KR20190030195A - Composite particle and liquid crystal display - Google Patents

Abstract

The present invention provides a composite particle capable of sufficiently suppressing a decrease in fracture strength even when the particle contains a pigment. 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 cyclic compound.

Description

Composite particle and liquid crystal display

The present invention relates to a composite particle containing a pigment. The present invention also relates to a liquid crystal display device using the composite particles.

In a liquid crystal display device, liquid crystal is arranged between two glass substrates. In the liquid crystal display device, a spacer is used as a gap control member in order to control the distance between two glass substrates and to maintain the thickness (cell gap) of a suitable liquid crystal layer. As the spacer, resin particles are generally used.

Further, the spacer is required to be colored in a high color in order to prevent light leakage transmitted through the spacer to light and to prevent the display contrast of the image from deteriorating.

As an example of the particles used for the spacer, Japanese Patent Application Laid-Open Publication No. 2001-34870 discloses a spacer for a liquid crystal display element containing a surface-coated carbon black.

WO 97/30374

In the conventional spacer as described in Patent Document 1, there is a tendency that the particles are easily decomposed by the carbon black which is a pigment, and the fracture strength of the particles is low. Particularly, when the particle diameter of the particles is small, it is difficult to sufficiently increase the fracture strength of the particles.

An object of the present invention is to provide a composite particle capable of sufficiently suppressing a decrease in fracture strength even when the particle contains a pigment. The present invention also provides a liquid crystal display device using the composite particles.

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

In a specific aspect of the composite particle according to the present invention, the structure in which the chain compound penetrates the inside of the ring of the cyclic compound is rotoquat.

In a specific aspect of the composite particle according to the present invention, the crosslinking agent is bonded to the cyclic compound.

In a specific aspect of the composite particle according to the present invention, in the total of 100% by weight of the cyclic compound and the chain compound, the total content of the cyclic compound excluding the crosslinking agent and the chain compound is 1% by weight or more and 70% By weight or less.

In a specific aspect of the composite particle according to the present invention, the crosslinking agent in the cyclic compound includes an acrylic polymer or a styrene polymer.

In a specific aspect of the composite particle according to the present invention, the particle diameter is 2 탆 or more and 15 탆 or less.

In a specific aspect of the composite particle according to the present invention, the pigment is a black pigment or a white pigment.

In a specific aspect of the composite particle according to the present invention, the pigment includes carbon black, titanium black, aniline black or iron oxide.

In a specific aspect of the composite particle according to the present invention, the weight average molecular weight of the chain compound is from 3,000 to 100,000.

In a specific aspect of the composite particle according to the present invention, the cyclic skeleton of the cyclic compound is a cyclic skeleton having 10 or more atoms connected thereto.

According to a broad aspect of the present invention, there is provided 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 passes through the inside of the ring of the cyclic compound, so that even if the particles contain a pigment, .

1 is a cross-sectional view schematically showing a liquid crystal display device using a composite particle according to an embodiment of the present invention as a spacer for a liquid crystal display device.

Hereinafter, the present invention will be described in detail. In the present specification, for example, "(meth) acrylate" means one or both of "acrylate" and "methacrylate", "(meth) acryl" &Quot; or " both. &Quot;

(Composite particle)

The composite particle according to the present invention contains a pigment, a chain compound and a cyclic compound. In the composite particle according to the present invention, 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 passes through the inside of the ring of the cyclic compound. The composite particle according to the present invention has, for example, a resin part. The composite particle according to the present invention is, for example, a resin particle containing a pigment in a resin portion.

In the composite particle according to the present invention, since the above-described constitution is provided, it is possible to sufficiently suppress the reduction of the fracture strength even when the particles contain a pigment. In general, when the pigment is dispersed in the composite particle, the composite particle tends to be broken at the interface between the resin portion of the composite particle and the pigment, and the fracture strength of the composite particle is lowered. 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 breakage of the composite particle can be suppressed. As a result, deterioration of the fracture strength of the composite particles can be suppressed. Further, in the present invention, since the chain compound penetrates the inside of the ring of the cyclic compound, it is possible to impart higher toughness to the composite particles, and further suppress destruction of the composite particles. As a result, the degradation of the fracture strength of the composite particles can be further suppressed.

From the standpoint of suppressing the fracture of the composite particles, the fracture strength (compressive fracture strain) of the composite particle is preferably 50% or more, more preferably 55% or more, further preferably 60% or more.

The compression fracture strain is measured as follows.

The composite particles are dispersed on the sample surface. For one dispersed composite particle, a load (inverse load value) is applied until the composite particle is broken in the direction of the center of the composite particle, using a micro compression tester. Thereafter, the displacement when the composite particles are broken is measured. The displacement ratio at the time of fracture with respect to the average particle diameter is defined as the compression fracture strain. The load speed is 0.33 mN / sec. As the micro-compression tester, for example, "Micro compression tester MCT-W200" manufactured by Shimadzu Seisakusho Co., Ltd. and "Fisher Scope H-100" manufactured by Fisher Co., Ltd. are used.

It is preferable that the composite particle contains a base particle body and further 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.

