Composite particles and liquid crystal display device

Abstract

Provided is a composite particle that sufficiently suppresses a decrease in the breaking strength even when the particle contains a pigment. The composite particle of the present invention contains a pigment, a chain compound, and a ring compound, and the chain compound penetrates the inside of the ring of the ring compound.

Description

[0001] This application is a divisional application of patent application No. 201780012472.0 with a filing date of July 11, 2017, which claims priority from a patent application with a filing date of July 13, 2016, and has the same title of "Composite Particle and Liquid Crystal Display Device". TECHNICAL FIELD

[0002] The present application relates to a composite particle containing a pigment. In addition, the present application relates to a liquid crystal display device using the composite particle. BACKGROUND

[0003] In a liquid crystal display device, a liquid crystal is disposed between two glass substrates. In this liquid crystal display device, in order to control the distance between the two glass substrates and maintain the appropriate thickness of the liquid crystal layer (cell gap), a spacer is used as a gap control material. A resin particle is generally used as this spacer.

[0004] In addition, in order to prevent light leakage from the spacer portion through which light is transmitted and prevent the display contrast of an image from decreasing, it is necessary to color the spacer dark.

[0005] As one example of a particle used as the spacer, a spacer for a liquid crystal display element containing carbon black whose surface is coated is disclosed in Patent Literature 1.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: WO97 / 30374 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] In the existing spacer described in Patent Literature 1, due to carbon black as a pigment, the particle is easily brittle, and sometimes the breaking strength of the particle decreases. In particular, in the case where the particle diameter of the particle is small, it is difficult to sufficiently improve the breaking strength of the particle.

[0011] An object of the present application is to provide a composite particle in which the decrease in breaking strength is sufficiently suppressed even when the particle contains a pigment. In addition, the present application also provides a liquid crystal display device using the composite particle.

[0012] MEANS OF SOLVING THE PROBLEMS

[0013] According to a broad aspect of the present application, there is provided a composite particle containing a pigment, a chain compound, and a ring compound, wherein the chain compound penetrates the inside of the ring of the ring compound.

[0014] In a particular aspect of the composite particle of the present application, the structure formed by the chain compound penetrating the inside of the ring of the ring compound is a rotaxane.

[0015] In a particular aspect of the composite particle of the present application, a crosslinking agent is bound to the ring compound.

[0016] In a particular aspect of the composite particle of the present application, the total content of the portion other than the crosslinking agent in the ring compound and the chain compound is 1% by weight or more and 70% by weight or less in 100% by weight of the total of the ring compound and the chain compound.

[0017] In a particular aspect of the composite particle of the present application, the crosslinking agent in the ring compound includes an acrylic polymer or a styrene-based polymer.

[0018] In a particular aspect of the composite particle of the present application, the particle diameter is 2 μm or more and 15 μm or less.

[0019] In a particular aspect of the composite particle of the present application, the pigment is a black pigment or a white pigment.

[0020] In a particular aspect of the composite particle of the present application, the pigment includes carbon black, titanium black, aniline black, or iron oxide.

[0021] In a particular aspect of the composite particle of the present application, the weight average molecular weight of the chain compound is 3000 or more and 100000 or less.

[0022] In a particular aspect of the composite particle of the present application, the ring skeleton in the ring compound is a ring skeleton formed by 10 or more atoms.

[0023] According to a broad aspect of the present application, there is provided a liquid crystal display device including a member for a liquid crystal display device and the composite particle described above.

[0024] Effects of the Invention

[0025] The composite particle of the present application contains a pigment, a chain compound, and a ring compound, and since the chain compound penetrates the inside of the ring of the ring compound, a decrease in the breaking strength is sufficiently suppressed even when the particle contains a pigment. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 is a cross-sectional view schematically showing a liquid crystal display device in which the composite particle of one embodiment of the present application is used as a spacer for a liquid crystal display device.

[0027] Explanation of Symbols

[0028] 11... composite particle

[0029] 81. Liquid crystal display device

[0030] 82. Transparent glass substrate

[0031] 83. Transparent electrode

[0032] 84. Alignment film

[0033] 85. Liquid crystal

[0034] 86. Sealing agent DETAILED DESCRIPTION

[0035] Hereinafter, the present application will be described in detail. Note that, in this specification, for example, "(meth)acrylate" means one or both of "acrylate" and "methacrylate", and "(meth)acrylic acid" means one or both of "acrylic acid" and "methacrylic acid".

[0036] (Composite particle)

[0037] The composite particle of the present application contains a pigment, a chain compound, and a ring compound. In the composite particle of the present application, the chain compound penetrates inside the ring of the ring compound. The composite particle of the present application has a structure in which the chain compound penetrates inside the ring of the ring compound. The composite particle of the present application has, for example, a resin portion. The composite particle of the present application is, for example, a resin particle in which the resin portion contains a pigment.

[0038] The composite particle of the present application has the above-described technical features, and thus can sufficiently suppress a decrease in the breaking strength even when the particle contains a pigment. In general, if a pigment is dispersed in a composite particle, the breaking of the composite particle easily occurs at the interface between the resin portion and the pigment, and the breaking strength of the composite particle decreases. In the case of the composite particle of the present application, since the chain compound and the ring compound are contained, the composite particle can be given higher toughness, and the breaking of the composite particle can be suppressed. As a result, a decrease in the breaking strength of the composite particle can be suppressed. Furthermore, in the present application, since the chain compound penetrates inside the ring of the ring compound, the composite particle can be further given higher toughness, and the breaking of the composite particle can be further suppressed. As a result, a decrease in the breaking strength of the composite particle can be further suppressed.

[0039] From the viewpoint of suppressing the breaking of the composite particle, the breaking strength (compressive breaking strain) of the composite particle is preferably 50% or more, more preferably 55% or more, and further preferably 60% or more.

[0040] The compressive breaking strain is measured by the following method.

