WO2018012484A1 - 複合粒子及び液晶表示装置 - Google Patents
複合粒子及び液晶表示装置 Download PDFInfo
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- WO2018012484A1 WO2018012484A1 PCT/JP2017/025224 JP2017025224W WO2018012484A1 WO 2018012484 A1 WO2018012484 A1 WO 2018012484A1 JP 2017025224 W JP2017025224 W JP 2017025224W WO 2018012484 A1 WO2018012484 A1 WO 2018012484A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/007—Polyrotaxanes; Polycatenanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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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
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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
- G02F1/13398—Spacer materials; Spacer properties
Definitions
- the present invention relates to composite particles containing a pigment.
- the present invention also relates to a liquid crystal display device using the composite particle.
- liquid crystal is disposed between two glass substrates.
- a spacer is used as a gap control material in order to control the distance between two glass substrates and maintain an appropriate liquid crystal layer thickness (cell gap).
- resin particles are generally used as the spacer.
- the spacer is required to be colored in a dark color in order to prevent light from being transmitted through the spacer portion and to prevent a reduction in image display contrast.
- Patent Document 1 discloses a spacer for a liquid crystal display element containing carbon black whose surface is coated.
- the carbon black which is a pigment, tends to make the particles fragile, and the fracture strength of the particles may be low.
- the particle diameter of the particles is small, it is difficult to sufficiently increase the breaking strength of the particles.
- An object of the present invention is to provide composite particles that can sufficiently suppress a decrease in breaking strength even if the particles contain a pigment. Moreover, this invention is providing the liquid crystal display device using the said composite particle.
- a composite particle containing a pigment, a chain compound, and a cyclic compound, wherein the chain compound penetrates the inside of the ring of the cyclic compound.
- the structure in which the chain compound penetrates the inside of the ring of the cyclic compound is a rotaxane.
- a crosslinking agent is bonded to the cyclic compound.
- the total content of the portion excluding the crosslinking agent in the cyclic compound and the total amount of the chain compound is 100% in total of 100% by weight of the cyclic compound and the chain compound. % By weight or more and 70% by weight or less.
- the crosslinking agent in the cyclic compound includes an acrylic polymer or a styrene polymer.
- the particle diameter is 2 ⁇ m or more and 15 ⁇ m or less.
- the pigment is a black pigment or a white pigment.
- the pigment contains carbon black, titanium black, aniline black, or iron oxide.
- the chain compound has a weight average molecular weight of 3000 or more and 100,000 or less.
- the cyclic skeleton in the cyclic compound is a cyclic skeleton in which 10 or more atoms are linked.
- a liquid crystal display device comprising a member for a liquid crystal display device and the composite particles described above.
- the composite particle according to the present invention contains a pigment, a chain compound, and a cyclic compound, and the chain compound penetrates the inside of the ring of the cyclic compound, so that the particle contains the pigment. However, it is possible to sufficiently suppress the decrease in the breaking strength.
- FIG. 1 is a cross-sectional view schematically showing a liquid crystal display device using composite particles according to an embodiment of the present invention as a spacer for a liquid crystal display device.
- (meth) acrylate means one or both of “acrylate” and “methacrylate”
- (meth) acryl means one or both of “acryl” and “methacryl”. Mean both.
- the composite particle according to the present invention contains a pigment, a chain compound, and a cyclic compound.
- the chain compound penetrates the inside of the ring of the cyclic compound.
- the composite particle according to the present invention has a structure in which the chain compound penetrates the inside of the ring of the cyclic compound.
- the composite particle according to the present invention has, for example, a resin portion.
- the composite particle according to the present invention is, for example, a resin particle in which a pigment is contained in the resin portion.
- the composite particle according to the present invention has the above-described configuration, even if the particle contains a pigment, it is possible to sufficiently suppress a decrease in breaking strength. Generally, when a pigment is dispersed in a composite particle, the composite particle is easily broken from the interface between the resin portion of the composite particle and the pigment, and the breaking strength of the composite particle is reduced. In the composite particle according to the present invention, since the chain compound and the cyclic compound are contained, high toughness can be imparted to the composite particle, and destruction of the composite particle can be suppressed. As a result, a decrease in the breaking strength of the composite particles can be suppressed.
- the chain compound penetrates the inside of the ring of the cyclic compound, higher toughness can be imparted to the composite particles, and the breakage of the composite particles can be further suppressed. As a result, a decrease in the breaking strength of the composite particles can be further suppressed.
- the fracture strength (compression fracture strain) of the composite particles is preferably 50% or more, more preferably 55% or more, and further preferably 60% or more.
- Compressive fracture strain is measured as follows.
- a load (reverse load value) is applied to the center of the composite particle until the composite particle breaks using a micro compression tester. Thereafter, the displacement when the composite particles are broken is measured. The ratio of displacement when fractured with respect to the average particle diameter is defined as compression fracture strain.
- the load speed is 0.33 mN / sec.
- micro compression tester for example, “Micro compression tester MCT-W200” manufactured by Shimadzu Corporation, “Fischer Scope H-100” manufactured by Fisher, etc. are used.
- the composite particle contains a base particle body, and contains a pigment, a chain compound, and a cyclic compound in the base particle body.
- the base particle body is preferably a resin particle body.
- the composite particle material and the base particle body material are suitably used as the composite particle material and the base particle body material.
- the material of the composite particle and the material of the base particle body include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; polymethyl methacrylate, polymethyl acrylate, and the like.
- Acrylic resin polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, Polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyether Ether ketone, polyether sulfone, divinyl benzene polymer, and divinylbenzene copolymer, and the like.