As the material of the composite particles and the material of the base particle body, various organic materials are suitably used. Examples of 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; Acrylic resins such as polymethyl methacrylate and polymethyl acrylate; 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 A resin, a saturated polyester resin, a polyethylene terephthalate, a polysulfone, a polyphenylene oxide, a polyacetal, a polyimide, a polyamideimide, a polyetheretherketone, a polyether sulfone, a divinylbenzene polymer, a divinylbenzene copolymer etc. . Examples of the divinylbenzene copolymer and the like include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylate copolymer. It is possible to easily control the hardness of the composite particles and the base material particle body within a suitable range, so that the material of the composite particles and the material of the base material particle body may contain one or more kinds of polymerizable monomers having an ethylenic unsaturated group It is preferable that the polymer is polymerized.

When the composite particles and the base particle body are obtained by polymerizing a polymerizable monomer having an ethylenic unsaturated group, examples of the polymerizable monomer having an ethylenic unsaturated group include a monomer which is incompatible with a crosslinking monomer.

Examples of the non-crosslinkable monomer include styrene monomers such as styrene,? -Methyl styrene and chlorostyrene; Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; Acid vinyl ester compounds such as vinyl acetate, vinyl butyrate, vinyl laurate and vinyl stearate; Halogen-containing monomers such as vinyl chloride and vinyl fluoride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Alkyl (meth) acrylate compounds such as acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; (Meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate; Nitrile-containing monomers such as (meth) acrylonitrile; Halogen-containing (meth) acrylate compounds such as trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate; As the? -olefin compounds, olefin compounds such as diisobutylene, isobutylene, linear ethylene, ethylene and propylene; Examples of the conjugated diene compound include isoprene and butadiene.

Examples of the crosslinkable monomer include vinyl monomers such as divinylbenzene, 1,4-divinyloxybutane and divinylsulfone; (Meth) acrylate compounds such as tetramethylolmethane tetra (meth) acrylate, polytetramethylene glycol diacrylate, tetramethylol methane tri (meth) acrylate, tetramethylolmethanedi (meth) acrylate, trimethylol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, polyethylene glycol di Polyfunctional (meth) acrylate compounds such as poly (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and 1,4-butanediol di (meth) acrylate; As the allyl compound, triallyl (iso) cyanurate, triallyl trimellitate, diallyl phthalate, diallylacrylamide, diallyl ether; Examples of the silane compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxy Silane, cyclohexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di Silane alkoxides such as isopropyldimethoxysilane, trimethoxysilylstyrene,? - (meth) acryloxypropyltrimethoxysilane, 1,3-divinyltetramethyldisiloxane, methylphenyldimethoxysilane and diphenyldimethoxysilane; Compound; Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, diethoxymethylvinylsilane, diethoxyethylvinylsilane, ethylmethyldivinylsilane, methylvinyldimethoxysilane, ethylvinyl Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, A polymerizable double bond-containing silane alkoxide such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane; Cyclic siloxanes such as decamethylcyclopentasiloxane; Modified (reactive) silicone oils such as one-end modified silicone oil, both-end silicone oil and side chain silicone oil; And carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride.

The composite particles and the base particle body can be obtained by uniformly mixing and dispersing the pigment, the chain compound and the cyclic compound in the polymerizable monomer having the ethylenic unsaturated group and polymerizing the mixture. The above polymerization method is not particularly limited, and polymerization can be carried out by a known method such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, polycondensation), addition condensation, living polymerization, and living radical polymerization. Examples of the method include suspension polymerization in the presence of a radical polymerization initiator and seed polymerization and dispersion polymerization, which are methods in which non-crosslinked seed particles are used to swell the monomer together with the radical polymerization initiator to polymerize have.

A ball mill, a bead mill, a sand mill, an attritor, a sand grinder, a nanometer and the like may be used for uniformly mixing and dispersing the pigment in the polymerizable monomer having the ethylenic unsaturated group. In this case, a dispersant or the like may be added in order to enhance the dispersibility of the pigment.

The dispersant is not particularly limited. Examples of the dispersing agent include water-soluble polymers such as polyvinyl alcohol, starch, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose and sodium poly (meth) acrylate, and water-soluble polymers such as barium sulfate, calcium sulfate, aluminum sulfate, calcium carbonate, Calcium, talc, clay and metal oxide powder.

From the viewpoints of practicality and usability of the spacer for a liquid crystal display device, the particle diameter of the composite particles is preferably 2 탆 or more, more preferably 3 탆 or more, and preferably 15 탆 Or less, more preferably 5 m or less.

The particle diameter of the composite particle means the diameter when the composite particle is a spherical phase and the diameter when the composite particle has a shape other than the contour shape, assuming a sphere corresponding to its volume.

When a plurality of composite particles are present, the particle diameter of the composite particles means the average particle diameter of the composite particles measured by an arbitrary particle diameter measuring apparatus. For example, a particle size distribution measuring device using principles such as laser light scattering, electrical resistance value change, image analysis after image pick-up, etc. can be used. Specifically, in the case of a plurality of composite particles, about 100,000 particle diameters are measured using, for example, a particle size distribution measuring apparatus ("Multisizer 4" manufactured by Beckman Coulter, Inc.) as a method for measuring the particle diameter of the composite particles, And a method of measuring the particle diameter. The average particle diameter represents the number average particle diameter.

The aspect ratio of the composite particles is preferably 1.10 or less, and more preferably 1.05 or less. The aspect ratio indicates a long diameter / short diameter. In the case of a plurality of composite particles, preferably, the aspect ratio is obtained by observing 10 arbitrary composite particles with an electron microscope or an optical microscope to determine the maximum diameter and the minimum diameter as long and short diameters respectively, And the average value of the long diameter / short diameter of the particles is calculated.