[0041] The composite particles are dispersed on a sample stage. With respect to one of the dispersed composite particles, a load (a value of the load is reversed) is applied in the central direction of the composite particle using a micro compression tester until the composite particle is broken. Thereafter, the displacement at the time of breaking of the composite particle is measured. The ratio of the displacement at the time of breaking to the average particle diameter is taken as the compression breaking deformation. Note that the load speed is 0.33 mN / second. As the micro compression tester, for example, "Micro Compression Tester MCT-W200" manufactured by Shimadzu Corporation, "Fischer scope H-100" manufactured by Fischer Corporation, or the like can be used.

[0042] The composite particle preferably contains a base particle body, and preferably contains a pigment, a chain compound, and a ring compound in the base particle body. The base particle body is preferably a resin particle body.

[0043] As the material of the composite particle and the material of the base particle body, various organic substances can be appropriately used. As the material of the composite particle and the material of the base particle body, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, polybutadiene, and the like polyolefin resins; polymethyl methacrylate, and polyacrylic acid esters, and the like acrylic resins; polycarbonates, polyamides, phenol-formaldehyde resins, melamine formaldehyde resins, benzoguanamine formaldehyde resins, urea-formaldehyde resins, phenol resins, melamine resins, benzoguanamine resins, urea resins, epoxy resins, unsaturated polyester resins, saturated polyester resins, polyethylene terephthalate, polysulfones, polyphenylene ether, polyacetals, polyimides, polyamide-imides, polyether ether ketone, polyether sulfone, divinylbenzene polymers, and divinylbenzene copolymers, and the like can be listed. As the divinylbenzene copolymers and the like, divinylbenzene-styrene copolymers and divinylbenzene-(meth)acrylic acid ester copolymers can be listed. 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 are preferably polymers obtained by polymerizing one or two or more kinds of polymerizable monomers having an ethylenic unsaturated group.

[0044] In the case where the composite particle and the base particle body are obtained by polymerizing a polymerizable monomer having an ethylenic unsaturated group, as the polymerizable monomer having an ethylenic unsaturated group, non-crosslinkable monomers and crosslinkable monomers can be listed.

[0045] As the non-crosslinkable monomer, for example, styrene monomers such as styrene, α-methylstyrene, chlorostyrene, and the like; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, and the like; acid vinyl ester compounds such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, and the like; halogen-containing monomers such as vinyl chloride, vinyl fluoride, and the like; (meth)acrylic acid alkyl ester compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and the like; (meth)acrylic acid ester compounds containing an oxygen atom such as 2-hydroxyethyl (meth)acrylate, glyceryl (meth)acrylate, polyoxyethylene (meth)acrylate, glycidyl (meth)acrylate, and the like; nitrile-containing monomers such as (meth)acrylonitrile; halogen-containing (meth)acrylic acid ester compounds such as trifluoromethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, and the like; olefin compounds such as diisobutylene, isobutylene, linseed oil, ethylene, propylene, and the like as α-olefin compounds; conjugated diene compounds such as isoprene, butadiene, and the like can be exemplified.

[0046] As the crosslinkable monomer, mention can be made of: as a vinyl compound, divinylbenzene, 1,4-divinyleneoxybutane, divinylsulfone, and the like vinyl monomers; as a (meth)acrylic compound, tetramethylolmethane tetra(meth)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, polytetramethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and the like multifunctional (meth)acrylate compounds; as an allyl compound, triallyl (iso)cyanurate, triallyl trimellitate, diallyl phthalate, diallyl acrylamide, diallyl ether; as a silane compound, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, trimethoxysilylstyrene, γ-(meth)acryloyloxypropyltrimethoxysilane, 1,3-divinyltetramethyldisiloxane, methylphenyldimethoxysilane, diphenyldimethoxysilane, and the like alkoxysilane compounds; vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, diethoxymethylvinylsilane, diethoxyethylvinylsilane, ethylmethyldivinylsilane, methylvinyl dimethoxysilane, ethylvinyl dimethoxysilane, methylvinyl diethoxysilane, ethylvinyl diethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and the like alkoxysilanes containing a polymerizable double bond; decamethylcyclopentasiloxane and the like cyclic siloxanes; mono-end-modified silicone oil, di-end-modified silicone oil, side-chain type silicone oil, and the like modified (reactive) silicone oils; (meth)acrylic acid, maleic acid, maleic anhydride, and the like carboxyl-containing monomers, and the like.

[0047] The composite particles and the base particle body can be obtained by uniformly mixing, dispersing, and polymerizing the polymerizable monomer having an ethylenic unsaturated group with the pigment, the chain compound, and the cyclic compound. The polymerization method is not particularly limited, and known methods such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, polycondensation), addition polymerization, living polymerization, and living radical polymerization can be used for polymerization. As the method, for example, a suspension polymerization method performed in the presence of a radical polymerization initiator; a seed polymerization method in which a radical polymerization initiator is allowed to swell together with a monomer using a non-crosslinked seed particle; and a dispersion polymerization method can be given.

[0048] In order to uniformly mix and disperse the pigment in the polymerizable monomer having an ethylenic unsaturated group, a ball mill, a bead mill, a sand mill, a mortar, a sand mill, and a nanomizer, or the like can be used. In this case, in order to improve the dispersibility of the pigment, a dispersant or the like can be added.

[0049] The dispersant is not particularly limited. As the dispersant, water-soluble polymers such as polyvinyl alcohol, starch, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and poly(sodium (meth)acrylate); barium sulfate, calcium sulfate, aluminum sulfate, calcium carbonate, calcium phosphate, talc, clay, and metal oxide powder can be given.

[0050] From the viewpoint of practicality and the viewpoint of being applicable to a spacer for a liquid crystal display device, the particle diameter of the composite particle is preferably 2 μm or more, more preferably 3 μm or more, and is preferably 15 μm or less, more preferably 5 μm or less.

[0051] In terms of the particle diameter of the composite particle, in the case where the composite particle is spherical, the diameter is meant, and in the case where the composite particle is in a shape other than spherical, the diameter of an assumed sphere having the same volume as the composite particle is meant.

