the siloxane bond, and a side chain of the siloxane bond.
- a silane compound having a radically polymerizable group bonded to a silicon atom and a hydrophobic group having a carbon number of 5 or more bonded to a silicon atom is bonded to a silicon atom in a siloxane bond, a radical polymerizable group bonded to a silicon atom at a terminal of the siloxane bond, and a side chain of the siloxane bond.
- a silane compound having a radically polymerizable group bonded to a silicon atom and a hydrophobic group having a carbon number of 5 or more bonded to a silicon atom is bonded to a silicon atom in a siloxane bond, a radical polymerizable group bonded to a silicon atom at
- silicone particle obtained by reacting with a silane compound having a siloxane bond to form a siloxane bond, or has a radical polymerizable group bonded to a silicon atom and bonded to a silicon atom By reacting a silane compound having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond. It is obtained silicone particles (Third silicone particles).
- the silicone particle is a silicone particle having a dimethylsiloxane skeleton in which two methyl groups are bonded to one silicon atom.
- the said silicone particle is a silicone particle whose compression elastic modulus when compressed 30% is 500 N / mm ⁇ 2 > or less.
- the silicone particle does not contain a metal catalyst or is a silicone particle containing a metal catalyst at 100 ppm or less.
- the silicone particle is a silicone particle containing a light shielding agent.
- the silicone particle is a silicone particle used in a sealing agent for a liquid crystal dropping method.
- the silicone particles according to the present invention are preferably silicone particles (first silicone particles) having a siloxane bond, a radical polymerizable group, and a hydrophobic group having 5 or more carbon atoms.
- Silicone particles according to the present invention are obtained by reacting a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond (second silicone particles). Or a silicone particle (third silicone particle) obtained by reacting a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms to form a siloxane bond. It is also preferable.
- the silicone particle is obtained by reacting a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms with a radical polymerization initiator.
- Silicone particles (second silicone particles) or silicone particles obtained by reacting a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms with a radical polymerization initiator Third silicone particles.
- a method for producing a silicone particle as described above wherein a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms are reacted with each other. 2) or a step of obtaining silicone particles (third silicone particles) by reacting a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms.
- a method for producing silicone particles is provided.
- a silicone particle (by reacting a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms with a radical polymerization initiator ( Second silicone particles) or by reacting a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms with a radical polymerization initiator (silicone particles (third silicone particles)) Get.
- a liquid crystal dropping method sealing agent comprising a thermosetting component and the above-described silicone particles.
- a first liquid crystal display element member, a second liquid crystal display element member, the first liquid crystal display element member, and the second liquid crystal display element member are provided.
- a seal portion that seals the outer periphery of the first liquid crystal display element member and the second liquid crystal display element member in an opposed state, and the first liquid crystal display element inside the seal portion A liquid crystal disposed between the member for liquid crystal display and the member for the second liquid crystal display element, and the seal portion is formed by thermally curing a sealant for a liquid crystal dropping method, and the liquid crystal dropping
- a sealing agent for a construction method contains a thermosetting component and the above-described silicone particles.
- the silicone particles according to the present invention are silicone particles having a particle size of 0.1 ⁇ m or more and 500 ⁇ m or less, and the silicone particles include a siloxane bond, a radical polymerizable group, and a hydrophobic group having 5 or more carbon atoms.
- a silicone particle obtained by reacting a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond or Silicone particles obtained by reacting a silane compound having a radically polymerizable group and having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond, increase chemical resistance and reduce moisture permeability. can do.
- FIG. 1 is a cross-sectional view schematically showing an example of a liquid crystal display element using silicone particles.
- FIG. 2 is a front cross-sectional view schematically showing an example of a connection structure using conductive particles.
- FIG. 3 is a cross-sectional view schematically showing an example of an electronic component device using silicone particles.
- FIG. 4 is an enlarged cross-sectional view showing a joint portion in the electronic component device shown in FIG.
- silicone particles are silicone particles having a particle size of 0.1 ⁇ m or more and 500 ⁇ m or less.
- the present invention has the following configuration.
- the silicone particles according to the present invention are (configuration 1) silicone particles (first silicone particles) having a siloxane bond, a radical polymerizable group, and a hydrophobic group having 5 or more carbon atoms, or (configuration 2) a radical.
- silicone particle obtained by reacting a silane compound having a polymerizable group with a silane compound having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond, or (configuration 3) Silicone particles (third silicone particles) obtained by reacting a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms to form a siloxane bond.
- the second silicone particle is a reaction product of a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms, and is a silicone particle having a siloxane bond.
- the third silicone particle is a reaction product of a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms, and is a silicone particle having a siloxane bond.
- the chemical resistance of the silicone particles according to the present invention can be increased, the moisture permeability can be decreased, and the moisture resistance can be increased.
- a conductive structure is obtained by forming a conductive part on the surface of the silicone particle according to the present invention to obtain conductive particles, and conductive connection is performed using a conductive material containing the obtained conductive particles.
- a liquid crystal display element using a sealing agent for a liquid crystal dropping method containing such silicone particles, or an electronic component device (such as an electronic device) in which two ceramic members are joined using the silicone particles according to the present invention as a gap adjusting material Chemical resistance can be increased and moisture permeability can be decreased, and reliability under high humidity can be increased.
- the moisture permeability of the connection part connecting the two connection target members can be lowered, and as a result, the connection resistance can be kept low.
- the moisture permeability of the seal portion can be lowered, and as a result, the intrusion of moisture into the liquid crystal can be suppressed, and unevenness of the liquid crystal display can be prevented.
- moisture permeability at the joint between two ceramic members can be lowered, and electronic components such as a pressure sensor, an acceleration sensor, a CMOS sensor element, and a CCD sensor element disposed in a ceramic package It is possible to suppress the deterioration of the electronic component and improve the reliability of the electronic component.
- the presence of a siloxane bond, a radical polymerizable group, and a hydrophobic group having 5 or more carbon atoms can be measured by NMR or the like.
- the silicone particles according to the present invention have (Configuration 1 ′) radical polymerization at the siloxane bond and at the terminal of the siloxane bond.
- Group and a silicone particle having a hydrophobic group having 5 or more carbon atoms in the side chain of the siloxane bond (first silicone particle) or (Configuration 2) a silane compound having a radical polymerizable group and 5 or more carbon atoms Or a silicone particle (second silicone particle) obtained by reacting with a silane compound having a hydrophobic group to form a siloxane bond, or (Configuration 3) having a radically polymerizable group and having a carbon number Silicone particles obtained by reacting a silane compound having 5 or more hydrophobic groups to form siloxane bonds (third silicone particles) ) It is preferred that.
- the radical polymerizable group at the terminal of the siloxane bond has an effect of relatively increasing the molecular weight of the polymer of the siloxane compound, and the desired particle size of the silicone particle of the present invention can be easily achieved by the radical polymerizable group. In addition, chemical resistance can be increased.
- the radical polymerizable group include a vinyl group, a (meth) acryloyl group, and a styryl group. From the viewpoint of increasing flexibility, a vinyl group is preferred.
- the hydrophobic group having 5 or more carbon atoms in the side chain of the siloxane bond has an effect of effectively reducing the moisture permeability of the polymer of the siloxane compound, and can increase the chemical resistance.
- Examples of the hydrophobic group having 5 or more carbon atoms include linear alkyl groups having 5 to 30 carbon atoms, cyclic alkyl groups having 5 to 30 carbon atoms, and aromatic groups having 5 to 30 carbon atoms. From the viewpoint of enhancing moisture resistance, an aromatic group having 5 to 30 carbon atoms is preferable, and a phenyl group is more preferable.
- the hydrophobic group having 5 or more carbon atoms is preferably a hydrocarbon group having 5 or more carbon atoms.
- the hydrophobic group preferably has 6 or more carbon atoms.
- the radical polymerizable group is preferably bonded to a silicon atom.
- the hydrophobic group having 5 or more carbon atoms is preferably bonded to a silicon atom.
- the silicone particle comprises (Constitution 1 ′′) a siloxane bond, a vinyl group bonded to a silicon atom at a terminal of the siloxane bond, and a silicon group in a side chain of the siloxane bond.
- Silicone particles having a phenyl group bonded to an atom (first silicone particle) or (Structure 2 ′) a silane compound having a vinyl group bonded to a silicon atom at a terminal and a phenyl bonded to a silicon atom in a side chain It is a silicone particle (second silicone particle) obtained by reacting with a silane compound having a group to form a siloxane bond, or (Constitution 3 ′) having a vinyl group bonded to a silicon atom at the terminal. And a silane compound having a phenyl group bonded to a silicon atom in the side chain is reacted with Silicone particles obtained by forming a hexane bond (Third silicone particles).