From the viewpoints of practicality and usability of the spacer for a liquid crystal display device, in the case of a plurality of composite particles, the particle diameter variation coefficient of the composite particles is preferably 7% or less, 5% or less.

The coefficient of variation (CV value) can be measured as follows.

CV value (%) = (rho / Dn) x100

ρ: standard deviation of particle diameter of composite particles

Dn: Average value of particle diameter of composite particles

The shape of the composite particles is not particularly limited. The shape of the composite particle may be spherical or may be a shape other than a spherical shape such as a flattened shape.

From the viewpoint of further preventing elution and diffusion of impurities, it is preferable that the composite particles are particles whose surfaces are coated with a coating agent such as a silane coupling agent. The coating by the coating agent is preferably a monomolecular thin film or a polymer thin film. The composite particle may not have the coating.

The silane coupling agent is not particularly limited. Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, 3- [N-allyl- )] Aminopropyltrimethoxysilane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N-allyl- Amino-based silane coupling agents such as (N, N-diglycidyl) aminopropyltrimethoxysilane; N, N-bis [3- (methyldimethoxysilyl) propyl] amine, N, N-bis [3- (trimethoxysilyl) Propyl] ethylamine, N-glycidyl-N, N-bis [3- (methyldimethoxysilyl) propyl] amine, N- Amide-based silane coupling agents such as glycidyl-N, N-bis [3- (trimethoxysilyl) propyl] amine; Vinyl silane coupling agents such as vinyltriethoxysilane and vinyltris (2-methoxyethoxy) silane; a methacryl silane coupling agent such as? -methacryloxypropyltrimethoxysilane; glycidyl silane coupling agents such as? -glycidoxypropyltrimethoxysilane; and mercapto-based silane coupling agents such as? -mercaptopropyltrimethoxysilane.

The method for coating the composite particle with a coating agent is not particularly limited. As a method for coating the composite particles with a coating agent, the particles and the coating agent are mixed in an inorganic solvent such as water or an organic solvent such as alcohol, and the mixture is heated under stirring. After heating, the composite particles are separated by decantation or the like, , A method of directly mixing the particles with the coating agent, and a method of heating.

(Pigment)

From the viewpoint of being suitable for use in a spacer for a liquid crystal display device, the pigment is preferably a black pigment or a white pigment, preferably a black pigment. The pigment may be a black pigment or a white pigment.

Examples of the black pigments include carbon black, lamp black, graphite, iron oxide, composite oxides of copper-chromium, and composite oxides of copper-chromium-zinc. The black pigment may be used alone or in combination of two or more.

Examples of the white pigment include titanium dioxide, calcium carbonate, zinc oxide and barium sulfate. The white pigment may be used alone or in combination of two or more.

The pigment preferably includes carbon black, titanium black, aniline black or iron oxide. The above-mentioned pigments may be used alone, or two or more pigments may be used in combination.

The carbon black is not particularly limited, and examples thereof include channel black, roll black, furnace black, thermal black, ketjen black and acetylene black. The carbon black may be used alone, or two or more carbon blacks may be used in combination.

From the viewpoint of further preventing elution and diffusion of impurities, it is preferable that the pigment is a pigment whose surface is coated. By using a pigment-coated pigment, deterioration of properties such as electrical resistance of the composite particles can be prevented even if the amount of the pigment to be incorporated is increased. Further, the surface is coated, whereby the dispersibility of the pigment is improved, and the composite particles can be colored with a smaller blending amount. As a material for covering the surface of the pigment, a thermoplastic resin and the like can be mentioned.

The thermoplastic resin is not particularly limited. Examples of the thermoplastic resin include a thermoplastic resin such as an alkyd resin, a modified alkyd resin, a phenol resin, a natural resin modified phenol resin, a maleic acid resin, a natural resin modified maleic resin, a fumaric acid resin, An epoxy resin, a phenoxy resin, a styrene resin, a vinyl resin, an acrylic resin, a chlorinated rubber, a benzoguanamine resin, a urea resin, a urea resin, a urea resin, a urea resin, a urea resin, a polyester resin, a polyimide resin, a polyamide resin, a polycarbonate resin, , A polyolefin resin, an ethylene-vinyl acetate copolymer and a urethane resin. The thermoplastic resin may be used singly or in combination of two or more.

The method of coating the surface of the pigment using the thermoplastic resin is not particularly limited and a method of pulverizing the pigment in a hydrophobic solvent containing the thermoplastic resin using a grinder such as a ball mill, A method of emulsifying a hydrophobic solvent by adding and mixing an aqueous dispersion of the pigment, and then distilling off the water by heating.

From the viewpoint of further suppressing the degradation of the breaking strength of the composite particles, the content of the pigment in 100 wt% of the composite particles is preferably at least 3 wt%, more preferably at least 5 wt% Is not more than 10% by weight, more preferably not more than 8% by weight.

(Chain compound)

The composite particle according to the present invention contains the chain compound and the cyclic compound. In the composite particle according to the present invention, the chain compound penetrates the inside of the ring of the cyclic compound. In the composite particle according to the present invention, since the above-described constitution is provided, it is possible to suppress the decrease of the fracture strength of the composite particle.