[0052] Further, in the case where a plurality of composite particles are present, the particle diameter of the composite particle means the average particle diameter measured by an arbitrary particle diameter measuring device. For example, a particle size distribution measuring machine using the principles of laser scattering, resistance value change, image analysis after imaging, or the like can be used. Specifically, in the case where a plurality of composite particles are present, as a method of measuring the particle diameter of the composite particle, a method of measuring the particle diameter of about 100000 particles and measuring the average particle diameter using a particle size distribution measuring device ("Multisizer 4" manufactured by Beckman Coulter) can be given. The average particle diameter indicates the number average particle diameter.

[0053] The aspect ratio of the composite particles is preferably 1.10 or less, more preferably 1.05 or less. The aspect ratio indicates the length of the long axis / short axis. In the case of a plurality of composite particles, the aspect ratio is preferably obtained by observing any 10 composite particles under an electron microscope or an optical microscope, taking the maximum diameter and the minimum diameter as the long axis and the short axis, and calculating the average of the long axis / short axis of each of the composite particles.

[0054] From the viewpoint of practicality and the viewpoint of applicability to spacers for liquid crystal display devices, when the composite particles are a plurality of particles, the coefficient of variation of the particle diameters of the composite particles is preferably 7% or less, more preferably 5% or less.

[0055] The coefficient of variation (CV value) can be determined in the following manner.

[0056] CV value (%) = (p / Dn) x 100

[0057] p: standard deviation of the particle diameters of the composite particles

[0058] Dn: average of the particle diameters of the composite particles

[0059] The shape of the composite particles is not particularly limited. The shape of the composite particles can be spherical, or a shape other than spherical such as a flat shape.

[0060] From the viewpoint of further preventing the elution and diffusion of impurities, the composite particles are preferably particles coated with a coating agent such as a silane coupling agent. The coating film formed based on the coating agent is preferably a monomolecular film or a polymer film. The composite particles can not have a coating film.

[0061] The silane coupling agent is not particularly limited. As the silane coupling agent, for example, amino-type silane coupling agents such as γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, 3-[N-allyl-N-(2-aminoethyl)]aminopropyltrimethoxysilane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-(N-allyl-N-methacryloyl)aminopropyltrimethoxysilane, and 3-(N,N-diglycidyl)aminopropyltrimethoxysilane; amide-type silane coupling agents such as N,N-bis[3-(methyldimethoxysilyl)propyl]amine, N,N-bis[3-(trimethoxysilyl)propyl]amine, N,N-bis[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and N-glycidyl-N,N-bis[3-(trimethoxysilyl)propyl]amine; vinyl-type silane coupling agents such as vinyltriethoxysilane and vinyltris(2-methoxyethoxy)silane; methacrylic acid-type silane coupling agents such as γ-methacryloyloxypropyltrimethoxysilane; glycidyl-type silane coupling agents such as γ-glycidoxypropyltrimethoxysilane; mercapto-type silane coupling agents such as γ-mercaptopropyltrimethoxysilane; and the like can be exemplified.

[0062] The method for coating the composite particles with the coating agent is not particularly limited. As the method for coating the composite particles with the coating agent, a method in which the particles and the coating agent are mixed in an inorganic solvent such as water or an organic solvent such as ethanol, heated with stirring, and then the composite particles are separated by decantation or the like and the solvent is removed by drying under reduced pressure or the like can be exemplified. A method in which the particles and the coating agent are directly mixed and heated can also be exemplified.

[0063] (Pigment)

[0064] From the viewpoint of suitability as a spacer for a liquid crystal display device, the pigment is preferably a black pigment or a white pigment, and is preferably a black pigment. The pigment can be a black pigment or a white pigment.

[0065] As the black pigment, carbon black, lamp black, graphite, iron oxide, a composite oxide of copper-chromium, a composite oxide of copper-chromium-zinc, and the like can be exemplified. The black pigment can be used singly or in combination of two or more.

[0066] As the white pigment, titanium dioxide, calcium carbonate, zinc oxide, barium sulfate, and the like can be exemplified. The white pigment can be used singly or in combination of two or more.

[0067] The pigment preferably contains carbon black, titanium black, aniline black, or iron oxide. The pigment can be used singly or in combination of two or more.

[0068] As the carbon black, there are no particular limitations, and examples include channel black, roll black, furnace black, thermal cracking carbon black, ketjen black, and acetylene black. The carbon black can be used alone or in combination with two or more kinds.

[0069] From the viewpoint of further preventing the elution and diffusion of impurities, the pigment is preferably a pigment whose surface is coated. By using a pigment whose surface is coated, even if the mixed amount of the pigment increases, the decrease in the properties such as the resistance of the composite particle can be prevented. Furthermore, since the surface is coated, the dispersibility of the pigment is improved, and the composite particle can be colored with a smaller mixed amount. As the material that coats the surface of the pigment, a thermoplastic resin or the like can be given.

[0070] The thermoplastic resin is not particularly limited. As the thermoplastic resin, for example, alkyd resin, modified alkyd resin, phenolic resin, natural resin-modified phenolic resin, maleic acid resin, natural resin-modified maleic acid 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 copolymer, and polyurethane resin, or the like can be given. The thermoplastic resin can be used alone or in combination with two or more kinds.

[0071] As the method of coating the surface of the pigment with the thermoplastic resin, there are no particular limitations, and examples include a method in which the pigment is pulverized using a pulverizer such as a ball mill in a hydrophobic solvent containing the thermoplastic resin, a method in which a water dispersion of the pigment is added and mixed into a hydrophobic solvent containing the thermoplastic resin to emulsify it, and the water is distilled off by heating, or the like.

[0072] From the viewpoint of further inhibiting the decrease in the breaking strength of the composite particle, the content of the pigment in 100% by mass of the composite particle is preferably 3% by mass or more, more preferably 5% by mass or more, and is preferably 10% by mass or less, more preferably 8% by mass or less.

[0073] (Chain compound)

[0074] The composite particle of the present application contains the chain compound and the cyclic compound. In the composite particle of the present application, the chain compound penetrates the inside of the ring of the cyclic compound. In the composite particle of the present application, since it has the above-described configuration, the decrease in the breaking strength of the composite particle can be inhibited.