- the silicone particles according to the present invention preferably have the above configuration 1, more preferably have the above configuration 1 ', and more preferably have the above configuration 1' '.
- the silicone particles according to the present invention preferably have the above configuration 2, and more preferably have the above configuration 2 '.
- the silicone particles according to the present invention preferably have the above configuration 3, and more preferably have the above configuration 3 '.
- the silicone particles according to the present invention preferably include the above configuration 2 or the above configuration 3, and more preferably include the above configuration 2 'or the above configuration 3'.
- the silicone particles according to the present invention preferably include the above configuration 1, the above configuration 2 or the above configuration 3, more preferably include the above configuration 1 ′, the above configuration 2 or the above configuration 3, and the above configuration. More preferably, 1 ′′ and the configuration 2 ′ or the configuration 3 ′ are provided.
- the compression elastic modulus (30% K value) when the silicone particles are compressed by 30% is preferable. Is 1000 N / mm 2 or less, more preferably 500 N / mm 2 or less, and still more preferably 300 N / mm 2 or less.
- the 30% K value may exceed 1 N / mm 2, may exceed 50 N / mm 2, and may exceed 100 N / mm 2 .
- the compression elastic modulus (30% K value) of the silicone particles can be measured as follows.
- one silicone particle is compressed with a smooth indenter end face of a cylinder (diameter 100 ⁇ m, made of diamond) under the conditions of 25 ° C., compression speed of 0.3 mN / second, and maximum test load of 20 mN.
- the load value (N) and compression displacement (mm) at this time are measured. From the measured value obtained, the compression elastic modulus can be obtained by the following formula.
- the micro compression tester for example, “Fischer Scope H-100” manufactured by Fischer is used.
- the particle size of the silicone particles is 0.1 ⁇ m or more and 500 ⁇ m or less.
- the silicone particles can be suitably used for a sealing agent for liquid crystal dropping method and the like.
- the particle size of the silicone particles is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
- silicone particles having a particle size of not less than the above lower limit and not more than the above upper limit can be easily obtained by using the silane compound of the above constitution 2 and the constitution 2 '.
- the above particle diameter indicates the maximum diameter. Accordingly, the particle diameter indicates the diameter when the silicone particles are spherical, and indicates the maximum diameter when the silicone particles are other than spherical.
- the CV value of the particle diameter of the silicone particles is preferably 40% or less.
- the aspect ratio of the silicone particles is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1.2 or less.
- the aspect ratio indicates a major axis / minor axis.
- the silicone particles preferably do not contain a metal catalyst or contain a metal catalyst at 100 ppm or less.
- the metal catalyst is a catalyst containing a metal atom. When using a metal catalyst, the lower the content of the metal catalyst, the better. When there is much content of a metal catalyst, there exists a tendency for pollution prevention property to fall.
- the content of the metal catalyst is more preferably 80 ppm or less, still more preferably 60 ppm or less, still more preferably 50 ppm or less, still more preferably 40 ppm or less, particularly preferably 30 ppm or less, and particularly preferably 20 ppm or less, most preferably 10 ppm or less. It is.
- silicone particles are often obtained by polymerizing monomers using a metal catalyst.
- the metal catalyst is contained inside, and the content of the metal catalyst may exceed 100 ppm.
- silicone particles obtained without using a metal catalyst generally do not contain a metal catalyst.
- the metal catalyst refers to a curing catalyst such as platinum or tin.
- the method for reducing the metal catalyst to 100 ppm or less is not particularly limited, and examples thereof include a method of condensing by adding a crosslinkable silane compound, a method of introducing a polymerizable functional group into a silicone compound and polymerizing with a polymerization initiator. It is done.
- the content of the metal catalyst can be measured by, for example, an inductively coupled plasma emission spectrometer.
- the use of the silicone particles is not particularly limited.
- the silicone particles are preferably used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer, or used as spacers for liquid crystal display elements.
- the silicone particles are preferably used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer. It is preferable that the said silicone particle is used as a spacer for liquid crystal display elements.
- silicone particles can be suitably used for joining two ceramic members to obtain an electronic component device (electronic device or the like).
- silicone particles are also suitably used as a filler, shock absorber or vibration absorber.
- the silicone particles can be used as an alternative to rubber or springs.
- the material of the silicone particles is preferably a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms, or having a radical polymerizable group and having 5 or more carbon atoms.
- a silane compound having a hydrophobic group is preferred.
- the said silicone particle can be obtained through the process of obtaining a silicone particle by making the silane compound mentioned above react and forming a siloxane bond. When these materials are reacted, a siloxane bond is formed. In the resulting silicone particles, radically polymerizable groups and hydrophobic groups having 5 or more carbon atoms generally remain.
- silicone particles having a particle size of 0.1 ⁇ m or more and 500 ⁇ m or less can be easily obtained, and the chemical resistance of the silicone particles can be increased and the moisture permeability can be decreased. it can.
- the radical polymerizable group is preferably directly bonded to a silicon atom.
- the silane compound which has the said radical polymerizable group only 1 type may be used and 2 or more types may be used together.
- the silane compound having a radical polymerizable group is preferably an alkoxysilane compound.
- examples of the silane compound having a radical polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, divinylmethoxyvinylsilane, divinylethoxyvinylsilane, divinyldimethoxysilane, divinyldiethoxysilane, and 1 , 3-divinyltetramethyldisiloxane and the like.
- the hydrophobic group having 5 or more carbon atoms is preferably directly bonded to a silicon atom. Only 1 type may be used for the said silane compound which has a C5 or more hydrophobic group, and 2 or more types may be used together.
- the silane compound having a hydrophobic group having 5 or more carbon atoms is preferably an alkoxysilane compound.
- Examples of the silane compound having a hydrophobic group having 5 or more carbon atoms include phenyltrimethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, dimethylmethoxyphenylsilane, dimethylethoxyphenylsilane, hexaphenyldisiloxane, 1,3, 3,5-tetramethyl-1,1,5,5-tetraphenyltrisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, hexaphenylcyclotrisiloxane, phenyl Examples include tris (trimethylsiloxy) silane and octaphenylcyclotetrasiloxane.
- the radical polymerizable group is preferably directly bonded to a silicon atom, and the hydrophobic group having 5 or more carbon atoms is bonded to a silicon atom. Direct bonding is preferred.
- the silane compound having a radical polymerizable group and having a hydrophobic group having 5 or more carbon atoms only one kind may be used, or two or more kinds may be used in combination.
- silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms examples include phenylvinyldimethoxysilane, phenylvinyldiethoxysilane, phenylmethylvinylmethoxysilane, phenylmethylvinylethoxysilane, and diphenylvinylmethoxysilane. , Diphenylvinylethoxysilane, phenyldivinylmethoxysilane, phenyldivinylethoxysilane, 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane, and the like.
- the silane compound having the radical polymerizable group and the silane compound having a hydrophobic group having 5 or more carbon atoms when using the silane compound having a radical polymerizable group and the silane compound having a hydrophobic group having 5 or more carbon atoms, the silane compound having the radical polymerizable group and the carbon number
- the silane compound having 5 or more hydrophobic groups is preferably used in a weight ratio of 1: 1 to 1:20, more preferably 1: 5 to 1:15.
- the skeleton derived from the silane compound having a radical polymerizable group and the skeleton derived from the silane compound having a hydrophobic group having 5 or more carbon atoms are in a weight ratio of 1: 1 to 1:20. It is preferable that the ratio is 1: 5 to 1:15.
- the number of radical polymerizable groups and the number of hydrophobic groups having 5 or more carbon atoms are preferably 1: 0.5 to 1:20, and 1: 1 to More preferably, it is 1:15.
- the silicone particles have two methyl groups bonded to one silicon atom.
- the silicone particle material includes a silane compound in which two methyl groups are bonded to one silicon atom.
- the silicone particles described above are obtained by using a radical polymerization initiator. It is preferable to react to form a siloxane bond.
- the silicone particles are preferably a radical polymerization reaction product of the silane compound described above.
- the said silicone particle can be obtained through the process of obtaining a silicone particle by making the silane compound mentioned above react with a radical polymerization initiator, and forming a siloxane bond.
