US20130109770A1 - Particles, particle dispersion, particle-dispersed resin composition, producing method therefor, resin molded article, producing method therefor, catalyst particles, catalyst solution, catalyst composition, catalyst molded article, titanium complex, titanium oxide particles and producing method therefor - Google Patents

Particles, particle dispersion, particle-dispersed resin composition, producing method therefor, resin molded article, producing method therefor, catalyst particles, catalyst solution, catalyst composition, catalyst molded article, titanium complex, titanium oxide particles and producing method therefor Download PDF

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Publication number
US20130109770A1
US20130109770A1 US13/640,911 US201113640911A US2013109770A1 US 20130109770 A1 US20130109770 A1 US 20130109770A1 US 201113640911 A US201113640911 A US 201113640911A US 2013109770 A1 US2013109770 A1 US 2013109770A1
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Prior art keywords
particles
organic
group
resin
inorganic
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US13/640,911
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Inventor
Yoshiharu Hatakeyama
Takahiro Fukuoka
Junichi Nagase
Shusaku Shibata
Tatsuki Nagatsuka
Saori Fukuzaki
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Nitto Denko Corp
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Nitto Denko Corp
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Priority claimed from PCT/JP2011/059040 external-priority patent/WO2011129311A1/ja
Assigned to NITTO DENKO CORPORATION reassignment NITTO DENKO CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NAGATSUKA, TATSUKI, SHIBATA, SHUSAKU, FUKUOKA, TAKAHIRO, FUKUZAKI, SAORI, HATAKEYAMA, YOSHIHARU, NAGASE, JUNICHI
Publication of US20130109770A1 publication Critical patent/US20130109770A1/en
Priority to US14/535,478 priority Critical patent/US20150065340A1/en
Priority to US15/097,400 priority patent/US20160222194A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2221—At least one oxygen and one phosphorous atom present as complexing atoms in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/005—General concepts, e.g. reviews, relating to methods of using catalyst systems, the concept being defined by a common method or theory, e.g. microwave heating or multiple stereoselectivity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
    • C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound

Definitions

  • the present invention relates to particles, a particle dispersion, a particle-dispersed resin composition and a resin molded article, and more particularly to a particle dispersion, a particle-dispersed resin composition and a resin molded article that are for use in various applications including optical applications, and particles that can be dispersed therein.
  • the present invention also relates to a particle-dispersed resin composition, a particle-dispersed resin molded article, and producing methods therefor.
  • the present invention also relates to catalyst particles, a catalyst solution, a catalyst composition and a catalyst molded article, and more particularly to catalyst particles, a catalyst solution, a catalyst composition and a catalyst molded article that have a catalytic action.
  • the present invention also relates to a resin molded article and a producing method therefor.
  • the present invention also relates to a titanium complex, titanium oxide particles and a producing method therefor, and more particularly to a titanium oxide particle producing method, a titanium complex that can be used in the producing method, and titanium oxide particles prepared by the producing method.
  • nanometer-sized particles are used in optical materials.
  • organomodified fine particles are obtained by subjecting fine particles of a metal oxide such as SiO 2 or TiO 2 and an organic modifier to a hydrothermal synthesis (see, for example, Patent Document 1 listed below).
  • oxides such as titanium oxide exert a photocatalytic action.
  • oxides such as titanium oxide, strontium titanate and tungsten oxide decompose organic substances by their photocatalytic action (see, for example, Non-Patent Document 1 listed below).
  • porous resin obtained by porosifying resin exhibits various physical properties due to porosification, in addition to the physical properties inherent to resin.
  • porous polyimide resin is obtained by blending polyethylene glycol dimethyl ether with a polyimide resin precursor so as to prepare a mixed resin solution, forming a coating and then bringing the coating into contact with hot high pressure carbon dioxide so as to extract polyethylene glycol dimethyl ether (see, for example, Patent Document 2 listed below).
  • the porous polyimide resin disclosed in Patent Document 2 has uniformly formed pores (cells), and the dielectric constant of the porous polyimide resin is set lower than that of non-porous polyimide resin.
  • titanium oxide particles for use in various industrial products are prepared in organic solvents or the like. Meanwhile, from a view point of reducing the environmental load in recent years, various methods are being studied to prepare titanium oxide particles in water, which imposes little load to the environment as compared to organic solvents or the like.
  • titanium oxide particle producing method has been proposed in which titanium oxide particles are prepared by treating a titanium complex containing glycolic acid as a ligand in hot high pressure water (see, for example, Non-Patent Document 2 listed below).
  • Particles for use in the above-described applications are required to have various characteristics, in addition to excellent optical characteristics.
  • organomodified fine particles coagulate.
  • the molded article is problematic in that it is easily degraded by the catalytic action of the oxide because the resin is in contact with the oxide in the molded article.
  • titanium oxide particles are white, but the titanium oxide particles prepared by the titanium oxide particle producing method disclosed in Non-Patent Document 2 described above are colored (brown) due to a decomposition product of the ligand (decomposition product of glycolic acid) of the titanium complex that has been decomposed in hot high pressure water.
  • a first object of the present invention is to provide particles that have excellent optical characteristics and excellent dispersibility, a particle dispersion, a particle-dispersed resin composition and a resin molded article.
  • a second object of the present invention is to provide a particle-dispersed resin composition that contains organic-inorganic composite particles uniformly dispersed in a resin, a particle-dispersed resin molded article, and producing methods therefor.
  • a third object of the present invention is to provide catalyst particles that have excellent dispersibility in a solvent and/or a resin, a catalyst solution in which catalyst particles are dispersed in a solvent and that has excellent clarity, and a catalyst composition and a catalyst molded article in which degradation of the resin is suppressed and that have excellent clarity.
  • a fourth object of the present invention is to provide a resin molded article that has excellent clarity and excellent mechanical strength, and a producing method therefor.
  • a fifth object of the present invention is to provide a titanium oxide particle producing method with which the environmental load as well as coloring of titanium oxide particles can be reduced, a titanium complex that can be used in the producing method, and titanium oxide particles prepared by the producing method.
  • a first group of inventions for achieving the first object is as follows.
  • particles according to the present invention are organic-inorganic composite particles that can be dispersed in a solvent and/or a resin as primary particles having an organic group on the surface of inorganic particles, the organic-inorganic composite particles having negative birefringence.
  • the inorganic particles are composed of a carbonate containing an alkaline earth metal and/or a composite oxide containing an alkaline earth metal.
  • the primary particles are obtained by surface-treating the inorganic particles with an organic compound, and the organic compound contains a binding group capable of binding to the surface of the inorganic particles and a hydrophobic group and/or a hydrophilic group serving as the organic group.
  • the particles of the present invention have an aspect ratio of 1000 or less.
  • the particles of the present invention have a maximum length of 200 ⁇ m or less.
  • the particles of the present invention are obtained by hydrothermal synthesis.
  • an inorganic compound for forming inorganic particles and the organic compound are subjected to a hydrothermal synthesis.
  • a metal hydroxide containing an alkaline earth metal, a carbonic acid source and the organic compound are subjected to a hydrothermal synthesis.
  • the carbonic acid source is formic acid and/or urea.
  • a metal hydroxide containing an alkaline earth metal, a metal complex and the organic compound are subjected to a hydrothermal synthesis.
  • the hydrothermal synthesis is performed in the presence of a pH adjusting agent.
  • the particles of the present invention are obtained by subjecting an inorganic compound for forming inorganic particles to a high temperature treatment in an organic compound containing the organic group.
  • the particles of the present invention are subjected to wet classification using the solvent.
  • a particle dispersion according to the present invention contains a solvent and particles that are dispersed as primary particles in the solvent, and the particles are organic-inorganic composite particles having an organic group on the surface of inorganic particles and have negative birefringence.
  • a particle-dispersed resin composition according to the present invention contains a resin and particles that are dispersed as primary particles in the resin, and the particles are organic-inorganic composite particles having an organic group on the surface of inorganic particles and have negative birefringence.
  • a resin molded article according to the present invention is formed of a particle-dispersed resin composition containing a resin and particles that are dispersed as primary particles in the resin, and the particles are organic-inorganic composite particles having an organic group on the surface of inorganic particles and have negative birefringence.
  • the resin molded article of the present invention is an optical film.
  • a second group of inventions for achieving the second object is as follows.
  • a particle-dispersed resin composition according to the present invention contains a resin and organic-inorganic composite particles having an organic group on the surface of inorganic particles, and the organic-inorganic composite particles have at least a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group and are dispersed as primary particles in the resin.
  • the resin has a functional group, and the organic group and the functional group both have a hydrophilic group or a hydrophobic group.
  • the resin contains a highly oriented resin.
  • the organic group contains a plurality of homologous organic groups.
  • the organic group contains a plurality of heterologous organic groups.
  • a particle-dispersed resin molded article according to the present invention is molded from a particle-dispersed resin composition containing a resin and organic-inorganic composite particles having an organic group on the surface of inorganic particles, and the organic-inorganic composite particles have at least a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group and are dispersed as primary particles in the resin.
  • a method for producing a particle-dispersed resin composition according to the present invention includes blending a resin and organic-inorganic composite particles having an organic group on the surface of inorganic particles such that the organic-inorganic composite particles are dispersed as primary particles in the resin by steric hindrance of the organic group.
  • the organic-inorganic composite particles are produced in a hot solvent. It is also preferable that the organic-inorganic composite particles are produced in hot high pressure water.
  • a method for producing a particle-dispersed resin molded article according to the present invention includes producing a particle-dispersed resin molded article by molding a particle-dispersed resin composition obtained by blending a resin and organic-inorganic composite particles having an organic group on the surface of inorganic particles such that the organic-inorganic composite particles are dispersed as primary particles in the resin by steric hindrance of the organic group.
  • a third group of inventions for achieving the third object is as follows.
  • catalyst particles according to the present invention contain inorganic particles with a catalytic action and an organic group that binds to the surface of the inorganic particles, and have a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group.
  • the catalyst particles of the present invention have a catalytic action for a gas and/or a liquid.
  • the catalyst particles of the present invention have a photocatalytic action for a gas and/or a liquid.
  • the catalyst particles of the present invention are dispersed as primary particles in a solvent and/or a resin.
  • the catalyst particles of the present invention contain a plurality of mutually different types of organic groups.
  • the organic group is bound to the surface of the inorganic particles via a binding group, and the binding group contains a phosphoric acid group and/or a phosphoric acid ester group.
  • the inorganic particles contain an oxide.
  • the inorganic particles contain at least one oxide selected from the group consisting of TiO 2 , WO 3 and SrTiO 3 , and also contain at least one inorganic substance selected from the group consisting of Pt, Pd, Cu, CuO, RuO 2 and NiO.
  • the catalyst particles of the present invention it is preferable that the catalyst particles have an average maximum length of 450 nm or less.
  • the catalyst particles of the present invention are obtained by surface-treating an inorganic substance and/or a complex thereof with an organic compound containing the organic group. It is also preferable that the inorganic substance and/or the complex are surface-treated with the organic compound in hot high pressure water, or that the inorganic substance and/or the complex are surface-treated in the organic compound heated to a high temperature.
  • a catalyst solution according to the present invention contains a solvent and catalyst particles dispersed in the solvent, the catalyst particles contain inorganic particles with a catalytic action and an organic group that binds to the surface of the inorganic particles, and the catalyst particles have a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group.
  • a catalyst composition according to the present invention contains a resin and catalyst particles dispersed in the resin, the catalyst particles contain inorganic particles with a catalytic action and an organic group that binds to the surface of the inorganic particles, and the catalyst particles have a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group.
  • a catalyst molded article according to the present invention is formed of a catalyst composition containing a resin and catalyst particles dispersed in the resin, the catalyst particles contain inorganic particles with a catalytic action and an organic group that binds to the surface of the inorganic particles, and the catalyst particles have a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group.
  • the catalyst molded article of the present invention is an optical film.
  • a fourth group of inventions for achieving the fourth object is as follows.
  • a resin molded article according to the present invention has micropores formed by removing organic-inorganic composite particles from a particle-containing resin molded article containing a resin and the organic-inorganic composite particles that contain inorganic particles and an organic group that binds to the surface of the inorganic particles and have a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group.
  • the organic-inorganic composite particles have an average maximum length of 400 nm or less.
  • the organic-inorganic composite particles are dispersed as primary particles in the resin, or that the particle-containing resin molded article has a phase separated structure formed of a resin phase composed of the resin and a particle phase that is composed of the organic-inorganic composite particles and phase-separated from the resin phase, and the phase separated structure is a bicontinuous phase separated structure in which the particle phase is three-dimensionally continuous.
  • the organic-inorganic composite particles partially remain, and the proportion of remaining organic-inorganic composite particles increases toward one side of the resin molded article.
  • the organic group contains a plurality of mutually different organic groups.
  • a method for producing a resin molded article according to the present invention includes the steps of: preparing organic-inorganic composite particles that contain inorganic particles and an organic group that binds to the surface of the inorganic particles and have a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group; blending the organic-inorganic composite particles with a resin so as to prepare a particle-containing resin composition and forming a particle-containing resin molded article from the particle-containing resin composition; and forming micropores formed by removing the organic-inorganic composite particles from the particle-containing resin molded article.
  • the step of preparing organic-inorganic composite particles involves surface-treating an inorganic material with an organic compound in hot high pressure water, or that the step of preparing organic-inorganic composite particles involves surface-treating an inorganic material in a hot organic compound.
  • a fifth group of inventions for achieving the fifth object is as follows.
  • a titanium complex according to the present invention contains a titanium atom as a central atom and a hydroxycarboxylic acid having a total of 7 or more carbon atoms as a ligand.
  • the hydroxycarboxylic acid is a hydroxyalkanoic acid having a total of 7 or more carbon atoms.
  • the hydroxyalkanoic acid is linear.
  • the hydroxycarboxylic acid is a hydroxymonocarboxylic acid.
  • the hydroxycarboxylic acid is a monohydroxycarboxylic acid.
  • the hydroxycarboxylic acid has a total of 13 or fewer carbon atoms.
  • the hydroxycarboxylic acid is 2-hydroxycarboxylic acid and/or 3-hydroxycarboxylic acid.
  • Titanium oxide particles according to the present invention are obtained by treating a titanium complex containing a titanium atom as a central atom and a hydroxycarboxylic acid having a total of 7 or more carbon atoms as a ligand in hot high pressure water.
  • a method for producing titanium oxide particles according to the present invention includes treating a titanium complex containing a titanium atom as a central atom and a hydroxycarboxylic acid having a total of 7 or more carbon atoms as a ligand in hot high pressure water.
  • the particles of the present invention can be dispersed as primary particles in a solvent and/or a resin, and therefore have excellent dispersibility in a solvent and/or a resin.
  • the particles are dispersed with good uniformity.
  • the resin molded article of the present invention can reliably have excellent optical characteristics.
  • the method for producing a particle-dispersed resin composition and the method for producing a particle-dispersed resin molded article of the present invention enable organic-inorganic composite particles to be dispersed in a resin with ease and uniformity by using a simple method in which the resin and the organic-inorganic composite particles are blended such that the organic-inorganic composite particles are dispersed as primary particles in the resin by steric hindrance of the organic group.
  • the particle-dispersed resin composition and particle-dispersed resin molded article of the present invention have excellent clarity and are suitably used in various industrial applications including optical applications.
  • the catalyst particles of the present invention have a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group, and therefore can be uniformly dispersed in a solvent and/or a resin.
  • the catalyst solution of the present invention in which the catalyst particles of the present invention are dispersed in a solvent can enhance clarity because the catalyst particles are uniformly dispersed.
  • the inorganic particles cannot easily come into direct contact with the resin due to the configuration based on the steric hindrance of the organic group of the catalyst particles. Accordingly, the catalytic action for a gas or a liquid can be exerted while degradation of the resin of the catalyst composition and the catalyst molded article is suppressed.
  • the catalyst composition of the present invention and the catalyst molded article of the present invention can exert various catalytic actions such as a detoxification action, a deodorization action, a disinfectant (or in other words, antimicrobial or germicidal) action, a dirt repellent action and a decomposition action while having excellent durability.
  • the catalyst composition of the present invention and the catalyst molded article of the present invention can enhance clarity because the catalyst particles are uniformly dispersed.
  • the catalyst molded article of the present invention can be used in various optical applications and various construction material applications.
  • the resin molded article of the present invention obtained by the method for producing a resin molded article of the present invention has excellent clarity and excellent mechanical strength.
  • the resin molded article of the present invention can be used in various industrial applications including optical applications as a resin molded article having excellent clarity and excellent reliability.
  • the titanium complex of the present invention contains a hydroxycarboxylic acid having a total of 7 or more carbon atoms as a ligand. For this reason, even when titanium oxide particles are prepared in hot high pressure water, decomposition of the ligand is suppressed, and thus coloring of the titanium oxide particles can be reduced.
  • FIG. 1 shows an image-processed FE-SEM micrograph obtained in Example 1-1;
  • FIG. 2 shows an image-processed FE-SEM micrograph obtained in Comparative Example 1-2;
  • FIG. 3 shows an image-processed TEM micrograph obtained in Example 1-17
  • FIG. 4 shows an image-processed FE-SEM micrograph obtained in Example 1-29;
  • FIG. 5 shows an image-processed FE-SEM micrograph obtained in Comparative Example 1-3
  • FIG. 6 shows an image-processed FE-SEM micrograph obtained in Example 1-47;
  • FIG. 7 shows an image-processed TEM micrograph obtained in Example 1-55
  • FIG. 8 shows an image-processed TEM micrograph obtained in Comparative Example 1-4
  • FIG. 9 shows an image-processed FE-SEM micrograph obtained in Example 1-56;
  • FIG. 10 shows a particle size distribution of particles in a particle dispersion obtained in Preparation Example 1-1;
  • FIG. 11 shows an image-processed FE-SEM micrograph of a cross section of a resin molded article in which particles obtained in Example 1-36 are dispersed;
  • FIG. 12 shows an image-processed FE-SEM micrograph of a cross section of a resin molded article in which particles obtained in Comparative Example 1-2 are dispersed;
  • FIG. 13 shows an image-processed FE-SEM micrograph of a cross section of an optical film in which particles obtained in Example 1-36 are dispersed;
  • FIG. 14 shows an image-processed FE-SEM micrograph of a cross section of an optical film in which particles obtained in Comparative Example 1-2 are dispersed;
  • FIG. 15 shows an image-processed TEM micrograph of organic-inorganic composite particles obtained in Preparation Example 2-1;
  • FIG. 16 shows an image-processed TEM micrograph of a cut surface of a film obtained in Example 2-1;
  • FIG. 17 shows an image-processed TEM micrograph of a cut surface of a film obtained in Example 2-2;
  • FIG. 18 shows an image-processed TEM micrograph of a cut surface of a film obtained in Example 2-3;
  • FIG. 19 shows an image-processed TEM micrograph of a cut surface of a film obtained in Example 2-4;
  • FIG. 20 shows an image-processed TEM micrograph of a cut surface of a film obtained in Example 2-7;
  • FIG. 21 shows an image-processed TEM micrograph of a cut surface of a film obtained in Example 2-8;
  • FIG. 22 shows an image-processed TEM micrograph of a cut surface of a film obtained in Example 2-11;
  • FIG. 23 shows an image-processed TEM micrograph of a cut surface of a film obtained in Example 2-13;
  • FIG. 24 shows an image-processed TEM micrograph of a cut surface of a film obtained in Example 2-14;
  • FIG. 25 shows UV-visible absorption spectra at the start of irradiation with light and 30 minutes, 1 hour, 2 hours, 3 hours and 4 hours after the irradiation, obtained in Example 3-10;
  • FIG. 26 shows UV-visible absorption spectra at the start of irradiation with light and 5 minutes, 10 minutes, 15 minutes, 30 minutes, 1 hour and 2 hours after the irradiation, obtained in Example 3-66;
  • FIG. 27 shows an image-processed TEM micrograph of a porous film obtained in Example 4-6;
  • FIG. 28 shows an image-processed TEM micrograph of a porous film obtained in Example 4-7.
  • FIG. 29 shows an image-processed TEM micrograph of a porous film obtained in Example 4-13.
  • the particles of the present invention are organic-inorganic composite particles that can be dispersed in a solvent and/or a resin as primary particles having an organic group on the surface of inorganic particles, and have negative birefringence.
  • the primary particles are obtained as organic-inorganic composite particles obtained by surface-treating inorganic particles with an organic compound.
  • the inorganic compound (inorganic material) for forming inorganic particles has negative birefringence (minus birefringence) and can be, for example, a carbonate containing an alkaline earth metal and/or a composite oxide containing an alkaline earth metal.
  • alkaline earth metal examples include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra) and the like. Magnesium and strontium are preferable.
  • the alkaline earth metals can be used singly or in a combination of two or more.