From the viewpoint of further suppressing the degradation of the fracture strength of the composite particles, it is preferable that 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. It is not necessary that all of the chain compounds penetrate the inside of the ring of the cyclic compound. The chain compound may not pass through the inside of all the rings in the cyclic compound.

As the structure in which the chain compound is formed through the inside of the ring of the cyclic compound as described above, for example, there is a structure referred to as " rotoaxic acid ". The structure in which the chain compound penetrates the inside of the ring of the cyclic compound is preferably a rotoacic acid. The above-mentioned roto-lactic acid is a structure in which the chain compound passes through the inside of the ring of the cyclic compound, and the cyclic compound is formed so as not to come off from the chain compound. On the other hand, the structure in which the chain compound penetrates the inside of the ring of the cyclic compound and the cyclic compound is allowed to fall off from the chain compound is called " Pseudorotaxane ", and is different from the above-mentioned cyclic acid. The above-mentioned roots may be polyrotaxane. The polyrotaxane is a structure in which a chain compound is rotoaxic acid which penetrates the inside of a ring of a plurality of cyclic compounds and is formed by a plurality of constituent molecules. From the viewpoint of further suppressing the degradation of the fracture strength of the composite particles, the structure formed by the chain compound and the cyclic compound is more preferably a polyrotaxane.

The material of the chain compound and the chain compound is not particularly limited and various polymers can be used, for example. Examples of the material of the chain compound and the chain compound include polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, poly (meth) acrylic acid, poly (meth) acrylamide, Cellulose resin such as ethyl cellulose, polyvinyl acetal resin, polysiloxane compound such as polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, polydimethylsiloxane, starch or the like and a copolymer including starch and the like, polyethylene, (Meth) acrylate, a (meth) acrylate ester copolymer, a polymethyl (meth) acrylate copolymer, a polystyrene resin such as a polystyrene and an acrylonitrile- Acrylonitrile-methyl acrylate copolymer and the like Acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, nylon , Polyimide compounds, polydiene compounds such as polyisoprene and polybutadiene, polysulfone compounds, polyimine compounds, polyanhydride acetic acid compounds, polyurea compounds, polysulfide compounds, polyphosphazene compounds, polyketone compounds Compounds, polyphenylene compounds, polyhaloolefin compounds, and the like. In addition, the material of the chain compound and the chain compound may be a derivative or a modified product of the various polymers described above. As the material of the chain compound, only one kind may be used, or two or more kinds may be used in combination.

The chain compound is preferably a polymer.

The chain compound may be a homopolymer composed of one kind of repeating constituent units or a copolymer composed of two or more kinds of repeating constituent units. When the chain compound is a copolymer, any structure such as a random copolymer, a block copolymer, and an alternating copolymer may be used.

From the viewpoint of further suppressing the degradation of the fracture strength of the composite particles, it is preferable that the chain compound has a molecular structure for preventing the cyclic compound from dropping out. From the viewpoint of further suppressing the degradation of the fracture strength of the composite particles, it is preferable that the chain compound penetrates the inside of the ring of the cyclic compound and the cyclic compound does not fall off with respect to the chain compound. Hereinafter, the molecular structure for preventing the cyclic compound from dropping out is referred to as a stopper group.

Examples of the stopper group 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 fluororesin compound, a pyrene compound, a cyclodextrin compound, Benzyloxy-L-tyrosine compound (ZL-tyrosine compound), and derivatives or modified forms thereof. Examples of other stopper groups include conventionally known functional groups and the like for preventing the cyclic compound from falling off in roto-taxane. The stopper group may have a substituent.

From the viewpoint of further suppressing the degradation of the fracture strength of the composite particles, it is preferable that the above-mentioned chain compound has the above-mentioned stopper group at both ends. When the chain compound has the stopper groups at both ends thereof, the cyclic compound is maintained in a skewered state by the chain compound. The cyclic compound can freely move the chain portion of the chain compound. By the stopper groups at both ends, the cyclic compound does not deviate from the chain compound. As a result, it is possible to impart higher toughness to the composite particles, and further suppress the reduction of the fracture strength of the composite particles.

The stopper group may be bonded directly to the chain skeleton of the chain compound, or may be indirectly bonded to the chain skeleton of the chain compound through amide bond, ester bond or the like.

The composite particle may include a chain compound having the stopper group, or may include both of the chain compound having the stopper group and the chain compound having no stopper group do. From the viewpoint of further suppressing the degradation of the fracture strength of the composite particles, it is preferable that the composite particles include a chain compound having the stopper group.

In the case where the chain compound does not have the stopper group, some cyclic compounds may be separated from the chain compound, but the cyclic compound that remains may remain in the composite particles.

In the case where the composite particle contains roto-taxane, examples of the material of the chain compound and the chain compound include polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, Polyethylene, polypropylene, polyvinyl alcohol, polyvinyl methyl ether, and the like. When the composite particle contains rocloic acid, it is preferable that the material of the chain compound and the chain compound include the above-mentioned compounds. These compounds may be used alone, or two or more of them may be used in combination. In this case, the chain compound tends to penetrate the inside of the ring of the cyclic compound (inside of the ring), and it is easy to form stable roto-taxane. In addition, the chain compound may have branched chains so as to penetrate the inside of the ring of the cyclic compound.

In the case where the chain compound constituting the cyclic lactic acid has a stopper group, since the cyclic compound does not fall off, the effect of the stress relaxation is maintained for a long period of time and the degradation of the fracture strength of the composite particles can be further suppressed. In addition, even when the chain compound does not have a stopper group, the effect of stress relaxation is exerted.