[0075] From the viewpoint of further inhibiting the decrease in the destruction strength of the composite particle, it is preferable that the chain compound penetrate the inside of the ring of the ring compound, and the chain compound and the ring compound form an inclusion compound. The chain compound does not necessarily penetrate the inside of the ring of the ring compound entirely. The chain compound does not necessarily penetrate the inside of the ring of the ring compound entirely.

[0076] In the structure formed by the chain compound penetrating the inside of the ring of the ring compound in the manner described above, there is, for example, a structure called "rotaxane". The structure in which the chain compound penetrates the inside of the ring of the ring compound is preferably a rotaxane. The rotaxane is a structure formed by the chain compound penetrating the inside of the ring of the ring compound and the ring compound not being detached from the chain compound. On the other hand, unlike the rotaxane, a structure formed by the chain compound penetrating the inside of the ring of the ring compound and the ring compound being able to be detached from the chain compound is called a "pseudo-rotaxane". The rotaxane can also be a polyrotaxane. The polyrotaxane is a rotaxane formed by the chain compound penetrating the inside of the ring of a plurality of ring compounds, and is also a structure formed by a plurality of component molecules. From the viewpoint of further inhibiting the decrease in the destruction strength of the composite particle, the structure formed by the chain compound and the ring compound is preferably a polyrotaxane.

[0077] As the material of the chain compound and the cyclic compound, there is no particular limitation, and various polymers can be used, for example. As the material of the chain compound and the cyclic compound, there can be mentioned, for example: a cellulose resin such as polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, poly(meth)acrylic acid, poly(meth)acrylamide, hydroxyethyl cellulose, and the like; a polyvinyl acetal resin; polyvinyl methyl ether; a polysiloxane compound such as polyamine, polyethyleneimine, casein, gelatin, polysiloxane, and the like; starch and the like or a copolymer containing starch and the like; a polyolefin resin such as polyethylene, polypropylene, and a copolymer of other olefin monomers; a polyester resin; a polyvinyl chloride resin; a polystyrene resin such as polystyrene and acrylonitrile-styrene copolymer; an acrylic resin such as polymethyl (meth)acrylate, (meth)acrylate copolymer, acrylonitrile-methyl acrylate copolymer, and the like; a polycarbonate resin; a polyurethane resin; a vinyl chloride-vinyl acetate copolymer; a polyvinyl butyral resin; polyisobutylene; polytetrahydrofuran; polyaniline; a polyacrylonitrile-diene-styrene copolymer; a polyamide compound such as nylon; a polyimide compound; a polydiene compound such as polyisoprene and polybutadiene; a polysulfone compound; a polyimine compound; a polyacetic anhydride compound; a polyurea compound; a polysulfur compound; a polyphosphazene compound; a polyketone compound; a polyphenylene compound; and a polyhaloolefin compound, and the like. In addition, the material of the chain compound and the cyclic compound can be a derivative or a modified body of the above various polymers. The material of the chain compound can be used singly or in combination of two or more.

[0078] The chain compound is preferably a polymer.

[0079] The chain compound can be a homopolymer composed of one repeating structural unit, or a copolymer composed of two or more repeating structural units. When the chain compound is a copolymer, it can be any of a random copolymer, a block copolymer, and an alternating copolymer.

[0080] From the viewpoint of further inhibiting the decrease in the destruction strength of the composite particles, the chain compound preferably has a molecular structure that prevents the cyclic compound from falling off. From the viewpoint of further inhibiting the decrease in the destruction strength of the composite particles, it is preferable that the chain compound penetrate the inside of the ring of the cyclic compound, and the cyclic compound does not fall off from the chain compound. Hereinafter, the molecular structure that prevents the cyclic compound from falling off is referred to as a stop group.

[0081] As the stop group, mention can be made of aryl groups such as a dinitrophenyl group, a trityl group, a pyrenyl group, a phenyl group, an adamantyl group, a 2-butyldecyl group, a fluorescein compound, a pyrene compound, a cyclodextrin compound, an N-benzyloxycarbonyl-L-tyrosine compound (Z-L-tyrosine compound), and derivatives or modifications thereof. In addition, as other stop groups, mention can be made of, for example, functional groups known at present for preventing the detachment of a cyclic compound from a wheel-like compound, and the like.

[0082] From the viewpoint of further inhibiting the decrease in the breaking strength of the composite particles, the chain compound preferably has the stop group at both terminals. If the chain compound has the stop group at both terminals, the cyclic compound can be maintained in a state of being threaded in a string by the chain compound. The chain portion of the chain compound of the cyclic compound can move freely. Based on the stop groups at both terminals, the cyclic compound does not detach from the chain compound. As a result, the composite particles can be given higher toughness, and the decrease in the breaking strength of the composite particles can be further inhibited.

[0083] Note that the stop group can be directly bonded to the chain skeleton of the chain compound, or can be indirectly bonded to the chain skeleton of the chain compound through an amide bond, an ester bond, or the like.

[0084] The composite particles can contain a chain compound having the stop group, can contain a chain compound not having the stop group, and can contain both a chain compound having the stop group and a chain compound not having the stop group. From the viewpoint of further inhibiting the decrease in the breaking strength of the composite particles, the composite particles preferably contain a chain compound having the stop group.

[0085] When the chain compound does not have the stop group, although a part of the cyclic compound sometimes detaches from the chain compound, the detached cyclic compound can continue to exist in the composite particles.

[0086] When the composite particle contains a rotaxan, as the chain compound and the material of the chain compound, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinyl methyl ether, etc. can be exemplified. When the composite particle contains a rotaxan, the chain compound and the material of the chain compound preferably contain the above-mentioned compounds. These compounds can be used singly or in combination of two or more. In this case, the chain compound easily penetrates the inside of the ring of the ring compound (the inside of the ring), and a stable rotaxan is easily formed. Note that the chain compound can have a branch capable of penetrating the inside of the ring of the ring compound.