- divinylbenzene copolymer examples include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester copolymer. Since the hardness of the composite particle and the base particle body can be easily controlled within a suitable range, the material of the composite particle and the material of the base particle body include a polymerizable monomer having an ethylenically unsaturated group. A polymer obtained by polymerizing one kind or two or more kinds is preferable.
- the polymerizable monomer having an ethylenically unsaturated group is a non-crosslinkable type.
- a monomer and a crosslinkable monomer are mentioned.
- non-crosslinkable monomer examples include, as vinyl compounds, styrene monomers such as styrene, ⁇ -methylstyrene, and chlorostyrene; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; vinyl acetate, butyric acid Acid vinyl ester compounds such as vinyl, vinyl laurate and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; methyl (meth) acrylate, ethyl (meth) acrylate, propyl as (meth) acrylic compounds (Meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, iso Alkyl (meth) acryl
- crosslinkable monomer examples include vinyl monomers such as divinylbenzene, 1,4-divinyloxybutane and divinylsulfone as vinyl compounds; tetramethylolmethanetetra (metha) as a (meth) acryl compound; ) Acrylate, polytetramethylene glycol diacrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (Meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate Polyfunctional (meth) acrylate compounds such as polyte
- Silane alkoxide compounds vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, diethoxymethylvinylsilane, diethoxyethylvinylsilane, ethylmethyldivinylsilane, methylvinyldimethoxysilane, ethylvinyldimethoxysilane, methyl Vinyldiethoxysilane, ethylvinyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloxyp Polymerizable double bond-containing silanes such as pyrmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Alkoxid
- the composite particle and the base particle body are obtained by uniformly mixing and dispersing the pigment, the chain compound, and the cyclic compound in the polymerizable monomer having the ethylenically unsaturated group, and polymerizing the mixture.
- the polymerization method is not particularly limited, and the polymerization can be performed by a known method such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, condensation polymerization), addition condensation, living polymerization, or living radical polymerization.
- This method includes, for example, a method of suspension polymerization in the presence of a radical polymerization initiator, and a seed polymerization method that is a method of swelling and polymerizing a monomer together with a radical polymerization initiator using non-crosslinked seed particles. And a dispersion polymerization method.
- a ball mill In order to uniformly mix and disperse the pigment in the polymerizable monomer having an ethylenically unsaturated group, a ball mill, a bead mill, a sand mill, an attritor, a sand grinder, a nanomizer, or the like may be used. In this case, a dispersant or the like may be added to improve the dispersibility of the pigment.
- the above dispersant is not particularly limited.
- examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, starch, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and sodium poly (meth) acrylate, and barium sulfate, calcium sulfate, aluminum sulfate, calcium carbonate, Examples include calcium phosphate, talc, clay, and metal oxide powder.
- the particle diameter of the composite particles is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, preferably 15 ⁇ m or less, More preferably, it is 5 ⁇ m or less.
- the particle diameter of the composite particle means a diameter when the composite particle is a true sphere, and when the composite particle is a shape other than a true sphere, it is assumed to be a true sphere corresponding to its volume. Means diameter.
- the particle size of the composite particles means an average particle size obtained by measuring the composite particles with an arbitrary particle size measuring device.
- a particle size distribution measuring machine using principles such as laser light scattering, electrical resistance value change, and image analysis after imaging can be used.
- a particle size distribution measuring apparatus (“Multizer 4” manufactured by Beckman Coulter, Inc.) And measuring the average particle diameter.
- the average particle diameter indicates a number average particle diameter.
- the aspect ratio of the composite particles is preferably 1.10 or less, more preferably 1.05 or less.
- the aspect ratio indicates a major axis / minor axis.
- the aspect ratio is preferably determined by observing 10 arbitrary composite particles with an electron microscope or an optical microscope, and setting the maximum diameter and the minimum diameter as the major axis and the minor axis, respectively. It is calculated
- the coefficient of variation of the particle diameter of the composite particles is preferably 7% or less. More preferably, it is 5% or less.
- the coefficient of variation (CV value) can be measured as follows.
- CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : standard deviation of particle diameter of composite particle Dn: average value of particle diameter of composite particle
- the shape of the composite particle is not particularly limited.
- the shape of the composite particles may be spherical or may be a shape other than a spherical shape such as a flat shape.
- the composite particles are preferably particles whose surfaces are coated with a coating agent such as a silane coupling agent.
- the coating with the coating agent is preferably a monomolecular thin film or a polymer thin film.
- the composite particles may not have the coating.
- the silane coupling agent is not particularly limited.
- Examples of the silane coupling agent include ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and 3- [N-allyl-N- (2-aminoethyl).
- the method for coating the composite particles with the coating agent is not particularly limited.
- the particles and the coating agent are mixed in an inorganic solvent such as water or an organic solvent such as alcohol, heated under stirring, and the composite particles are decanted after heating. And a method of removing the solvent by drying under reduced pressure, and a method of directly mixing and heating the particles and the coating agent.
- the pigment is preferably a black pigment or a white pigment, and more preferably a black pigment, from the viewpoint of enabling it to be suitably used for a liquid crystal display device spacer.
- the pigment may be a black pigment or a white pigment.
- black pigment examples include carbon black, lamp black, graphite, iron oxide, copper-chromium composite oxide, and copper-chromium-zinc composite oxide. As for the said black pigment, only 1 type may be used and 2 or more types may be used together.
- Examples of the white pigment include titanium dioxide, calcium carbonate, zinc oxide, and barium sulfate. As for the said white pigment, only 1 type may be used and 2 or more types may be used together.
- the pigment preferably contains carbon black, titanium black, aniline black or iron oxide. As for the said pigment, only 1 type may be used and 2 or more types may be used together.