  • carbonate containing an alkaline earth metal examples include beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, radium carbonate and the like. These carbonates can be used singly or in a combination of two or more.
  • Examples of the composite oxide containing an alkaline earth metal include alkaline earth metal salts of metal acids such as alkaline earth metal titanates, alkaline earth metal ferrates, alkaline earth metal stannates and alkaline earth metal zirconates.
  • the composite oxides can be used singly or in a combination of two or more.
  • Alkaline earth metal titanates are preferable.
  • alkaline earth metal titanates examples include beryllium titanate (BeTiO 3 ), magnesium titanate (MgTiO 3 ), calcium titanate (CaTiO 3 ), strontium titanate (SrTiO 3 ), barium titanate (BaTiO 3 ), radium titanate (RaTiO 3 ) and the like.
  • the alkaline earth metal titanates can be used singly or in a combination of two or more.
  • the organic compound is, for example, a hydrophobic organic compound and/or a hydrophilic organic compound that imparts hydrophobicity and/or hydrophilicity to the surface of the inorganic particles.
  • the organic compound contains a binding group capable of binding to the surface of the inorganic particles and a hydrophobic group and/or a hydrophilic group.
  • the binding group is selected as appropriate according to the type of inorganic particles, and examples thereof include functional groups such as carboxyl group, phosphoric acid group (—PO(OH) 2 , phosphono group), amino group and sulfo group.
  • One or more of these binding groups may be contained in the organic compound.
  • the hydrophobic group contained in the hydrophobic organic compound can be, for example, a hydrocarbon group having 4 to 20 carbon atoms, and examples thereof include alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenylalkylene group, aryl group, aralkyl group and the like.
  • alkyl group examples include linear or branched alkyl groups having 4 to 20 carbon atoms such as butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and icosyl.
  • a linear or branched alkyl group having 6 to 18 carbon atoms is preferable.
  • alkenyl group examples include alkenyl groups having 4 to 20 carbon atoms such as hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl and icosenyl.
  • alkynyl group examples include alkynyl groups having 4 to 20 carbon atoms such as hexynyl, heptynyl, octynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl and octadecynyl.
  • cycloalkyl group examples include cycloalkyl groups having 4 to 20 carbon atoms such as cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl.
  • cycloalkenylalkylene group examples include norbornene decyl (norboneryl decyl, bicyclo[2.2.1]hepta-2-enyl-decyl) and the like.
  • aryl group examples include aryl groups having 6 to 20 carbon atoms such as phenyl, xylyl, naphthyl and biphenyl.
  • aralkyl group examples include aralkyl groups having 7 to 20 carbon atoms such as benzyl, phenylethyl, phenylpropyl, diphenylmethyl, phenylbutyl, phenylpentyl, phenylhexyl and phenylheptyl.
  • the hydrophobic group is preferably an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenylalkylene group or an aralkyl group.
  • hydrophobic organic compound examples include alkyl group-containing compounds such as hexanoic acid, 3,3,5-trimethylhexanoic acid, decanoic acid, decylamine, lauric acid, decylphosphonic acid, trioctylphosphinoxide; alkenyl group-containing compounds such as 10-undecenoic acid, oleic acid; cycloalkyl group-containing compounds such as cyclohexanepentanoic acid (cyclohexylpentanoic acid), cyclopentanedecanoic acid; cycloalkenylalkylene group-containing compounds such as norbornene decanoic acid; aralkyl group-containing compounds such as 6-phenylhexanoic acid, and the like.
  • alkyl group-containing compounds such as hexanoic acid, 3,3,5-trimethylhexanoic acid, decanoic acid, decylamine, lauric acid, decylphospho
  • the hydrophilic group contained in the hydrophilic organic compound can be a hydroxyl group, a carbonyl groups or the like. One or more of the hydrophilic groups may be contained in the hydrophilic organic compound.
  • hydrophilic organic compound examples include hydroxyl group-containing compounds (monohydroxycarboxylic acids or esters thereof) such as ethyl 6-hydroxyhexanoate, 4-hydroxyphenylacetic acid and 3-(4-hydroxyphenyl)propionic acid; carbonyl group-containing compounds (or in other words, monocarbonylcarboxylic acids) such as 4-oxovaleric acid; and the like.
  • hydroxyl group-containing compounds monohydroxycarboxylic acids or esters thereof
  • carbonyl group-containing compounds or in other words, monocarbonylcarboxylic acids
  • 4-oxovaleric acid and the like.
  • the hydrophobic group and/or the hydrophilic group serve as the organic group that is present on the surface of the inorganic particles of the organic-inorganic composite particles.
  • the particles of the present invention can be obtained by subjecting the inorganic compound and the organic compound to a reaction treatment, preferably, a high temperature treatment.
  • the particles of the present invention can be obtained by subjecting the inorganic compound and the organic compound to a high temperature treatment in water under high pressure (hydrothermal synthesis: hydrothermal reaction) or by subjecting the inorganic compound to a high temperature treatment in the organic compound (high temperature treatment in the organic compound).
  • the particles of the present invention can be obtained by surface-treating the surface of inorganic particles formed by the inorganic compound with the organic group.
  • the inorganic compound and the organic compound are reacted under high-temperature and high-pressure conditions in the presence of water (first hydrothermal synthesis).
  • a reaction system is prepared under high-temperature and high-pressure conditions by placing the inorganic compound, the organic compound and water in a pressure-resistant airtight container and heating them.
  • the proportions of respective components per 100 parts by weight of the inorganic compound are as follows: the proportion of the organic compound is, for example, 5 to 160 parts by weight and preferably 10 to 110 parts by weight; and the proportion of water is, for example, 200 to 1000 parts by weight and preferably 400 to 700 parts by weight.
  • the proportion of the organic compound is below the above range, the degree of progress of the surface modification reaction will be small, which may result in poor dispersibility in a solvent and/or a resin. If, on the other hand, the proportion of the organic compound exceeds the above range, the surface modification reaction will proceed sufficiently, but due to the excessive use of organic compound, the cost may increase.
  • the proportion of water exceeds the above range, the concentration of the inorganic compound will be excessively high, and the intended particles may not be produced.
  • the density of the organic compound is usually 0.8 to 1.1 g/mL, and thus the proportion of the organic compound in terms of volume is, for example, 10 to 150 mL and preferably 20 to 100 mL per 100 g of the inorganic compound.
  • the number of moles of the organic compound can be, for example, 0.01 to 1000 mol and preferably 0.1 to 10 mol per mol of metal contained in the inorganic compound.
  • the density of water is usually approximately 1 g/mL, and thus the proportion of water in terms of volume is, for example, 200 to 1000 mL and preferably 400 to 700 mL per 100 g of the inorganic compound.
  • the surface of inorganic particles can be reliably surface-treated.
  • the heating temperature is, for example, 100 to 500° C. and preferably 200 to 400° C.
  • the heating temperature is below the above range, the hydrothermal reaction will not proceed sufficiently, as a result of which the inorganic compound may remain. If, on the other hand, the heating temperature exceeds the above range, although the hydrothermal reaction will proceed, an excessive amount of heat will be generated, and thus the cost and the environmental load may increase.
  • the pressure is, for example, 10 to 50 MPa, and preferably 20 to 40 MPa.
  • the hydrothermal reaction will not proceed sufficiently, as a result of which the inorganic compound may remain. If, on the other hand, the pressure falls within the above range, the hydrothermal reaction will proceed and the level of safety can be enhanced.
  • the reaction time is, for example, 1 to 200 minutes and preferably 3 to 150 minutes.
  • reaction time is below the above range, the hydrothermal reaction will not proceed sufficiently, as a result of which the inorganic compound may remain. If, on the other hand, the reaction time exceeds the above range, although the hydrothermal reaction will proceed, the particle growth will also proceed to give coarse particles which may be unsuitable for optical applications. Also, due to the long reaction time, the cost may increase.
  • the airtight container After the hydrothermal reaction, the airtight container is cooled, and then, for example, a precipitate precipitated on the bottom wall of the airtight container or a deposit adhering to the inner wall of the airtight container is recovered.
  • the precipitate is obtained by, for example, sedimentation separation in which the reaction product is settled by gravity or a centrifugal field.
  • the precipitate is obtained as a precipitate of the reaction product by centrifugal sedimentation (centrifugal separation) in which the reaction product is settled by a centrifugal field.
  • the deposit is recovered by, for example, a scraper (spatula) or the like.
  • the reaction product can also be recovered (separated) by adding a solvent to wash away an unreacted organic compound (or in other words, dissolving the organic compound in the solvent) and thereafter removing the solvent.
  • an alcohol such as methanol, ethanol, propanol or isopropanol or a ketone such as acetone or methyl ethyl ketone can be used, and an alcohol is preferably used.
  • the washed reaction product is separated from the solvent (supernatant liquid) by, for example, filtration, decantation or the like, and recovered.
  • the particles of the present invention can also be obtained by subjecting a metal hydroxide containing an alkaline earth metal, a carbonic acid source and an organic compound to a hydrothermal synthesis (second hydrothermal synthesis).
  • alkaline earth metal contained in the metal hydroxide containing an alkaline earth metal examples include the same alkaline earth metals as those of the carbonates listed above.
  • metal hydroxide examples include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, radium hydroxide and the like.
  • the carbonic acid source is, for example, formic acid and/or urea.
  • organic compound examples include the same organic compounds as those used in the first hydrothermal synthesis described above.
  • the metal hydroxide, the carbonic acid source and the organic compound are reacted under high-temperature and high-pressure conditions in the presence of water.
  • the proportions of respective components per 100 parts by weight of the metal hydroxide are as follows: the proportion of the carbonic acid source is, for example, 5 to 140 parts by weight and preferably 10 to 70 parts by weight; the proportion of the organic compound is, for example, 4 to 550 parts by weight and preferably 15 to 330 parts by weight; and the proportion of water is, for example, 150 to 2500 parts by weight and preferably 300 to 500 parts by weight.
  • the proportion of the carbonic acid source is below the above range, the concentration of the metal hydroxide will be excessively low, and the particles may not be obtained. If, on the other hand, the proportion of the carbonic acid source exceeds the above range, although the reaction will proceed, coarse particles which may be unsuitable for optical applications will be obtained.
  • the proportion of the organic compound is below the above range, the surface modification reaction will not proceed sufficiently, which may result in poor dispersibility in a solvent and/or a resin. If, on the other hand, the proportion of the organic compound exceeds the above range, the surface modification reaction will proceed sufficiently, but due to the excessive use of organic compound, the cost may increase.
  • the proportion of water is below the above range, although the reaction will proceed, coarse particles which may be unsuitable for optical applications will be obtained. If, on the other hand, the proportion of water exceeds the above range, the concentration of the metal hydroxide will be excessively high, and the intended particles may not be produced.
  • the density of the carbonic acid source is usually 1.1 to 1.4 g/mL, and thus the proportion of the carbonic acid source in terms of volume is, for example, 5 to 100 mL and preferably 10 to 50 mL per 100 g of the metal hydroxide.
  • the number of moles of the carbonic acid source may be, for example, 0.4 to 100 mol, preferably 1.01 to 10.0 mol and more preferably 1.05 to 1.30 mol per mol of the metal hydroxide.
  • the proportion of the organic compound in terms of volume is, for example, 5 to 500 mL, and preferably 20 to 300 mL per 100 g of the metal hydroxide, and the number of moles of the organic compound may be, for example, 0.01 to 10000 mol and preferably 0.1 to 10 mol per mol of the metal hydroxide.
  • the proportion of water in terms of volume is, for example, 150 to 2500 mL and preferably 300 to 500 mL per 100 g of the metal hydroxide.
  • the surface of inorganic particles can be reliably surface-treated.
  • reaction conditions for the second hydrothermal synthesis are the same as those for the first hydrothermal synthesis described above.
  • the particles of the present invention can also be obtained by subjecting a metal hydroxide containing an alkaline earth metal, a metal complex and an organic compound to a hydrothermal synthesis (third hydrothermal synthesis).
  • Examples of the metal hydroxide containing an alkaline earth metal include the same metal hydroxides containing an alkaline earth metal as those used in the second hydrothermal synthesis described above.
  • the metal element contained in the metal complex is a metal element that constitutes a composite oxide with the alkaline earth metal contained in the metal hydroxide, and examples thereof include elemental titanium, elemental iron, elemental tin, elemental zirconium and the like. Elemental titanium is preferable.
  • Examples of the ligand of the metal complex include monohydroxycarboxylic acids such as 2-hydroxyoctanoic acid and the like.
  • the metal complex examples include 2-hydroxyoctanoic acid titanate and the like.
  • the metal complex can be obtained by preparation from the metal element and the ligand.
  • organic compound examples include the same organic compounds as those used in the first hydrothermal synthesis described above.
  • the metal hydroxide, the metal complex and the organic compound are reacted under high-temperature and high-pressure conditions in the presence of water.
  • the proportions of respective components per 100 parts by weight of the metal complex are as follows: the proportion of the metal hydroxide is, for example, 1 to 50 parts by weight and preferably 5 to 30 parts by weight; the proportion of the organic compound is, for example, 4 to 550 parts by weight and preferably 15 to 330 parts by weight; and the proportion of water is, for example, 200 to 1000 parts by weight and preferably 300 to 700 parts by weight.
  • the proportion of the metal hydroxide is below the above range, the concentration of the metal hydroxide will be excessively low, and the particles may not be obtained. If, on the other hand, the proportion of the metal hydroxide exceeds the above range, although the surface modification reaction will proceed, coarse particles which may be unsuitable for optical applications will be obtained.
  • the proportion of the organic compound is below the above range, the surface modification reaction will not proceed sufficiently, which may result in poor dispersibility in a solvent and/or a resin. If, on the other hand, the proportion of the organic compound exceeds the above range, the surface modification reaction will proceed sufficiently, but due to the excessive use of organic compound, the cost may increase.
  • the proportion of water is below the above range, although the reaction will proceed, coarse particles which may be unsuitable for optical applications will be obtained. If, on the other hand, the proportion of water exceeds the above range, the concentration of the metal hydroxide will be excessively high, and the intended particles may not be produced.
  • the proportion of the organic compound in terms of volume is, for example, 5 to 500 mL and preferably 20 to 300 mL per 100 g of the metal complex, and the number of moles of the organic compound may be 0.01 to 1000 per mol of the organic compound.
  • the proportion of water in terms of volume is, for example, 200 to 1000 mL and preferably 300 to 700 mL per 100 g of the metal complex.
  • the surface of inorganic particles can be reliably surface-treated.
  • reaction conditions for the third hydrothermal synthesis are the same as those for the first hydrothermal synthesis described above.
  • hydrothermal syntheses (first, second and third hydrothermal syntheses) may also be carried out in the presence of a pH adjusting agent.
  • the second hydrothermal synthesis is carried out in the presence of a pH adjusting agent.
  • the pH adjusting agent can be an alkali or acid.
  • alkali examples include inorganic alkalis such as potassium hydroxide and sodium hydroxide; organic alkalis such as ammonia; and the like.
  • the acid examples include inorganic acids such as sulfuric acid, nitric acid and hydrochloric acid; organic acids such as formic acid and acetic acid; and the like.
  • an alkali is used.
  • the pH of the reaction system is set to, for example, 8 to 12 by using the pH adjusting agent.
  • the average particle size of the resulting particles in the desired range, more specifically, to a smaller value. Accordingly, the particles having a small average particle size (or lengthwise length LL and sideways length SL, which will be described later) can be suitably used in optical applications.
  • Examples of the inorganic compound subjected to the high temperature treatment in the organic compound include the same inorganic compounds as those listed above.
  • the inorganic compound and the organic compound are blended and heated under, for example, normal atmospheric pressure conditions.
  • the proportion of the organic compound is, for example, 10 to 10000 parts by weight and preferably 100 to 1000 parts by weight per 100 parts by weight of the inorganic compound.
  • the proportion of the organic compound in terms of volume is, for example, 10 to 10000 mL and preferably 100 to 1000 mL per 100 g of the inorganic compound.
  • the heating temperature is, for example, a temperature above 100° C., preferably 125° C. or higher and more preferably 150° C. or higher, and usually for example, 300° C. or lower, and preferably 275° C. or lower.
  • the heating time is, for example, 1 to 60 minutes and preferably 3 to 30 minutes.
  • the particles (primary particles) thus obtained are mostly acicular, with a lengthwise length (maximum length) LL of, for example, 200 ⁇ m or less, preferably 5 nm to 200 ⁇ m, more preferably 10 nm to 50 ⁇ m and even more preferably 40 nm to 10 ⁇ m and a sideways length (minimum length) SL of, for example, 1 nm to 20 ⁇ m, preferably 3 nm to 10 ⁇ m and more preferably 5 nm to 5 ⁇ m.
  • the particles (primary particles) obtained by hydrothermal synthesis in the presence of a pH adjusting agent have a lengthwise length LL of, for example, 1 nm to 20 ⁇ m and preferably 10 nm to 10 ⁇ m and a sideways length SL of, for example, 0.5 nm to 2 ⁇ m and preferably 1 nm to 1 ⁇ m.
  • the lengthwise length LL is below the above range, the particles will be too small, which may result in poor physical strength. If, on the other hand, the lengthwise length LL exceeds the above range, good optical characteristics will be obtained, but the particles may be crushed when mixed with a resin or the like.
  • the sideways length SL is below the above range, the particles will be too small, which may result in poor physical strength. If, on the other hand, the sideways length SL exceeds the above range, a sufficient aspect ratio may not be obtained.
  • the particles have an aspect ratio of, for example, 1000 or less, specifically, 1 to 1000, preferably 3 to 100 and more preferably 5 to 30.
  • the aspect ratio is below the above range, poor optical characteristics will be obtained. If, on the other hand, the aspect ratio exceeds the above range, good optical characteristics will be obtained, but the particles may be crushed when mixed with a resin or the like.
  • the particles thus obtained are unlikely to coagulate in a dry state, and even if the particles appear coagulated in a dry state, the coagulation (formation of secondary particles) will be reliably prevented in a particle dispersion and/or a particle-dispersed resin composition, which will be described next, and therefore the particles are dispersed as primary particles substantially uniformly in a solvent and/or a resin.
  • the particles obtained in the above-described manner can be subjected to wet classification.
  • a solvent is added to the particles, and the resulting mixture is stirred and allowed to stand still, and thereafter separated into a supernatant and a precipitate.
  • the same solvents as those listed above can be used.
  • the supernatant is recovered to give particles having a small particle size.
  • the lengthwise length LL of the resulting particles can be adjusted to, for example, 10 nm to 400 nm and preferably 20 nm to 200 nm, and the sideways length SL can be adjusted to, for example, 1 nm to 100 nm and preferably 5 nm to 50 nm.
  • the lengthwise length LL is below the above range, the particle will be too small, which may result in poor physical strength. If, on the other hand, the lengthwise length LL exceeds the above range, good optical characteristics will be obtained, but the particles may be crushed when mixed with a resin or the like.
  • the sideways length SL is below the above range, the particles will be too small, which may result in poor physical strength. If, on the other hand, the sideways length SL exceeds the above range, a sufficient aspect ratio may not be obtained.
  • the solvent for dispersing the particles obtained above examples thereof include the solvents used in washing described above, and other examples include halogenated hydrocarbons such as chloroform, dichloromethane, 1,1,1-trichloroethane, chlorobenzene and dichlorobenzene; alkanes such as pentane, hexane and heptane; cycloalkanes such as cyclopentane and cyclohexane; esters such as ethyl acetate; polyols such as ethylene glycol and glycerin; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as tetrahydrofuran; nitrogen-containing compounds such as N-methylpyrrolidone, pyridine, acetonitrile and dimethylformamide; and the like.
  • halogenated hydrocarbons such as chloroform, dichloromethane, 1,1,1-trichloroethane, chlorobenz
  • solvents can be used singly or in a combination of two or more.
  • the proportion of the solvent is not particularly limited, and the concentration of the particles in the particle dispersion is adjusted to, for example, 0.1 to 70 wt % and preferably 1 to 50 wt %.
  • the concentration of the particles in the particle dispersion is below the above range, the particle dispersion will be too dilute, and thus sufficient optical characteristics may not be obtained when mixed with a resin or the like. If, on the other hand, the concentration of the particles in the particle dispersion exceeds the above range, the dispersibility will be low.
  • thermosetting resins include epoxy resin, polyimide resin (thermosetting polyimide resin), phenol resin, urea resin, melamine resin, diallyl phthalate resin, silicone resin, urethane resin (thermosetting urethane resin) and the like.