The weight average molecular weight of the chain compound is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, further preferably 10000 or more, preferably 100000 or less, more preferably 50000 or less. The weight average molecular weight of the chain compound is particularly preferably from 10000 to 50,000. When the weight average molecular weight of the chain compound is not lower than the lower limit, the lowering of the fracture strength of the composite particles can be further suppressed. When the weight average molecular weight of the chain compound is not more than the upper limit, the compatibility of the base particle body and the cyclic compound can be further enhanced.

(Cyclic compound)

From the viewpoint of further suppressing the lowering of the fracture strength, the cyclic skeleton of the cyclic compound is preferably a cyclic skeleton having three or more atoms (the number of atoms connected in a cyclic manner), and more preferably a cyclic skeleton having 5 or more atoms More preferably a cyclic skeleton having 10 or more atoms connected thereto. The number of atoms connected to the cyclic structure may be 1000 or less, or 500 or less. The number of atoms connected to the cyclic structure is a value calculated so that the number of atoms constituting the ring is the smallest among the atoms constituting the ring. The atom constituting the cyclic skeleton is preferably a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, and is preferably a carbon atom or an oxygen atom.

From the viewpoint of further suppressing the lowering of the breaking strength, the cyclic compound is preferably a cyclic sugar compound.

Examples of the material of the cyclic compound and the cyclic compound include cyclodextrin compounds such as? -Cyclodextrin,? -Cyclodextrin,? -Cyclodextrin, dimethylcyclodextrin and gluco-carried clodextrin; Cyclic monomers such as crown ethers, cyclopants, calixarenes, cucurbiturils, pilararenes, cyclic amides and the like; Cyclic oligomers; And cyclic macromonomers. The cyclodextrin compound may be a derivative or a modified product. Examples of the cyclic oligomer include oligomers of ethylene glycol, oligomers of ethylene oxide, oligomers of propylene glycol, and polysaccharides. The cyclic compound and the cyclic compound may be used either singly or in combination of two or more.

From the viewpoint of further suppressing the degradation of the fracture strength of the composite particles, it is preferable that the material of the cyclic compound (the material that becomes the cyclic compound in the composite particle) contained in the composite particle has a polymerizable functional group. The polymerizable functional group in the material of the cyclic compound can be polymerized, for example, with the material of the base particle body. The polymerizable functional group in the material of the cyclic compound can be polymerized with, for example, a crosslinking agent.

Examples of the polymerizable functional group include an alkenyl group, a vinyl group, a hydroxyl group, a mercapto group, an amino group, a carboxyl group, a sulfo group and a phosphoric group. The polymerizable functional group may further have at least one substituent. The polymerizable functional group is preferably a functional group capable of radical polymerization and is preferably an alkenyl group or a vinyl group, for example, from the viewpoint of more efficiently forming the material of the base particle body and the polymerization with the crosslinking agent.

As an example of the cyclic compound having a polymerizable functional group, cyclic macromonomers represented by the following formula (1) can be given.

Wherein R 1 and R 2 are each a hydrogen atom or an alkyl group having 1 or 2 carbon atoms and R 3 is a hydrogen atom or a methyl group. M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, and n represents the number of repeating units of the structure in parentheses and is an integer of 5 to 100. The (n + 1) M may be the same or different.

Another example of the cyclic compound having a polymerizable functional group includes a cyclic macromonomer represented by the following formula (2).

Wherein M represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms and n represents the number of repeating units of the structure in parentheses and is an integer of 5 to 100. The (n + 1) M may be the same or different.

The cyclic compound preferably contains an? -Cyclodextrin structure, a? -Cyclodextrin structure or a? -Cyclodextrin structure. These structures may be of only one kind, or two or more kinds.

When the composite particle contains roto-taxane, when the amount of the cyclic compound encapsulating the maximum amount of the cyclic compound when the chain compound passes through the cyclic compound is taken as 1, the content of the cyclic compound Is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 0.05 or more. In the case where the composite particle contains roto-taxane, when the amount of the cyclic compound encapsulating the cyclic compound at the time when the chain compound passes through the cyclic compound is taken as 1 (the maximum inclusion amount), the inclusion amount of the cyclic compound is , Preferably not more than 0.6, more preferably not more than 0.5, still more preferably not more than 0.4. In addition, 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 lower limit and not more than the upper limit, the lowering of the fracture strength of the composite particles is further suppressed.

From the viewpoint of further suppressing the degradation of the fracture strength of the composite particles, it is preferable to adjust the maximum inclusion amount of the cyclic compound as described above.

Crosslinking agent bonded to cyclic compound:

From the viewpoint of further suppressing the degradation of the fracture strength of the composite particles, it is preferable that the cyclic compound is bonded to the cyclic compound. The crosslinking agent may be a side chain in the cyclic compound. The presence of this cross-linking agent greatly contributes to suppressing the decrease of the fracture strength of the composite particles.

Examples of the crosslinking agent include polyolefin resins such as polyethylene, polypropylene, polystyrene, silicone resin, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; Acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Phenol resin, melamine resin, urea resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, urea resin, Various polymerizable monomers having an epoxy resin, an unsaturated polyester resin, a saturated polyester resin, a polysulfone, a polyphenylene oxide, a polyacetal, a polyimide, a polyamideimide, a polyetheretherketone, a polyether sulfone and an ethylenic unsaturated group And polymers obtained by polymerization of one kind or two or more kinds. The crosslinking agent may be used alone, or two or more crosslinking agents may be used in combination.