- the carbon black is not particularly limited, and examples thereof include channel black, roll black, furnace black, thermal black, ketjen black, and acetylene black. As for the said carbon black, only 1 type may be used and 2 or more types may be used together.
- the pigment is preferably a pigment whose surface is coated.
- a pigment whose surface is coated even if the amount of the pigment is increased, it is possible to prevent a decrease in properties such as electric resistance of the composite particles. Furthermore, the dispersibility of the pigment is improved by coating the surface, and the composite particles can be colored with a smaller amount.
- the material for covering the surface of the pigment include thermoplastic resins.
- thermoplastic resin is not particularly limited.
- examples of the thermoplastic resin include alkyd resin, modified alkyd resin, phenol resin, natural resin modified phenol resin, maleic resin, natural resin modified maleic resin, fumaric acid resin, ester gum, rosin, petroleum resin, coumarone resin. , Indene resin, polyester resin, polyimide resin, polyamide resin, polycarbonate resin, polyethylene resin, epoxy resin, phenoxy resin, styrene resin, vinyl resin, acrylic resin, chlorinated rubber, benzoguanamine resin, urea resin, polyolefin resin, ethylene-vinyl acetate A copolymer, a urethane resin, etc. are mentioned.
- the said thermoplastic resin only 1 type may be used and 2 or more types may be used together.
- the method for coating the surface of the pigment with the thermoplastic resin is not particularly limited, and the method for finely pulverizing the pigment in a hydrophobic solvent containing the thermoplastic resin using a pulverizing device such as a ball mill, the heat Examples include a method in which water is distilled off by heating after emulsification by adding and mixing an aqueous dispersion of a pigment in a hydrophobic solvent containing a plastic resin.
- the content of the pigment is preferably 3% by weight or more, more preferably 5% by weight or more, preferably 100% by weight of the composite particles. Is 10% by weight or less, more preferably 8% by weight or less.
- the composite particle according to the present invention contains the chain compound and the cyclic compound.
- the chain compound penetrates the inside of the ring of the cyclic compound. Since the composite particles according to the present invention have the above-described configuration, it is possible to suppress a decrease in the breaking strength of the composite particles. From the viewpoint of further suppressing the reduction in the breaking strength of the composite particles, the chain compound penetrates the inside of the ring of the cyclic compound, and the chain compound and the cyclic compound form an inclusion compound. Is preferred. All of the chain compounds may not penetrate the inside of the ring of the cyclic compound. The chain compound may not penetrate through all the rings in the cyclic compound.
- the structure in which the chain compound is formed so as to penetrate the inside of the ring of the cyclic compound as described above includes, for example, a structure called “rotaxane”.
- the structure in which the chain compound penetrates the inside of the ring of the cyclic compound is preferably a rotaxane.
- the rotaxane has a structure in which the chain compound penetrates the inside of the ring of the cyclic compound so that the cyclic compound does not fall off the chain compound.
- the structure formed such that the chain compound penetrates the inside of the ring of the cyclic compound and the cyclic compound can be removed from the chain compound is called “pseudo-rotaxane” and is different from the above rotaxane.
- the rotaxane may be a polyrotaxane.
- the polyrotaxane is a rotaxane in which a chain compound penetrates the inside of a ring of a large number of cyclic compounds, and has a structure formed by a large number of constituent molecules. From the viewpoint of further suppressing the decrease in the breaking strength of the composite particles, the structure formed by the chain compound and the cyclic compound is more preferably a polyrotaxane.
- the chain compound and the material of the chain compound are not particularly limited, and for example, various polymers can be used.
- the chain compound and the material of the chain compound include cellulose resins such as polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, poly (meth) acrylic acid, poly (meth) acrylamide, and hydroxyethyl cellulose.
- polystyrene resins such as polystyrene and acrylonitrile-styrene copolymers
- Acrylic resin such as methyl (meth) acrylate, (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate copolymer, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral resin, polyisobutylene, Polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer, polyamide compounds such as nylon, polyimide compounds, polydiene compounds such as polyisoprene and polybutadiene, polysulfone compounds, polyimine compounds, polyacetic anhydride compounds, polyurea compounds
- the chain compound is preferably a polymer.
- the chain compound may be a homopolymer composed of one type of repeating structural unit or a copolymer composed of two or more types of repeating structural units.
- the chain compound when it is a copolymer, it may have any structure such as a random copolymer, a block copolymer, and an alternating copolymer.
- the chain compound preferably has a molecular structure for preventing the cyclic compound from dropping off. From the viewpoint of further suppressing the decrease in the breaking strength of the composite particles, the chain compound penetrates the inside of the ring of the cyclic compound, and the cyclic compound does not fall off the chain compound. preferable.
- the molecular structure for preventing the cyclic compound from dropping is referred to as a stopper group.
- the stopper group examples include an aryl group such as a dinitrophenyl group, a trityl group, a pyrenyl group, and a phenyl group, an adamantane group, a 2-butyldecyl group, a fluorescein compound, a pyrene compound, a cyclodextrin compound, and N-carbobenzoxy-L. -Tyrosine compounds (ZL-tyrosine compounds), and derivatives or modified products thereof.
- Other examples of the stopper group include conventionally known functional groups for preventing the cyclic compound from dropping off in the rotaxane.
- the stopper group may have a substituent.
- the chain compound preferably has the stopper groups at both ends.
- the cyclic compound is held in a skewered state by the chain compound.
- the cyclic compound can move freely in the chain portion of the chain compound. Due to the stopper groups at both ends, the cyclic compound does not deviate from the chain compound. As a result, higher toughness can be imparted to the composite particles, and a decrease in the fracture strength of the composite particles can be further suppressed.