  • thermoplastic resins include polyolefin (for example, polyethylene, polypropylene, ethylene-propylene copolymer and the like), acrylic resin (for example, polymethyl methacrylate and the like), polyvinyl acetate, ethylene-vinylacetate copolymer (EVA), polyvinyl chloride, polystyrene, polyacrylonitrile, polyamide (PA; nylon), polycarbonate, polyacetal, polyester (for example, polyarylate, polyethylene terephthalate (PET) and the like), polyphenylene oxide, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone (PEEK), polyallylsulfone, thermoplastic polyimide resin, thermoplastic urethane resin, polyaminobismaleimide, polyamideimide, polyetherimide, bismaleimidetriazine resin, polymethylpentene, fluorine resin, liquid crystal polymer, olefin-vinyl
  • These resins can be used singly or in a combination of two or more.
  • the resin (specifically, thermoplastic resin) has a melting temperature of, for example, 200 to 300° C. and a softening temperature of, for example, 150 to 280° C.
  • the particles and the resin are blended, and the resulting mixture is stirred.
  • the particles, the solvent and the resin are blended, the resulting mixture is stirred to prepare a particle-dispersed resin solution, and thereafter the solvent in the particle-dispersed resin solution is removed.
  • Blending a solvent allows the particles to be more uniformly dispersed in the resin.
  • a resin solution and/or a resin dispersion that has been dissolved and/or dispersed in a solvent are/is blended with the particle dispersion.
  • the same solvents as those listed above can be used.
  • the proportion of the solvent is adjusted to, for example, 40 to 2000 parts by weight and preferably 50 to 1000 parts by weight per 100 parts by weight of the resin solution and/or the resin dispersion.
  • the proportion between the resin solution and/or the resin dispersion and the particle dispersion is adjusted such that the proportion of the particles is, for example, 0.1 to 240 parts by weight and preferably 5 to 100 parts by weight per 100 parts by weight of the resin (solids content).
  • the concentration of the particles in the particle-dispersed resin composition is adjusted to 0.1 to 70 wt % and preferably 1 to 50 wt %.
  • the proportion of the particles is below the above range, the particle-dispersed resin composition will be too dilute, and thus sufficient optical characteristics may not be obtained in the particle-dispersed resin composition. If, on the other hand, the proportion of the particles exceeds the above range, the dispersibility of the particles will be low.
  • the particle-dispersed resin composition is dried by application of heat at, for example, 40 to 60° C. to remove the solvent, and thereby a particle-dispersed resin composition is obtained.
  • the particle-dispersed resin composition is injected into a metal mold or the like and then subjected to, for example, heat molding such as heat pressing, whereby the resin molded article of the present invention can be obtained.
  • heat pressing for example, vacuum pressing is used.
  • the conditions are as follows: the temperature is greater than or equal to the melting temperature or softening temperature of the resin, specifically, 100 to 300° C. and preferably 150 to 250° C.; and the pressing pressure is, for example, 20 to 1000 MPa and preferably 40 to 80 MPa.
  • the heating temperature is below the above range, it may not be possible to soften the resin. If, on the other hand, the heating temperature exceeds the above range, the resin may be thermally decomposed, and also the cost may increase due to an excessive amount of heat generated.
  • the resin may not be sufficiently deformed (molded). If, on the other hand, the pressing pressure exceeds the above range, the resin can be sufficiently molded, but the pressing pressure will be excessively high, which may increase the cost.
  • the resin molded article of the present invention can be obtained by (application method) applying the particle-dispersed resin solution onto a support plate by using, for example, an application method such as spin coating or roll coating, subsequently removing the solvent at the same temperature as described above, and then if necessary curing the resultant by application of heat so as to form a coating that is made of the particle-dispersed resin composition, and if necessary further drying the coating.
  • an application method such as spin coating or roll coating
  • the resin molded article of the present invention can also be obtained by an extrusion method in which the particle-dispersed resin composition is extruded by an extruding machine or the like.
  • the particles are uniformly dispersed as primary particles in the resin, or in other words, without coagulation of the particles.
  • the thickness of the optical film is, for example, 1 to 100 ⁇ m and preferably 5 to 50 ⁇ m.
  • the thickness of the optical film is below the above range, sufficient optical characteristics may not be obtained. If, on the other hand, the thickness of the optical film exceeds the above range, although sufficient optical characteristics can be obtained, it may be difficult to form a uniform film and the cost may increase.
  • the particles of the present invention can be dispersed as primary particles in a solvent and/or a resin, and therefore have excellent dispersibility in a solvent and/or a resin.
  • the particles of the present invention have negative birefringence.
  • the resin molded article of the present invention can reliably have excellent optical characteristics and thus is useful as an optical member, in particular, as an optical film.
  • the particles of the present invention have a particle size (lengthwise length LL and sideways length SL) that is smaller than the wavelength of light (for example, 380 to 800 nm in the case of visible light) and are dispersed in the resin molded article of the present invention, and therefore negative birefringence can be imparted to the optical film with excellent reliability.
  • the optical film of the present invention can be suitably used in phase difference plates or polarizing plates for plasma display panels or liquid crystal televisions, or the like.
  • the particle-dispersed resin composition of the present invention contains a resin and organic-inorganic composite particles.
  • thermosetting resins examples include thermosetting resins, thermoplastic resins and the like.
  • thermoplastic resins include olefin resin, acrylic resin, polystyrene resin, polyester resin, polyacrylonitrile resin, maleimide resin, polyvinyl acetate resin, ethylene-vinylacetate copolymer, polyvinyl alcohol resin, polyamide resin, polyvinyl chloride resin, polyacetal resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyallylsulfone resin, thermoplastic polyimide resin (including thermoplastic fluorine-based polyimide resin), thermoplastic urethane resin, polyetherimide resin, polymethylpentene resin, cellulose resin, liquid crystal polymer, ionomer and the like.
  • These resins can be used singly or in a combination of two or more.
  • the resin is preferably a highly oriented resin having high orientation, and specific examples thereof include olefin resin, acrylic resin, polystyrene resin, polyester resin, polyvinyl alcohol resin, thermoplastic polyimide resin, polyetherimide resin, liquid crystal polymer and the like.
  • olefin resin examples include cyclic olefin resin, chain olefin resin and the like. Cyclic olefin resin is preferable.
  • cyclic olefin resin examples include polynorbornene, ethylene-norbornene copolymers, and derivative thereof.
  • chain olefin resin examples include polyethylene, polypropylene, ethylene-propylene copolymer and the like.
  • acrylic resin examples include polymethyl methacrylate and the like.
  • polyester resin examples include polyarylate, polyethylene terephthalate, polyethylene naphthalate and the like.
  • the polyvinyl alcohol resin is obtained by, for example, complete or partial saponification of polyvinyl acetate resin obtained by polymerizing vinyl monomers containing vinyl acetate as a primary component by an appropriate method.
  • the saponification degree of polyvinyl alcohol resin is, for example, 70 to 99.99 mol % and preferably 70 to 99.9 mol %.
  • the resin preferably has a functional group.
  • the functional group include hydrophilic groups such as carboxyl group and hydroxyl group; hydrophobic groups such as hydrocarbon group; and the like.
  • the organic-inorganic composite particles are particles that can be dispersed as primary particles in a solvent (described later) and/or a resin and that have an organic group on the surface of the inorganic particles. Specifically, the organic-inorganic composite particles are obtained by surface-treating inorganic particles with an organic compound.
  • the organic-inorganic composite particles can be used singly or in a combination of two or more.
  • the inorganic substance for forming inorganic particles can be a metal composed of a metal element such as a main group element or a transition element, a nonmetal composed of a nonmetal element such as boron or silicon, an inorganic compound containing a metal element and/or a nonmetal, or the like.
  • Examples of the metal element and the nonmetal element include elements that are located on the left side and the lower side of a border line that is assumed to pass through boron (B) of the IIIB group, silicon (Si) of the IVB group, arsenic (As) of the VB group, tellurium (Te) of the VIB group and astatine (At) of the VIIB group on the long-form periodic table (IUPAC, 1989), as well as the elements that are located on the border line.
  • group IIIA elements such as Sc and Y; the group WA elements such as Ti, Zr, and Hf; the group VA elements such as V, Nb, and Ta; the group VIA elements such as Cr, Mo, and W; the group VIIA elements such as Mn and Re; the group VIIIA elements such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt; the group IB elements such as Cu, Ag, and Au; the group IIB elements such as Zn, Cd, and Hg; the group IIIB elements such as B, Al, Ga, In, and Tl; the group IVB elements such as Si, Ge, Sn, and Pb; the group VB elements such as As, Sb, and Bi; the group VIB elements such as Te and Po; the lanthanide series elements such as La, Ce, Pr, and Nd; the actinium series elements such as Ac, Th, and U; and the like.
  • group IIIA elements such as Sc and Y
  • the group WA elements such as Ti, Zr, and
  • the inorganic compound can be, for example, a hydrogen compound, a hydroxide, a nitride, a halide, an oxide, a carbonate, a sulfate, a nitrate, a metal complex, a sulfide, a carbide, a phosphorus compound, or the like.
  • the inorganic compound may be a composite compound such as, for example, an oxynitride or a composite oxide.
  • the inorganic substance is preferably an inorganic compound, and more preferable examples include an oxide, a composite oxide, a carbonate, a sulfate and the like.
  • oxides examples include metal oxides, and preferable examples include titanium oxide (titanium dioxide, titanium oxide (IV), titania: TiO 2 ), cerium oxide (cerium dioxide, cerium oxide (IV), ceria: CeO 2 ) and the like.
  • the oxides can be used singly or in a combination of two or more.
  • the composite oxide is a compound consisting of oxygen and a plurality of elements, and the plurality of elements may be a combination of at least two elements selected from the elements other than oxygen contained in the oxides listed above, the group I elements, and the group II elements.
  • Examples of the group I elements include alkali metals such as Li, Na, K, Rb, and Cs.
  • Examples of the group II elements include the same alkaline earth metals as those listed in the first embodiment.
  • Preferable examples of the combination of a plurality of elements include combinations that contain at least a group II element such as a combination of a group II element and a group IVB element, a combination of a group II element and a group VIIIB element, and a combination of a group II element and a group IVA element.
  • a group II element such as a combination of a group II element and a group IVB element, a combination of a group II element and a group VIIIB element, and a combination of a group II element and a group IVA element.
  • Examples of the composite oxide containing at least a group II element include alkaline earth metal titanates, alkaline earth metal zirconates, alkaline earth metal ferrates, alkaline earth metal stannates, and the like.
  • Preferable composite oxides are alkaline earth metal titanates.
  • alkaline earth metal titanates include the same alkaline earth metal titanates as those listed in the first embodiment.
  • the composite oxides can be used singly or in a combination of two or more.
  • the element that combines with carbonic acid can be, for example, an alkali metal, an alkaline earth metal or the like.
  • the alkali metal and the alkaline earth metal can be the same alkali metals and alkaline earth metals as those listed above.
  • the element that combines with carbonic acid is preferably an alkaline earth metal.
  • the carbonate is preferably a carbonate containing an alkaline earth metal, and examples of such a carbonate include the same carbonates as those listed in the first embodiment. These carbonates can be used singly or in a combination of two or more.
  • the sulfate is a compound consisting of a sulfate ion (SO 4 2 ⁇ ) and a metal cation (more specifically, a compound formed by substitution of the hydrogen atoms of sulfuric acid (H 2 SO 4 ) with a metal), and the metal contained in the sulfate can be, for example, an alkali metal, an alkaline earth metal or the like.
  • the alkali metal and the alkaline earth metal can be the same alkali metals and alkaline earth metals as those listed above.
  • the metal is preferably an alkaline earth metal.
  • preferable sulfates are sulfates containing an alkaline earth metal, and examples of such sulfates include beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, radium sulfate and the like. Barium sulfate is preferable.
  • sulfates can be used singly or in a combination of two or more.
  • the organic compound is, for example, an organic group-introducing compound that introduces (disposes) an organic group on the surface of inorganic particles.
  • the organic compound contains a binding group capable of binding to the surface of inorganic particles and an organic group.
  • the binding group may be selected as appropriate according to the type of inorganic particles, and examples thereof include functional groups such as carboxyl group, phosphoric acid group (—PO(OH) 2 , phosphono group), amino group, sulfo group, hydroxyl group, thiol group, epoxy group, isocyanate group (cyano group), nitro group, azo group, silyloxy group, imino group, aldehyde group (acyl group), nitrile group, vinyl group (polymerizable group), and the like.
  • Preferable examples include carboxyl group, phosphoric acid group, amino group, sulfo group, hydroxyl group, thiol group, epoxy group, azo group, vinyl group, and the like. More preferable examples include carboxyl group and phosphoric acid group.
  • the carboxyl group includes a carboxylic acid ester group (carboxy ester group).
  • the phosphoric acid group includes a phosphoric acid ester group (phosphonate group).
  • binding groups are contained in the organic compound. Specifically, the binding group is bound to a terminal or a side chain of the organic group.
  • the binding group is selected as appropriate according to the type of inorganic particles. Specifically, when the inorganic particles contain cerium oxide, strontium carbonate and/or barium sulfate, for example, a carboxyl group is selected. When the inorganic particles contain titanium oxide, for example, a phosphoric acid group is selected.
  • the organic group includes, for example, a hydrocarbon group such as an aliphatic group, an alicyclic group, an araliphatic group or an aromatic group, or the like.
  • the aliphatic group includes, for example, a saturated aliphatic group, an unsaturated aliphatic group and the like.
  • saturated aliphatic group examples include alkyl groups having 1 to 20 carbon atoms and the like.
  • alkyl group examples include linear or branched alkyl groups (paraffin hydrocarbon groups) having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and icosyl, and the like.
  • Examples of the unsaturated aliphatic group include alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and the like.
  • alkenyl group examples include alkenyl groups (olefin hydrocarbon groups) having 2 to 20 carbon atoms such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl (oleyl) and icosenyl.
  • alkynyl group examples include alkynyl groups (acetylene hydrocarbon groups) having 2 to 20 carbon atoms such as ethynyl, propynyl, butyryl, pentynyl, hexynyl, heptynyl, octynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl and octadecynyl.
  • alkynyl groups acetylene hydrocarbon groups
  • Examples of the alicyclic group include cycloalkyl groups having 4 to 20 carbon atoms, cycloalkenylalkylene groups having 7 to 20 carbon atoms, and the like.
  • cycloalkyl group examples include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl and the like.
  • cycloalkenylalkylene group examples include norbornene decyl (norboneryl decyl, bicyclo[2.2.1]hept-2-enyl-decyl) and the like.
  • araliphatic group examples include aralkyl groups having 7 to 20 carbon atoms such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl and diphenylmethyl.
  • aromatic group examples include aryl groups having 6 to 20 carbon atoms such as phenyl, xylyl, naphthyl and biphenyl.
  • the organic group is used as a hydrophobic group for imparting hydrophobicity to the surface of inorganic particles.
  • organic compounds containing a hydrophobic group described above are used as hydrophobic organic compounds for hydrophobic treatment of inorganic particles.
  • hydrophobic organic compounds in the case where the binding group is a carboxyl group include aliphatic group-containing carboxylic acids including saturated aliphatic group-containing carboxylic acids (saturated fatty acids) such as hexanoic acid and decanoic acid and unsaturated aliphatic group-containing carboxylic acids (unsaturated fatty acids) such as oleic acid, and the like.
  • hydrophobic organic compounds in the case where the binding group is a carboxyl group include alicyclic group-containing carboxylic acids (alicyclic carboxylic acids) such as cyclohexyl monocarboxylic acid, araliphatic group-containing carboxylic acids (araliphatic carboxylic acids) such as 6-phenylhexanoic acid, aromatic group-containing carboxylic acids (aromatic carboxylic acids) such as benzoic acid and toluenecarboxylic acid, and the like.
  • alicyclic carboxylic acids such as cyclohexyl monocarboxylic acid
  • araliphatic group-containing carboxylic acids such as 6-phenylhexanoic acid
  • aromatic carboxylic acids aromatic carboxylic acids
  • benzoic acid and toluenecarboxylic acid and the like.
  • hydrophobic organic compounds in the case where the binding group is a phosphoric acid group (including phosphoric acid ester group), aliphatic group-containing phosphate esters including saturated aliphatic group-containing phosphate esters such as ethyl octylphosphonate and ethyl decylphosphonate.
  • the organic compound can also be used as a hydrophilic organic compound for hydrophilic treatment of inorganic particles.
  • the organic group contained in the hydrophilic organic compound includes any of the above hydrocarbon groups and a hydrophilic group that binds to the hydrocarbon group.
  • the hydrophilic group is bound to a terminal (the terminal (the other terminal) opposite the terminal that is bound to the binding group (one terminal)) or a side chain of the hydrocarbon group.
  • the hydrophilic group is a functional group having a polarity (or in other words, polar group), and examples thereof include a carboxyl group, a hydroxyl group, a phosphoric acid group, an amino group, a sulfo group, a carbonyl group, a cyano group, a nitro group, an aldehyde group, a thiol group and the like.
  • polar group a functional group having a polarity (or in other words, polar group)
  • examples thereof include a carboxyl group, a hydroxyl group, a phosphoric acid group, an amino group, a sulfo group, a carbonyl group, a cyano group, a nitro group, an aldehyde group, a thiol group and the like.
  • One or more of the hydrophilic groups are contained in the hydrophilic organic compound.
  • Examples of the organic group containing a carboxyl group include carboxyaliphatic groups including carboxysaturated aliphatic groups such as 3-carboxypropyl, 4-carboxybutyl, 6-carboxyhexyl, 8-carboxyoctyl and 10-carboxydecyl and carboxyunsaturated aliphatic groups such as carboxybutenyl, and the like.
  • Other examples of the organic group containing a carboxyl group include carboxyalicyclic groups such as carboxycyclohexyl, carboxyaraliphatic groups such as carboxyphenylhexyl, carboxyaromatic groups such as carboxyphenyl, and the like.
  • organic group containing a hydroxyl group examples include hydroxysaturated aliphatic groups (hydroxy aliphatic groups) such as 4-hydroxybutyl, 6-hydroxylhexyl and 8-hydroxyoctyl, hydroxyaraliphatic groups such as 4-hydroxybenzyl, 2-(4-hydroxyphenyl)ethyl, 3-(4-hydroxyphenyl)propyl and 6-(4-hydroxyphenyl)hexyl, hydroxyaromatic groups such as hydroxy phenyl, and the like.
  • hydroxysaturated aliphatic groups such as 4-hydroxybutyl, 6-hydroxylhexyl and 8-hydroxyoctyl
  • hydroxyaraliphatic groups such as 4-hydroxybenzyl, 2-(4-hydroxyphenyl)ethyl, 3-(4-hydroxyphenyl)propyl and 6-(4-hydroxyphenyl)hexyl
  • hydroxyaromatic groups such as hydroxy phenyl, and the like.
  • organic group containing a phosphoric acid group examples include phosphonosaturated aliphatic groups (phosphonoaliphatic groups) such as 6-phosphonohexyl, phosphonoaraliphatic groups such as 6-phosphonophenylhexyl, and the like.
  • phosphonosaturated aliphatic groups such as 6-phosphonohexyl
  • phosphonoaraliphatic groups such as 6-phosphonophenylhexyl, and the like.
  • Examples of the organic group containing an amino group include aminosaturated aliphatic groups (aminoaliphatic groups) such as 6-aminohexyl, aminoaraliphatic groups such as 6-aminophenylhexyl, and the like.
  • organic group containing a sulfo group examples include sulphosaturated aliphatic groups (sulphoaliphatic groups) such as 6-sulphohexyl, sulphoaraliphatic groups such as 6-sulphophenylhexyl, and the like.
  • organic group containing a carbonyl group examples include oxosaturated aliphatic groups (oxoaliphatic groups) such as 3-oxopentyl, and the like.
  • Examples of the organic group containing a cyano group include cyanosaturated aliphatic groups (cyanoaliphatic groups) such as 6-cyanohexyl, and the like.
  • nitro group-containing organic group examples include nitrosaturated aliphatic groups (nitroaliphatic groups) such as 6-nitrohexyl, and the like.
  • aldehyde group-containing organic group examples include aldehydesaturated aliphatic groups (aldehydealiphatic groups) such as 6-aldehydehexyl, and the like.
  • Examples of the organic group containing a thiol group include thiolsaturated aliphatic groups (thiolaliphatic groups) such as 6-thiolhexyl, and the like.
  • the organic compound containing a hydrophilic group can be, for example, a carboxyl group-containing organic compound, a hydroxyl group-containing organic compound, a phosphoric acid group-containing organic compound, an amino group-containing organic compound, a sulfo group-containing organic compound, a carbonyl group-containing organic compound, a cyano group-containing organic compound, a nitro group-containing organic compound, an aldehyde group-containing organic compound, a thiol group-containing organic compound, and the like.
  • the carboxyl group-containing organic compound can be, for example, a dicarboxylic acid or the like in the case where both the binding group and the hydrophilic group are carboxyl groups.