- silicone particles having a particle size of 0.1 ⁇ m or more and 500 ⁇ m or less using a radical polymerization initiator, and it is particularly difficult to obtain silicone particles having a particle size of 100 ⁇ m or less.
- a radical polymerization initiator used, by using the silane compound of the above configuration 2 and the above configuration 2 ′, silicone particles having a particle diameter of 0.1 ⁇ m or more and 500 ⁇ m or less can be obtained, Silicone particles having a particle size of 100 ⁇ m or less can also be obtained.
- a silane compound having a hydrogen atom bonded to a silicon atom may not be used.
- the silane compound can be polymerized using a radical polymerization initiator without using a metal catalyst.
- the metal particles can be prevented from being contained in the silicone particles, the content of the metal catalyst in the silicone particles can be reduced, the chemical resistance is effectively increased, and the moisture permeability is effectively increased.
- the 30% K value can be controlled within a suitable range.
- the method for producing the silicone particle body include a method of producing a silicone particle by performing a polymerization reaction of a silane compound by a suspension polymerization method, a dispersion polymerization method, a miniemulsion polymerization method, an emulsion polymerization method, or the like. .
- a polymerization reaction of the silane compound that is a polymer is performed by a suspension polymerization method, a dispersion polymerization method, a miniemulsion polymerization method, or an emulsion polymerization method
- Silicone particles may be produced.
- a silane compound having a vinyl group bonded to a silicon atom at the terminal may be obtained as a polymer (such as an oligomer) by polymerizing a silane compound having a vinyl group.
- a silane compound having a phenyl group may be polymerized to obtain a silane compound having a phenyl group bonded to a silicon atom in the side chain as a polymer (oligomer or the like).
- a silane compound having a vinyl group and a silane compound having a phenyl group are polymerized to form a polymer (such as an oligomer) having a vinyl group bonded to a silicon atom at a terminal and a phenyl group bonded to a silicon atom in a side chain You may obtain the silane compound which has this.
- the silicone particles may have a plurality of particles on the outer surface.
- the silicone particle includes a silicone particle body and a plurality of particles disposed on the surface of the silicone particle body, and the silicone particle body includes the configuration 1, the configuration 1 ′, and the configuration 1 ′′. , The configuration 2, the configuration 2 ′, the configuration 3 or the configuration 3 ′.
- the plurality of particles include silicone particles and spherical silica. The presence of the plurality of particles can suppress aggregation of the silicone particles.
- the silicone particles may contain a light shielding agent.
- a liquid crystal display element sealing agent containing silicone particles can be suitably used as a light shielding sealant.
- the light-shielding agent examples include polypyrrole, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Titanium black is preferred.
- the said light shielding material may exist in the inside of a silicone particle, and may exist in the outer surface.
- the sealing agent for liquid crystal display elements is preferably a sealing agent for liquid crystal dropping method.
- the said silicone particle can be used suitably for the sealing compound for liquid crystal dropping methods.
- the liquid crystal dropping method sealing agent (hereinafter sometimes abbreviated as sealing agent) is preferably cured by heating.
- the sealing agent preferably contains a thermosetting component and the silicone particles.
- the sealing agent may or may not contain a photocurable component.
- the sealing agent may be irradiated with light for curing, or may not be irradiated with light.
- you may store under irradiation of light.
- the thermosetting component preferably contains a thermosetting compound and a polymerization initiator or a thermosetting agent.
- a polymerization initiator and a thermosetting agent may be used in combination.
- the content of the silicone particles is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, preferably 70 parts by weight or less, more preferably 50 parts by weight or less with respect to 100 parts by weight of the thermosetting compound. It is. When the content of the silicone particles is not less than the above lower limit and not more than the above upper limit, the adhesiveness of the obtained liquid crystal dropping method sealing agent is further improved.
- thermosetting compound examples include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds.
- oxetane compounds examples include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds.
- oxetane compounds examples include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds.
- the said thermosetting compound only 1 type may be used and 2 or more types may be used together.
- the thermosetting compound preferably contains a (meth) acrylic compound, and more preferably contains an epoxy (meth) acrylate.
- the “(meth) acrylic compound” means a compound having a (meth) acryloyl group.
- epoxy (meth) acrylate means a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.
- (Meth) acryl means one or both of “acryl” and “methacryl”
- (meth) acryloyl means one or both of “acryloyl” and “methacryloyl”.
- “Acrylate” means one or both of "acrylate” and "methacrylate”.
- Examples of the epoxy compound as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl bisphenol A type epoxy resin. , Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, Dripping down phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds, and bisphenol A type episulfide resins.
- Examples of commercially available products of the bisphenol A type epoxy resin include jER828EL, jER1001, and jER1004 (all manufactured by Mitsubishi Chemical Corporation); Epicron 850-S (manufactured by DIC Corporation) and the like.
- Examples of commercially available products of the bisphenol F type epoxy resin include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
- Examples of commercially available products of the above bisphenol S type epoxy resin include Epicron EXA1514 (manufactured by DIC).
- Examples of the commercially available 2,2′-diallylbisphenol A type epoxy resin include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of commercially available hydrogenated bisphenol type epoxy resins include Epicron EXA7015 (manufactured by DIC).
- Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
- Examples of commercially available resorcinol-type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
- biphenyl type epoxy resins examples include jERYX-4000H (manufactured by Mitsubishi Chemical Corporation).
- Examples of the commercially available sulfide type epoxy resin include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- diphenyl ether type epoxy resins examples include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
- naphthalene type epoxy resins examples include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC Corporation), and the like.
- phenol novolac epoxy resins examples include Epicron N-770 (manufactured by DIC).
- Examples of commercially available ortho cresol novolac epoxy resins include Epicron N-670-EXP-S (manufactured by DIC).
- Examples of commercially available dicyclopentadiene novolac epoxy resins include Epicron HP7200 (manufactured by DIC).
- biphenyl novolac epoxy resins examples include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
- naphthalene phenol novolac epoxy resins examples include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available products of the above glycidylamine type epoxy resin include jER630 (manufactured by Mitsubishi Chemical Corporation); Epicron 430 (manufactured by DIC Corporation); TETRAD-X (manufactured by Mitsubishi Gas Chemical Company) and the like.
- Examples of commercially available rubber-modified epoxy resins include YR-450 and YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epolide PB (manufactured by Daicel).
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
- Examples of commercially available products of the bisphenol A type episulfide resin include jERYL-7000 (manufactured by Mitsubishi Chemical Corporation).
- epoxy resins include, for example, YDC-1312, YSLV-80XY, and YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); XAC4151 (manufactured by Asahi Kasei Co., Ltd.); And EXA-7120 (manufactured by DIC); TEPIC (manufactured by Nissan Chemical).
- Examples of commercially available epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3702 1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.); Epoxy ester M-600A, Epoxy ester 40EM, Epoxy ester 70PA, Epoxy ester 200PA , Epoxy ester 80MFA, epoch Siester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, and Epoxy ester 400EA (all manufactured by Kyoeisha
- Examples of other (meth) acrylic compounds other than the above epoxy (meth) acrylate include, for example, ester compounds obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, and isocyanate compounds having a hydroxyl group (meth). Examples thereof include urethane (meth) acrylate obtained by reacting an acrylic acid derivative.
- ester compound obtained by reacting the (meth) acrylic acid with a compound having a hydroxyl group any of a monofunctional ester compound, a bifunctional ester compound, and a trifunctional or higher functional ester compound may be used. .
- Examples of the monofunctional ester compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, Methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (Meth) acrylate, phenoxy
- bifunctional ester compound examples include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate Relate, propylene oxide-added bisphenol A di (meth) acrylate
- trifunctional or higher functional ester compound examples include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri (meth).
- the urethane (meth) acrylate is obtained, for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. be able to. Further, an isocyanate compound having two or more isocyanate groups may be used.
- Examples of the isocyanate compound that is a raw material of the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4.
- MDI '-Diisocyanate
- hydrogenated MDI polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris ( Isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, and 1,6,10-undecant Isocyanate, and the like.
- Examples of the isocyanate compound that is the raw material of the urethane (meth) acrylate include polyols such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, or polycaprolactone diol. And chain-extended isocyanate compounds obtained by reaction with excess isocyanate can also be used.
- Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material of the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- 2-hydroxybutyl (meth) acrylate divalents such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol
- divalents such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol
- Mono (meth) acrylates of alcohol mono (meth) acrylates and di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane, and glycerin
- epoxy (meta) such as bisphenol A type epoxy acrylate Acrylate, and the like.
- Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.); EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803 , EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, and EBECRYL9200 Resin UN- 255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, and Art Resin SH-500B (all manufactured by Negami Industrial Co., Ltd.); U-122P, U-108A, U-340P, U-4HA U-6HA, U-324A, U
- the (meth) acrylic compound preferably has a hydrogen-bonding unit such as an —OH group, —NH— group, and —NH 2 group.
- the (meth) acrylic compound preferably has two or three (meth) acryloyl groups.
- thermosetting compound may contain an epoxy compound.
- Examples of the epoxy compound include an epoxy compound that is a raw material for synthesizing the epoxy (meth) acrylate and a partially (meth) acryl-modified epoxy compound.
- the partial (meth) acryl-modified epoxy compound means a compound having at least one epoxy group and one (meth) acryloyl group.
- the partial (meth) acryl-modified epoxy compound can be obtained, for example, by reacting (meth) acrylic acid with a part of two or more epoxy groups in a compound having two or more epoxy groups.
- Examples of commercially available partial (meth) acrylic-modified epoxy compounds include KRM8287 (manufactured by Daicel Ornex).
- the epoxy group is preferably 20 in a total of 100 mol% of the (meth) acryloyl group and the epoxy group in the whole thermosetting compound. It is at least mol%, preferably at most 50 mol%.
- the epoxy group is less than or equal to the above upper limit, the liquid crystal display element sealant is less soluble in liquid crystals and liquid crystal contamination is less likely to occur, and the display performance of the liquid crystal display element is further improved.
- polymerization initiator examples include radical polymerization initiators and cationic polymerization initiators. As for the said polymerization initiator, only 1 type may be used and 2 or more types may be used together.
- radical polymerization initiator examples include a photo radical polymerization initiator that generates radicals by light irradiation, and a thermal radical polymerization initiator that generates radicals by heating.
- the above radical polymerization initiator has a markedly faster curing rate than the thermosetting agent. For this reason, by using a radical polymerization initiator, it is possible to suppress the occurrence of seal breaks and liquid crystal contamination, and also to suppress the spring back that is easily generated by the silicone particles.
- photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone.
- Photo radical polymerization initiator examples include, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Rusilin TPO (all manufactured by BASF Methyl Benin, Inc. Examples include ether and benzoin isopropyl ether (both manufactured by Tokyo Chemical Industry Co., Ltd.).
- thermal radical polymerization initiator examples include azo compounds and organic peroxides. Azo compounds are preferred, and polymer azo initiators that are polymer azo compounds are more preferred.
- the polymer azo compound means a compound having an azo group, generating a radical capable of curing a (meth) acryloyloxy group by heat, and having a number average molecular weight of 300 or more.
- the number average molecular weight of the polymeric azo initiator is preferably 1000 or more, more preferably 5000 or more, still more preferably 10,000 or more, preferably 300,000 or less, more preferably 100,000 or less, and still more preferably 90,000 or less. It is. When the number average molecular weight of the polymeric azo initiator is not less than the above lower limit, the polymeric azo initiator is unlikely to adversely affect the liquid crystal. When the number average molecular weight of the polymer azo initiator is not more than the above upper limit, mixing with the thermosetting compound becomes easy.
- the above-mentioned number average molecular weight is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- Examples of the column used for GPC measurement include Shodex LF-804 (manufactured by Showa Denko KK).
- polymer azo initiator examples include a polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
- the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group preferably has a polyethylene oxide structure.
- examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid).
- VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 for example. All of them are manufactured by Wako Pure Chemical Industries, Ltd.). *
- organic peroxide examples include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
- a photocationic polymerization initiator As the cationic polymerization initiator, a photocationic polymerization initiator can be suitably used.
- the photocationic polymerization initiator generates a protonic acid or a Lewis acid when irradiated with light.
- the kind of said photocationic polymerization initiator is not specifically limited, An ionic photoacid generation type may be sufficient and a nonionic photoacid generation type may be sufficient.
- photocationic polymerization initiator examples include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts; iron-allene complexes; titanocene complexes; organometallic complexes such as arylsilanol-aluminum complexes, etc. Is mentioned.
- photocationic polymerization initiators examples include Adekaoptomer SP-150 and Adekaoptomer SP-170 (both manufactured by ADEKA).
- the content of the polymerization initiator is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 30 parts by weight or less, more preferably 10 parts by weight with respect to 100 parts by weight of the thermosetting compound. It is 5 parts by weight or less, more preferably 5 parts by weight or less.
- the sealing agent for liquid crystal display elements can be sufficiently cured.
- the storage stability of the sealing agent for liquid crystal display elements is increased.
- thermosetting agent examples include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, and acid anhydrides.
- Organic acid hydrazide solid at 23 ° C. is preferably used.
- the said thermosetting agent only 1 type may be used and 2 or more types may be used together.
- Examples of the organic acid hydrazide solid at 23 ° C. include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide. It is done.
- Examples of commercial products of organic acid hydrazide solid at 23 ° C. include Amicure VDH and Amicure UDH (all manufactured by Ajinomoto Fine Techno Co.); SDH, IDH, ADH, MDH (all manufactured by Otsuka Chemical Co., Ltd.) Is mentioned.
- the content of the thermosetting agent with respect to 100 parts by weight of the thermosetting compound is preferably 1 part by weight or more, preferably 50 parts by weight or less, more preferably 30 parts by weight or less.
- the content of the thermosetting agent is not less than the above lower limit, the liquid crystal display element sealing agent can be sufficiently thermoset.
- the content of the thermosetting agent is not more than the above upper limit, the viscosity of the sealing agent for liquid crystal display elements does not become too high, and the coating property becomes good.
- the liquid crystal display element sealing agent preferably contains a curing accelerator.
- the sealing agent can be sufficiently cured without heating at a high temperature.
- Examples of the curing accelerator include polyvalent carboxylic acids having an isocyanuric ring skeleton and epoxy resin amine adducts. Specific examples include tris (2-carboxymethyl) isocyanurate, tris (2-carboxyl). And ethyl) isocyanurate, tris (3-carboxypropyl) isocyanurate, and bis (2-carboxyethyl) isocyanurate.
- the content of the curing accelerator is preferably 0.1 parts by weight or more and preferably 10 parts by weight or less with respect to 100 parts by weight of the thermosetting compound.
- the content of the curing accelerator is not less than the above lower limit, the liquid crystal display element sealing agent is sufficiently cured, and heating at a high temperature is not necessary for curing. Adhesiveness of the sealing agent for liquid crystal display elements becomes it high that content of the said hardening accelerator is below the said upper limit.
- the liquid crystal display element sealing agent preferably contains a filler for the purpose of improving the viscosity, improving the adhesion due to the stress dispersion effect, improving the linear expansion coefficient, and improving the moisture resistance of the cured product.
- the filler examples include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, water Inorganic fillers such as aluminum oxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, and aluminum nitride, polyester particles, polyurethane particles, vinyl polymer particles, acrylic polymer particles, and Examples thereof include organic fillers such as core-shell acrylate copolymer particles. As for the said filler, only 1 type may be used and 2 or more types may be used together.
- the content of the filler is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 70% by weight or less, more preferably 60% by weight or less, in 100% by weight of the liquid crystal display element sealing agent. It is. When the content of the filler is not less than the above lower limit, effects such as improvement in adhesiveness are sufficiently exhibited. When the content of the filler is not more than the above upper limit, the viscosity of the sealing agent for liquid crystal display elements does not become too high, and the coating property is improved.
- the liquid crystal display element sealing agent preferably contains a silane coupling agent.
- the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
- a silane coupling agent only 1 type may be used and 2 or more types may be used together.
- the silane coupling agent is excellent in the effect of improving the adhesion to the substrate and the like, and can be prevented from flowing out of the curable resin into the liquid crystal by chemically bonding with the curable resin.
- -Phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane or 3-isocyanatopropyltrimethoxysilane is preferred.
- the content of the silane coupling agent is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and preferably 20% by weight or less. More preferably, it is 10% by weight or less.
- blending a silane coupling agent is fully exhibited as content of the said silane coupling agent is more than the said minimum.
- the content of the silane coupling agent is not more than the above upper limit, the contamination of the liquid crystal by the liquid crystal display element sealing agent is further suppressed.
- the liquid crystal display element sealing agent may contain a light shielding agent.
- the liquid crystal display element sealing agent can be suitably used as a light shielding sealant.
- Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Titanium black is preferred.