- the stopper group may be directly bonded to the chain skeleton of the chain compound, or may be indirectly bonded to the chain skeleton of the chain compound via an amide bond, an ester bond, or the like. Good.
- the composite particle may contain a chain compound having the stopper group, or may contain a chain compound not having the stopper group, and the chain compound having the stopper group and the stopper group. Both of them may contain a chain compound that does not have. From the viewpoint of further suppressing the decrease in the breaking strength of the composite particles, the composite particles preferably include a chain compound having the stopper group.
- the chain compound and the material of the chain compound include polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, Examples thereof include polyvinyl alcohol and polyvinyl methyl ether.
- the chain compound and the material of the chain compound preferably include the above-described compound. As for these compounds, only 1 type may be used and 2 or more types may be used together.
- the chain compound is likely to penetrate the inside (ring inside) of the ring of the cyclic compound, and a stable rotaxane is easily formed.
- the chain compound may have a branched chain to the extent that it can penetrate the inside of the ring of the cyclic compound.
- the chain compound constituting the rotaxane has a stopper group
- the cyclic compound does not fall off, so that the stress relaxation effect is maintained over a long period of time, and the degradation of the fracture strength of the composite particles can be further suppressed. it can. Further, even when the chain compound does not have a stopper group, the stress relaxation effect is exhibited.
- the weight average molecular weight of the chain compound is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, still more preferably 10,000 or more, preferably 100,000 or less, more preferably 50000 or less.
- the weight average molecular weight of the chain compound is particularly preferably 10,000 or more and 50,000 or less.
- the weight average molecular weight of the chain compound is equal to or higher than the lower limit, it is possible to further suppress a decrease in the breaking strength of the composite particles.
- the weight average molecular weight of the chain compound is not more than the above upper limit, the compatibility of the base particle body and the cyclic compound can be further enhanced.
- the cyclic skeleton of the cyclic compound is preferably a cyclic skeleton in which 3 or more atoms (the number of atoms connected in a ring) are connected, and preferably 5 or more.
- a cyclic skeleton in which atoms are continuous is more preferable, and a cyclic skeleton in which 10 or more atoms are continuous is more preferable.
- the number of atoms connected in a ring may be 1000 or less, or 500 or less.
- the number of atoms linked in a ring is a value counted so that the number of atoms constituting the ring is minimized among the atoms constituting the ring.
- the atoms constituting the cyclic skeleton are preferably carbon atoms, oxygen atoms, nitrogen atoms or sulfur atoms, and are preferably carbon atoms or oxygen atoms.
- the cyclic compound is preferably a cyclic sugar compound.
- Examples of the cyclic compound and the material of the cyclic compound include cyclodextrin compounds such as ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, dimethylcyclodextrin, glucosylcyclodextrin; crown ether, cyclophane, calixarene Cyclic monomers such as cucurbituril, pillar arene, and cyclic amides; cyclic oligomers; and cyclic macromonomers.
- the cyclodextrin compound may be a derivative or a modified product.
- cyclic oligomer examples include ethylene glycol oligomers, ethylene oxide oligomers, propylene glycol oligomers, and polysaccharides.
- material of the said cyclic compound and the said cyclic compound only 1 type may be used and 2 or more types may be used together.
- the material of the cyclic compound contained in the composite particles preferably has a polymerizable functional group.
- the polymerizable functional group in the material of the cyclic compound can be polymerized with the material of the base particle body, for example.
- the polymerizable functional group in the material of the cyclic compound can be polymerized with, for example, a crosslinking agent.
- the polymerizable functional group examples include alkenyl group, vinyl group, hydroxyl group, mercapto group, amino group, carboxyl group, sulfo group, and phosphate group.
- the polymerizable functional group may further have one or more substituents.
- the polymerizable functional group is preferably a radical polymerizable functional group, such as an alkenyl group, vinyl A group or the like is preferable.
- cyclic compound having a polymerizable functional group is a cyclic macromonomer represented by the following formula (1).
- R1 and R2 are each a hydrogen atom or an alkyl group having 1 or 2 carbon atoms
- R3 is a hydrogen atom or a methyl group
- M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms
- n represents the number of repeating units of the structure in parentheses and is an integer of 5 to 100. Further, n + 1 Ms may be the same or different.
- cyclic compound having a polymerizable functional group is a cyclic macromonomer represented by the following formula (2).
- M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms
- n represents the number of repeating units in the structure in parentheses and is an integer of 5 to 100. Further, n + 1 Ms may be the same or different.
- the cyclic compound preferably contains an ⁇ -cyclodextrin structure, ⁇ -cyclodextrin structure or ⁇ -cyclodextrin structure. These structures may be only one type or two or more types.
- the amount of maximum inclusion of the cyclic compound when the chain compound penetrates the cyclic compound is 1.
- the inclusion amount of the cyclic compound is preferably 0.001 or more, more preferably 0.01 or more, and still more preferably 0.05 or more.
- the amount of maximum inclusion of the cyclic compound when the chain compound penetrates the cyclic compound is 1.
- the inclusion amount of the cyclic compound is preferably 0.6 or less, more preferably 0.5 or less, and still more preferably 0.4 or less.
- the inclusion amount of the cyclic compound can be determined by a known method. When the inclusion amount of the cyclic compound is not less than the above lower limit and not more than the above upper limit, a decrease in the breaking strength of the composite particles is further suppressed.
- Crosslinker bound to cyclic compound From the viewpoint of further suppressing the decrease in the breaking strength of the composite particles, it is preferable that a crosslinking agent is bonded to the cyclic compound.