  • the dicarboxylic acid include aliphatic dicarboxylic acids including saturated aliphatic dicarboxylic acids such as propanedioic acid (malonic acid), butanedioic acid (succinic acid), hexanedioic acid (adipic acid), octanedioic acid, decanedioic acid (sebacic acid) and unsaturated aliphatic dicarboxylic acids such as itaconic acid; alicyclic dicarboxylic acids such as cyclohexyl dicarboxylic acid; araliphatic dicarboxylic acids such as 6-carboxyphenyl hexanoic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid; and the
  • the carboxyl group-containing organic compound can be a carboxyl group-containing phosphate ester or the like in the case where the binding group is a carboxyl group and the hydrophilic group is a phosphoric acid ester group (in the case where the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate), or in the case where the binding group is a phosphoric acid ester group and the hydrophilic group is a carboxyl group (in the case where the inorganic particles include, for example, zinc oxide or barium sulfate). Specific examples thereof include ethyl carboxydecylphosphate, ethyl carboxyoctylphosphate, and the like.
  • the hydroxyl group-containing organic compound can specifically be, for example, a monohydroxyl carboxylic acid in the case where the binding group is a carboxyl group and the hydrophilic group is a hydroxyl group (in the case where the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate).
  • the monohydroxyl carboxylic acid include 4-hydroxybutanoic acid, 6-hydroxyhexanoic acid, 8-hydroxyoctanoic acid, 4-hydroxyphenylacetic acid, 3-(4-hydroxyphenyl)propionic acid, 6-(4-hydroxyphenyl)hexanoic acid, hydroxybenzoic acid, and the like.
  • the phosphoric acid group-containing organic compound can be, for example, a monophosphonocarboxylic acid in the case where the binding group is a carboxyl group and the hydrophilic group is a phosphoric acid group (in the case where the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate).
  • the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate.
  • specific examples thereof include 6-phosphonohexanoic acid, 6-phosphonophenylhexanoic acid, as well as the carboxyl group-containing phosphate esters listed above.
  • the amino group-containing organic compound can specifically be, for example, a monoaminocarboxylic acid in the case where the binding group is a carboxyl group and the hydrophilic group is an amino group (in the case where the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate).
  • the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate.
  • specific examples thereof include 6-aminohexanoic acid, 6-aminophenylhexanoic acid, and the like.
  • the sulfo group-containing organic compound can specifically be, for example, a monosulfocarboxylic acid in the case where the binding group is a carboxyl group and the hydrophilic group is a sulfo group (in the case where the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate).
  • the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate.
  • specific examples thereof include 6-sulfohexanoic acid, 6-sulfophenylhexanoic acid, and the like.
  • the carbonyl group-containing organic compound can specifically be, for example, a monocarbonylcarboxylic acid in the case where the binding group is a carboxyl group and the hydrophilic group is a carbonyl group (in the case where the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate). Specific examples thereof include 4-oxovaleric acid, and the like.
  • the cyano group-containing organic compound can specifically be, for example, a monocyanocarboxylic acid in the case where the binding group is a carboxyl group and the hydrophilic group is a cyano group (in the case where the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate). Specific examples thereof include 6-cyano hexanoic acid, and the like.
  • the nitro group-containing organic compound can specifically be, for example, a mononitrocarboxylic acid in the case where the binding group is a carboxyl group and the hydrophilic group is a nitro group (in the case where the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate). Specific examples thereof include 6-nitro hexanoic acid, and the like.
  • the aldehyde group-containing organic compound can specifically be, for example, a monoaldehydecarboxylic acid in the case where the binding group is a carboxyl group and the hydrophilic group is an aldehyde group (in the case where the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate).
  • a specific example is 6-aldehydehexanoic acid.
  • the thiol group-containing organic compound can specifically be, for example, a monothiolcarboxylic acid in the case where the binding group is a carboxyl group and the hydrophilic group is a thiol group (in the case where the inorganic particles include, for example, cerium oxide, strontium carbonate or barium sulfate). Specific examples include 6-thiolhexanoic acid, and the like.
  • the same or mutually different organic groups may be used.
  • the organic group contains a plurality of different types of organic groups, a plurality of homologous organic groups and/or a plurality of heterologous organic groups are contained.
  • Examples of the homologous organic groups include a combination of a plurality of aliphatic groups, a combination of a plurality of alicyclic groups, a combination of a plurality of araliphatic groups and a combination of a plurality of aromatic groups.
  • homologous organic groups include a combination of a plurality of carboxyaliphatic groups, a combination of a plurality of carboxyalicyclic groups, a combination of a plurality of carboxyaraliphatic groups, a combination of a plurality of carboxyaromatic groups, a combination of a plurality of hydroxy aliphatic groups, a combination of a plurality of hydroxyaraliphatic groups, a combination of a plurality of hydroxyaromatic groups, a combination of a plurality of phosphonoaliphatic groups, a combination of a plurality of phosphonoaraliphatic groups, a combination of a plurality of aminoaliphatic groups, a combination of a plurality of aminoaraliphatic groups, a combination of a plurality of sulphoaliphatic groups, a combination of a plurality of sulphoaraliphatics, a combination of a plurality of oxoaliphatic groups, a combination of a plurality of a plurality
  • a preferable example is a combination of a plurality of aliphatic groups
  • a more preferable example is a combination of a plurality of saturated aliphatic groups
  • a particularly preferable example is a combination of a saturated aliphatic group having less than 10 carbon atoms and a saturated aliphatic group having 10 or more carbon atoms, specifically, a combination of hexyl and decyl.
  • the organic group contains a plurality of homologous organic groups
  • a plurality of organic groups having different sizes (lengths or/and dimensions, or in other words, the number of carbon atoms) are contained in the organic group. Accordingly, in a space between adjacent larger organic groups, a resin molecule enters a gap (pocket) formed in accordance with the smaller organic group, and the interaction between the larger organic group and the resin molecule can be enhanced. As a result, the dispersibility of the organic-inorganic composite particles can be enhanced.
  • heterologous organic groups include a combination of at least two different groups selected from the group consisting of an aliphatic group, an alicyclic group, an araliphatic group, an aromatic group, a carboxyaliphatic group, a carboxyalicyclic group, a carboxyaraliphatic group, a carboxyaromatic group, a hydroxy aliphatic group, a hydroxyaraliphatic group, a hydroxyaromatic group, a phosphonoaliphatic group, a phosphonoaraliphatic group, an aminoaliphatic group, an aminoaraliphatic group, a sulphoaliphatic group, a sulphoaraliphatic group, an oxoaliphatic group, a cyanoaliphatic group, a nitroaliphatic group, an aldehydealiphatic group and a thiolaliphatic group.
  • a preferable example of the heterologous organic groups is a combination of an araliphatic group and an aromatic group, and a more preferable example is a combination of an araliphatic group having 7 to 15 carbon atoms and an aromatic group having 6 to 12 carbon atoms, specifically, a combination of phenylhexyl and phenyl.
  • heterologous organic groups is a combination of an aliphatic group and a hydroxy aliphatic group
  • a more preferable example is a combination of a saturated aliphatic group and a hydroxysaturated aliphatic group
  • a particularly preferable example is a combination of a saturated aliphatic group having 10 or more carbon atoms and a hydroxysaturated aliphatic group having less than 10 carbon atoms, specifically, a combination of decyl and 6-hydroxyhexyl.
  • the organic group contains a plurality of heterologous organic groups
  • the organic group when the resin is prepared as a mixture of a plurality of resin components, the organic group can exert excellent compatibility with the resin molecules of the respective resin components having excellent compatibility with the organic groups of the respective groups. Accordingly, the interaction between the organic groups and the resin molecules of the resin components can be enhanced. As a result, the dispersibility of the organic-inorganic composite particles can be enhanced.
  • the organic groups are present on the surface of inorganic particles in the organic-inorganic composite particles. Specifically, the organic groups are bound to the surface of inorganic particles via a binding group. Also, the organic groups extend from the surface of inorganic particles toward the outside of the inorganic particles via the binding group.
  • the organic-inorganic composite particles are produced by subjecting an inorganic substance and an organic compound to a reaction treatment, preferably to a high temperature treatment.
  • the high temperature treatment is carried out in a solvent.
  • a solvent for example, water and any of the organic compounds listed above can be used.
  • the organic-inorganic composite particles are obtained by subjecting an inorganic substance and an organic compound to a high temperature treatment in water under high pressure conditions (hydrothermal synthesis: hydrothermal reaction), or subjecting an inorganic substance to a high temperature treatment in an organic compound (high temperature treatment in an organic compound).
  • the organic-inorganic composite particles are obtained by surface-treating the surface of inorganic particles formed by an inorganic substance with an organic compound.
  • the inorganic substance and the organic compound are reacted under high-temperature and high-pressure conditions in the presence of water (first hydrothermal synthesis).
  • the inorganic substance subjected to the first hydrothermal synthesis is preferably a carbonate or a sulfate.
  • a reaction system is prepared under high-temperature and high-pressure conditions by placing the inorganic substance, the organic compound and water in a pressure-resistant airtight container and heating them.
  • the proportions of respective components per 100 parts by mass of the inorganic substance are as follows: the proportion of the organic compound is, for example, 1 to 1500 parts by mass, preferably 5 to 500 parts by mass and more preferably 5 to 250 parts by mass; and the proportion of water is, for example, 50 to 8000 parts by mass, preferably 80 to 6600 parts by mass and more preferably 100 to 4500 parts by mass.
  • the density of the organic compound is usually 0.8 to 1.1 g/mL, and thus the proportion of the organic compound is, for example, 1 to 1500 mL, preferably 5 to 500 mL and more preferably 5 to 250 mL per 100 g of the inorganic substance.
  • the number of moles of the organic compound may be, for example, 0.01 to 1000 mol, preferably 0.02 to 50 mol, and more preferably 0.1 to 10 mol per mol of the inorganic substance.
  • the organic compound contains a plurality of (for example, two) different types of organic groups
  • the molar ratio between an organic compound containing one type of organic groups and an organic compound containing the other type of organic group is, for example, 10:90 to 99.9:0.1 and preferably 20:80 to 99:1.
  • the density of water is usually approximately 1 g/mL, and thus the proportion of water is, for example, 50 to 8000 mL, preferably 80 to 6600 mL, and more preferably 100 to 4500 mL per 100 g of the inorganic substance.
  • the heating temperature is, for example, 100 to 500° C. and preferably 200 to 400° C.
  • the pressure is, for example, 0.2 to 50 MPa, preferably 1 to 50 MPa and more preferably 10 to 50 MPa.
  • the reaction time is, for example, 1 to 200 minutes and preferably 3 to 150 minutes. In the case where a continuous reactor is used, the reaction time can be set to one minute or less.
  • the reaction product obtained by the above reaction includes a precipitate that mostly precipitates in water and a deposit that adheres to the inner wall of the airtight container.
  • the precipitate is obtained by, for example, sedimentation separation in which the reaction product is settled by gravity or a centrifugal field.
  • the precipitate is obtained as a precipitate of the reaction product by centrifugal sedimentation (centrifugal separation) in which the reaction product is settled by a centrifugal field.
  • the deposit is recovered by, for example, a scraper (spatula) or the like.
  • the reaction product can also be recovered (separated) by adding a solvent to wash away an unreacted organic compound (or in other words, dissolving the organic compound in the solvent) and thereafter removing the solvent.
  • the solvent can be, for example, an alcohol (hydroxyl group-containing aliphatic hydrocarbon) such as methanol, ethanol, propanol or isopropanol, a ketone (carbonyl group-containing aliphatic hydrocarbon) such as acetone, methyl ethyl ketone, cyclohexanone or cyclopentanone, an aliphatic hydrocarbon such as pentane, hexane or heptane, a halogenated aliphatic hydrocarbon such as dichloromethane, chloroform or trichloroethane, a halogenated aromatic hydrocarbon such as chlorobenzene or dichlorobenzene, an ether such as tetrahydrofuran, an aromatic hydrocarbon such as benzene, toluene or xylene, an aqueous pH adjusting solution such as aqueous ammonia, or the like.
  • An alcohol hydroxyl group-containing aliphatic hydrocarbon
  • the washed reaction product is separated from the solvent (supernatant liquid) by, for example, filtration, decantation or the like, and recovered. After that, the reaction product is dried by, for example, application of heat, an air stream or the like if necessary.
  • the inorganic substance before reaction and the inorganic substance after reaction that forms inorganic particles are the same.
  • the inorganic substance subjected to the second hydrothermal synthesis can be, for example, a hydroxide, a metal complex, a nitrate, a sulfate or the like.
  • a hydroxide and a metal complex are preferable.
  • the element (element that constitutes a cation that combines with a hydroxyl ion (OH ⁇ )) contained in the hydroxide can be the same as the element that combines with oxygen in an oxide listed above.
  • the hydroxide can be, for example, titanium hydroxide (Ti(OH) 4 ) or cerium hydroxide (Ce(OH) 4 ).
  • the metal element contained in the metal complex is a metal element that constitutes a composite oxide with the metal contained in the hydroxide, and examples thereof include titanium, iron, tin, zirconium and the like. Titanium is preferable.
  • the ligand of the metal complex can be, for example, a monohydroxycarboxylic acid such as 2-hydroxyoctanoic acid, or the like.
  • the metal complex examples include 2-hydroxyoctanoic acid titanate and the like.
  • the metal complex can be obtained by preparation from a metal element and a ligand described above.
  • organic compound for example, the same organic compounds as those that can be used in the first hydrothermal synthesis described above can be used.
  • the inorganic substance and the organic compound are reacted under high-temperature and high-pressure conditions in the presence of water.
  • the proportions of respective components per 100 parts by mass of the inorganic compound are as follows: the proportion of the organic compound is, for example, 1 to 1500 parts by mass, preferably 5 to 500 parts by mass, and more preferably 5 to 250 parts by mass; and the proportion of water is, for example, 50 to 8000 parts by mass, preferably 80 to 6600 parts by mass, and more preferably 80 to 4500 parts by mass.
  • the proportion of the organic compound is, for example, 0.9 to 1880 mL, preferably 4.5 to 630 mL, and more preferably 4.5 to 320 mL per 100 g of the hydroxide, and the number of moles of the organic compound may be, for example, 0.01 to 10000 mol, and preferably 0.1 to 10 mol per mol of the hydroxide.
  • the proportion of water is, for example, 50 to 8000 mL, preferably 80 to 6600 mL, and more preferably 5 to 4500 mL per 100 g of the hydroxide.
  • reaction conditions for the second hydrothermal synthesis are the same as those for the first hydrothermal synthesis described above.
  • the organic-inorganic composite particles containing an organic group on the surface of inorganic particles formed of an inorganic substance that is different from the inorganic substance serving as a starting material are obtained.
  • a carbonic acid source or a hydrogen source can be blended with the components described above.
  • the carbonic acid source can be, for example, carbon dioxide (carbonic acid gas), formic acid and/or urea.
  • the hydrogen source can be, for example, hydrogen (hydrogen gas), an acid such as formic acid or lactic acid, a hydrocarbon such as methane or ethane, or the like.
  • the proportion of the carbonic acid source or hydrogen source is, for example, 5 to 140 parts by mass and preferably 10 to 70 parts by mass per 100 parts by mass of the inorganic substance.
  • the proportion of the carbonic acid source can be, for example, 5 to 100 mL and preferably 10 to 50 mL per 100 g of the inorganic substance.
  • the number of moles of the carbonic acid source can be, for example, 0.4 to 100 mol, preferably 1.01 to 10.0 mol and more preferably 1.05 to 1.30 mol per mol of the inorganic substance.
  • the proportion of the hydrogen source can be, for example, 5 to 100 mL and preferably 10 to 50 mL per 100 g of the inorganic substance.
  • the number of moles of the hydrogen source can be, for example, 0.4 to 100 mol, preferably 1.01 to 10.0 mol and more preferably 1.05 to 2.0 mol per mol of the inorganic substance.
  • an inorganic substance and an organic compound are blended and heated under, for example, normal atmospheric pressure conditions.
  • the organic compound is subjected to the high-temperature treatment while serving as an organic group-introducing compound as well as a solvent for dispersing or dissolving the inorganic substance.
  • the proportion of the organic compound is, for example, 10 to 10000 parts by mass and preferably 100 to 1000 parts by mass per 100 parts by mass of the inorganic substance.
  • the proportion of the organic compound in terms of volume is, for example, 10 to 10000 mL and preferably 100 to 1000 mL per 100 g of the inorganic substance.
  • the heating temperature is, for example, a temperature above 100° C., preferably 125° C. or higher, and more preferably 150° C. or higher, and, usually for example, 300° C. or lower, and preferably 275° C. or lower.
  • the heating time is, for example, 1 to 60 minutes and preferably 3 to 30 minutes.
  • the organic-inorganic composite particles may be anisotropic or isotropic, with an average particle size (maximum length in the case where they are anisotropic) of, for example, 200 ⁇ m or less, preferably 1 nm to 200 ⁇ m, more preferably 3 nm to 50 ⁇ m and particularly preferably 3 nm to 10 ⁇ m.
  • the average particle size of the organic-inorganic composite particles is determined by measurement by dynamic light scattering (DLS) and/or calculated from a transmission electron microscopic (TEM) or scanning electron microscopic (SEM) image analysis.
  • DLS dynamic light scattering
  • TEM transmission electron microscopic
  • SEM scanning electron microscopic
  • the proportion of the volume of the organic group relative to the surface of the organic-inorganic composite particles will be high, and the function of the inorganic particles is unlikely to be obtained.
  • the organic-inorganic composite particles may be crushed when mixed with the resin or the like.
  • the organic-inorganic composite particles have at least a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group.
  • the proportion of the surface area of the organic group relative to the surface area of the inorganic particles, or in other words, the surface coverage by the organic group in the organic-inorganic composite particles is, for example, 30% or greater and preferably 60% or greater and usually 200% or less.
  • the shape of the inorganic particles is checked with a transmission electron microscope (TEM), the average particle size is then calculated, and the specific surface area of the particles is calculated from the shape of the inorganic particles and the average particle size.
  • the proportion of the organic group in the organic-inorganic composite particles is calculated from the weight change as a result of the organic-inorganic composite particles being heated to 800° C. with a differential thermal balance (TG-DTA).
  • TG-DTA differential thermal balance
  • the amount of the organic group per particle is calculated from the molecular weight of the organic group, the particle density and the average volume. Then, the surface coverage is determined from the calculated results.
  • the type of solvent (medium) for dispersing the organic-inorganic composite particles can be controlled (designed or managed) according to the type of organic group.
  • the organic-inorganic composite particles obtained in the above-described manner can be subjected to wet classification.
  • a solvent is added to the organic-inorganic composite particles, and the resulting mixture is stirred and allowed to stand still, and thereafter separated into a supernatant and a precipitate.
  • the solvent varies depending on the type of organic groups, but for example, the same solvents as those listed above can be used.
  • the solvent is a hydroxyl group-containing aliphatic hydrocarbon, a carbonyl group-containing aliphatic hydrocarbon, an aliphatic hydrocarbon, a halogenated aliphatic hydrocarbon or an aqueous pH adjusting solution.
  • the average particle size of the resulting organic-inorganic composite particles can be adjusted to, for example, 1 nm to 450 nm, preferably 3 nm to 200 nm and more preferably 3 nm to 100 nm.
  • solubility parameters SP values
  • Preferable hydrophilic groups included in both the functional group and the organic group are a carboxyl group and a hydroxyl group
  • preferable hydrophobic groups included in both the functional group and the organic group are a hydrocarbon group and the like.
  • the affinity between the organic-inorganic composite particles and the resin can be enhanced as a result of both the functional group and the organic group having any of the above groups having the same property (hydrophilicity or hydrophobicity).
  • a particle-dispersed resin composition for example, a solvent, organic-inorganic composite particles and a resin are blended, and the resulting mixture is stirred (solution preparation).
  • the thus-prepared particle-dispersed resin composition is a varnish (solution) containing a solvent.
  • the solvent can be any of the solvents used in washing described above.
  • Other examples include alicyclic hydrocarbons such as cyclopentane and cyclohexane; esters such as ethyl acetate; polyols such as ethylene glycol and glycerol; nitrogen-containing compounds such as N-methylpyrrolidone, pyridine, acetonitrile and dimethylformamide; acryl-based monomers such as isostearyl acrylate, lauryl acrylate, isoboronyl acrylate, butyl acrylate, methacrylate, acrylic acid, tetrahydrofurfuryl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxyethyl acrylate, and acryloylmorpholine; vinyl group-containing monomers such as styrene and ethylene; epoxy-containing monomers such as
  • solvents can be used singly or in a combination of two or more.
  • a halogenated aliphatic hydrocarbon and an aqueous pH adjusting solution are preferable.