- a liquid crystal display device manufactured using a sealing agent for liquid crystal display devices containing a light-shielding agent has sufficient light-shielding properties, and thus has high contrast without light leakage, and has excellent image display quality. An element can be realized.
- the above-mentioned titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm.
- the titanium black has a property of providing light shielding properties to the sealing agent for liquid crystal display elements by sufficiently shielding light having a wavelength in the visible light region, and has a property of transmitting light having a wavelength in the vicinity of the ultraviolet region. .
- the insulating property of the light-shielding agent contained in the liquid crystal display element sealing agent is preferably high, and titanium black is suitable as the light-shielding agent having high insulation.
- the optical density (OD value) per 1 ⁇ m of the titanium black is preferably 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better.
- the OD value of the titanium black is not particularly limited, but the OD value is usually 5 or less.
- titanium black and carbon black exhibit a sufficient effect even if they are not surface-treated.
- Surface treated with titanium black whose surface was treated with an organic component such as a coupling agent or titanium black coated with inorganic components such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide and magnesium oxide. Titanium black can also be used. Titanium black treated with an organic component is preferable because it can enhance insulation.
- titanium black examples include 12S, 13M, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi Materials Corporation); Tilac D (manufactured by Ako Kasei Co., Ltd.) and the like.
- the specific surface area of the titanium black is preferably 13 m 2 / g or more, more preferably 15 m 2 / g or more, preferably 30 m 2 / g or less, more preferably 25 m 2 / g or less.
- the volume resistance of the titanium black is preferably 0.5 ⁇ ⁇ cm or more, more preferably 1 ⁇ ⁇ cm or more, preferably 3 ⁇ ⁇ cm or less, more preferably 2.5 ⁇ ⁇ cm or less.
- the primary particle size of the light shielding agent affects the distance between the two liquid crystal display element members.
- the primary particle size of the light-shielding agent is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, preferably 5 ⁇ m or less, more preferably 200 nm or less, still more preferably 100 nm or less.
- the primary particle diameter of the light-shielding agent is not less than the above lower limit, the viscosity and thixotropy of the sealing agent for liquid crystal display elements are hardly increased and workability is improved.
- the primary particle diameter of the light-shielding agent is not more than the above upper limit, the applicability of the liquid crystal display element sealing agent is improved.
- the content of the light-shielding agent is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 30% by weight or more, and preferably 80% by weight or less with respect to 100 parts by weight of the thermosetting compound. More preferably, it is 70 weight% or less, More preferably, it is 60 weight% or less.
- the content of the light shielding agent is not less than the above lower limit, sufficient light shielding properties can be obtained.
- the content of the light-shielding agent is not more than the above upper limit, the adhesion of the sealing agent for liquid crystal display elements and the strength after curing are increased, and the drawing property is further improved.
- the liquid crystal display element sealing agent contains a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives as necessary. May be.
- the method for producing the sealing agent for liquid crystal display elements is not particularly limited.
- thermosetting using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.
- the method etc. which mix a compound, a polymerization initiator or a thermosetting agent, silicone particles, and additives, such as a silane coupling agent added as needed, are mentioned.
- the viscosity of the sealing agent for liquid crystal display elements at 25 ° C. and 1 rpm is preferably 50,000 Pa ⁇ s or more, preferably 500,000 Pa ⁇ s or less, more preferably 400,000 Pa ⁇ s or less.
- the viscosity is measured using an E-type viscometer.
- a liquid crystal display element can be obtained by using the liquid crystal display element sealant.
- the first liquid crystal display element member, the second liquid crystal display element member, the first liquid crystal display element member, and the second liquid crystal display element member face each other.
- a seal portion that seals the outer periphery of the first liquid crystal display element member and the second liquid crystal display element member, and the first liquid crystal display element member and the above inside the seal portion.
- a liquid crystal disposed between the second liquid crystal display element member In this liquid crystal display element, a liquid crystal dropping method is applied, and the seal portion is formed by thermosetting a sealing agent for a liquid crystal dropping method.
- the said seal part is the thermosetting material of the sealing compound for liquid crystal dropping methods.
- FIG. 1 is a cross-sectional view schematically showing an example of a liquid crystal display element using silicone particles.
- a liquid crystal display element 1 shown in FIG. 1 has a pair of transparent glass substrates 2.
- the transparent glass substrate 2 has an insulating film (not shown) on the opposing surface. Examples of the material for the insulating film include SiO 2 .
- a transparent electrode 3 is formed on the insulating film in the transparent glass substrate 2. Examples of the material of the transparent electrode 3 include ITO.
- the transparent electrode 3 can be formed by patterning, for example, by photolithography.
- An alignment film 4 is formed on the transparent electrode 3 on the surface of the transparent glass substrate 2. Examples of the material of the alignment film 4 include polyimide.
- the liquid crystal 5 is sealed between the pair of transparent glass substrates 2.
- a plurality of spacer particles 7 are disposed between the pair of transparent glass substrates 2.
- the space between the pair of transparent glass substrates 2 is regulated by the plurality of spacer particles 7.
- a seal portion 6 is disposed between the outer peripheral edges of the pair of transparent glass substrates 2. Outflow of the liquid crystal 5 to the outside is prevented by the seal portion 6.
- the seal portion 6 includes silicone particles 6A.
- the member positioned above the liquid crystal 5 is a first liquid crystal display element member
- the member positioned below the liquid crystal is a second liquid crystal display element member.
- liquid crystal display element shown in FIG. 1 is an example, and the structure of the liquid crystal display element can be changed as appropriate.
- connection structure The silicone particles are used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer.
- a connection structure can be obtained by connecting the connection target member using the conductive particles or using the conductive material including the conductive particles and the binder resin described above.
- connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member, and the connection portion.
- connection portion connecting the first connection target member and the second connection target member, and the connection portion.
- the connection part is the conductive particles. That is, the first and second connection target members are connected by the conductive particles.
- the conductive material used for obtaining the connection structure is preferably an anisotropic conductive material.
- the first connection object member preferably has a first electrode on the surface.
- the second connection target member preferably has a second electrode on the surface. It is preferable that the first electrode and the second electrode are electrically connected by the conductive particles.
- FIG. 2 is a front cross-sectional view schematically showing an example of a connection structure using conductive particles.
- connection structure 51 shown in FIG. 2 is a connection that connects the first connection target member 52, the second connection target member 53, and the first connection target member 52 and the second connection target member 53.
- the connecting portion 54 is formed of a conductive material including conductive particles 54A and a binder resin.
- Connection portion 54 includes conductive particles 54A.
- the conductive particles 54A include silicone particles and a conductive layer disposed on the surface of the silicone particles. In FIG. 2, the conductive particles 54A are schematically shown for convenience of illustration.
- the first connection target member 52 has a plurality of first electrodes 52a on the surface (upper surface).
- the second connection target member 53 has a plurality of second electrodes 53a on the surface (lower surface).
- the first electrode 52 a and the second electrode 53 a are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1.
- the manufacturing method of the connection structure is not particularly limited.
- a method of manufacturing a connection structure a method of placing the conductive material between a first connection target member and a second connection target member to obtain a laminate, and then heating and pressurizing the laminate Etc.
- the pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
- the heating temperature is about 120 to 220 ° C.
- the pressure applied to connect the electrode of the flexible printed board, the electrode disposed on the resin film, and the electrode of the touch panel is about 9.8 ⁇ 10 4 to 1.0 ⁇ 10 6 Pa.
- connection target member examples include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, glass epoxy boards, and glass boards.
- the conductive material is preferably a conductive material for connecting electronic components.
- the conductive paste is a paste-like conductive material, and is preferably applied on the connection target member in a paste-like state.
- connection target member is preferably a flexible substrate or a connection target member in which electrodes are arranged on the surface of the resin film.
- the connection target member is preferably a flexible substrate, and is preferably a connection target member in which an electrode is disposed on the surface of the resin film.
- the flexible substrate is a flexible printed substrate or the like, the flexible substrate generally has electrodes on the surface.
- the electrode provided on the connection target member examples include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a molybdenum electrode, and a tungsten electrode.
- the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode.
- the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode.
- the said electrode is an aluminum electrode, the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
- the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.
- the silicone particles are disposed between the first ceramic member and the second ceramic member at the outer periphery of the first ceramic member and the second ceramic member, and can also be used as a gap control material.
- FIG. 3 is a cross-sectional view schematically showing an example of an electronic component device using silicone particles.
- FIG. 4 is an enlarged cross-sectional view showing a joint portion (portion surrounded by a broken line in FIG. 3) in the electronic component device shown in FIG.