- the cross-linking agent may be a side chain in the cyclic compound. The presence of this crosslinking agent greatly contributes to the suppression of the decrease in the breaking strength of the composite particles.
- crosslinking agent examples include polyolefin resins such as polyethylene, polypropylene, polystyrene, silicon resin, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polyalkylene terephthalate, Polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene oxide, polyacetal , Polyimide, polyamideimide, polyetheretherketo , Polyethersulfone, and polymers such as obtained by a variety of polymerizable monomer having an ethylenically unsaturated group is polymerized with one or more thereof.
- the crosslinking agent in the cyclic compound preferably includes an acrylic polymer or a styrene polymer, and more preferably includes an acrylic polymer.
- the crosslinking agent in the cyclic compound may be a monomer, an oligomer, or a polymer. From the viewpoint of further suppressing the decrease in the breaking strength of the composite particles, the crosslinking agent in the cyclic compound is preferably a polymer.
- the polymer may be a homopolymer composed of one type of repeating structural unit or a copolymer composed of two or more types of repeating structural units. When the polymer is a copolymer, it may have any structure such as a random copolymer, a block copolymer, and an alternating copolymer.
- the crosslinking agent in the cyclic compound is preferably a polymer of a polymerizable monomer having an ethylenically unsaturated group.
- the crosslinking agent in the cyclic compound may be a polymer of only one type of polymerizable monomer or a polymer of two or more types of polymerizable monomers.
- the crosslinking agent in the cyclic compound is a polymer of a monomer having an ethylenically unsaturated group
- the monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and a crosslinkable monomer. And a polymer.
- the non-crosslinkable monomer includes the above-mentioned non-crosslinkable monomers.
- Examples of the crosslinkable monomer include the crosslinkable monomers described above.
- the above crosslinking agent can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method.
- this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
- the structure of the cyclic compound having a crosslinking agent include, for example, a structure in which the crosslinking agent is bonded to the cyclic portion of the cyclic compound in the rotaxane described above.
- One end of the cross-linking agent may be bonded to a cyclic portion in one cyclic compound, and the other end of the cross-linking agent may be bonded to a cyclic portion in another cyclic compound.
- the cyclic portion in the cyclic compound in the rotaxane and the crosslinking agent may form a three-dimensional network structure.
- the cyclic moiety in the cyclic compound in the rotaxane serves as a starting point (bonding point) of the crosslinking agent.
- the cyclic compound can move freely in the chain portion of the chain compound. Therefore, the bonding point in the cyclic compound can move the chain portion of the chain compound.
- the cyclic compound having the crosslinking agent is a material capable of moving the chain portion of the chain compound. Even when stress is applied, the cyclic compound having such a crosslinking agent has flexibility because the bonding point moves following the stress, and the stress is easily relaxed. It has the property of excellent resilience.
- the cyclic compound When the cyclic compound has a structure in which a cross-linking agent is bonded to the cyclic portion of the cyclic compound in the rotaxane, it has particularly excellent stress relaxation performance and can further suppress the decrease in the fracture strength of the composite particles. it can. Further, when the composite particles contain a pigment, the breaking strength of the composite particles decreases as the particle size of the composite particles decreases. However, if the cyclic compound has a structure in which a crosslinking agent is bonded to the cyclic portion of the cyclic compound in the rotaxane, even if the particle size of the composite particle is reduced, the decrease in the breaking strength of the composite particle is further suppressed. can do.
- the method for producing the cyclic compound having a crosslinking agent is not particularly limited.
- a polymer having a crosslinking agent in the cyclic portion of the cyclic compound is produced by reacting a mixture of a rotaxane having a cyclic compound having a polymerizable functional group and a polymerizable monomer for forming a crosslinking agent. can do.
- the polymerizable functional group is a radical polymerizable functional group (such as a vinyl group) with a polymerizable monomer
- radical polymerization of the rotaxane and the polymerizable monomer allows the cyclic moiety in the cyclic compound.
- a polymer having a crosslinking agent can be produced. This radical polymerization can be performed by a known method.
- the kind of the rotaxane provided with a cyclic compound having a polymerizable functional group is not particularly limited.
- Examples of the rotaxane having a cyclic compound having a polymerizable functional group include “Celum (registered trademark) superpolymer SM3403P” and “Celum (registered trademark) superpolymer SM1313P, which are commercially available from Advanced Soft Materials, Inc.
- the total content of the cyclic compound and the chain compound in the cyclic compound and the chain compound are included in 100% by weight of the cyclic compound and the chain compound.
- the amount is preferably 1% by weight or more, more preferably 3% by weight or more, preferably 70% by weight or less, more preferably 20% by weight or less.
- a rotaxane and a polymerizable monomer for forming a crosslinking agent are prepared in the presence of a polymerization initiator.
- examples include suspension polymerization.
- the rotaxane has a cyclic compound having a radical polymerizable functional group
- the rotaxane and the radical polymerizable monomer for forming a crosslinking agent are subjected to suspension polymerization in the presence of a polymerization initiator.
- composite particles having a structure in which a crosslinking agent is bonded to a cyclic portion of the cyclic compound in the rotaxane can be obtained.
- the type of the polymerization initiator is not particularly limited, and compounds generally used in suspension polymerization, emulsion polymerization, dispersion polymerization and the like can be used. Moreover, you may use a dispersion stabilizer etc. in the case of superposition
- the type of the dispersion stabilizer is not particularly limited, and a known dispersion stabilizer can be used. There are no particular limitations on the polymerization conditions, and for example, the polymerization can be carried out under suitable conditions conventionally known.