  • a particle-dispersed resin composition first, the above solvent and a resin are blended so as to dissolve the resin in the solvent to prepare a resin solution. After that, the resin solution is blended with organic-inorganic composite particles, and the resulting mixture is stirred to prepare a particle-dispersed resin composition (first preparation method).
  • the proportion of resin per 100 parts by mass of the resin solution is, for example, 40 parts by mass or less, preferably 35 parts by mass or less, and more preferably 30 parts by mass or less, and usually 1 part by mass or greater. If the proportion of resin exceeds the above range, the solubility of resin may be low.
  • the proportion of the organic-inorganic composite particles per 100 parts by mass of the solids content (resin) of the resin solution is, for example, 1 to 1000 parts by mass, preferably 5 to 500 parts by mass and more preferably 10 to 300 parts by mass. Also, the proportion of the organic-inorganic composite particles per 100 parts by mass of the total amount of the resin solution (the total amount of the resin and the solvent) is, for example, 0.1 to 300 parts by mass, preferably 1 to 200 parts by mass and more preferably 3 to 100 parts by mass.
  • the particle-dispersed resin composition can also be prepared by blending a solvent and organic-inorganic composite particles to disperse the organic-inorganic composite particles in the solvent to prepare a particle dispersion, and then blending the particle dispersion with a resin and stirring the resulting mixture (second preparation method).
  • the organic-inorganic composite particles are dispersed in the solvent as primary particle.
  • the proportion of the organic-inorganic composite particles per 100 parts by mass of the particle dispersion is, for example, 0.1 to 70 parts by mass, preferably 0.2 to 60 parts by mass, and more preferably 0.5 to 50 parts by mass.
  • the proportion of resin per 100 parts by mass of the solids content (organic-inorganic composite particles) of the particle dispersion is, for example, 10 to 10000 parts by mass, preferably 20 to 2000 parts by mass and more preferably 40 to 1000 parts by mass.
  • the particle-dispersed resin composition can also be prepared by, for example, blending a solvent, organic-inorganic composite particles and a resin simultaneously and stirring the resulting mixture (third preparation method).
  • the proportions of respective components per 100 parts by mass of the total amount of the particle-dispersed resin composition are as follows: the proportion of the organic-inorganic composite particles is, for example, 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass and more preferably 3 to 30 parts by mass; and the proportion of resin is, 40 parts by mass or less, preferably 35 parts by mass or less and more preferably 30 parts by mass or less, and unusually 1 part by mass or greater.
  • the proportion of the solvent is the remainder obtained by excluding the organic-inorganic composite particles and the resin from the particle-dispersed resin composition.
  • the proportion of resin in the resin solution is the same as those shown in the first preparation method described above.
  • the proportion of the organic-inorganic composite particles in the particle dispersion is the same as those shown in the second preparation method described above.
  • the resin solution and the particle dispersion are blended such that the proportion of resin relative to the organic-inorganic composite particles in terms of mass is, for example, 99:1 to 10:90, preferably 95:5 to 20:80 and more preferably 90:10 to 30:70.
  • the particle-dispersed resin composition can also be prepared without the use of a solvent by, for example, melting a resin by application of heat and blending the resin with organic-inorganic composite particles (fifth preparation method).
  • the thus-prepared particle-dispersed resin composition is a melt of the particle-dispersed resin composition which does not include a solvent.
  • the heating temperature is, in the case where the resin is a thermoplastic resin, greater than or equal to the melting temperature of the resin, specifically, 200 to 350° C.
  • the heating temperature is a temperature at which the resin is B-staged, for example, 85 to 140° C.
  • the proportion of resin relative to the organic-inorganic composite particles in terms of mass is, for example, 99:1 to 10:90, preferably 95:5 to 20:80 and more preferably 90:10 to 30:70.
  • the organic-inorganic composite particles are uniformly dispersed in the resin. Specifically, in the particle-dispersed resin composition, the organic-inorganic composite particles are dispersed as primary particles in the resin (without substantial coagulation).
  • the obtained particle-dispersed resin composition is applied to, for example, a known support plate to form a coating, and the coating is dried, whereby a particle-dispersed resin molded article as a film is molded.
  • the thickness of the obtained film can be set as appropriate according to the use and purpose, and the thickness is, for example, 0.1 to 2000 ⁇ m, preferably 0.5 to 1000 ⁇ m and more preferably 1.0 to 500 ⁇ m.
  • the particle-dispersed resin molded article as a film can also be molded by a melt molding method in which the particle-dispersed resin composition is extruded by an extruding machine or the like.
  • the particle-dispersed resin molded article can also be molded as a block (mass) by injecting the particle-dispersed resin composition into a metal mold or the like and thereafter subjecting the resultant to, for example, heat molding such as heat pressing.
  • the organic-inorganic composite particles are dispersed as primary particles in the resin.
  • the organic-inorganic composite particles can be easily and uniformly dispersed in the resin in the particle dispersion and the particle-dispersed resin molded article.
  • the organic-inorganic composite particles can be dispersed as primary particles in the resin.
  • the organic-inorganic composite particles can be dispersed as primary particles in the resin regardless of the type of inorganic particles with the above-described simple operation.
  • the particle-dispersed resin compositions and the particle-dispersed resin molded articles obtained by the above-described methods have excellent clarity because the organic-inorganic composite particles are uniformly dispersed in the resin, and therefore they can be suitably used in various industrial applications including optical applications.
  • the catalyst particles of the present invention contain inorganic particles with a catalytic action and an organic group that binds to the surface of the inorganic particles.
  • the inorganic particles preferably have a photocatalytic action that exerts a catalytic action for a gas and/or a liquid (described later) by absorbing light.
  • Such catalyst particles can be obtained by, for example, surface-treating an inorganic substance and/or a complex thereof with an organic compound.
  • the inorganic substance include a metal composed of a metal element such as a main group element or a transition element, a nonmetal composed of a nonmetal element such as boron or silicon, an inorganic compound containing a metal element and/or a nonmetal, or the like.
  • Examples of the metal element and the nonmetal element include elements that are located on the left side and the lower side of a border line that is assumed to pass through boron (B) of the IIIB group, silicon (Si) of the IVB group, arsenic (As) of the VB group, tellurium (Te) of the VIB group and astatine (At) of the VIIB group on the long-form periodic table (IUPAC, 1989), as well as the elements that are located on the border line, and the same elements as those listed in the second embodiment.
  • the inorganic compound can be, for example, a hydrogen compound, a hydroxide, a nitride, a halide, an oxide, a carbonate, a sulfate, a nitrate, an acetate, a formate, a sulfide, a carbide, a phosphorus compound, or the like.
  • the inorganic compound may be a composite compound such as, for example, an oxynitride or a composite oxide.
  • a preferable example is an inorganic compound, and more preferable examples are an oxide, a sulfate, a nitrate, an acetate, a formate and a composite oxide.
  • An oxide is particularly preferable.
  • the oxide examples include metal oxides, and preferable examples include titanium oxide (titanium dioxide, titanium oxide (IV), titania: TiO 2 ), tungsten oxide (tungsten trioxide, tungsten oxide (VI), WO 3 ), cerium oxide (cerium dioxide, cerium oxide (IV), ceria: CeO 2 ), zirconium oxide (zirconium dioxide, zirconium oxide (IV), zirconia: ZrO 2 ), tantalum oxide (tantalum dioxide, tantalum oxide (IV), TaO 2 ) and the like.
  • the arrangement of atoms in an oxide is not particularly limited, and can be, for example, either crystalline or non-crystalline (amorphous).
  • the oxides can be used singly or in a combination of two or more
  • the sulfate is a compound consisting of a sulfate ion (SO 4 2 ⁇ ) and a metal cation (more specifically, a compound formed by substitution of the hydrogen atoms of sulfuric acid (H 2 SO 4 ) with a metal), and the metal element contained in the sulfate can be, for example, a group IVA element or a group IB element. Ti and Cu are preferable.
  • the sulfate is preferably titanium sulfate, zirconium sulfate, hafnium sulfate, copper sulfate, silver sulfate or the like. Titanium sulfate and copper sulfate are more preferable.
  • the sulfates can be used singly or in a combination of two or more.
  • the nitrate is a compound consisting of a nitrate ion (NO 3 ⁇ ) and a metal cation (more specifically, a compound formed by substitution of the hydrogen atom of nitric acid (HNO 3 ) with a metal), and the metal element contained in the nitrate can be, for example, a group VIII element. Pd and Pt are preferable.
  • nitrates are iron nitrate, cobalt nitrate, nickel nitrate, ruthenium nitrate, rhodium nitrate, palladium nitrate, osmium nitrate, iridium nitrate and the like. Palladium nitrate and platinum nitrate are more preferable.
  • the nitrates can be used singly or in a combination of two or more.
  • the acetate is a compound consisting of an acetate ion (CH 3 COO ⁇ ) and a metal cation (more specifically, a compound formed by substitution of the hydrogen atom of the carboxyl group (—COOH) in acetic acid with a metal), and the metal element contained in the acetate can be, for example, a group VIII element. Ni is preferable.
  • a preferable acetate is nickel acetate.
  • the acetates can be used singly or in a combination of two or more.
  • the formate is a compound consisting of a formate ion (HCOO ⁇ ) and a metal cation (more specifically, a compound formed by substitution of the hydrogen atom of the carboxyl group (—COOH) in formic acid with a metal), and the metal element contained in the formate can be, for example, a group IB element. Cu is preferable.
  • a preferable formate is copper formate.
  • the formates can be used singly or in a combination of two or more.
  • the composite oxide is a compound consisting of oxygen and a plurality of elements, and the plurality of elements is a combination of at least two elements selected from the elements other than oxygen contained in the oxides listed above, the group I elements, and the group II elements.
  • Examples of the group I elements include alkali metals such as Li, Na, K, Rb, and Cs.
  • Examples of the group II elements include the same alkaline earth metals as those listed in the second embodiment.
  • Examples of the combination of a plurality of elements include combinations that include at least a group II element such as a combination of a group II element and a group IVB element, a combination of a group II element and a group VIII element, a combination of a group II element and a group IVA element, and a combination of a group II element and a group VA element; combinations that include at least a group I element such as a combination of a group I element and a group IVA element, a combination of a group I element, a group IVA element and a lanthanide series element, and a combination of a group I element and a group VA element; a combination of a group VA element and a group JIB element; and the like.
  • a group II element such as a combination of a group II element and a group IVB element, a combination of a group II element and a group VIII element, a combination of a group II element and a group IVA element, and a combination of a group II element
  • Examples of the composite oxide containing at least a group II element include alkaline earth metal titanates, alkaline earth metal zirconates, alkaline earth metal ferrates, alkaline earth metal stannates, alkaline earth metal niobates and the like.
  • Examples of the composite oxide containing at least a group I element include alkali metal titanates, alkali metal zirconates, alkali metal vanadates, alkali metal niobates and the like.
  • Examples of the composite oxide containing a group VA element and a group JIB group element include metal niobates and the like.
  • Preferable composite oxides are alkaline earth metal titanates, alkali metal titanates, alkaline earth metal niobates, alkali metal niobates and metal niobates.
  • alkaline earth metal titanates examples include beryllium titanate (BeTiO 3 ), magnesium titanate (MgTiO 3 ), calcium titanate (CaTiO 3 ), strontium titanate (SrTiO 3 ), barium titanate (BaTiO 3 ), barium tetratitinate (BaTi 4 O 9 ), radium titanate (RaTiO 3 ) and the like.
  • alkali metal titanates examples include sodium hexatitanate (Na 2 Ti 6 O 13 ), potassium lanthanum titanate (K 2 La 2 Ti 3 O 10 ) and the like.
  • alkaline earth metal niobates examples include strontium diniobate (Sr 2 Nb 2 O 7 ) and the like.
  • alkali metal niobates examples include potassium hexaniobate (K 4 Nb 6 O 17 ) and the like.
  • metal niobates examples include zinc diniobate (ZnNb 2 O 6 ) and the like.
  • the composite oxides can be used singly or in a combination of two or more.
  • Examples of the central atom include the same metal elements as those listed above.
  • Preferable examples include a group IVA element, a group VIII element and a group IVB element. More preferable examples include Ti, Zr, Fe, Ni, Ru, Sn and the like.
  • Examples of the central ion include cations of the metal elements listed above.
  • Examples of the ligand include coordinating compounds such as carboxylic acid, hydroxycarboxylic acid and acetylacetone; coordinating ions such as cations and hydroxide ions of the above coordinating compounds; and the like.
  • carboxylic acid examples include dicarboxylic acids such as oxalic acid, succinic acid, phthalic acid, and the like.
  • the coordination number is, for example, 1 to 6 and preferably 1 to 3.
  • the complex can be obtained by preparation from a metal element and a ligand described above.
  • the inorganic substance specifically, oxide, composite oxide
  • the complex can be formed (prepared) as salts and/or hydrates.
  • the salts include salts with cations such as ammonium ions.
  • inorganic substances and the complexes listed above can be used singly or in a combination of two or more.
  • the combination of an inorganic substance and/or a complex can be, for example, a combination of a plurality of types of inorganic substances (first combination) or a combination of an inorganic substance and a complex (second combination).
  • the first combination can be, for example, a combination of a plurality of types of inorganic substances.
  • Specific examples include a combination of an oxide (first inorganic substance) and at least one inorganic substance (second inorganic substance) selected from the group consisting of metals, sulfates, nitrates and formates.
  • examples of the first combination include a combination of a metal oxide and a metal (group VIII element), a combination of a metal oxide and a sulfate, and a combination of a metal oxide and a formate.
  • Specific examples of the first combination include a combination of tungsten oxide and palladium, a combination of tungsten oxide and platinum, a combination of tungsten oxide and copper sulfate, and a combination of tungsten oxide and copper formate.
  • Examples of the second combination include a combination of a complex whose ligand is hydroxycarboxylic acid and a metal, a combination of a complex whose ligand is hydroxycarboxylic acid, a hydroxide and an acetate, and a combination of a complex whose ligand is hydroxycarboxylic acid, a hydroxide and a complex whose ligand is acetylacetone.
  • the second combination include a combination of a titanium complex whose central atom is titanium and whose ligand is 2-hydroxyoctanoic acid and platinum, a combination of a titanium complex whose central atom is titanium and whose ligand is 2-hydroxyoctanoic acid, strontium hydroxide and nickel acetate, and a combination of a titanium complex whose central atom is titanium and whose ligand is 2-hydroxyoctanoic acid, strontium hydroxide and a ruthenium complex whose central atom is ruthenium and ligand is acetylacetone.
  • the organic compound is, for example, an organic group-introducing compound that introduces (disposes) an organic group on the surface of inorganic particles.
  • the organic compound contains a binding group capable of binding to the surface of inorganic particles and an organic group.
  • the organic group is bound to the surface of inorganic particles via a binding group.
  • the binding group is selected as appropriate according to the type of inorganic particles and examples thereof include functional groups such as phosphoric acid group (—PO(OH) 2 , phosphono group), phosphoric acid ester group (phosphonate group), carboxyl group, carboxylic acid ester group (carboxy ester group), amino group, sulfo group, hydroxyl group, thiol group, epoxy group, isocyanate group, nitro group, azo group, silyloxy group, imino group, aldehyde group (acyl group), nitrile group and vinyl group (polymerizable group).
  • functional groups such as phosphoric acid group (—PO(OH) 2 , phosphono group), phosphoric acid ester group (phosphonate group), carboxyl group, carboxylic acid ester group (carboxy ester group), amino group, sulfo group, hydroxyl group, thiol group, epoxy group, isocyanate group, nitro group, azo group, silyloxy
  • Preferable examples include phosphoric acid group, phosphoric acid ester group, carboxyl group, amino group, sulfo group, hydroxyl group, thiol group, epoxy group, azo group, vinyl group and the like. More preferable examples include phosphoric acid group, phosphoric acid ester group, carboxyl group, amino group and hydroxyl group.
  • Phosphoric acid ester groups are, for example, alkyl ester groups of phosphoric acid (specifically, orthophosphoric acid), or in other words, alkoxy phosphonyls, and can be represented by the following formula (1):
  • Examples of phosphoric acid ester groups include dialkyl phosphate esters such as dimethyl phosphate esters (dimethoxy phosphonyl: —PO(OCH 3 ) 2 ), diethyl phosphate esters (diethoxy phosphonyl: —PO(OC 2 H 5 ) 2 ), dipropyl phosphate esters (dipropoxy phosphonyl: —PO(OC 3 H 7 ) 2 ); monoalkyl phosphate esters such as monomethyl phosphate esters (monomethoxy phosphonyl: —PO(OCH 3 )H), monoethyl phosphate esters (monoethoxy phosphonyl: —PO(O 2 CH 5 )H) and monopropyl phosphate esters (monopropoxy phosphonyl: —PO(O 3 CH 7 )H); and the like. Dialkyl phosphate esters are preferable.
  • the binding group is selected as appropriate according to the type of inorganic particles. Specifically, when the inorganic particles contain titanium oxide, for example, a phosphoric acid group and/or a phosphoric acid ester group are selected. When the inorganic particles contain tungstic acid (described later), for example, an amino group is selected. When the inorganic particles contain strontium titanate, for example, a carboxylic acid, a phosphoric acid group and/or a phosphoric acid ester group are selected.
  • binding groups are contained in the organic compound. Specifically, the binding group is bound to a terminal or a side chain of the organic group.
  • the organic group includes, for example, a hydrocarbon group such as an aliphatic group, an alicyclic group, an araliphatic group or an aromatic group, or the like.
  • a hydrocarbon group such as an aliphatic group, an alicyclic group, an araliphatic group or an aromatic group, or the like.
  • Examples of the hydrocarbon group include the same hydrocarbon groups as those listed in the second embodiment.
  • the organic group is a hydrophobic group for imparting hydrophobicity to the surface of inorganic particles.
  • organic compounds containing a hydrophobic group described above are used as hydrophobic organic compounds for hydrophobic treatment of inorganic particles.
  • hydrophobic organic compounds in the case where the binding group is a phosphoric acid group include aliphatic group-containing phosphonic acids including saturated aliphatic group-containing phosphonic acids (saturated phosphonic acids) such as methylphosphonic acid, hexyl phosphonic acid, octylphosphonic acid and decylphosphonic acid, and the like.
  • hydrophobic organic compounds include alicyclic group-containing phosphonic acids (alicyclic phosphonic acids) such as cyclohexyl phosphonic acid; araliphatic group-containing phosphonic acids (araliphatic phosphonic acids) such as 6-phenylhexyl phosphonic acid; aromatic group-containing phosphonic acids (aromatic phosphonic acids) such as phenyl phosphonic acid and toluenephosphonic acid; and the like.
  • alicyclic phosphonic acids such as cyclohexyl phosphonic acid
  • araliphatic group-containing phosphonic acids such as 6-phenylhexyl phosphonic acid
  • aromatic group-containing phosphonic acids aromatic phosphonic acids
  • aromatic phosphonic acids such as phenyl phosphonic acid and toluenephosphonic acid
  • hydrophobic organic compounds in the case where the binding group is a phosphoric acid ester group include aliphatic group-containing phosphonate esters including saturated aliphatic group-containing phosphonate esters (saturated phosphonic acid dialkyl esters) such as hexyl phosphonic acid diethyl ester, octylphosphonic acid diethyl ester and decylphosphonic acid diethyl ester, and the like.
  • hydrophobic organic compounds include alicyclic group-containing phosphonic acid alkyl esters (alicyclic phosphonic acid dialkyl esters) such as cyclohexanephosphonic acid diethyl ester; araliphatic group-containing phosphonate esters (araliphatic phosphonic acid dialkyl esters) such as 6-phenylhexyl phosphonic acid diethyl ester; aromatic group-containing phosphonic acid alkyl esters (aromatic phosphonic acid dialkyl esters) such as phenyl phosphonic acid diethyl ester and toluenephosphonic acid diethyl ester; and the like.
  • alicyclic group-containing phosphonic acid alkyl esters such as cyclohexanephosphonic acid diethyl ester
  • araliphatic group-containing phosphonate esters such as 6-phenylhexyl phosphonic acid diethyl ester
  • hydrophobic organic compounds in the case where the binding group is a carboxyl group include aliphatic group-containing carboxylic acids (fatty acids) such as hexanoic acid, octanoic acid and decanoic acid; araliphatic group-containing carboxylic acids such as 6-phenylhexanoic acid; and the like.
  • fatty acids such as hexanoic acid, octanoic acid and decanoic acid
  • araliphatic group-containing carboxylic acids such as 6-phenylhexanoic acid
  • hydrophobic organic compounds in the case where the binding group is an amino group include aliphatic group-containing amines such as hexylamine, octylamine and decylamine; and the like.