- 3 and 4 includes a first ceramic member 72, a second ceramic member 73, a joint 74, an electronic component 75, and a lead frame 76.
- the first and second ceramic members 72 and 73 are each formed of a ceramic material. Each of the first and second ceramic members 72 and 73 is, for example, a casing.
- the first ceramic member 72 is, for example, a substrate.
- the second ceramic member 73 is a lid, for example.
- the 1st ceramic member 72 has the convex part which protruded in the outer peripheral part to the 2nd ceramic member 73 side (upper side).
- the first ceramic member 72 has a recess that forms an internal space R for accommodating the electronic component 75 on the second ceramic member 73 side (upper side). Note that the first ceramic member 72 may not have a convex portion.
- the second ceramic member 73 has a convex portion that protrudes toward the first ceramic member 72 (lower side) on the outer peripheral portion.
- the second ceramic member 73 has a recess that forms an internal space R for housing the electronic component 75 on the first ceramic member 72 side (lower side). Note that the second ceramic member 73 may not have a conve
- the joining portion 74 joins the outer peripheral portion of the first ceramic member 72 and the outer peripheral portion of the second ceramic member 73. Specifically, the joint portion 74 joins the convex portion on the outer peripheral portion of the first ceramic member 72 and the convex portion on the outer peripheral portion of the second ceramic member 73.
- a package is formed by the first and second ceramic members 72 and 73 joined by the joining portion 74.
- An internal space R is formed by the package.
- the junction 74 seals the internal space R in a liquid-tight and air-tight manner.
- the joining part 74 is a sealing part.
- the electronic component 75 is disposed in the internal space R of the package. Specifically, the electronic component 75 is disposed on the first ceramic member 72. In the present embodiment, two electronic components 75 are used.
- the joining portion 74 includes a plurality of silicone particles 74A and glass 74B.
- the joining part 74 is formed using a joining material including a plurality of particles 74A and glass 74B different from glass particles.
- This bonding material is a bonding material for ceramic packages.
- the bonding material may contain a solvent or a resin.
- the glass 74B such as glass particles is solidified after melting and bonding.
- Examples of electronic components include sensor elements, MEMS, and bare chips.
- Examples of the sensor element include a pressure sensor element, an acceleration sensor element, a CMOS sensor element, and a CCD sensor element.
- the lead frame 76 is disposed between the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73.
- the lead frame 76 extends to the internal space R side and the external space side of the package.
- a terminal of the electronic component 75 and the lead frame 76 are electrically connected via a wire.
- the joining part 74 joins the outer peripheral part of the first ceramic member 72 and the outer peripheral part of the second ceramic member 73 directly and partially indirectly.
- the joining portion 74 is an outer peripheral portion of the first ceramic member 72 at a portion where the lead frame 76 exists between the outer peripheral portion of the first ceramic member 72 and the outer peripheral portion of the second ceramic member 73.
- the outer peripheral portion of the second ceramic member 73 are indirectly joined via the lead frame 76.
- the first ceramic member 72 is in contact with the lead frame 76 at a portion where the lead frame 76 is between the outer peripheral portion of the first ceramic member 72 and the outer peripheral portion of the second ceramic member 73.
- the first ceramic member 72 is in contact with the joint portion 74, the joint portion 74 is in contact with the lead frame 76 and the second ceramic member 73, and the second ceramic member 73 is in contact with the joint portion 74. .
- the joining portion 74 is formed at a portion where the lead frame 76 between the outer peripheral portion of the first ceramic member 72 and the outer peripheral portion of the second ceramic member 73 is not present, and the second ceramic and the outer peripheral portion of the first ceramic member 72.
- the outer periphery of the member 73 is directly joined.
- the joining portion 74 is connected to the first ceramic member 72 and the second ceramic member 73. Is in contact with
- the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73 Is controlled by the plurality of particles 74 ⁇ / b> A included in the joint 74.
- the joining part should just join the outer peripheral part of the 1st ceramic member, and the outer peripheral part of the 2nd ceramic member directly or indirectly.
- An electrical connection method other than the lead frame may be employed.
- the electronic component device includes, for example, a first ceramic member formed of a ceramic material, a second ceramic member formed of a ceramic material, a joint portion, and an electronic component. And the joint portion directly or indirectly joins the outer peripheral portion of the first ceramic member and the outer peripheral portion of the second ceramic member, and the first and first joints joined by the joint portion.
- a package is formed of two ceramic members, the electronic component is disposed in the internal space of the package, and the joint includes a plurality of silicone particles and glass.
- the ceramic package bonding material is used to form the bonding portion in the electronic component device, and includes silicone particles and glass.
- the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.
- Example 1 Preparation of silicone oligomer
- 1 part by weight of 1,3-divinyltetramethyldisiloxane and 20 parts by weight of 0.5 wt% p-toluenesulfonic acid aqueous solution were added. I put it in. After stirring at 40 ° C. for 1 hour, 0.05 part by weight of sodium bicarbonate was added.
- aqueous solution B was prepared by mixing 80 parts by weight of a 5% by weight aqueous solution of “GOHSENOL GH-20”).
- the aqueous solution B was added. Then, emulsification was performed using a Shirasu Porous Glass (SPG) membrane (pore average diameter of about 5 ⁇ m). Then, it heated up to 85 degreeC and superposition
- SPG Shirasu Porous Glass
- Example 2 Silicone particles were obtained in the same manner as in Example 1 except that 49 parts by weight of dimethyldimethoxysilane was changed to 49 parts by weight of a both-end carbinol-modified reactive silicone oil (“KF-6001” manufactured by Shin-Etsu Chemical Co., Ltd.). .
- Example 3 Silicone particles were obtained in the same manner as in Example 1 except that 3.6 parts by weight of methyltrimethoxysilane was changed to 3.6 parts by weight of tetraethoxysilane.
- Example 4 Silicone particles were obtained in the same manner as in Example 1 except that 3.6 parts by weight of methyltrimethoxysilane was changed to 3.6 parts by weight of phenyltrimethoxysilane.
- Example 5 Example 1 except that 1 part by weight of 1,3-divinyltetramethyldisiloxane was changed to 1.2 parts by weight of 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane, Silicone particles were obtained.
- Example 6 Silicone particles were obtained in the same manner as in Example 1 except that the Shirasu Porous Glass (SPG) membrane (pore average diameter of about 5 ⁇ m) was changed to a membrane having a pore average diameter of 1 ⁇ m.
- SPG Shirasu Porous Glass
- Example 7 Tert-butyl-2-ethylperoxyhexanoate (polymerization initiator, “Perbutyl O” manufactured by NOF Corporation) 0.5 to 20 parts by weight of acrylic silicone oil at both ends and 10 parts by weight of p-styryltrimethoxysilane A solution A in which parts by weight were dissolved was prepared.
- polymerization initiator “Perbutyl O” manufactured by NOF Corporation
- aqueous solution B was prepared by mixing 80 parts by weight of a 5 wt% aqueous solution of “GOHSENOL GH-20” manufactured by Synthetic Chemical Co., Ltd. After the said solution A was put into the separable flask installed in the warm bath, the said aqueous solution B was added.
- Example 2 Silicone particles were synthesized in the same manner as in Example 1 except that 1,3-divinyltetramethyldisiloxane, p-toluenesulfonic acid, and tert-butyl-2-ethylperoxyhexanoate were not added. However, the obtained particles were gel-like.
- liquid crystal display elements 1 part by weight of spacer particles (“Micropearl SP-2050” manufactured by Sekisui Chemical Co., Ltd.) having an average particle diameter of 5 ⁇ m is uniformly dispersed by a planetary stirrer with respect to 100 parts by weight of the obtained sealing agent for liquid crystal display elements.
- the obtained spacer-containing sealant was filled into a dispensing syringe (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.) and subjected to defoaming treatment. Then, the sealing agent was apply
- JC-5001LA manufactured by Chisso Corporation
- JC-5001LA manufactured by Chisso Corporation
- the laminated cell was irradiated with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to thermally cure the sealing agent, and a liquid crystal display element (cell gap 5 ⁇ m) was obtained. Obtained.
- Method for evaluating liquid crystal contamination prevention About the obtained liquid crystal display element, the display nonuniformity produced in the liquid crystal (especially corner part) around a seal part was observed visually.
- the liquid crystal contamination prevention property was determined according to the following criteria.