- the liquid crystal display device includes a member for a liquid crystal display device and the composite particles described above. Moreover, the said composite particle is used suitably as a spacer for liquid crystal display devices. That is, the composite particle includes a liquid crystal display device including a pair of substrates constituting a liquid crystal cell, a liquid crystal sealed between the pair of substrates, and a spacer for a liquid crystal display device disposed between the pair of substrates. It is preferably used for obtaining.
- the spacer for a liquid crystal display device may be included in a peripheral sealant.
- FIG. 1 is a cross-sectional view schematically showing a liquid crystal display device using composite particles according to an embodiment of the present invention as a spacer for a liquid crystal display device.
- a liquid crystal display device 81 shown in FIG. 1 has a pair of transparent glass substrates 82.
- the transparent glass substrate 82 has an insulating film (not shown) on the opposing surface. Examples of the material for the insulating film include SiO 2 .
- a transparent electrode 83 is formed on the insulating film in the transparent glass substrate 82. Examples of the material of the transparent electrode 83 include ITO.
- the transparent electrode 83 can be formed by patterning, for example, by photolithography.
- An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. Examples of the material of the alignment film 84 include polyimide.
- a liquid crystal 85 is sealed between the pair of transparent glass substrates 82.
- a plurality of composite particles 11 are arranged between the pair of transparent glass substrates 82.
- the composite particle 11 is the composite particle described above.
- the composite particle 11 is used as a spacer for a liquid crystal display device.
- the interval between the pair of transparent glass substrates 82 is regulated by the plurality of composite particles 11.
- a sealing agent 86 is disposed between the edges of the pair of transparent glass substrates 82. Outflow of the liquid crystal 85 to the outside is prevented by the sealing agent 86.
- the arrangement density of spacers for liquid crystal display device per 1 mm 2 is preferably 10 pieces / mm 2 or more, and preferably 1000 pieces / mm 2 or less.
- the arrangement density is 10 pieces / mm 2 or more, the cell gap becomes even more uniform.
- the arrangement density is 1000 / mm 2 or less, the contrast of the liquid crystal display device is further improved.
- the use of the composite particles is not particularly limited.
- the composite particles are suitably used not only as spacers for liquid crystal display devices but also for various applications.
- the composite particles are preferably used as a light control glass spacer, and are preferably used as a light control film spacer.
- the composite particles are also suitably used as inorganic fillers, toner additives, impact absorbers, or vibration absorbers.
- the composite particles can be used as a substitute for rubber or a spring.
- Example 1 Preparation of Composite Particles A dispersion liquid in which 5 parts by weight of surface-coated carbon black, 475 parts by weight of divinylbenzene, and 475 parts by weight of tetramethylol methane triacrylate were mixed was added to Celum (registered trademark) superpolymer SM1313P (chain). Molecular weight: about 11,000, total molecular weight: 180,000 (representative value) 50 parts by weight were added. Next, 20 parts by weight of benzoyl peroxide was added and mixed uniformly at each addition stage to obtain a mixture.
- Celum registered trademark
- SM1313P chain
- This mixed solution was put in 8500 parts by weight of a 3% by weight aqueous polyvinyl alcohol solution, sufficiently stirred, and then emulsified with a homogenizer so that the emulsified diameter was about 3 to 10 ⁇ m.
- This emulsion was transferred to a 20 liter reaction kettle equipped with a thermometer, a stirrer and a reflux condenser, heated to 85 ° C. with stirring in a nitrogen atmosphere, and subjected to a polymerization reaction for 7 hours.
- the polymerization reaction was performed by heating for a period of time.
- the polymerization reaction liquid was cooled, and the generated particles were washed with water, methanol, and acetone in this order, followed by classification and drying at 55 ° C. overnight to obtain composite particles.
- An SiO 2 film was deposited on one surface of a pair of transparent glass plates (length 50 mm, width 50 mm, thickness 0.4 mm) by a CVD method, and then an ITO film was formed on the entire surface of the SiO 2 film by sputtering.
- a polyimide alignment film composition (SE3510, manufactured by Nissan Chemical Industries, Ltd.) was applied to the obtained glass substrate with an ITO film by spin coating, and baked at 280 ° C. for 90 minutes to form a polyimide alignment film. After the alignment film was rubbed, the spacer dispersion liquid for liquid crystal display device was wet-sprayed on the alignment film side of one substrate so that 100 spacers per 1 mm 2 .
- this substrate and the substrate on which the spacers were spread were placed opposite to each other so that the rubbing direction was 90 °, and both were bonded together. Then, it processed at 160 degreeC for 90 minute (s), the sealing agent was hardened, and the empty cell (screen which does not contain a liquid crystal) was obtained. An STN liquid crystal containing a chiral agent (manufactured by DIC) was injected into the resulting empty cell, and then the injection port was closed with a sealant, followed by heat treatment at 120 ° C. for 30 minutes to produce an STN liquid crystal display device. Obtained.
- Example 2 Composite particles and a liquid crystal display device were obtained in the same manner as in Example 1 except that the blending amount of CELUM (registered trademark) superpolymer SM1313P was changed from 50 parts by weight to 100 parts by weight.
- CELUM registered trademark
- Example 3 Composite particles and a liquid crystal display device were obtained in the same manner as in Example 1 except that the blending amount of CELUM (registered trademark) superpolymer SM1313P was changed from 50 parts by weight to 150 parts by weight.
- CELUM registered trademark
- Example 4 Composite particles and a liquid crystal display device were obtained in the same manner as in Example 1 except that 475 parts by weight of divinylbenzene and 475 parts by weight of tetramethylolmethane triacrylate were changed to 950 parts by weight of divinylbenzene.
- Example 5 Example 1 except that Celum® superpolymer SM1313P was changed to Celum® superpolymer SA1313P (chain compound molecular weight: about 11,000, total molecular weight: 190,000 (representative value)). Similarly, composite particles and a liquid crystal display device were obtained.