  • the hydrophilic group is a functional group having a polarity (or in other words, polar group), and examples thereof include a phosphoric acid group, a phosphoric acid ester group, a hydroxyl group, a carboxyl group, an amino group, a sulfo group, a carbonyl group, a cyano group, a nitro group, an aldehyde group, a thiol group and the like.
  • organic group containing a phosphoric acid group examples include phosphonosaturated aliphatic groups (phosphonoaliphatic groups) such as 3-phosphonopropyl, 6-phosphonohexyl and 10-phosphonodecyl; phosphonoaraliphatic groups such as 6-phosphonophenylhexyl; and the like.
  • phosphonosaturated aliphatic groups such as 3-phosphonopropyl, 6-phosphonohexyl and 10-phosphonodecyl
  • phosphonoaraliphatic groups such as 6-phosphonophenylhexyl
  • Examples of the organic group containing a phosphoric acid ester group include alkoxyphosphonyl hydrocarbon groups including alkoxyphosphonyl saturated aliphatic groups (alkoxyphosphonyl aliphatic groups) such as 3-(diethoxy-phosphonyl)propyl, 6-(diethoxy-phosphonyl)hexyl and 10-(diethoxy-phosphonyl)decyl; and alkoxyphosphonyl araliphatic groups such as 6-(diethoxy-phosphonyl)phenylhexyl.
  • alkoxyphosphonyl hydrocarbon groups including alkoxyphosphonyl saturated aliphatic groups (alkoxyphosphonyl aliphatic groups) such as 3-(diethoxy-phosphonyl)propyl, 6-(diethoxy-phosphonyl)hexyl and 10-(diethoxy-phosphonyl)decyl
  • alkoxyphosphonyl araliphatic groups such as 6-(diethoxy-phosphonyl
  • organic group containing a hydroxyl group examples include hydroxy aliphatic groups such as 10-hydroxydecyl; and the like.
  • Examples of the organic group containing a carboxyl group include carboxysaturated aliphatic groups (carboxyaliphatic groups) such as 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 7-carboxyheptyl, 8-carboxyoctyl, 9-carboxynonyl and 10-carboxydecyl; and the like.
  • carboxysaturated aliphatic groups such as 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 7-carboxyheptyl, 8-carboxyoctyl, 9-carboxynonyl and 10-carboxydecyl; and the like.
  • Examples of the organic group containing a carboxylic acid ester group include carboxy ester aliphatic groups such as 2-(methoxy-carbonyl)ethyl, 3-(methoxy-carbonyl)propyl, 4-(methoxy-carbonyl)butyl, 5-(methoxy-carbonyl)pentyl, 6-(methoxy-carbonyl)hexyl, 7-(methoxy-carbonyl)heptyl, 8-(methoxy-carbonyl)octyl, 9-(methoxy-carbonyl)nonyl and 10-(methoxy-carbonyl)decyl.
  • carboxy ester aliphatic groups such as 2-(methoxy-carbonyl)ethyl, 3-(methoxy-carbonyl)propyl, 4-(methoxy-carbonyl)butyl, 5-(methoxy-carbonyl)pentyl, 6-(methoxy-carbonyl)hexyl, 7-(
  • Examples of the organic group containing an amino group and a sulfo group include amino/sulphoaliphatic groups such as 2-amino-3-sulfopropyl.
  • examples of the organic compound containing a hydrophilic group include a phosphoric acid group-containing organic compound, a phosphoric acid ester group-containing organic compound, a hydroxyl group-containing organic compound, a carboxyl ester group-containing organic compound, an amino group-containing organic compound, a sulfo group-containing organic compound, a carbonyl group-containing organic compound, a cyano group-containing organic compound, a nitro group-containing organic compound, an aldehyde group-containing organic compound, a thiol group-containing organic compound and the like.
  • Examples of the phosphoric acid group-containing organic compound in the case where the binding group is a phosphoric acid group and the polar group is a carboxyl group include monophosphonocarboxylic acids, and specific examples include 3-phosphono propionic acid, 6-phosphonohexanoic acid, 10-phosphono decanoic acid, 6-phosphonophenylhexanoic acid, and the like.
  • Examples of the phosphoric acid ester group-containing organic compound in the case where the binding group is a phosphoric acid ester group and the polar group is a carboxy ester group include 3-(diethoxy-phosphonyl)ethyl propionic acid ester, 6-(diethoxy-phosphonyl)hexanoic acid ethyl ester, 10-(diethoxy-phosphonyl)decanoic acid ethyl ester and the like.
  • the above-listed phosphoric acid ester group-containing organic compounds are also regarded as carboxy ester group-containing organic compounds.
  • the same or mutually different organic groups may be used.
  • the organic group contains a plurality of different types of organic groups, a plurality of homologous organic groups and/or a plurality of heterologous organic groups are contained.
  • the combination of a plurality of aliphatic groups can be, for example, a combination of a saturated aliphatic group having less than 10 carbon atoms and a saturated aliphatic group having 10 or more carbon atoms. Specific examples include a combination of octyl and decyl, and a combination of methyl and decyl. Another example of the combination of a plurality of aliphatic groups is a combination of a saturated aliphatic group having less than 7 carbon atoms and a saturated aliphatic group having 7 or more carbon atoms.
  • Specific examples include a combination of methyl and octyl, a combination of hexyl and decyl, and a combination of hexyl and octyl.
  • Another example is a combination of a saturated aliphatic group having less than 5 carbon atoms and a saturated aliphatic group having 5 or more carbon atoms.
  • a specific example is a combination of methyl and hexyl.
  • Examples of the combination of a plurality of phosphonoaliphatic groups include a combination of a phosphonoaliphatic group having less than 5 carbon atoms and a phosphonoaliphatic group having 5 or more carbon atoms.
  • a specific example is a combination of 3-phosphonopropyl and 6-phosphonohexyl.
  • Examples of the combination of a plurality of alkoxyphosphonyl aliphatic groups include a combination of an alkoxyphosphonyl aliphatic group having less than 10 carbon atoms and an alkoxyphosphonyl aliphatic group having 10 or more carbon atoms. Specific examples include a combination of 3-(diethoxy-phosphonyl)propyl and 6-(diethoxy-phosphonyl)hexyl, and a combination of 3-(diethoxy-phosphonyl)propyl and 10-(diethoxy-phosphonyl)decyl.
  • the combination of a plurality of carboxy ester aliphatic groups can be, for example, a combination of a carboxy ester aliphatic group having less than 7 carbon atoms and a carboxy ester aliphatic group having 7 or more carbon atoms.
  • Specific examples include a combination of 2-(methoxy-carbonyl)ethyl and 5-(methoxy-carbonyl)heptyl, and a combination of 2-(methoxy-carbonyl)ethyl and 9-(methoxy-carbonyl)nonyl.
  • the organic group contains a plurality of homologous organic groups
  • a plurality of organic groups having different sizes (lengths or/and dimensions, or in other words, the number of carbon atoms) are contained in the organic group. Accordingly, in a space between adjacent larger organic groups, a resin molecule enters a gap (pocket) formed in accordance with the smaller organic group, and the interaction between the larger organic group and the resin molecule can be enhanced. As a result, the dispersibility of the catalyst particles can be enhanced.
  • heterologous organic groups include a combination of two different groups selected from the group consisting of an aliphatic group, an alicyclic group, an araliphatic group, an aromatic group, a phosphonoaliphatic group, a phosphonoaraliphatic group, an alkoxyphosphonyl aliphatic group, an alkoxyphosphonyl araliphatic group, a hydroxy aliphatic group, a carboxyaliphatic group, a carboxyaraliphatic group, a carboxyaromatic group, a carboxy ester aliphatic group and an amino/sulphoaliphatic group.
  • heterologous organic groups include a combination of an aliphatic group and an araliphatic group, a combination of an aliphatic group and a carboxyaliphatic group, a combination of an aliphatic group and a carboxy ester aliphatic group, and a combination of a carboxyaliphatic group and a carboxy ester aliphatic group.
  • the combination of an aliphatic group and an araliphatic group can be, for example, a combination of a saturated aliphatic group having 6 to 12 carbon atoms and an araliphatic group having 7 to 15 carbon atoms, and a specific example is a combination of octyl and phenylhexyl.
  • the combination of an aliphatic group and a carboxyaliphatic group can be, for example, a combination of an aliphatic group having less than 6 carbon atoms and a carboxyaliphatic group having less than 6 carbon atoms. Specific examples include a combination of methyl and 2-carboxyethyl and a combination of methyl and 5-carboxypentyl. Another example is a combination of an aliphatic group having 6 or more carbon atoms and a carboxyaliphatic group having less than 6 carbon atoms, and specific examples include a combination of octyl and 2-carboxyethyl and a combination of octyl and 5-carboxypentyl.
  • the combination of an aliphatic group and a carboxy ester aliphatic group can be, for example, a combination of an aliphatic group having less than 6 carbon atoms and a carboxy ester aliphatic group having less than 6 carbon atoms, and a specific example is a combination of methyl and 2-(methoxy-carbonyl)ethyl.
  • the combination of an aliphatic group and a carboxy ester aliphatic group can be, for example, a combination of an aliphatic group having less than 6 carbon atoms and a carboxy ester aliphatic group having 6 or more carbon atoms, and a specific example is a combination of methyl and 9-(methoxy-carbonyl)nonyl.
  • Another example of the combination of an aliphatic group and a carboxy ester aliphatic group is a combination of an aliphatic group having 7 or more carbon atoms and a carboxy ester aliphatic group having 7 or more carbon atoms, and specific examples include a combination of octyl and 9-(methoxy-carbonyl)nonyl and a combination of decyl and 9-(methoxy-carbonyl)nonyl.
  • Another example of the combination of an aliphatic group and a carboxy ester aliphatic group is a combination of an aliphatic group having 6 or more carbon atoms and a carboxy ester aliphatic group having less than 6 carbon atoms, and a specific example is a combination of decyl and 2-(methoxy-carbonyl)ethyl.
  • the combination of a carboxyaliphatic group and a carboxy ester aliphatic group can be, for example, a combination of a carboxyaliphatic group having less than 5 carbon atoms and a carboxy ester aliphatic group having 6 or more carbon atoms, and a specific example is a combination of 2-carboxyethyl and 9-(methoxy-carbonyl)nonyl.
  • the organic group contains a plurality of heterologous organic groups
  • the organic group when the resin is prepared as a mixture of a plurality of resin components, the organic group can exert excellent compatibility with the resin molecules of the respective resin components having excellent compatibility with the organic groups of the respective groups. Accordingly, the interaction between the organic groups and the resin molecules of the resin components can be enhanced. As a result, the dispersibility of the catalyst particles can be enhanced.
  • the organic groups are present on the surface of inorganic particles in the catalyst particles. Specifically, the organic groups extend from the surface of inorganic particles toward the outside of the inorganic particles via a binding group.
  • the catalyst particles are produced by subjecting an inorganic substance and/or a complex and an organic compound to a reaction treatment, preferably to a high temperature treatment.
  • the high temperature treatment is carried out in a solvent.
  • a solvent for example, water and any of the organic compounds listed above can be used.
  • the catalyst particles are obtained by surface-treating (hydrothermal synthesis: hydrothermal reaction) an inorganic substance and/or a complex with an organic compound in hot high pressure water, or surface-treating an inorganic substance and/or a complex in a hot organic compound.
  • the catalyst particles are obtained by surface-treating the surface of (inorganic particles formed of) the inorganic substance and/or the complex with any of the organic compounds containing an organic group listed above.
  • the inorganic substance and the organic compound are reacted under high-temperature and high-pressure conditions in the presence of water (first hydrothermal synthesis).
  • Preferable examples of the inorganic substance subjected to the first hydrothermal synthesis include an oxide, a sulfate, a nitrate, a formate, a hydroxide and a metal.
  • the inorganic substances subjected to the first hydrothermal synthesis can be used singly or in combination. In the case where the inorganic substances are used in combination, the first combination mentioned above is used.
  • a reaction system is prepared under high-temperature and high-pressure conditions by placing an inorganic substance, an organic compound and water in a pressure-resistant airtight container and heating them.
  • the amount of the first inorganic substance is greater than that of the second inorganic substance when they are blended.
  • the proportion of the second inorganic substance per 100 parts by mass of the first inorganic substance is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, and usually 0.01 parts by mass or greater.
  • the proportion of the second inorganic substance per mol of the first inorganic substance is, for example, 0.2 mol or less, preferably 0.1 mol or less, and more preferably 0.05 mol or less, and usually 0.0001 mol or greater.
  • the heating temperature is, for example, 100 to 600° C., and preferably 200 to 500° C.
  • the pressure is, for example, 0.2 to 50 MPa, preferably 1 to 50 MPa, and more preferably 10 to 50 MPa.
  • the reaction time is, for example, 1 to 2000 minutes, preferably 2 to 1000 minutes, and more preferably 3 to 500 minutes. In the case where a continuous reactor is used, the reaction time is set to, for example, one minute or less.
  • the reaction product obtained by the above reaction includes a precipitate that mostly precipitates in water and a deposit that adheres to the inner wall of the airtight container.
  • the precipitate is obtained by, for example, sedimentation separation in which the reaction product is settled by gravity or a centrifugal field.
  • the precipitate is obtained as a precipitate of the reaction product by centrifugal sedimentation (centrifugal separation) in which the reaction product is settled by a centrifugal field.
  • the reaction product can also be recovered (separated) by adding a solvent to wash away an unreacted organic compound (or in other words, dissolving the organic compound in the solvent) and thereafter removing the solvent.
  • the same solvents as those listed in the second embodiment can be used.
  • the washed reaction product is separated from the solvent (supernatant liquid) by, for example, filtration, decantation or the like, and recovered. After that, the reaction product is dried by, for example, application of heat, an air stream or the like if necessary.
  • the catalyst particles containing inorganic particles and an organic group that binds to the surface of the inorganic particles are obtained.
  • Examples of the inorganic substance subjected to the second hydrothermal synthesis include a hydroxide, a sulfate, an acetate, a metal, hydrates thereof and the like.
  • the element (element that constitutes a cation that combines with a hydroxyl ion (OH ⁇ )) contained in the hydroxide can be the same as the element that combines with oxygen in an oxide listed above.
  • the hydroxide can be, for example, strontium hydroxide (Sr(OH) 2 ) or the like.
  • the complex subjected to the second hydrothermal synthesis can be, for example, titanium complex or the like.
  • Examples of the hydrates subjected to the second hydrothermal synthesis include tungstic acid (WO 3 .H 2 O), ammonium tungstate pentahydrate ((NH 4 ) 2 WO 4 .5H 2 O) and the like. These hydrates produce tungsten oxide as a result of elimination of water of hydration in the second hydrothermal synthesis.
  • Such inorganic substances and complexes can be used singly or in a combination of two or more.
  • the second inorganic substance does not cause a change in the chemical composition before and after the reaction (second hydrothermal synthesis).
  • the metal or oxide forming the second inorganic substance is supported on the first inorganic substance.
  • supported as used herein is defined as the state in which the metal or oxide is present substantially uniformly inside of and/or on the surface of the first inorganic substance.
  • a metal (copper) forming a sulfate (copper) is supported on an oxide (tungsten oxide) after the second hydrothermal synthesis.
  • a group VIII element palladium or platinum
  • a metal (copper) forming a formate is supported on tungsten oxide after the second hydrothermal synthesis.
  • the proportions of respective components in the second hydrothermal synthesis per 100 parts by mass of the inorganic substance and the complex are as follows: the proportion of the organic compound is, for example, 1 to 1500 parts by mass, preferably 5 to 500 parts by mass and more preferably 5 to 250 parts by mass; and the proportion of water is, for example, 50 to 8000 parts by mass, preferably 80 to 6600 parts by mass and more preferably 80 to 4500 parts by mass.
  • the proportion of the organic compound is, for example, 0.9 to 1880 mL, preferably 4.5 to 630 mL and more preferably 4.5 to 320 mL per 100 g of the inorganic substance and the complex, and the number of moles of the organic compound may be, for example, 0.01 to 10000 mol and preferably 0.1 to 10 mol per mol of the inorganic substance and the complex.
  • the proportion of water is, for example, 50 to 8000 mL, preferably 80 to 6600 mL and more preferably 100 to 4500 mL per 100 g of the inorganic substance and the complex.
  • the second combination mentioned above is used. More specifically, when a combination of a complex and an inorganic substance is used, the proportion of the inorganic substance per 100 parts by mass of the complex is, for example, 10 parts by mass or less, preferably 8 parts by mass or less and more preferably 5 parts by mass or less, and usually 0.001 parts by mass or greater. In other words, the proportion of the inorganic substance per mol of the complex is, for example, 0.1 mol or less, preferably 0.08 mol or less and more preferably 0.05 mol or less, and usually 0.00001 mol or greater.
  • the proportion of the ruthenium complex per 100 parts by mass of the titanium complex is, for example, 50 parts by mass or less, preferably 25 parts by mass or less and usually 0.1 parts by mass or greater.
  • the proportion of the ruthenium complex per mol of the titanium complex is, for example, 0.5 mol or less, preferably 0.25 mol or less, and usually 0.0001 mol or greater.
  • reaction conditions for the second hydrothermal synthesis are the same as those for the first hydrothermal synthesis described above.
  • the titanium complex produces titanium oxide as a result of the reaction (second hydrothermal synthesis) while platinum does not cause a change in the chemical reaction in the chemical composition before and after the reaction.
  • the titanium complex and strontium hydroxide produce strontium titanate (SrTiO 3 ) as a result of the reaction (second hydrothermal synthesis) while nickel acetate produces nickel oxide (NiO).
  • the titanium complex and strontium hydroxide produce strontium titanate (SrTiO 3 ) as a result of the reaction (second hydrothermal synthesis), while the ruthenium complex produces ruthenium oxide (RuO 2 ).
  • the catalyst particles containing inorganic particles formed of an inorganic substance that is different from the inorganic substance serving as a starting material and a complex, and an organic group that binds to the surface of the inorganic particles are obtained.
  • a pH adjusting agent can be blended with the components in an appropriate proportion.
  • the pH adjusting agent can be, for example, an aqueous ammonia solution, an aqueous sodium hydroxide solution or the like.
  • an inorganic substance and/or a complex and an organic compound are blended and heated, for example, under normal atmospheric pressure conditions.
  • the organic compound is subjected to the high temperature treatment while serving as an organic group-introducing compound as well as a solvent for dispersing or dissolving the inorganic substance and/or the complex.
  • the proportion of the organic compound is, for example, 1 to 10000 parts by mass, preferably 10 to 5000 parts by mass, and more preferably 20 to 1000 parts by mass per 100 parts by mass of the inorganic substance and the complex.
  • the proportion of the organic compound in terms of volume is, for example, 1 to 10000 mL, preferably 10 to 5000 mL, and more preferably 20 to 1000 mL per 100 g of the inorganic substance and the complex.
  • the heating temperature is, for example, a temperature above 100° C., preferably 125° C. or higher, and more preferably 150° C. or higher, and usually for example, 600° C. or lower.
  • the heating time is, for example, 1 to 2000 minutes, preferably 2 to 1000 minutes, and more preferably 3 to 500 minutes. In the case where a continuous reactor is used, the reaction time is set to, for example, one minute or less.
  • heating can be carried out under, for example, high pressure.
  • high pressure conditions the same pressures as those used in the hydrothermal synthesis shown above can be used.
  • the catalyst particles containing inorganic particles formed of a metal oxide forming an inorganic substance and/or a complex, and an organic group that binds to the surface of the inorganic particles are obtained.
  • the high temperature treatment (surface treatment) described above can be carried out once, or can be carried out a plurality of times from a view point of enhancing treatment efficiency.
  • the method for carrying out the high temperature treatment a plurality of times for example, a method in which each of the first hydrothermal synthesis, the second hydrothermal synthesis and the surface treatment in a hot organic compound is repeated, or a method in which the above treatments are carried out in combination is used.
  • the method in which the above treatments are carried out in combination is used.
  • a method in which the surface treatment in a hot organic compound is performed after the second hydrothermal synthesis is used.
  • organic-inorganic composite particles in which a carboxyaliphatic group is bound to titanium oxide via a phosphoric acid group are obtained by subjecting a titanium complex to a high temperature treatment in any of the phosphoric acid ester group-containing organic compounds (carboxy ester group-containing organic compounds) listed above. After that, the obtained organic-inorganic composite particles are subjected to a high temperature treatment in an alcohol, whereby in the organic group, a carboxy ester group-containing organic group is produced from the carboxyaliphatic group. In other words, a carboxyl group binding to a terminal of an aliphatic group is esterified by the alcohol.
  • the catalyst particles may be anisotropic or isotropic, with an average particle size (average maximum length in the case where they are anisotropic) of, for example, 450 nm or less, preferably 1 to 450 nm, more preferably 1 to 200 nm and particularly preferably 1 to 100 nm from a view point of clarity.