- Evaluation method of low moisture permeability The obtained liquid crystal display element was stored for 72 hours in an environment of a temperature of 80 ° C. and a humidity of 90% RH, and then driven with a voltage of AC 3.5 V, and the periphery of the halftone sealant was visually observed. Low moisture permeability was determined according to the following criteria.
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Abstract
Description
本発明に係るシリコーン粒子は0.1μm以上、500μm以下の粒子径を有するシリコーン粒子である。
F:シリコーン粒子が30%圧縮変形したときの荷重値(N)
S:シリコーン粒子が30%圧縮変形したときの圧縮変位(mm)
R:シリコーン粒子の半径(mm)
上記シリコーン粒子の材料は、好ましくは、ラジカル重合性基を有するシラン化合物と炭素数5以上の疎水基を有するシラン化合物とであるか、もしくは、ラジカル重合性基を有しかつ炭素数5以上の疎水基を有するシラン化合物であることが好ましい。上記シリコーン粒子は、上述したシラン化合物を反応させ、シロキサン結合を形成させることによりシリコーン粒子を得る工程を経て得ることができる。これらの材料を反応させた場合には、シロキサン結合が形成される。得られるシリコーン粒子において、ラジカル重合性基及び炭素数5以上の疎水基は一般に残存する。このような材料を用いることで、0.1μm以上、500μm以下の粒子径を有するシリコーン粒子を容易に得ることができ、しかもシリコーン粒子の耐薬品性を高くし、かつ透湿性を低くすることができる。
液晶表示素子用シール剤は、液晶滴下工法用シール剤であることが好ましい。上記シリコーン粒子は、液晶滴下工法用シール剤に好適に用いることができる。
上記液晶表示素子用シール剤を用いて、液晶表示素子を得ることができる。液晶表示素子は、第1の液晶表示素子用部材と、第2の液晶表示素子用部材と、上記第1の液晶表示素子用部材と上記第2の液晶表示素子用部材とが対向した状態で、上記第1の液晶表示素子用部材と上記第2の液晶表示素子用部材との外周をシールしているシール部と、上記シール部の内側で、上記第1の液晶表示素子用部材と上記第2の液晶表示素子用部材との間に配置されている液晶とを備える。この液晶表示素子では、液晶滴下工法が適用され、かつ上記シール部が、液晶滴下工法用シール剤を熱硬化させることにより形成されている。上記シール部が、液晶滴下工法用シール剤の熱硬化物である。
上記シリコーン粒子は、表面上に導電層が形成され、上記導電層を有する導電性粒子を得るために用いられる。上記導電性粒子を用いて、又は上述した導電性粒子とバインダー樹脂とを含む導電材料を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。
上記シリコーン粒子は、第1のセラミック部材と第2のセラミック部材との外周部において、第1のセラミック部材と第2のセラミック部材の間に配置され、ギャップ制御材として用いることもできる。
以下、実施例及び比較例を挙げて、本発明を具体的に説明する。本発明は、以下の実施例のみに限定されない。
(1)シリコーンオリゴマーの作製
温浴槽内に設置した100mlのセパラブルフラスコに、1,3-ジビニルテトラメチルジシロキサン1重量部と、0.5重量%p-トルエンスルホン酸水溶液20重量部とを入れた。40℃で1時間撹拌した後、炭酸水素ナトリウム0.05重量部を添加した。その後、ジメトキシメチルフェニルシラン10重量部、ジメチルジメトキシシラン49重量部、トリメチルメトキシシラン0.6重量部、及びメチルトリメトキシシラン3.6重量部を添加し、1時間撹拌を行った。その後、10重量%水酸化カリウム水溶液1.9重量部を添加して、85℃まで昇温してアスピレーターで減圧しながら、10時間撹拌、反応を行った。反応終了後、常圧に戻し40℃まで冷却して、酢酸0.2重量部を添加し、12時間以上分液漏斗内で静置した。二層分離後の下層を取り出して、エバポレーターにて精製することでシリコーンオリゴマーを得た。
得られたシリコーンオリゴマー30重量部に、tert-ブチル-2-エチルペルオキシヘキサノアート(重合開始剤、日油社製「パーブチルO」)0.5重量部を溶解させた溶解液Aを用意した。また、イオン交換水150重量部に、ポリオキシエチレンアルキルフェニルエーテル(乳化剤)0.8重量部とポリビニルアルコール(重合度:約2000、けん化度:86.5~89モル%、日本合成化学社製「ゴーセノールGH-20」)の5重量%水溶液80重量部とを混合して、水溶液Bを用意した。
ジメチルジメトキシシラン49重量部を両末端カルビノール変性反応性シリコーンオイル(信越化学工業社製「KF-6001」)49重量部に変更したこと以外は実施例1と同様にして、シリコーン粒子を得た。
メチルトリメトキシシラン3.6重量部をテトラエトキシシラン3.6重量部に変更したこと以外は実施例1と同様にして、シリコーン粒子を得た。
メチルトリメトキシシラン3.6重量部をフェニルトリメトキシシラン3.6重量部に変更したこと以外は実施例1と同様にして、シリコーン粒子を得た。
1,3-ジビニルテトラメチルジシロキサン1重量部を1,1,3,3-テトラフェニル-1,3-ジビニルジシロキサン1.2重量部に変更したこと以外は実施例1と同様にして、シリコーン粒子を得た。
Shirasu Porous Glass(SPG)膜(細孔平均径約5μm)を細孔平均径1μmの膜に変更したこと以外は実施例1と同様にして、シリコーン粒子を得た。
両末端アクリルシリコーンオイル20重量部と、p-スチリルトリメトキシシラン10重量部とに、tert-ブチル-2-エチルペルオキシヘキサノアート(重合開始剤、日油社製「パーブチルO」)0.5重量部を溶解させた溶解液Aを用意した。また、イオン交換水150重量部に、ラウリル硫酸トリエタノールアミン塩40重量%水溶液(乳化剤)0.8重量部とポリビニルアルコール(重合度:約2000、けん化度:86.5~89モル%、日本合成化学社製「ゴーセノールGH-20」)の5重量%水溶液80重量部とを混合して、水溶液Bを用意した。温浴槽中に設置したセパラブルフラスコに、上記溶解液Aを入れた後、上記水溶液Bを添加した。その後、Shirasu Porous Glass(SPG)膜(細孔平均径約20μm)を用いることで、乳化を行った。その後、85℃に昇温して、9時間重合を行った。重合後の粒子の全量を遠心分離により水洗浄した後、分級操作を行ってシリコーン粒子Aを得た。
メトキシメチルフェニルシラン10重量部を添加しなかったこと以外は実施例1と同様にして、シリコーン粒子を得た。
1,3-ジビニルテトラメチルジシロキサンと、p-トルエンスルホン酸と、tert-ブチルー2-エチルペルオキシヘキサノアートとを添加しなかったこと以外は実施例1と同様にして、シリコーン粒子を合成したが、得られた粒子は、ゲル状であった。
イオン交換水150重量部に、ポリオキシエチレンアルキルフェニルエーテル0.8重量部とポリビニルアルコール(重合度:約2000、けん化度:86.5~89モル%、日本合成化学社製「ゴーセノールGH-20」)の5重量%水溶液80重量部との混合液を用意した。
(1)シリコーン粒子の粒子径
得られたシリコーン粒子について、レーザー回折式粒度分布測定装置(マルバーン社製「マスターサイザー2000」)を用いて粒子径を測定し、平均値を算出した。
得られたシリコーン粒子の上記圧縮弾性率(30%K値)を、23℃の条件で、上述した方法により、微小圧縮試験機(フィッシャー社製「フィッシャースコープH-100」)を用いて測定した。
液晶滴下工法用シール剤の調製:
ビスフェノールA型エポキシメタクリレート(熱硬化性化合物、ダイセル・オルネクス社製「KRM7985」)50重量部と、カプロラクトン変性ビスフェノールA型エポキシアクリレート(熱硬化性化合物、ダイセル・オルネクス社製「EBECRYL3708」)20重量部と、部分アクリル変性ビスフェノールE型エポキシ樹脂(熱硬化性化合物、ダイセル・オルネクス社製「KRM8276」)30重量部と、2,2-ジメトキシ-2-フェニルアセトフェノン(光ラジカル重合開始剤、BASF Japan社製「IRGACURE651」)2重量部と、マロン酸ジヒドラジド(熱硬化剤、大塚化学社製「MDH」)10重量部と、得られたシリコーン粒子30重量部と、シリカ(充填剤、アドマテックス社製「アドマファインSO-C2」)20重量部と、3-グリシドキシプロピルトリメトキシシラン(シランカップリング剤、信越化学工業社製「KBM-403」)2重量部と、コアシェルアクリレート共重合体微粒子(応力緩和剤、ゼオン化成社製「F351」)とを配合し、遊星式撹拌装置(シンキー社製「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合させて液晶表示素子用シール剤を得た。
得られた各液晶表示素子用シール剤100重量部に対して平均粒子径5μmのスペーサ粒子(積水化学工業社製「ミクロパールSP-2050」)1重量部を遊星式撹拌装置によって均一に分散させ、得られたスペーサ含有シール剤をディスペンス用のシリンジ(武蔵エンジニアリング社製「PSY-10E」)に充填し、脱泡処理を行った。その後、ディスペンサー(武蔵エンジニアリング社製「SHOTMASTER300」)を用いて、ITO薄膜付きの透明電極基板に長方形の枠を描くように、シール剤を塗布した。続いて、TN液晶(チッソ社製「JC-5001LA」)の微小滴を液晶滴下装置にて滴下して塗布し、他方の透明基板を、真空貼り合わせ装置を用いて5Paの真空下にて貼り合わせた。貼り合わせた後のセルに、メタルハライドランプを用いて100mW/cm2の紫外線を30秒照射した後、120℃で1時間加熱してシール剤を熱硬化させ、液晶表示素子(セルギャップ5μm)を得た。
得られた液晶表示素子について、シール部周辺の液晶(特にコーナー部)に生じる表示むらを目視にて観察した。液晶汚染防止性を下記の基準で判定した。
○○:表示むら全くなし
○:ごくわずかに表示むら発生
△:目立つ表示むら発生
×:ひどい表示むら発生
上記(3)の評価で得られた液晶表示素子を用意した。
得られた液晶表示素子を温度80℃、湿度90%RHの環境下にて72時間保管した後、AC3.5Vの電圧駆動をさせ、中間調のシール剤周辺を目視で観察した。低透湿性を下記の基準で判定した。
○○:シール部周辺に色むらが全くなし
○:ごくわずかに色むら発生
△:目立つ色むら発生
×:ひどい色むら発生
得られたシリコーン粒子10重量部をガラス瓶に計量し、そこへ各種溶剤100重量部を添加して、30℃の浴槽中で24時間振とうさせた。24時間後に、ろ過してシリコーン粒子を取り出し、72時間凍結乾燥を行った。乾燥後のサンプルの重量を測定して、重量減差を評価した。
2…透明ガラス基板
3…透明電極
4…配向膜
5…液晶
6…シール部
6A…シリコーン粒子
7…スペーサ粒子
51…接続構造体
52…第1の接続対象部材
52a…第1の電極
53…第2の接続対象部材
53a…第2の電極
54…接続部
54A…導電性粒子
71…電子部品装置
72…第1のセラミック部材
73…第2のセラミック部材
74…接合部
74A…シリコーン粒子
74B…ガラス
75…電子部品
76…リードフレーム
R…内部空間
Claims (15)
- 0.1μm以上、500μm以下の粒子径を有するシリコーン粒子であり、かつ、
前記シリコーン粒子は、シロキサン結合と、ラジカル重合性基と、炭素数5以上の疎水基とを有するシリコーン粒子であるか、ラジカル重合性基を有するシラン化合物と炭素数5以上の疎水基を有するシラン化合物とを反応させ、シロキサン結合を形成させることにより得られるシリコーン粒子であるか、もしくは、ラジカル重合性基を有しかつ炭素数5以上の疎水基を有するシラン化合物を反応させ、シロキサン結合を形成させることにより得られるシリコーン粒子である、シリコーン粒子。 - シロキサン結合と、前記シロキサン結合の末端においてラジカル重合性基と、前記シロキサン結合の側鎖において炭素数5以上の疎水基とを有するシリコーン粒子であるか、ラジカル重合性基を有するシラン化合物と炭素数5以上の疎水基を有するシラン化合物とを反応させ、シロキサン結合を形成させることにより得られるシリコーン粒子であるか、もしくは、ラジカル重合性基を有しかつ炭素数5以上の疎水基を有するシラン化合物を反応させ、シロキサン結合を形成させることにより得られるシリコーン粒子である、請求項1に記載のシリコーン粒子。
- シロキサン結合と、前記シロキサン結合の末端において珪素原子に結合したラジカル重合性基と、前記シロキサン結合の側鎖において珪素原子に結合した炭素数5以上の疎水基とを有するシリコーン粒子であるか、珪素原子に結合したラジカル重合性基を有するシラン化合物と珪素原子に結合した炭素数5以上の疎水基を有するシラン化合物とを反応させ、シロキサン結合を形成させることにより得られるシリコーン粒子であるか、もしくは、珪素原子に結合したラジカル重合性基を有しかつ珪素原子に結合した炭素数5以上の疎水基を有するシラン化合物を反応させ、シロキサン結合を形成させることにより得られるシリコーン粒子である、請求項2に記載のシリコーン粒子。
- 1つの珪素原子に2つのメチル基が結合したジメチルシロキサン骨格を有するシリコーン粒子である、請求項1~3のいずれか1項に記載のシリコーン粒子。
- 30%圧縮したときの圧縮弾性率が500N/mm2以下であるシリコーン粒子である、請求項1~4のいずれか1項に記載のシリコーン粒子。
- 金属触媒を含まないか、又は、金属触媒を100ppm以下で含むシリコーン粒子である、請求項1~5のいずれか1項に記載のシリコーン粒子。
- 遮光剤を含むシリコーン粒子である、請求項1~6のいずれか1項に記載のシリコーン粒子。
- 液晶滴下工法用シール剤に用いられるシリコーン粒子である、請求項1~7のいずれか1項に記載のシリコーン粒子。
- シロキサン結合と、ラジカル重合性基と、炭素数5以上の疎水基とを有するシリコーン粒子である、請求項1~8のいずれか1項に記載のシリコーン粒子。
- ラジカル重合性基を有するシラン化合物と炭素数5以上の疎水基を有するシラン化合物とを反応させ、シロキサン結合を形成させることにより得られるシリコーン粒子であるか、もしくは、ラジカル重合性基を有しかつ炭素数5以上の疎水基を有するシラン化合物を反応させ、シロキサン結合を形成させることにより得られるシリコーン粒子である、請求項1~8のいずれか1項に記載のシリコーン粒子。
- ラジカル重合性基を有するシラン化合物と炭素数5以上の疎水基を有するシラン化合物とをラジカル重合開始剤により反応させることにより得られるシリコーン粒子であるか、もしくは、ラジカル重合性基を有しかつ炭素数5以上の疎水基を有するシラン化合物をラジカル重合開始剤により反応させることにより得られるシリコーン粒子である、請求項10に記載のシリコーン粒子。
- 請求項10に記載のシリコーン粒子の製造方法であって、
ラジカル重合性基を有するシラン化合物と炭素数5以上の疎水基を有するシラン化合物とを反応させ、シロキサン結合を形成させることによりシリコーン粒子を得るか、もしくは、ラジカル重合性基を有しかつ炭素数5以上の疎水基を有するシラン化合物を反応させ、シロキサン結合を形成させることによりシリコーン粒子を得る工程を備える、シリコーン粒子の製造方法。 - ラジカル重合性基を有するシラン化合物と炭素数5以上の疎水基を有するシラン化合物とをラジカル重合開始剤により反応させることによりシリコーン粒子を得るか、もしくは、ラジカル重合性基を有しかつ炭素数5以上の疎水基を有するシラン化合物をラジカル重合開始剤により反応させることによりシリコーン粒子を得る、請求項12に記載のシリコーン粒子の製造方法。
- 熱硬化性成分と、
請求項1~11のいずれか1項に記載のシリコーン粒子とを含む、液晶滴下工法用シール剤。 - 第1の液晶表示素子用部材と、
第2の液晶表示素子用部材と、
前記第1の液晶表示素子用部材と前記第2の液晶表示素子用部材とが対向した状態で、前記第1の液晶表示素子用部材と前記第2の液晶表示素子用部材との外周をシールしているシール部と、
前記シール部の内側で、前記第1の液晶表示素子用部材と前記第2の液晶表示素子用部材との間に配置されている液晶とを備え、
前記シール部が、液晶滴下工法用シール剤を熱硬化させることにより形成されており、
前記液晶滴下工法用シール剤が、熱硬化性成分と、請求項1~11のいずれか1項に記載のシリコーン粒子とを含む、液晶表示素子。
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