- Example 6 The same procedure as in Example 1 was conducted except that Celum (registered trademark) superpolymer SM1313P was changed to Celum (registered trademark) superpolymer SM2403P (chain compound molecular weight: about 20,000, total molecular weight: 600,000 (representative value)). Thus, composite particles and a liquid crystal display device were obtained.
- Example 1 Composite particles and a liquid crystal display device were obtained in the same manner as in Example 1 except that Celum (registered trademark) superpolymer SM1313P was not added.
- Celum registered trademark
- compression fracture strain The compression fracture strain was measured for the obtained composite particles. The compression fracture strain was measured as follows. The compression fracture strain was determined according to the following criteria.
- Compression fracture strain measurement method The composite particles were sprayed on the sample stage. Using one micro-compression tester (“Small Compression Tester MCT-W200” manufactured by Shimadzu Corp.), load (inverted load value) until the composite particle breaks in the direction of the center of the composite particle. ) was given. Thereafter, the displacement when the composite particles were broken was measured. The ratio of displacement when fractured with respect to the average particle diameter was defined as compression fracture strain. The load speed was 0.33 mN / sec.
- Compression fracture strain is 50% or more
- Compression fracture strain is 45% or more and less than 50%
- Compression fracture strain is less than 45%
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Abstract
Description
本発明に係る複合粒子は、顔料と鎖状化合物と環状化合物とを含有する。本発明に係る複合粒子では、上記鎖状化合物が、上記環状化合物の環の内側を貫通している。本発明に係る複合粒子は、上記鎖状化合物が、上記環状化合物の環の内側を貫通している構造を有する。本発明に係る複合粒子では、例えば、樹脂部を有する。本発明に係る複合粒子は、例えば、樹脂部に顔料が含まれており、樹脂粒子である。
ρ:複合粒子の粒子径の標準偏差
Dn:複合粒子の粒子径の平均値
液晶表示装置用スペーサの用途に好適に使用可能にする観点からは、上記顔料は、黒色顔料又は白色顔料であることが好ましく、黒色顔料であることが好ましい。上記顔料は、黒色顔料であってもよく、白色顔料であってもよい。
本発明に係る複合粒子は、上記鎖状化合物と上記環状化合物とを含有する。本発明に係る複合粒子では、上記鎖状化合物は、上記環状化合物の環の内側を貫通している。本発明に係る複合粒子では、上記の構成が備えられているので、複合粒子の破壊強度の低下を抑制することができる。
複合粒子の破壊強度の低下をより一層抑制する観点から、上記鎖状化合物が上記環状化合物の環の内側を貫通して、鎖状化合物と環状化合物とが、包接化合物を形成していることが好ましい。上記鎖状化合物の全てが上記環状化合物の環の内側を貫通していなくてもよい。上記鎖状化合物は上記環状化合物における全ての環の内側を貫通していなくてもよい。
破壊強度の低下をより一層抑える観点からは、上記環状化合物の環状骨格は、3個以上(環状に連なっている原子の数)の原子が連なった環状骨格であることが好ましく、5個以上の原子が連なった環状骨格であることがより好ましく、10個以上の原子が連なった環状骨格であることが更に好ましい。環状に連なっている原子の数は、1000個以下であってもよく、500個以下であってもよい。環状に連なっている原子の数は、環を構成している原子のうち、環を構成している原子の数が最小となるように数えた値である。環状骨格を構成する原子は、炭素原子、酸素原子、窒素原子又は硫黄原子であることが好ましく、炭素原子又は酸素原子であることが好ましい。
複合粒子の破壊強度の低下をより一層抑制する観点から、上記環状化合物に架橋剤が結合していることが好ましい。上記架橋剤は上記環状化合物における側鎖であってもよい。この架橋剤の存在は、複合粒子の破壊強度の低下の抑制に大きく寄与する。
本発明に係る液晶表示装置は、液晶表示装置用部材と、上述した複合粒子とを備える。また、上記複合粒子は、液晶表示装置用スペーサとして好適に用いられる。すなわち、上記複合粒子は、液晶セルを構成する一対の基板と、該一対の基板間に封入された液晶と、上記一対の基板間に配置された液晶表示装置用スペーサとを備える液晶表示装置を得るために好適に用いられる。上記液晶表示装置用スペーサは、周辺シール剤に含まれていてもよい。
上記複合粒子の用途は特に限定されない。上記複合粒子は、液晶表示装置用スペーサとしてだけではなく、様々な用途に好適に用いられる。上記複合粒子は、調光ガラス用スペーサとして用いられることが好ましく、調光フィルム用スペーサとして用いられることが好ましい。