[0087] In the case where the chain compound constituting the rotaxan has a stop group, since the ring compound does not fall off, the stress relaxation effect can be maintained for a long time, and the decrease in the breaking strength of the composite particle can be further inhibited. In addition, even in the case where the chain compound does not have a stop group, the stress relaxation effect can be exerted.

[0088] The weight average molecular weight of the chain compound is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, and further preferably 10000 or more, and is preferably 100000 or less, and more preferably 50000 or less. The weight average molecular weight of the chain compound is particularly preferably 10000 or more and 50000 or less. When the weight average molecular weight of the chain compound is the above lower limit or more, the decrease in the breaking strength of the composite particle can be further inhibited. When the weight average molecular weight of the chain compound is the above upper limit or less, the compatibility of the matrix particle main body and the ring compound can be further improved.

[0089] (Ring compound)

[0090] From the viewpoint of further inhibiting the decrease in the breaking strength, the ring skeleton of the ring compound is preferably a ring skeleton formed by 3 or more atoms (the number of atoms connected in the ring) being connected, more preferably a ring skeleton formed by 5 or more atoms being connected, and further preferably a ring skeleton formed by 10 or more atoms being connected. The number of atoms connected in the ring can be 1000 or less, or 500 or less. The number of atoms connected in the ring is a value counted in such a manner that the number of atoms constituting the ring is minimized. The atoms constituting the ring skeleton are preferably carbon atoms, oxygen atoms, nitrogen atoms, or sulfur atoms, and are preferably carbon atoms or oxygen atoms.

[0091] From the viewpoint of further inhibiting the decrease in the breaking strength, the ring compound is preferably a cyclic sugar compound.

[0092] As the cyclic compound and the material of the cyclic compound, for example, a-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, dimethyl cyclodextrin, glucosyl cyclodextrin, and the like can be exemplified. As the cyclic monomer, crown ether, cyclacene, calixarene, cucurbituril, pillararene, cyclic amide, and the like can be exemplified. As the cyclic oligomer, oligomers of ethylene glycol, oligomers of oxirane, oligomers of propylene glycol, polysaccharides, and the like can be exemplified. As the cyclic macromonomer, the above-mentioned cyclic monomers and the like can be exemplified. The cyclic compound and the material of the cyclic compound can be used alone or in combination of two or more.

[0093] From the viewpoint of further inhibiting the decrease in the destruction strength of the composite particles, the material of the cyclic compound contained in the composite particles (the material of the cyclic compound in the composite particles) preferably contains 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 a crosslinking agent, for example.

[0094] As the polymerizable functional group, an alkenyl group, a vinyl group, a hydroxyl group, a mercapto group, an amino group, a carboxyl group, a sulfo group, a phosphoric acid group, and the like can be exemplified. The polymerizable functional group can further contain one or more substituents. From the viewpoint of more efficiently polymerizing the material of the base particle body and the crosslinking agent, the polymerizable functional group is preferably a radical polymerizable functional group, and is preferably an alkenyl group, a vinyl group, and the like, for example.

[0095] As one example of the cyclic compound containing a polymerizable functional group, a cyclic macromonomer represented by the following formula (1), for example, can be exemplified.

[0096] [Chemical Formula 1]

[0097]

[0098] In the above formula, R1and R2are each a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R3is a hydrogen atom or a methyl group. In addition, M is a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units of the structure in the parentheses, and is an integer of 5 to 100. In addition, the n+1 M's can be the same or different.

[0099] As another example of the cyclic compound containing a polymerizable functional group, a cyclic macromonomer represented by the following formula (2) can be exemplified.

[0100] [Chemical Formula 2]

[0101] As another example of the cyclic compound containing a polymerizable functional group, a cyclic macromonomer represented by the following formula (2) can be exemplified.

[0102] In the above formula, M is a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, n represents the number of repeating units of the structure within the parentheses, and is an integer of 5 to 100. Further, the n + 1 M's can be the same or different.

[0103] The cyclic compound preferably contains an α-cyclodextrin structure, a β-cyclodextrin structure, or a γ-cyclodextrin structure. These structures can be one alone or two or more.

[0104] When the complex particle contains a rotaxane, if the chain compound is threaded through the cyclic compound, the amount of the chain compound maximally included in the cyclic compound (the maximum inclusion amount) is set to 1, the inclusion amount of the cyclic compound is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 0.05 or more. When the complex particle contains a rotaxane, if the chain compound is threaded through the cyclic compound, the amount of the chain compound maximally included in the cyclic compound (the maximum inclusion amount) is set to 1, the inclusion amount of the cyclic compound is preferably 0.6 or less, more preferably 0.5 or less, and further preferably 0.4 or less. Note that the inclusion amount of the cyclic compound can be determined by a well-known method. When the inclusion amount of the cyclic compound is above the lower limit and below the upper limit, the decrease in the breaking strength of the complex particle can be further suppressed.

[0105] From the viewpoint of further suppressing the decrease in the breaking strength of the complex particle, it is preferable to adjust the maximum inclusion amount of the cyclic compound as described above.

[0106] Crosslinking agent bound to the cyclic compound:

[0107] From the viewpoint of further suppressing the decrease in the breaking strength of the complex particle, it is preferable that a crosslinking agent is bound to the cyclic compound. The crosslinking agent can be a side chain on the cyclic compound. The presence of this crosslinking agent greatly contributes to the suppression of the decrease in the breaking strength of the complex particle.

[0108] As the cross-linking agent, for example, polyethylene, polypropylene, polystyrene, silicone resin, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, polybutadiene, and the like polyolefin resins; polymethyl methacrylate and polyacrylate, and the like acrylic resins; polyethylene terephthalate, polycarbonate, polyamide, phenol-formaldehyde resin, melamine-formaldehyde resin, benzoguanamine-formaldehyde resin, urea-formaldehyde resin, phenol-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene ether, polyacetal, polyimide, polyamide-imide, polyether ether ketone, polyether sulfone, and a polymer obtained by polymerizing one or two or more kinds of various polymerizable monomers having an ethylenic unsaturated group, and the like can be exemplified. The cross-linking agent can be used alone or in combination with two or more kinds.