  • the average particle size of the catalyst particles is determined by measurement by dynamic light scattering (DLS) or calculated from a transmission electron microscopic (TEM) or scanning electron microscopic (SEM) image analysis or with the Scherrer's equation based on data of X-ray diffractometry (XRD).
  • DLS dynamic light scattering
  • TEM transmission electron microscopic
  • SEM scanning electron microscopic
  • the clarity of the catalyst solution, the catalyst resin composition or the catalyst molded article will be low, or the particles may be crushed when mixed with a resin or the like.
  • the average particle size is below the above range, the proportion of the volume of the organic group relative to the surface of the catalyst particles will be high, and the inorganic particles may be unlikely to exert its catalytic action.
  • the catalyst particles thus obtained are unlikely to coagulate in a dry state, and even if the catalyst particles appear coagulated in a dry state, the coagulation (formation of secondary particles) will be reliably prevented in a catalyst composition and a catalyst molded article, and therefore the catalyst particles are dispersed substantially uniformly in a resin as primary particles.
  • the proportion of the surface area of the organic group relative to the surface area of the inorganic particles, or in other words, the surface coverage by the organic group in the catalyst particles is, for example, 30% or greater and preferably 60% or greater and usually 200% or less.
  • the surface coverage is determined by the same method as that described in the second embodiment.
  • the type of solvent (medium) for dispersing the catalyst particles can be controlled (designed or managed) according to the type of organic group.
  • the catalyst particles obtained in the above-described manner can be subjected to wet classification.
  • a solvent is added to the catalyst particles, and the resulting mixture is stirred and allowed to stand still, and thereafter separated into a supernatant and a precipitate.
  • the solvent varies depending on the type of organic group, but for example, the same solvents as those listed above can be used, and preferable examples include a hydroxyl group-containing aliphatic hydrocarbon, a carbonyl group-containing aliphatic hydrocarbon, an aliphatic hydrocarbon, a halogenated aliphatic hydrocarbon and an aqueous pH adjusting solution.
  • the average particle size of the resulting catalyst particles can be adjusted to, for example, 400 nm or less, 1 nm to 400 nm, preferably 1 nm to 200 nm and more preferably 1 nm to 100 nm.
  • the catalyst particles obtained in the above-described manner can be dispersed in a solvent or a resin to prepare a catalyst solution or a catalyst composition.
  • the catalyst solution contains a solvent and catalyst particles described above.
  • a solvent and catalyst particles are blended, and the resulting mixture is stirred so as to disperse the catalyst particles in the solvent.
  • solvents used in washing described above include alicyclic hydrocarbons such as cyclopentane and cyclohexane; esters such as ethyl acetate; polyols such as ethylene glycol and glycerol; nitrogen-containing compounds such as N-methylpyrrolidone, pyridine, acetonitrile and dimethylformamide; acrylic monomers such as isostearyl acrylate, lauryl acrylate, isoboronyl acrylate, butyl acrylate, methacrylate, acrylic acid, tetrahydrofurfuryl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxyethyl acrylate and acryloylmorpholine; vinyl group-containing monomers such as styrene and ethylene; epoxy-containing monomers such as bisphenol A epoxy; and the
  • solvents can be used singly or in a combination of two or more.
  • a halogenated aliphatic hydrocarbon is preferable.
  • the proportion of the catalyst particles is, for example, 0.1 to 70 parts by mass, preferably 0.2 to 60 parts by mass and more preferably 0.5 to 50 parts by mass per 100 parts by mass of the catalyst solution.
  • the catalyst particles have a configuration that does not allow the inorganic particles to contact with each other, and therefore are uniformly dispersed as primary particles in the solvent. Accordingly, the clarity of the catalyst solution can be enhanced.
  • the catalyst composition contains a resin and catalyst particles described above.
  • the same resins as those listed in the second embodiment can be used. These resins can be used singly or in a combination of two or more.
  • solubility parameters SP values
  • the catalyst particles and the resin are selected so as to attain a predetermined SP difference ( ⁇ SP, specifically, the absolute value of the difference between the solubility parameter of resin (SP RESIN value) and the solubility parameter of catalyst particles (SP PARTICLE value)).
  • ⁇ SP specifically, the absolute value of the difference between the solubility parameter of resin (SP RESIN value) and the solubility parameter of catalyst particles (SP PARTICLE value)
  • a highly oriented resin having high orientation is preferable.
  • the highly oriented resin the same highly oriented resins as those listed in the second embodiment can be used.
  • the resin has, for example, a hydrophilic group such as a carboxyl group or a hydroxyl group, a hydrophobic group such as a hydrocarbon group, and the like.
  • a solvent and a resin described above are blended so as to dissolve the resin in the solvent to prepare a resin solution. After that, the resin solution is blended with catalyst particles, and the resulting mixture is stirred to prepare a catalyst composition (first preparation method).
  • the proportion of resin relative to the resin solution is the same as those shown in the second embodiment.
  • the proportion of the catalyst particles is, for example, 1 to 1000 parts by mass, preferably 5 to 500 parts by mass and more preferably 10 to 300 parts by mass per 100 parts by mass of the solids content (resin) of the resin solution.
  • the proportion of the catalyst particles is also, for example, 0.1 to 300 parts by mass, preferably 1 to 200 parts by mass and more preferably 3 to 100 parts by mass per 100 parts by mass of the total amount of the resin solution (the total amount of the resin and the solvent).
  • the catalyst composition can also be prepared by, first, preparing a catalyst solution described above, and then blending the catalyst solution with a resin and stirring the resulting mixture (second preparation method).
  • the catalyst particles are dispersed as primary particles in the solvent.
  • the proportion of resin is, for example, 10 to 10000 parts by mass, preferably 20 to 2000 parts by mass and more preferably 40 to 1000 parts by mass per 100 parts by mass of the solids content (catalyst particle) of the catalyst solution.
  • the catalyst composition can also be prepared by, for example, blending a solvent, catalyst particles and a resin simultaneously and stirring the resulting mixture (third preparation method).
  • the proportions of respective components per 100 parts by mass of the total amount of the catalyst composition are as follows: the proportion of the catalyst particles is, for example, 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass and more preferably 3 to 30 parts by mass; and the proportion of resin is, 40 parts by mass or less, preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and usually 1 part by mass or greater.
  • the proportion of the solvent is the remainder obtained by excluding the catalyst particles and the resin from the catalyst composition.
  • the catalyst composition can also be prepared by, first, preparing a resin solution and a catalyst solution in a separate manner and then blending and stirring the resin solution and the catalyst solution (fourth preparation method).
  • the proportion of resin in the resin solution is the same as those shown in the first preparation method described above.
  • the proportion of the catalyst particles in the catalyst solution is the same as those shown in the preparation method for a catalyst solution described above.
  • the resin solution and the catalyst solution are blended such that the proportion of resin relative to the catalyst particles in terms of mass is, for example, 99:1 to 10:90, preferably 95:5 to 20:80 and more preferably 90:10 to 30:70.
  • the catalyst composition can also be prepared without the use of a solvent by, for example, melting a resin by application of heat and blending the resin with catalyst particles (fifth preparation method).
  • the thus-prepared catalyst composition is a melt of the catalyst composition without a solvent.
  • the heating temperature is, in the case where the resin is a thermoplastic resin, greater than or equal to the melting temperature of the resin, specifically, 200 to 350° C.
  • the heating temperature is a temperature at which the resin is B-staged, for example, 85 to 140° C.
  • the proportion of resin relative to the catalyst particles in terms of mass is, for example, 99:1 to 10:90, preferably 95:5 to 20:80 and more preferably 90:10 to 30:70.
  • the catalyst particles are uniformly dispersed in the resin. Specifically, in the catalyst composition, the catalyst particles are dispersed as primary particles in the resin (without substantial coagulation).
  • the obtained catalyst composition is applied to, for example, a known support plate to form a coating, and the coating is dried, whereby a catalyst molded article as a film is molded.
  • the catalyst composition is applied by using, for example, a known application method such as spin coating or bar coating. Simultaneously with or immediately after application of the catalyst composition, the solvent is removed by volatilization. If necessary, the solvent can be dried by application of heat after application of the catalyst composition.
  • a known application method such as spin coating or bar coating.
  • the thickness of the obtained film can be set as appropriate according to the use and purpose, and the thickness is, for example, 0.1 to 2000 ⁇ m, preferably 0.1 to 1000 ⁇ m and more preferably 0.1 to 500 ⁇ m.
  • the catalyst molded article as a film can also be molded by a melt molding method in which the catalyst composition is extruded by an extruding machine or the like.
  • the catalyst molded article can also be molded as a block (mass) by injecting the catalyst composition into a metal mold or the like and thereafter subjecting the resultant to, for example, heat molding such as heat pressing.
  • the catalyst molded article is formed of the catalyst composition in which the catalyst particles are dispersed in the resin, and the inorganic particles cannot easily come into direct contact with the resin due to the configuration based on the steric hindrance of the organic group of the catalyst particles. Accordingly, the catalyst molded article can, while suppressing degradation of the resin, exert a catalytic action for a gas or a liquid.
  • the catalyst molded article can exert a detoxification action, a deodorization action, a disinfectant (or in other words, antimicrobial or germicidal) action and a decomposition action for toxins, odor (malodor), fungi and organic substances contained in a gas such as the air by absorbing light, specifically, for example, light having a wavelength of 1000 nm or less, preferably light having a wavelength of 900 nm or less and more preferably light having a wavelength of 800 nm or less.
  • the catalyst molded article can exert a detoxification action, a disinfectant action, a dirt repellent action and a decomposition action for toxins, fungi, excrements and organic substances contained in a liquid such as water.
  • the catalyst molded article can be used as a catalyst molded article having various catalytic actions (photocatalytic actions) such as a detoxification action, a deodorization action, a disinfectant action, a dirt repellent action and a decomposition action while maintaining excellent durability.
  • catalytic actions photocatalytic actions
  • the catalyst particles are uniformly dispersed, and thus clarity can be enhanced.
  • the catalyst molded article can be used in various optical applications and various construction material applications where clarity is required.
  • the catalyst molded article can be used as, in the case where it is molded as a film, for example, an optical film for use in an image display apparatus (liquid crystal display, organic electroluminescent apparatus or the like) such as a polarizing film, a phase diference film, a brightness enhancing film, a viewing angle enhancing film, a high-refractive index film or a light diffusing film.
  • an image display apparatus liquid crystal display, organic electroluminescent apparatus or the like
  • polarizing film such as a polarizing film, a phase diference film, a brightness enhancing film, a viewing angle enhancing film, a high-refractive index film or a light diffusing film.
  • the catalyst molded article can also be used as, in the case where it is molded as a film, for example, a construction material (construction) film such as an ultraviolet absorbing film, a dirt repellent film, an antimicrobial film, a deodorizing film, a super-hydrophilic film, a germicidal film, a detoxification film or a chemical substance decomposing film.
  • a construction material (construction) film such as an ultraviolet absorbing film, a dirt repellent film, an antimicrobial film, a deodorizing film, a super-hydrophilic film, a germicidal film, a detoxification film or a chemical substance decomposing film.
  • the resin molded article of the present invention can be obtained by removing organic-inorganic composite particles from a particle-containing resin molded article containing a resin and the organic-inorganic composite particles.
  • the resin is a matrix component forming the resin molded article and can be, for example, a thermosetting resin, a thermoplastic resin or the like.
  • thermosetting resin and the thermoplastic resin include the same thermosetting resins and thermoplastic resins as those listed in the second embodiment. These resins can be used singly or in a combination of two or more.
  • the resin is preferably a polyester resin, a thermoplastic polyimide resin, a polyetherimide resin or the like.
  • the resin preferably has a functional group.
  • the functional group include hydrophilic groups such as a carboxyl group and a hydroxyl group; hydrophobic groups such as a hydrocarbon group; and the like.
  • the resin has a refractive index for light having a wavelength of 633 nm of, for example, greater than 1 and 3 or less, preferably 1.2 to 2.5, and more preferably 1.3 to 2.0.
  • the refractive index is measured by, for example, a refractometer.
  • the resin has a reflectance for light having a wavelength of 550 nm of, for example, 1 to 10%, preferably 2 to 9% and more preferably 3 to 8%.
  • the reflectance is measured by, for example, a spectrophotometer.
  • the resin has a dielectric constant of, for example, 1.5 to 1000, preferably 2 to 100 and more preferably 2 to 10.
  • the dielectric constant is measured by, for example, an automatic dielectric loss measurement apparatus at a frequency of 1 MHz.
  • the organic-inorganic composite particles are particles that can be dispersed as primary particles in a solvent (described later) and/or a resin and extracted from the resin with an extraction solvent, and contain inorganic particles and an organic group that binds to the surface of the inorganic particles.
  • the organic-inorganic composite particles are obtained by surface-treating an inorganic material form inorganic particles with an organic compound.
  • the organic-inorganic composite particles can be used singly or in a combination of two or more.
  • the inorganic material form inorganic particles can be a metal composed of a metal element such as a main group element or a transition element, a nonmetal composed of a nonmetal element such as boron or silicon, an inorganic compound and/or a complex containing a metal element and/or a nonmetal.
  • Examples of the metal element and the nonmetal element include elements that are located on the left side and the lower side of a border line that is assumed to pass through boron (B) of the IIIB group, silicon (Si) of the IVB group, arsenic (As) of the VB group, tellurium (Te) of the VIB group and astatine (At) of the VIIB group on the long-form periodic table (IUPAC, 1989), as well as the elements that are located on the border line.
  • Specific examples thereof include the group I elements (alkali metals) such as Li, Na, K, Rb and Cs; the group II elements (alkaline earth metals) such as Be, Mg, Ca, Sr, Ba and Ra; and the same elements as those listed in the second embodiment.
  • Examples of the inorganic compound include the same inorganic compounds as those listed in the second embodiment.
  • the inorganic compound include an oxide, a carbonate, a sulfate and the like.
  • the oxide can be, for example, a metal oxide.
  • a metal oxide Preferable examples include titanium oxide (titanium dioxide, titanium oxide (IV), titania: TiO 2 ), cerium oxide (cerium dioxide, cerium oxide (IV), ceria: CeO 2 ), zinc oxide (zinc oxide (II), flowers of zinc or zinc white, ZnO) and the like.
  • the oxides can be used singly or in a combination of two or more.
  • the element that combines with carbonic acid can be, for example, an alkali metal, an alkaline earth metal or the like.
  • the alkali metal and the alkaline earth metal can be the same alkali metals and alkaline earth metals as those listed above.
  • the element that combines with carbonic acid is preferably an alkaline earth metal.
  • the carbonate is preferably a carbonate containing an alkaline earth metal, and examples of such a carbonate include beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, radium carbonate and the like. These carbonates can be used singly or in a combination of two or more.
  • the sulfate is a compound consisting of a sulfate ion (SO 4 2 ⁇ ) and a metal cation (more specifically, a compound formed by substitution of the hydrogen atoms of sulfuric acid (H 2 SO 4 ) with a metal), and the metal contained in the sulfate can be, for example, an alkali metal, an alkaline earth metal or the like.
  • the alkali metal and the alkaline earth metal can be the same alkali metals and alkaline earth metals as those listed above.
  • the metal is preferably an alkaline earth metal.
  • the sulfate is preferably a sulfate containing an alkaline earth metal, and examples of such a sulfate include beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, radium sulfate and the like. Barium sulfate is preferable.
  • the sulfates can be used singly or in a combination of two or more.
  • the inorganic materials listed above can be used singly or in a combination of two or more.
  • the organic compound is, for example, an organic group-introducing compound that introduces (disposes) an organic group on the surface of inorganic particles.
  • the organic compound contains a binding group capable of binding to the surface of inorganic particles and an organic group.
  • the binding group may be selected as appropriate according to the type of inorganic particles, and examples thereof include functional groups such as carboxyl group, phosphoric acid group (—PO(OH) 2 , phosphono group), amino group, sulfo group, hydroxyl group, thiol group, epoxy group, isocyanate group (cyano group), nitro group, azo group, silyloxy group, imino group, aldehyde group (acyl group), nitrile group, vinyl group (polymerizable group) and the like.
  • Preferable examples include carboxyl group, phosphoric acid group, amino group, sulfo group, hydroxyl group, thiol group, epoxy group, azo group, vinyl group, and the like. More preferable examples include carboxyl group and phosphoric acid group.
  • the carboxyl group includes a carboxylic acid ester group (carboxy ester group).
  • the phosphoric acid group includes a phosphoric acid ester group (phosphonate group).
  • binding groups are contained in the organic compound. Specifically, the binding group is bound to a terminal or a side chain of the organic group.
  • the binding group is selected as appropriate according to the type of inorganic particles. Specifically, when the inorganic particles contain cerium oxide, strontium carbonate and/or barium sulfate, for example, carboxyl group is selected. When the inorganic particles contain titanium oxide and/or zinc oxide, for example, a phosphoric acid group is selected.
  • the organic group includes, for example, a hydrocarbon group such as an aliphatic group, an alicyclic group, an araliphatic group or an aromatic group, or the like.
  • hydrocarbon groups examples include the same hydrocarbon groups as those listed in the second embodiment.
  • the organic group is a hydrophobic group for imparting hydrophobicity to the surface of inorganic particles.
  • the organic compounds containing a hydrophobic group described above are used as hydrophobic organic compounds for hydrophobic treatment of inorganic particles.
  • specific examples of such hydrophobic organic compounds include the same hydrophobic organic compounds as those listed in the second embodiment.
  • the organic compound can also be used as a hydrophilic organic compound for hydrophilic treatment of inorganic particles.
  • the organic group contained in the hydrophilic organic compound includes any of the above hydrocarbon groups and a hydrophilic group that binds to the hydrocarbon group.
  • the hydrophilic group is bound to a terminal (the terminal (the other terminal) opposite the terminal that is bound to the binding group (one terminal)) or a side chain of the hydrocarbon group.
  • the hydrophilic group is a functional group having a polarity (or in other words, polar group), and examples thereof include the same functional groups as those listed in the second embodiment.
  • One or more of the hydrophilic groups are contained in the hydrophilic organic compound.
  • organic compound containing a hydrophilic group examples include the same carboxyl group-containing organic compounds, hydroxyl group-containing organic compounds, phosphoric acid group-containing organic compounds, amino group-containing organic compounds, sulfo group-containing organic compounds, carbonyl group-containing organic compounds, cyano group-containing organic compounds, nitro group-containing organic compounds, aldehyde group-containing organic compounds and thiol group-containing organic compounds as those listed in the second embodiment.
  • the same or mutually different organic groups may be used.
  • the organic group contains a plurality of mutually different types of organic groups, a plurality of homologous organic groups and/or a plurality of heterologous organic groups are contained.
  • homologous organic groups examples include the same combinations as those listed in the second embodiment.
  • a preferable example of the homologous organic groups is a combination of a plurality of aliphatic groups, a more preferable example is a combination of a plurality of saturated aliphatic groups, and a particularly preferable example is a combination of a saturated aliphatic group having less than 10 carbon atoms and a saturated aliphatic group having 10 or more carbon atoms.
  • Specific examples include a combination of hexyl and decyl and a combination of octyl and decyl.
  • the organic group contains a plurality of homologous organic groups
  • a plurality of organic groups having different sizes (lengths or/and dimensions, or in other words, the number of carbon atoms) are contained in the organic group. Accordingly, in a space between adjacent larger organic groups, a resin molecule enters a gap (pocket) formed in accordance with the smaller organic group, and the interaction between the larger organic group and the resin molecule can be enhanced. As a result, the dispersibility of the organic-inorganic composite particles can be enhanced.
  • heterologous organic groups examples include the same combinations as those listed in the second embodiment.
  • the organic group contains a plurality of heterologous organic groups
  • the organic group when the resin is prepared as a mixture of a plurality of resin components, the organic group can exert excellent compatibility with the resin molecules of the respective resin components having excellent compatibility with the organic groups of the respective groups. Accordingly, the interaction between the organic groups and the resin molecules of the resin components can be enhanced. As a result, the dispersibility of the organic-inorganic composite particles can be enhanced.
  • the organic groups are present on the surface of inorganic particles in the organic-inorganic composite particles. Specifically, the organic groups are bound to the surface of inorganic particles via a binding group. Also, the organic groups extend from the surface of inorganic particles toward the outside of the inorganic particles via a binding group.
  • the organic-inorganic composite particles are prepared by subjecting an inorganic material and an organic compound to a reaction treatment, preferably to a high temperature treatment.
  • the high temperature treatment is carried out in a solvent.
  • a solvent for example, water and any above-listed organic compounds can be used.
  • the organic-inorganic composite particles are obtained by subjecting an inorganic material and an organic compound to a high temperature treatment in water under high pressure conditions (hydrothermal synthesis: hydrothermal reaction), or subjecting an inorganic material to a high temperature treatment in an organic compound (high temperature treatment in an organic compound).