From the viewpoint of further suppressing the degradation of the breaking strength of the composite particles, the crosslinking agent in the cyclic compound preferably includes an acrylic polymer or a styrene polymer, and more preferably 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 degradation of the fracture 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 kind of repeating constituent units or a copolymer composed of two or more kinds of repeating constituent units. When the polymer is a copolymer, any structure such as a random copolymer, a block copolymer, and an alternate copolymer may be used.

From the viewpoint of easily controlling the hardness of the composite particles to a suitable range, the crosslinking agent in the cyclic compound is preferably a polymer of a polymerizable monomer having an ethylenic unsaturated group. The crosslinking agent in the cyclic compound may be a polymer of one kind of polymerizable monomer or a polymer of two or more kinds of polymerizable monomers.

When the crosslinking agent in the cyclic compound is a polymer of a monomer having an ethylenically unsaturated group, examples of the monomer having an ethylenically unsaturated group include a monomer that is incompatible with the monomer and a monomer that is crosslinkable.

Examples of the monomer that is non-crosslinkable include the above-mentioned non-crosslinkable monomers. Examples of the crosslinkable monomer include the above-mentioned crosslinkable monomers.

The above-mentioned crosslinking agent can be obtained by polymerizing the ethylenically unsaturated group-containing polymerizable monomer by a known method. Examples of the method include suspension polymerization in the presence of, for example, a radical polymerization initiator, and polymerization by swelling the monomer together with the radical polymerization initiator using non-crosslinked seed particles.

Specific examples of the structure of the cyclic compound having a crosslinking agent include a structure in which the cyclic compound is bonded to the cyclic portion in the cyclic compound in the above-mentionedloxanic acid. One end of the crosslinking agent may be bonded to the cyclic portion of one cyclic compound and the other end of the crosslinking agent may be bonded to the cyclic portion of the other cyclic compound. The cyclic moiety in the cyclic compound in rosin and the crosslinking agent may form a three-dimensional network structure.

In the structure in which the cyclic portion in the cyclic compound in rosin is bonded to the cross-linking agent, the cyclic portion in the cyclic compound becomes the bonding origin (bonding point) of the cross-linking agent. In cyclic acid, the cyclic compound can freely move the chain portion of the chain compound. As a result, the point of attachment in the cyclic compound can shift the chain portion of the chain compound. The cyclic compound having a crosslinking agent is a material capable of moving the chain portion of the chain compound. Such a cyclic compound having a cross-linking agent has properties of being excellent in stretchability and stability since it has flexibility and has a tendency to relax stress even when stress is applied, so as to follow the stress.

When the cyclic compound has a structure in which the cyclic compound is bonded to the cyclic compound in the cyclic compound in roto-taxane, the cyclic compound has particularly excellent stress relaxation performance and further suppresses the degradation of the fracture strength of the composite particle. When the composite particle contains a pigment, the breaking strength of the composite particle is lowered as the particle diameter of the composite particle is reduced. However, if the cyclic compound has a structure in which the cyclic compound is bonded to the cyclic compound in the cyclic compound in ropacanic acid, the decrease of the fracture strength of the composite particle can be further suppressed even if the particle diameter of the composite particle is small .

The method for producing the cyclic compound having a crosslinking agent is not particularly limited. For example, a polymer having a crosslinking agent at the cyclic portion in the cyclic compound can be produced by reacting a mixture of a cyclic acid having a cyclic compound having a polymerizable functional group and a polymerizable monomer for forming a crosslinking agent. Further, if the polymerizable functional group is a functional group radically polymerizable with the polymerizable monomer (such as a vinyl group), a polymer having a crosslinking agent at the cyclic portion in the cyclic compound can be produced by radical polymerization of the cyclic acid and the polymerizable monomer. This radical polymerization can be carried out by a known method.

The kind of the lactic acid having a cyclic compound having a polymerizable functional group is not particularly limited. Examples of the latexic acid having a cyclic compound having a polymerizable functional group include "SILM (registered trademark) Super Polymer SM3403P", "SILM (registered trademark) super" available from Advance Soft Materials, Polymer SM1313P "," SILM (registered trademark) Super Polymer SA3403P "," SILM (registered trademark) Super Polymer SA2403P "," SILM (registered trademark) Super Polymer SA1313P "," SILM (registered trademark) Super Polymer SM3405P " (Registered trademark) key mixer SM3400C "," SILM (registered trademark) Super polymer SA3405P "," SILM (registered trademark) Super polymer SA2405P "," SILM (registered trademark) key mixer SA3400C " (Registered trademark) Superpolymer SA3405P "and" SILM (registered trademark) Superpolymer SA2405P ". The polyrotaxane may be prepared by a known production method.

From the viewpoint of further suppressing the degradation of the fracture strength of the composite particles, the total content of the cyclic compound excluding the crosslinking agent and the chain compound in the cyclic compound in the total of 100% by weight of the cyclic compound and the chain compound is preferably Is not less than 1% by weight, more preferably not less than 3% by weight, preferably not more than 70% by weight, more preferably not more than 20% by weight.