[0109] From the viewpoint of further inhibiting the decrease in the destruction strength of the composite particles, the cross-linking agent in the cyclic compound preferably contains an acrylic polymer or a styrene-based polymer, and more preferably contains an acrylic polymer.

[0110] The cross-linking agent in the cyclic compound can be a monomer, can be an oligomer, or can be a polymer. From the viewpoint of further inhibiting the decrease in the destruction strength of the composite particles, the cross-linking agent in the cyclic compound is preferably a polymer. The polymer can be a homopolymer formed of one kind of repeating structural unit, or a copolymer formed of two or more kinds of repeating structural units. When the polymer is a copolymer, it can be any structure of a random copolymer, a block copolymer, an alternating copolymer, or the like.

[0111] From the viewpoint of easily controlling the hardness of the composite particles within a preferable range, the cross-linking agent in the cyclic compound is preferably a polymer of a polymerizable monomer having an ethylenic unsaturated group. The cross-linking agent in the cyclic compound can be a polymer of one kind of polymerizable monomer alone, or a polymer of two or more kinds of polymerizable monomers.

[0112] When the cross-linking agent in the cyclic compound is a polymer of a monomer having an ethylenic unsaturated group, as the monomer having an ethylenic unsaturated group, a non-cross-linking monomer and a cross-linking monomer can be exemplified.

[0113] As the non-cross-linking monomer, the non-cross-linking monomer described above can be exemplified. As the cross-linking monomer, the cross-linking monomer described above can be exemplified.

[0114] The polymerizable monomer having an ethylenically unsaturated group can be polymerized by a well-known method to obtain the crosslinking agent. As the method, for example, a method of performing suspension polymerization in the presence of a radical polymerization initiator; and a method of swelling a monomer with a non-crosslinking seed particle together with a radical polymerization initiator to perform polymerization, and the like can be exemplified.

[0115] As a specific form of the structure of the cyclic compound having a crosslinking agent, for example, a structure in which the crosslinking agent is bound to the cyclic portion of the cyclic compound in the rotaxane described above can be exemplified. The terminal of one end of the crosslinking agent is bound to the cyclic portion of one cyclic compound, and the terminal of the other end of the crosslinking agent can be bound to the cyclic portion of another cyclic compound. The cyclic portion of the cyclic compound and the crosslinking agent in the rotaxane can form a three-dimensional network structure.

[0116] As for the structure in which the cyclic portion of the cyclic compound in the rotaxane is bound to the crosslinking agent, the cyclic portion of the cyclic compound is the starting point (point of binding) of the binding of the crosslinking agent. In the rotaxane, the cyclic compound can move freely in the chain portion of the chain compound. Therefore, the point of binding in the cyclic compound can move in the chain portion of the chain compound. The cyclic compound having a crosslinking agent is a material that can move in the chain portion of the chain compound. As described above, the cyclic compound having a crosslinking agent has flexibility because the point of binding moves with stress, and has more excellent stretchability and recovery because stress is easily alleviated.

[0117] As for the cyclic compound, when having a structure in which the crosslinking agent is bound to the cyclic portion of the cyclic compound in the rotaxane, particularly excellent stress alleviating properties are obtained, and further suppression of the decrease in the breaking strength of the composite particle can be performed. In addition, when the composite particle contains a pigment, the breaking strength of the composite particle decreases as the particle diameter of the composite particle becomes smaller. However, as for the cyclic compound, when having a structure in which the crosslinking agent is bound to the cyclic portion of the cyclic compound in the rotaxane, even if the particle diameter of the composite particle becomes smaller, the decrease in the breaking strength of the composite particle can be further suppressed.

[0118] The method for producing the cyclic compound having a crosslinking agent is not particularly limited. For example, by reacting a rotaxane having a cyclic compound containing a polymerizable functional group with a mixture of polymerizable monomers used for forming a crosslinking agent, a polymer having a crosslinking agent on the cyclic moiety of the cyclic compound can be produced. In addition, if the polymerizable functional group is a functional group (vinyl group or the like) capable of undergoing radical polymerization with the polymerizable monomers, by causing the rotaxane to undergo radical polymerization with the polymerizable monomers, a polymer having a crosslinking agent on the cyclic moiety of the cyclic compound can be produced. This radical polymerization can be performed by a well-known method.

[0119] The kind of the rotaxane having a cyclic compound containing a polymerizable functional group is not particularly limited. As the rotaxane having a cyclic compound containing a polymerizable functional group, for example, "CELM (registered trademark) Super Polymer SM3403P", "CELM (registered trademark) Super Polymer SM1313P", "CELM (registered trademark) Super Polymer SA3403P", "CELM (registered trademark) Super Polymer SA2403P", "CELM (registered trademark) Super Polymer SA1313P", "CELM (registered trademark) Super Polymer SM3405P", "CELM (registered trademark) Key-Mixture SM3400C", "CELM (registered trademark) Super Polymer SA3405P", "CELM (registered trademark) Super Polymer SA2405P", "CELM (registered trademark) Key-Mixture SA3400C", "CELM (registered trademark) Key-Mixture SA2400C", "CELM (registered trademark) Super Polymer SA3405P", and "CELM (registered trademark) Super Polymer SA2405P" and the like sold by Advanced Soft Materials Co., Ltd. can be listed. Note that the polyrotaxane can be produced using a well-known production method.

[0120] From the viewpoint of further inhibiting the decrease in the destruction strength of the composite particles, the combined content of the portion other than the crosslinking agent in the cyclic compound and the chain compound is preferably 1% by mass or more, more preferably 3% by mass or more, and is preferably 70% by mass or less, more preferably 20% by mass or less, in 100% by mass of the total of the cyclic compound and the chain compound.