(1)複合粒子の作製
表面被覆されたカーボンブラック5重量部、ジビニルベンゼン475重量部、及びテトラメチロールメタントリアクリレート475重量部が混合された分散液に、セルム(登録商標)スーパーポリマーSM1313P(鎖状化合物分子量:約1.1万、全体分子量:18万(代表値))50重量部を添加した。次に過酸化ベンゾイル20重量部を添加し、それぞれの添加段階で均一に混合し、混合液を得た。この混合液を3重量%のポリビニルアルコール水溶液8500重量部中に入れ、十分に撹拌した後、ホモジナイザーで乳化径が約3~10μmになるように乳化した。
STN型液晶表示装置の作製:
イソプロピルアルコール70重量部と水30重量部とを含む分散媒に、得られた複合粒子を、得られるスペーサ分散液100重量%中で固形分濃度が2重量%となるように添加し、撹拌し、液晶表示装置用スペーサ分散液を得た。
セルム(登録商標)スーパーポリマーSM1313Pの配合量を50重量部から100重量部に変更したこと以外は、実施例1と同様にして複合粒子及び液晶表示装置を得た。
セルム(登録商標)スーパーポリマーSM1313Pの配合量を50重量部から150重量部に変更したこと以外は、実施例1と同様にして複合粒子及び液晶表示装置を得た。
ジビニルベンゼン475重量部とテトラメチロールメタントリアクリレート475重量部とを、ジビニルベンゼン950重量部に変更したこと以外は、実施例1と同様にして複合粒子及び液晶表示装置を得た。
セルム(登録商標)スーパーポリマーSM1313Pをセルム(登録商標)スーパーポリマーSA1313P(鎖状化合物分子量:約1.1万、全体分子量:19万(代表値))に変更したこと以外は、実施例1と同様にして複合粒子及び液晶表示装置を得た。
セルム(登録商標)スーパーポリマーSM1313Pをセルム(登録商標)スーパーポリマーSM2403P(鎖状化合物分子量:約2万、全体分子量:60万(代表値))に変更したこと以外は、実施例1と同様にして複合粒子及び液晶表示装置を得た。
セルム(登録商標)スーパーポリマーSM1313Pを添加しなかったこと以外は、実施例1と同様にして複合粒子及び液晶表示装置を得た。
表面被覆されたカーボンブラックを添加しなかったこと以外は、実施例1と同様にして複合粒子及び液晶表示装置を得た。
(1)粒子径
得られた複合粒子について、粒度分布測定装置(ベックマンコールター社製「Multisizer4」)を用いて、約100000個の粒径を測定し、平均粒子径及び標準偏差を測定した。
得られた複合粒子について、上述した方法により、変動係数(CV値)を測定した。
得られた複合粒子について、圧縮破壊歪を測定した。上記圧縮破壊歪は、以下のようにして測定した。圧縮破壊歪を下記の基準で判定した。
試料台上に複合粒子を散布した。散布された複合粒子1個について、微小圧縮試験機(島津製作所社製「微小圧縮試験機MCT-W200」)を用いて、複合粒子の中心方向に、複合粒子が破壊するまで負荷(反転荷重値)を与えた。その後、複合粒子が破壊したときの変位を測定した。平均粒子径に対する破壊したときの変位の割合を圧縮破壊歪とした。なお、負荷速度は0.33mN/秒とした。
○:圧縮破壊歪が50%以上
△:圧縮破壊歪が45%以上、50%未満
×:圧縮破壊歪が45%未満
得られた液晶表示装置に所定の電圧を印加して、液晶表示装置用スペーサに起因する光抜け等の表示不良の有無を電子顕微鏡で観察し、表示品質を下記の基準で判定した。
○:液晶表示装置用スペーサに起因する基板の間隔(ギャップ)ムラや光抜け等の表示不良は全く認められず、優れた表示品質であった
△:液晶表示装置用スペーサに起因する基板の間隔(ギャップ)ムラや光抜け等の表示不良が若干認められた
×:液晶表示装置用スペーサに起因する基板の間隔(ギャップ)ムラや光抜け等の表示不良が著しく認められた
81…液晶表示装置
82…透明ガラス基板
83…透明電極
84…配向膜
85…液晶
86…シール剤
Claims (11)
- 顔料と、鎖状化合物と、環状化合物とを含有し、
前記鎖状化合物が、前記環状化合物の環の内側を貫通している、複合粒子。 - 前記鎖状化合物が前記環状化合物の環の内側を貫通している構造が、ロタキサンである、請求項1に記載の複合粒子。
- 前記環状化合物に架橋剤が結合している、請求項1又は2に記載の複合粒子。
- 前記環状化合物及び前記鎖状化合物の合計100重量%中、前記環状化合物における前記架橋剤を除く部分及び前記鎖状化合物の合計の含有量が1重量%以上、70重量%以下である、請求項3に記載の複合粒子。
- 前記環状化合物における前記架橋剤が、アクリル重合体又はスチレン重合体を含む、請求項3又は4に記載の複合粒子。
- 粒子径が2μm以上、15μm以下である、請求項1~5のいずれか1項に記載の複合粒子。
- 前記顔料が、黒色顔料又は白色顔料である、請求項1~6のいずれか1項に記載の複合粒子。
- 前記顔料が、カーボンブラック、チタンブラック、アニリンブラック又は酸化鉄を含む、請求項1~7のいずれか1項に記載の複合粒子。
- 前記鎖状化合物の重量平均分子量が3000以上、100000以下である、請求項1~8のいずれか1項に記載の複合粒子。
- 前記環状化合物における環状骨格が、10個以上の原子が連なった環状骨格である、請求項1~9のいずれか1項に記載の複合粒子。
- 液晶表示装置用部材と、
請求項1~10のいずれか1項に記載の複合粒子とを備える、液晶表示装置。
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CN201780012472.0A CN108699342B (zh) | 2016-07-13 | 2017-07-11 | 复合粒子和液晶显示装置 |
KR1020187021152A KR102457397B1 (ko) | 2016-07-13 | 2017-07-11 | 복합 입자 및 액정 표시 장치 |
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WO2022202825A1 (ja) * | 2021-03-25 | 2022-09-29 | デンカ株式会社 | 窒化ホウ素粉末及び樹脂組成物 |
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CN108699342B (zh) | 2022-11-01 |
KR20220147145A (ko) | 2022-11-02 |
KR102457397B1 (ko) | 2022-10-25 |
JP7372729B2 (ja) | 2023-11-01 |
KR102639948B1 (ko) | 2024-02-27 |
CN108699342A (zh) | 2018-10-23 |
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