Examples of a method for producing a composite particle having a structure in which a crosslinking agent is bonded to a cyclic portion in a cyclic compound in ropaconic acid include suspension polymerization of a polymerizable monomer for forming a crosslinking agent and a solution of a cyclic acid in the presence of a polymerization initiator have. In the case where the cyclic compound having a radically polymerizable functional group is present, the cyclic compound and the radically polymerizable monomer for forming the crosslinking agent are subjected to suspension polymerization in the presence of a polymerization initiator to obtain a cyclic compound A composite particle having a structure in which a cross-linking agent is bonded to a portion can be obtained.

The kind of the polymerization initiator is not particularly limited, and a compound generally used in suspension polymerization, emulsion polymerization, dispersion polymerization and the like can be used. In the polymerization, a dispersion stabilizer or the like may be used, if necessary. The kind of the dispersion stabilizer is not particularly limited, and a known dispersion stabilizer and the like can be used. Polymerization conditions are not particularly limited, and polymerization can be carried out under suitable conditions known in the prior art, for example.

(Liquid crystal display device and other uses)

A liquid crystal display device according to the present invention comprises a member for a liquid crystal display device and the composite particles described above. The composite particles are suitably used as a spacer for a liquid crystal display device. That is, the composite particle is a liquid crystal display device having a pair of substrates constituting a liquid crystal cell, a liquid crystal sealed between the pair of substrates, and a liquid crystal display spacer disposed between the pair of substrates Is suitably used to obtain the < / RTI > The liquid crystal display spacer may be included in the peripheral sealing agent.

1 is a cross-sectional view schematically showing a liquid crystal display device using a composite particle according to an embodiment of the present invention as a spacer for a liquid crystal display device.

The liquid crystal display device 81 shown in Fig. 1 has a pair of transparent glass substrates 82. Fig. The transparent glass substrate 82 has an insulating film (not shown) on the opposite surface. As a material of the insulating film, for example, SiO ₂ and the like can be mentioned. A transparent electrode 83 is formed on the insulating film of the transparent glass substrate 82. As the material of the transparent electrode 83, ITO and the like can be mentioned. The transparent electrode 83 can be formed by, for example, patterning by photolithography. An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. The material of the alignment film 84 may be polyimide or the like.

A liquid crystal 85 is sealed between the pair of transparent glass substrates 82. Between the pair of transparent glass substrates 82, a plurality of composite particles 11 are arranged. The composite particles 11 are the composite particles described above. The composite particle 11 is used as a spacer for a liquid crystal display device. The spacing of the pair of transparent glass substrates 82 is regulated by the plurality of composite particles 11. 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.

In the liquid crystal display device, the arrangement density of the spacers for a liquid crystal display device per 1 mm 2 is preferably 10 / mm 2 or more, and preferably 1000 / mm 2 or less. When the arrangement density is 10 pieces / mm < 2 > or more, the cell gaps become even more uniform. When the arrangement density is 1000 pieces / mm 2 or less, the contrast of the liquid crystal display device is further improved.

(Usage)

The use of the composite particles is not particularly limited. The composite particle is suitably used not only as a spacer for a liquid crystal display device, but also for various applications. The composite particle is preferably used as a spacer for a light control glass, and is preferably used as a spacer for a light control film.

The composite particle is also suitably used as an inorganic filler, an additive for a toner, an impact absorbing agent, or a vibration absorbing agent. For example, the composite particles can be used as a substitute for rubber or a spring.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. The present invention is not limited to the following examples.

(Example 1)

(1) Fabrication of composite particles

5 parts by weight of surface-coated carbon black, 475 parts by weight of divinylbenzene, and 475 parts by weight of tetramethylolmethane triacrylate was added to a dispersion of SURM (registered trademark) Super Polymer SM1313P (chain compound: molecular weight: about 1.1,000, : 180,000 (typical value)) was added. Next, 20 parts by weight of benzoyl peroxide was added and uniformly mixed in each addition step to obtain a mixed solution. This mixed solution was put into 8500 parts by weight of a 3% by weight aqueous solution of polyvinyl alcohol, stirred sufficiently, and then emulsified with a homogenizer to have an emulsified diameter of about 3 to 10 μm.

The emulsion thus obtained was transferred to a 20 liter reaction kettle equipped with a thermometer, a stirrer and a reflux condenser, and heated in a nitrogen atmosphere with stirring at 85 DEG C for 7 hours, followed by heating at 90 DEG C for 3 hours to effect polymerization Respectively.

Thereafter, the polymerization reaction solution was cooled, and the resulting particles were washed in the order of water, methanol and acetone, followed by classification operation and drying overnight at 55 ° C to obtain composite particles.

(2) Fabrication of liquid crystal display device

Production of STN type liquid crystal display device:

The obtained composite particles were added to a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water in an amount of 2% by weight of the resulting spacer dispersion in a solid content concentration of 2% by weight and stirred to obtain a dispersion liquid for a liquid crystal display .

An SiO ₂ film was deposited on one surface of a pair of transparent glass plates (50 mm in length, 50 mm in width, and 0.4 mm in thickness) by the 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 ITO-film-provided glass substrate by spin coating and baked at 280 占 폚 for 90 minutes to form a polyimide alignment film. After the rubbing treatment was applied to the alignment film, a spacer liquid dispersion for a liquid crystal display was wet-coated on the alignment film side of one substrate so that the number of spacers per 1 mm square was 100. After a sealing agent was formed around the other substrate, the substrate and the substrate on which the spacer was scattered were arranged opposite to each other so that the rubbing direction was 90 deg. Thereafter, the sealing agent was cured at 160 DEG C for 90 minutes to obtain an empty cell (a screen containing no liquid crystal). An STN type liquid crystal display device (STN type liquid crystal display device) was obtained by injecting a chiral dopant liquid crystal (manufactured by DIC) into the obtained empty cell, sealing the injection port with a sealing agent, and then performing heat treatment at 120 deg.