[0121] As a method for producing the composite particle having the structure in which the crosslinking agent is bound to the cyclic portion of the cyclic compound in the rotaxane, a method in which the rotaxane and a polymerizable monomer for forming the crosslinking agent are subjected to suspension polymerization in the presence of a polymerization initiator, and the like can be given. When the rotaxane has a cyclic compound containing a functional group capable of radical polymerization, the composite particle having the structure in which the crosslinking agent is bound to the cyclic portion of the cyclic compound in the rotaxane can be obtained by subjecting the rotaxane and a polymerizable monomer for forming the crosslinking agent to suspension polymerization in the presence of a polymerization initiator.

[0122] The kind of the polymerization initiator is not particularly limited, and a compound generally used for suspension polymerization, emulsion polymerization, dispersion polymerization, and the like can be used. Furthermore, a dispersion stabilizer or the like can be used as necessary at the time of polymerization. The kind of the dispersion stabilizer is not particularly limited, and a well-known dispersion stabilizer or the like can be used. The polymerization conditions are not particularly limited, and polymerization can be performed under a currently known suitable condition, for example.

[0123] (Liquid crystal display device and other uses)

[0124] The liquid crystal display device of the present application has a component for a liquid crystal display device and the composite particle. In addition, the composite particle is suitable for use as a spacer for a liquid crystal display device. That is, the composite particle is preferably used for obtaining a liquid crystal display device having a pair of substrates constituting a liquid crystal cell, a liquid crystal enclosed between the pair of substrates, and a spacer for a liquid crystal display device disposed between the liquid crystal of the pair of substrates. The spacer for a liquid crystal display device can be contained in an outer periphery sealant.

[0125] Figure 1 is a cross-sectional view schematically showing a liquid crystal display device using the composite particle as a spacer for a liquid crystal display device in one embodiment of the present application.

[0126] Figure 1 The liquid crystal display device 81 shown has a pair of transparent glass substrates 82. The transparent glass substrates 82 have an insulating film (not shown) on the opposing surfaces. As a material for the insulating film, SiO2or the like can be given, for example. A transparent electrode 83 is formed on the insulating film of the transparent glass substrate 82. As a material for the transparent electrode 83, ITO or the like can be given. The transparent electrode 83 can be pattern-formed by a photolithography method, for example. An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. As a material for the alignment film 84, polyimide or the like can be given.

[0127] Liquid crystal 85 is sealed between a pair of transparent glass substrates 82. A plurality of composite particles 11 are disposed between the pair of transparent glass substrates 82. The composite particles 11 are the aforementioned composite granules. The composite particles 11 can be used as spacers for a liquid crystal display device. The plurality of composite particles 11 restrict the spacing between the pair of transparent glass substrates 82. A sealant 86 is disposed between the edges of the pair of transparent glass substrates 82. The sealant 86 prevents the liquid crystal 85 from flowing out.

[0128] In the liquid crystal display device, corresponding to 1mm 2 The preferred density of spacers for a liquid crystal display device is 10 per mm. 2 The above, and preferably 1000 pieces / mm 2 The following applies when the configuration density is 10 units / mm. 2 At the above levels, the battery spacing becomes more uniform. When the configuration density is 1000 cells / mm², the spacing becomes more uniform. 2 In the following cases, the contrast of the liquid crystal display device becomes better.

[0129] (use)

[0130] The application of the composite particles is not particularly limited. The composite particles are suitable not only as spacers for liquid crystal display devices but also for various other applications. Specifically, the composite particles are preferably used as spacers for dimming glass, and even more preferably as spacers for dimming films.

[0131] Furthermore, the composite particles can also be used as inorganic fillers, additives to colorants, shock absorbers, or vibration absorbers. For example, the composite particles can be used as substitutes for rubber or springs.

[0132] Hereinafter, embodiments and comparative examples are given, and the present invention is described in detail. The present invention is not limited to the following embodiments.

[0133] (Example 1)

[0134] (1) Fabrication of composite particles

[0135] To a dispersion containing 5 parts by weight of surface-coated carbon black, 475 parts by weight of divinylbenzene, and 475 parts by weight of tetramethylolmethane triacrylate, 50 parts by weight of CELM (registered trademark) SuperPolymer SM1313P (chain compound molecular weight: approximately 11,000, total molecular weight: 180,000 (representative value)) was added. Then, 20 parts by weight of benzoyl peroxide were added, and the mixture was homogenized at each addition stage to obtain a mixture. This mixture was added to 8500 parts by weight of a 3% by weight aqueous solution of polyvinyl alcohol, thoroughly stirred, and then emulsified using a homogenizer to achieve an emulsion diameter of approximately 3–10 μm.

[0136] The emulsion was transferred to a 20 liter reaction vessel equipped with a thermometer, a stirrer, and a reflux cooler, and stirring was performed under a nitrogen atmosphere, and heating was performed to 85°C and a polymerization reaction was performed for 7 hours, and then, heating was performed at 90°C for 3 hours to perform a polymerization reaction.

[0137] Then, the polymerization reaction liquid was cooled, and the resulting particles were washed with water, methanol, and acetone in this order, and then, fractionation was performed and drying was performed at 55°C for one night to obtain composite particles.

[0138] (2) Production of liquid crystal display device

[0139] Production of STN type liquid crystal display device:

[0140] The resulting composite particles were added to a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, and the solid content concentration was made to be 2% by weight in 100% by weight of the resulting spacer dispersion liquid, and stirring was performed to obtain a spacer dispersion liquid for a liquid crystal display device.

[0141] On one surface of a pair of transparent glass plates (length 50 mm, width 50 mm, thickness 0.4 mm), a SiO2 film was vapor-deposited by a CVD method, and then, an ITO film was formed on the entire surface of the silica film by sputtering. On the resulting glass substrate with the ITO film, a polyimide alignment film composition (manufactured by Nissan Chemical Industries, Ltd., SE3510) was applied by a spin coating method, and an alignment film was formed by performing baking at 280°C for 90 minutes. The alignment film was subjected to polishing treatment, and then, the spacer dispersion liquid for a liquid crystal display device was wetly scattered on the alignment film side of the one-side substrate so that the number of spacers of 1 mm 2 was 100. A sealant was formed around the other-side substrate, and then, the substrate and the spacer-dispersed substrate were opposed to each other with the rubbing direction being 90°, and were adhered to each other. Thereafter, the sealant was cured by performing treatment at 160°C for 90 minutes, and thus, an empty cell (a picture without a liquid crystal) was obtained. In the resulting empty cell, an STN type liquid crystal to which a chiral agent (manufactured by DIC Corporation) was added was injected, and then, the injection port was plugged with a sealant, and heat treatment was performed at 120°C for 30 minutes, and thus, an STN type liquid crystal display device was obtained.