(Example 2)

A composite particle and a liquid crystal display were obtained in the same manner as in Example 1 except that the blending amount of SILM (registered trademark) super polymer SM1313P was changed from 50 parts by weight to 100 parts by weight.

(Example 3)

A composite particle and a liquid crystal display device were obtained in the same manner as in Example 1 except that the blending amount of SILM (registered trademark) super polymer SM1313P was changed from 50 parts by weight to 150 parts by weight.

(Example 4)

A composite particle 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)

Except that the SILM (registered trademark) super polymer SM1313P was changed to SILM (registered trademark) Super polymer SA1313P (chain compound: molecular weight: about 1.1 million, total molecular weight: 190,000 Particles and a liquid crystal display device were obtained.

(Example 6)

Except that SILM (registered trademark) super polymer SM1313P was changed to SILM (registered trademark) SUPER POLYMER SM2403P (chain compound: molecular weight: about 20,000, total molecular weight: 600,000 (typical value)), Particles and a liquid crystal display device were obtained.

(Comparative Example 1)

A composite particle and a liquid crystal display were obtained in the same manner as in Example 1 except that the SILM (registered trademark) super polymer SM1313P was not added.

(Comparative Example 2)

Composite particles and a liquid crystal display were obtained in the same manner as in Example 1 except that no surface-coated carbon black was added.

(evaluation)

(1) Particle diameter

The obtained composite particles were measured for particle diameters of about 100,000 by using a particle size distribution analyzer ("Multisizer 4" manufactured by Beckmann Coulter), and the average particle diameter and standard deviation were measured.

(2) Coefficient of variation (CV value)

With respect to the obtained composite particles, the coefficient of variation (CV value) was measured by the method described above.

(3) Fracture strength (compression fracture distortion)

Compression fracture strain of the obtained composite particles was measured. The compression fracture strain was measured as follows. The compression fracture strain was judged based on the following criteria.

Method of measuring compression fracture strain:

The composite particles were dispersed on the sample surface. Using a micro compression tester (" MCT-W200 " manufactured by Shimadzu Seisakusho Co., Ltd.) with respect to one dispersed composite particle, the load was measured in the center direction of the composite particle until the composite particle was broken ). Thereafter, the displacement when the composite particles were broken was measured. The displacement ratio at the time of fracture with respect to the average particle diameter was defined as the compression fracture strain. The load speed was 0.33 mN / sec.

[Judgment Criteria of Fracture Strength (Compressive Fracture Distortion)] [

○: Compression failure distortion of 50% or more

?: Compression failure distortion is 45% or more and less than 50%

X: Compression failure distortion less than 45%

(4) Display quality

A predetermined voltage was applied to the obtained liquid crystal display device to observe the display defects such as light leakage caused by the spacer for the liquid crystal display device with an electron microscope to judge the display quality as the following criteria.

[Judgment criteria of display quality]

?: Display defects such as unevenness in spacing (gap) between substrates caused by a spacer for a liquid crystal display and light leakage were not recognized completely, and the display quality was excellent

DELTA: Poor indication such as unevenness of spacing (gap) of substrates due to a spacer for a liquid crystal display or light leakage was slightly recognized

X: Display failure such as gap (gap) unevenness or light leakage of the substrate due to a spacer for a liquid crystal display was remarkably recognized

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

11: Composite particle
81: Liquid crystal display
82: transparent glass substrate
83: Transparent electrode
84: Orientation film
85: liquid crystal
86: sealant

Claims (11)

A pigment, a chain compound, and a cyclic compound,
Wherein the chain compound passes through the inside of the ring of the cyclic compound. 2. The composite particle according to claim 1, wherein the chain compound is a roto-tacane having a structure that penetrates the inside of the ring of the cyclic compound. The composite particle according to claim 1 or 2, wherein the cyclic compound is bonded to a crosslinking agent. The composite particle according to claim 3, wherein, in the total of 100% by weight of the cyclic compound and the chain compound, the content of the cyclic compound excluding the crosslinking agent and the chain compound is 1% by weight or more and 70% . The composite particle according to claim 3 or 4, wherein the cross-linking agent in the cyclic compound comprises an acrylic polymer or a styrene polymer. The composite particle according to any one of claims 1 to 5, wherein the particle diameter is 2 탆 or more and 15 탆 or less. The composite particle according to any one of claims 1 to 6, wherein the pigment is a black pigment or a white pigment. 8. The composite particle according to any one of claims 1 to 7, wherein the pigment comprises carbon black, titanium black, aniline black or iron oxide. The composite particle according to any one of claims 1 to 8, wherein the weight average molecular weight of the chain compound is not less than 3000 and not more than 100000. 10. The composite particle according to any one of claims 1 to 9, wherein the cyclic skeleton in the cyclic compound is a cyclic skeleton having 10 or more atoms connected thereto. A liquid crystal display device member,
A liquid crystal display device comprising the composite particle according to any one of claims 1 to 10.

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