[0142] (Example 2)

[0143] Except that the blending amount of CELM (registered trademark) Super Polymer SM1313P was changed from 50 parts by weight to 100 parts by weight, the operation was performed in the same manner as in Example 1, and thus, a composite particle and a liquid crystal display device were obtained.

[0144] (Example 3)

[0145] Except that the blending amount of CELM (registered trademark) Super Polymer SM1313P was changed from 50 parts by weight to 150 parts by weight, the operation was performed in the same manner as in Example 1 to obtain a composite particle and a liquid crystal display device.

[0146] (Example 4)

[0147] 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, the operation was performed in the same manner as in Example 1 to obtain a composite particle and a liquid crystal display device.

[0148] (Example 5)

[0149] Except that CELM (registered trademark) Super Polymer SM1313P was changed to CELM (registered trademark) Super Polymer SA1313P (chain compound molecular weight: about 11,000, total molecular weight: 190,000 (representative value)), the operation was performed in the same manner as in Example 1 to obtain a composite particle and a liquid crystal display device.

[0150] (Example 6)

[0151] Except that CELM (registered trademark) Super Polymer SM1313P was changed to CELM (registered trademark) Super Polymer SM2403P (chain compound molecular weight: about 20,000, total molecular weight: 600,000 (representative value)), the operation was performed in the same manner as in Example 1 to obtain a composite particle and a liquid crystal display device.

[0152] (Comparative Example 1)

[0153] Except that CELM (registered trademark) Super Polymer SM1313P was not added, the operation was performed in the same manner as in Example 1 to obtain a composite particle and a liquid crystal display device.

[0154] (Comparative Example 2)

[0155] Except that the carbon black on which surface coating was performed was not added, the operation was performed in the same manner as in Example 1 to obtain a composite particle and a liquid crystal display device.

[0156] (Evaluation)

[0157] (1) Particle diameter

[0158] For the obtained composite particles, 100,000 particle diameters were measured using a particle size distribution measuring device ("Multisizer 4" manufactured by Beckman Coulter), and the average particle diameter and standard deviation were measured.

[0159] (2) Coefficient of variation (CV value)

[0160] For the obtained composite particles, the coefficient of variation (CV value) was measured by the above method.

[0161] (3) Breaking strength (compression breaking deformation)

[0162] For the obtained composite particles, the compression breaking deformation was measured. The compression breaking deformation was measured by the following method. The compression breaking deformation was determined by the following criteria.

[0163] Method for measuring compression breaking deformation:

[0164] The composite particles were spread on a sample stage. Using a micro compression tester ("Micro Compression Tester MCT-W200" manufactured by Shimadzu Corporation), a load (reverse load value) was applied to one of the spread composite particles in the direction of the center of the composite particle until the composite particle was broken. Thereafter, the displacement at the time of breaking of the composite particle was measured. The ratio of the displacement at the time of breaking to the average particle diameter was taken as the compression breaking deformation. Note that the load speed was 0.33 mN / second.

[0165] [Criteria for breaking strength (compression breaking deformation)]

[0166] O: Compression breaking deformation is 50% or more

[0167] Δ: Compression breaking deformation is more than 45% and less than 50%

[0168] X: Compression breaking deformation is less than 45%

[0169] (4) Display quality

[0170] A specified voltage was applied to the obtained liquid crystal display device, and display defects such as light leakage caused by the spacers for liquid crystal display devices were observed by electron microscopy, and the display quality was determined according to the following criteria.

[0171] [Criteria for display quality]

[0172] O: No display defects such as unevenness of the gap between the substrates and light leakage caused by the spacers for liquid crystal display devices were observed, and the display quality was excellent

[0173] Δ: Some display defects such as unevenness of the gap between the substrates and light leakage caused by the spacers for liquid crystal display devices were observed

[0174] X: Display defects such as unevenness of the interval (gap) between substrates caused by the spacer for liquid crystal display device and light leakage were obviously observed

[0175] Details and results of the composite particles are shown in Table 1 below.

[0176] [Table 1]

[0177]

Claims

1. A composite particle containing a pigment, a chain compound, and a cyclic compound, wherein the chain compound penetrates the inside of a ring of the cyclic compound, the chain compound penetrates the inside of a ring of the cyclic compound, a weight average molecular weight of the chain compound is 3000 or more and 100000 or less, a structure formed by the chain compound penetrating the inside of a ring of the cyclic compound is a polyrotaxane, a crosslinking agent is bound to the cyclic compound, a particle diameter of the composite particle is 2 μm or more and 15 μm or less, the pigment is dispersed in the composite particle.

2. The composite particle of claim 1, wherein, a content of a portion other than the crosslinking agent in the cyclic compound and the chain compound in total is 1% by weight or more and 70% by weight or less in 100% by weight in total of the cyclic compound and the chain compound.

3. The composite particle according to claim 1 or 2, wherein the crosslinking agent in the cyclic compound includes an acrylic polymer or a styrene-based polymer.

4. The composite particle according to claim 1 or 2, wherein the pigment is a black pigment or a white pigment.

5. The composite particle of claim 1 or 2, wherein, the pigment includes carbon black, titanium black, aniline black, or iron oxide.

6. The composite particle of claim 1 or 2, wherein, a cyclic skeleton in the cyclic compound is a cyclic skeleton formed by 10 or more atoms.

7. A liquid crystal display device provided with: a member for a liquid crystal display device, and the composite particle according to any one of claims 1 to 6.

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