  • the organic-inorganic composite particles are obtained by surface-treating the surface of inorganic particles formed by an inorganic material with (or in the presence of) an organic compound.
  • the inorganic material and the organic compound are reacted under high-temperature and high-pressure conditions in the presence of water (first hydrothermal synthesis).
  • the inorganic material subjected to the first hydrothermal synthesis is preferably an inorganic compound, and more preferably a carbonate or a sulfate.
  • a reaction system is prepared under high-temperature and high-pressure conditions by placing an inorganic material, an organic compound and water in a pressure-resistant airtight container and heating them.
  • the proportions of respective components per 100 parts by mass of the inorganic material are as follows: the proportion of the organic compound is, for example, 1 to 1500 parts by mass, preferably 5 to 500 parts by mass and more preferably 5 to 250 parts by mass; and the proportion of water is, for example, 50 to 8000 parts by mass, preferably 80 to 6600 parts by mass and more preferably 100 to 4500 parts by mass.
  • the density of the organic compound is usually 0.8 to 1.1 g/mL, and thus the proportion of the organic compound is, for example, 1 to 1500 mL, preferably 5 to 500 mL and more preferably 5 to 250 mL per 100 g of the inorganic material.
  • the number of moles of the organic compound can be, for example, 0.01 to 1000 mol, preferably 0.02 to 50 mol, and more preferably 0.1 to 10 mol per mol of the inorganic material.
  • the organic compound contain a plurality of (for example, two) different types of organic groups
  • the molar ratio between an organic compound containing one type of organic group and an organic compound containing the other type of organic group is, for example, 10:90 to 99.9:0.1, and preferably 20:80 to 99:1.
  • the density of water is usually approximately 1 g/mL, and thus the proportion of water is, for example, 50 to 8000 mL, preferably 80 to 6600 mL, and more preferably 100 to 4500 mL per 100 g of the inorganic material.
  • reaction conditions for the hydrothermal reaction are the same reaction conditions as those shown in the second embodiment.
  • an aqueous pH adjusting solution such as an aqueous ammonia solution or an aqueous solution of potassium hydroxide can be added in an appropriate proportion.
  • the reaction product obtained by the above reaction includes a precipitate that mostly precipitates in water and a deposit that adheres to the inner wall of the airtight container.
  • the precipitate is obtained by, for example, sedimentation separation in which the reaction product is settled by gravity or a centrifugal field.
  • the precipitate is obtained as a precipitate of the reaction product by centrifugal sedimentation (centrifugal separation) in which the reaction product is settled by a centrifugal field.
  • the deposit is recovered by, for example, a scraper (spatula) or the like.
  • the reaction product can also be recovered (separated) by adding a solvent to wash away an unreacted organic compound (or in other words, dissolving the organic compound in the solvent) and thereafter removing the solvent (recovering step).
  • the solvent can be, for example, an alcohol (hydroxyl group-containing aliphatic hydrocarbon) such as methanol, ethanol, propanol or isopropanol; a ketone (carbonyl group-containing aliphatic hydrocarbon) such as acetone, methyl ethyl ketone, cyclohexanone or cyclopentanone; an aliphatic hydrocarbon such as pentane, hexane or heptane; a halogenated aliphatic hydrocarbon such as dichloromethane, chloroform or trichloroethane; a halogenated aromatic hydrocarbon such as chlorobenzene or dichlorobenzene; an ether such as tetrahydrofuran; an aromatic hydrocarbon such as benzene, toluene or xylene; an aqueous pH adjusting solution described above; or the like.
  • an alcohol hydroxyl group-containing aliphatic hydrocarbon
  • a ketone carbon
  • the washed reaction product is separated from the solvent (supernatant liquid) by, for example, filtration, decantation or the like, and recovered. After that, the reaction product is dried by, for example, application of heat, an air stream or the like if necessary.
  • the organic-inorganic composite particles containing inorganic particles and an organic group that binds to the surface of the inorganic particles are obtained.
  • the inorganic material before reaction and the inorganic particles after reaction have the same composition.
  • the organic-inorganic composite particles containing inorganic particles formed of an inorganic substance that is different from the inorganic material serving as a starting material can also be obtained by subjecting an inorganic material (starting material) and an organic compound to a hydrothermal synthesis (second hydrothermal synthesis).
  • the inorganic material subjected to the second hydrothermal synthesis can be, for example, a hydroxide, an acetate, a complex or the like.
  • the element (element that constitutes a cation that combines with a hydroxyl ion (OH ⁇ )) contained in the hydroxide can be the same as the element that combines with oxygen in an oxide listed above.
  • the hydroxide can be, for example, titanium hydroxide (Ti(OH) 4 ) or cerium hydroxide (Ce(OH) 4 ).
  • the element contained in the acetate that combine with an acetic acid ion can be a group JIB element, preferably Zn, Cd or the like.
  • the acetate is preferably an acetate containing a group IIB element, and specific examples of such an acetate include zinc acetate, cadmium acetate and the like. These acetates can be used singly or in a combination of two or more.
  • the complex contains a central atom and/or a central ion and a ligand that coordinates thereto.
  • Examples of the central atom include the same metal elements as those listed above.
  • a group IVA element is preferable, and Ti is more preferable.
  • Examples of the central ion include cations of the metal elements listed above.
  • Examples of the ligand include coordinating compounds such as carboxylic acid, hydroxycarboxylic acid and acetylacetone; coordinating ions such as cations and hydroxide ions in the above coordinating compounds; and the like.
  • carboxylic acid examples include dicarboxylic acids such as oxalic acid, succinic acid and phthalic acid, and the like.
  • hydroxycarboxylic acid examples include monohydroxymonocarboxylic acid (specifically, ⁇ -monohydroxycarboxylic acids) such as 2-hydroxyoctanoic acid, lactic acid and glycolic acid; monohydroxydicarboxylic acids such as malic acid; monohydroxytricarboxylic acids such as citric acid; and the like.
  • monohydroxymonocarboxylic acid specifically, ⁇ -monohydroxycarboxylic acids
  • 2-hydroxyoctanoic acid lactic acid and glycolic acid
  • monohydroxydicarboxylic acids such as malic acid
  • monohydroxytricarboxylic acids such as citric acid
  • the coordination number is, for example, 1 to 6 and preferably 1 to 3.
  • the complex can be obtained by preparation from a metal element and a ligand described above.
  • the complex can also be formed (prepared) as a salt and/or a hydrate.
  • the salt include salts with cations such as ammonium ions.
  • organic compound for example, the same organic compounds as those that can be used in the first hydrothermal synthesis described above can be used.
  • the inorganic material and the organic compound are reacted under high-temperature and high-pressure conditions in the presence of water.
  • the proportions of respective components per 100 parts by mass of the inorganic compound are as follows: the proportion of the organic compound is, for example, 1 to 1500 parts by mass, preferably 5 to 500 parts by mass and more preferably 5 to 250 parts by mass; and the proportion of water is, for example, 50 to 8000 parts by mass, preferably 80 to 6600 parts by mass and more preferably 80 to 4500 parts by mass.
  • the proportion of the organic compound is, for example, 0.9 to 1880 mL, preferably 4.5 to 630 mL and more preferably 4.5 to 320 mL per 100 g of the hydroxide, and the number of moles of the organic compound can be, for example, 0.01 to 10000 mol and preferably 0.1 to 10 mol per mol of the hydroxide.
  • the proportion of water is, for example, 50 to 8000 mL, preferably 80 to 6600 mL and more preferably 100 to 4500 mL per 100 g of the hydroxide.
  • reaction conditions for the second hydrothermal synthesis are the same as those for the first hydrothermal synthesis described above.
  • the organic-inorganic composite particles containing inorganic particles formed of an inorganic substance having a different composition as that of the starting inorganic material and an organic group that binds to the surface of the inorganic particles are obtained.
  • an inorganic material and an organic compound are blended and heated, for example, under normal atmospheric pressure conditions.
  • the organic compound is subjected to the high temperature treatment while serving as an organic group-introducing compound as well as a solvent for dispersing or dissolving the inorganic material.
  • the proportion of the organic compound is, for example, 10 to 10000 parts by mass and preferably 100 to 1000 parts by mass per 100 parts by mass of the inorganic material.
  • the proportion of the organic compound in terms of volume is, for example, 10 to 10000 mL and preferably 100 to 1000 mL per 100 g of the inorganic material.
  • the heating temperature is the same as those shown in the second embodiment.
  • the heating time is the same as those shown in the second embodiment.
  • the organic-inorganic composite particles may be anisotropic or isotropic, with an average particle size (average maximum length in the case where they are anisotropic) of, for example, 400 nm or less, preferably 200 nm or less and more preferably 100 nm or less, and usually for example, 1 nm or greater and preferably 3 nm or greater.
  • the average particle size of the organic-inorganic composite particles is determined by measurement by dynamic light scattering (DLS) and/or calculated from a transmission electron microscopic (TEM) or scanning electron microscopic (SEM) image analysis.
  • DLS dynamic light scattering
  • TEM transmission electron microscopic
  • SEM scanning electron microscopic
  • the average particle size of the organic-inorganic composite particles exceeds the above range, the micropores (described later) will be too large, and the clarity of the resin molded article (porous film, described later) will be low. Also, the organic-inorganic composite particles may be crushed when mixed with the resin or the like. If the average particle size exceeds the above range, the organic-inorganic composite particles may be crushed when mixed with the resin or the like.
  • the average particle size of the organic-inorganic composite particles is below the above range, the proportion of the volume of the organic group relative to the surface of the organic-inorganic composite particles will be high, and the function of the inorganic particles is unlikely to be obtained.
  • the organic-inorganic composite particles thus obtained are unlikely to coagulate in a dry state, and even if the organic-inorganic composite particles appear coagulated in a dry state, the coagulation between inorganic particles is prevented in a particle-containing resin composition and a particle-containing resin molded article.
  • the organic-inorganic composite particles have at least a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group.
  • the organic-inorganic composite particles are also particles that can be easily re-dispersed by simply adding a solvent (described later) even if they are once dried.
  • the proportion of the surface area of the organic group relative to the surface area of the inorganic particles, or in other words, the surface coverage by the organic group in the organic-inorganic composite particles is, for example, 30% or greater and preferably 60% or greater and usually 200% or less.
  • the surface coverage is determined by the same method as that described in the second embodiment.
  • the type of solvent (medium) for dispersing the organic-inorganic composite particles can be controlled (designed or managed) according to the type of organic group.
  • the organic-inorganic composite particles obtained in the above-described manner can be subjected to wet classification.
  • wet classification the same wet classification as that shown in the second embodiment is used.
  • organic-inorganic composite particles having a small average particles size can be obtained.
  • the average particle size of the resulting organic-inorganic composite particles can be adjusted to, for example, 400 nm or less, preferably 200 nm or less and more preferably 100 nm or less, and usually, for example, 0.1 nm or greater, and preferably 0.3 nm or greater.
  • solubility parameters SP values
  • the resin and the organic-inorganic composite particles are selected so as to attain a predetermined SP difference ( ⁇ SP, specifically, the absolute value of the difference between the solubility parameter of resin (SP RESIN value) and the solubility parameter of organic-inorganic composite particles (SP PARTICLE value)).
  • ⁇ SP specifically, the absolute value of the difference between the solubility parameter of resin (SP RESIN value) and the solubility parameter of organic-inorganic composite particles (SP PARTICLE value)).
  • Preferable hydrophilic groups included in both the functional group and the organic group are a carboxyl group and a hydroxyl group
  • preferable hydrophobic groups included in both the functional group and the organic group are a hydrocarbon group and the like.
  • the affinity between the organic-inorganic composite particles and the resin can be enhanced as a result of both the functional group and the organic group having any of the above groups having the same property (hydrophilicity or hydrophobicity).
  • a particle-containing resin composition is prepared by blending a resin and organic-inorganic composite particles described above.
  • the existing (dispersed) state of organic-inorganic composite particles in the particle-containing resin composition varies depending on the composition of organic group contained in the organic-inorganic composite particles. Accordingly, the existing (dispersed) state of organic-inorganic composite particles in the particle-containing resin composition is not limited to the proportion of resin to organic-inorganic composite particles (described later).
  • the same solvents as those listed in the second embodiment can be used. These solvents can be used singly or in a combination of two or more.
  • the solvent is preferably a halogenated aliphatic hydrocarbon.
  • a solvent and a resin described above are blended so as to dissolve the resin in the solvent to prepare a resin solution.
  • the resin solution is blended with organic-inorganic composite particles, and the resulting mixture is stirred to prepare a particle-containing resin composition (first preparation method).
  • the proportion of resin relative to the resin solution is the same as those (in terms of mass, volume, mol, and the like) shown in the second embodiment.
  • the proportion of the organic-inorganic composite particles is, for example, 1 to 5000 parts by mass, preferably 5 to 3000 parts by mass and more preferably 10 to 300 parts by mass per 100 parts by mass of the solids content (resin) of the resin solution.
  • the proportion of the organic-inorganic composite particles is set to be relatively low (or in other words, the organic-inorganic composite particles are blended at a low concentration).
  • the proportion of the organic-inorganic composite particles is set to, for example, less than 1000 parts by mass, preferably 500 parts by mass or less, and more preferably 300 parts by mass or less, and for example, 1 part by mass or greater per 100 parts by mass of the solids content (resin) of the resin solution.
  • the proportion of the organic-inorganic composite particles is set to be relatively high (or in other words, the organic-inorganic composite particles are blended at a high concentration).
  • the proportion of the organic-inorganic composite particles is set to, for example, 5 parts by mass or greater, preferably 10 parts by mass or greater, more preferably 20 parts by mass or greater and usually, for example, 5000 parts by mass or less per 100 parts by mass of the solids content (resin) of the resin solution.
  • the proportion of the organic-inorganic composite particles is, for example, 50 to 500% and preferably 80 to 400% of that when the particle-containing resin molded article is formed so as to have a bicontinuous structure.
  • the particle-containing resin composition can also be prepared by blending a solvent and organic-inorganic composite particles to disperse the organic-inorganic composite particles in the solvent to prepare a particle dispersion, and then blending the particle dispersion with a resin and stirring the resulting mixture (second preparation method).
  • the organic-inorganic composite particles are dispersed as primary particles in the solvent.
  • the proportion of the organic-inorganic composite particles is, for example, 0.1 to 80 parts by mass, preferably 0.2 to 60 parts by mass and more preferably 0.5 to 50 parts by mass per 100 parts by mass of the particle dispersion.
  • the proportion of resin relative to the solids content (organic-inorganic composite particles) of the particle dispersion is the same as those (in terms of mass, volume, mol, and the like) shown in the second embodiment.
  • the proportion of resin is set to be relatively high (or in other words, the resin is blended at a high concentration).
  • the proportion of resin is, for example, 1 part by mass or greater, preferably 10 parts by mass or greater, more preferably 20 parts by mass or greater, particularly preferably 40 parts by mass or greater, and for example, 10000 parts by mass or less per 100 parts by mass of the solids content (organic-inorganic composite particles) of the particle dispersion.
  • the proportion of resin is set to be relatively low (or in other words, the resin is blended at a low concentration).
  • the proportion of resin is set to, for example, less than 2000 parts by mass, preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and for example, 1 part by mass or greater per 100 parts by mass of the solids content (organic-inorganic composite particles) of the particle dispersion.
  • the proportion of resin is, for example, 10 to 300% and preferably 20 to 200% of that when the particle-containing resin molded article is formed so as to have a bicontinuous structure.
  • the particle-containing resin composition can also be prepared by, for example, blending a solvent, organic-inorganic composite particles and a resin simultaneously and stirring the resulting mixture (third preparation method).
  • the proportions of respective components per 100 parts by mass of the total amount of the organic-inorganic composite particles and the resin are as follows: the proportion of the organic-inorganic composite particles is, for example, 0.1 to 99.9 parts by mass, preferably 1 to 99 parts by mass and more preferably 3 to 95 parts by mass; and the proportion of resin is 0.1 to 99.9 parts by mass, preferably 1 to 99 parts by mass and more preferably 5 to 97 parts by mass.
  • the proportion of the solvent is, for example, 1 to 10000 parts by mass and preferably 10 to 5000 parts by mass per 100 parts by mass of the total amount of the organic-inorganic composite particles and the resin.
  • the proportion of the organic-inorganic composite particles is set to be relatively low (or in other words, the organic-inorganic composite particles are blended at a low concentration).
  • the proportion of the organic-inorganic composite particles is set to, for example, less than 99 parts by mass, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, particularly preferably 70 parts by mass or less and for example, 0.1 parts by mass or greater per 100 parts by mass of the total amount of the organic-inorganic composite particles and the resin.
  • the proportion of the organic-inorganic composite particles is set to be relatively high (or in other words, the organic-inorganic composite particles are blended at a high concentration).
  • the proportion of the organic-inorganic composite particles is set to, for example, 5 parts by mass or greater, preferably 10 parts by mass or greater, more preferably 20 parts by mass or greater and for example, 99 parts by mass or less per 100 parts by mass of the total amount of the organic-inorganic composite particles and the resin.
  • the proportion of the organic-inorganic composite particles is, for example, 50 to 500% and preferably 80 to 400% of that when the particle-containing resin molded article is formed so as to have a bicontinuous structure.
  • the particle-containing resin composition can also be prepared by, first, preparing a resin solution and a particle dispersion in a separate manner, and then blending and stirring the resin solution and the particle dispersion (fourth preparation method).
  • the proportion of resin in the resin solution is the same as those shown in the first preparation method described above.
  • the proportion of the organic-inorganic composite particles in the particle dispersion is the same as those shown in the second preparation method described above.
  • the resin solution and the particle dispersion are blended such that the proportion of the organic-inorganic composite particles is, for example, 0.1 to 99.9 parts by mass, preferably 1 to 99 parts by mass and more preferably 3 to 95 parts by mass per 100 parts by mass of the total amount of the organic-inorganic composite particles and the resin.
  • the resin solution and the particle dispersion are blended such that the proportion of the organic-inorganic composite particles is relatively low (or in other words, the concentration of the organic-inorganic composite particles is low).
  • the resin solution and the particle dispersion are blended such that the proportion of the organic-inorganic composite particles is, for example, less than 99 parts by mass, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, particularly preferably 70 parts by mass or less and for example, 0.1 parts by mass or greater per 100 parts by mass of the total amount of the organic-inorganic composite particles and the resin.
  • the resin solution and the particle dispersion are blended such that the proportion of the organic-inorganic composite particles is relatively high (or in other words, the concentration of the organic-inorganic composite particles is high).
  • the resin solution and the particle dispersion are blended such that the proportion of the organic-inorganic composite particles is, for example, less than 99.9 parts by mass, preferably 99 parts by mass or less, more preferably 95 parts by mass or less, particularly preferably 90 parts by mass or less, for example, 5 parts by mass or greater, preferably 10 parts by mass or greater, and more preferably 20 parts by mass or greater per 100 parts by mass of the total amount of the organic-inorganic composite particles and the resin.
  • the proportion of the organic-inorganic composite particles is, for example, 50 to 500% and preferably 80 to 400% of that when the particle-containing resin molded article is formed so as to have a bicontinuous structure.
  • the particle-containing resin composition can also be prepared by without the use of a solvent by, for example, melting a resin by application of heat and blending the resin with organic-inorganic composite particles (fifth preparation method).
  • the thus-prepared particle-containing resin composition is a melt of the particle-containing resin composition without a solvent.
  • the heating temperature is the same as those shown in the second embodiment.
  • the proportion of resin is, for example, 1 to 90 parts by mass, preferably 5 to 80 parts by mass and more preferably 10 to 70 parts by mass per 100 parts by mass of the total amount of the resin and the organic-inorganic composite particles.
  • the proportion of the organic-inorganic composite particles is set to be relatively low (or in other words, the organic-inorganic composite particles are blended at a low concentration).
  • the proportion of the organic-inorganic composite particles is, for example, less than 99 parts by mass, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, particularly preferably 70 parts by mass or less, for example, 0.01 parts by mass or greater, preferably 0.1 parts by mass or greater, and more preferably 1 part by mass or greater per 100 parts by mass of the total amount of the resin and the organic-inorganic composite particles.
  • the proportion of the organic-inorganic composite particles is set to be relatively high (or in other words, the organic-inorganic composite particles are blended at a high concentration).
  • the proportion of the organic-inorganic composite particles is set to, for example, 5 parts by mass or greater, preferably 10 parts by mass or greater, more preferably 20 parts by mass or greater and for example, 99 parts by mass or less per 100 parts by mass of the total amount of the organic-inorganic composite particles and the resin.
  • the proportion of the organic-inorganic composite particles is, for example, 50 to 500% and preferably 80 to 400% of that when the particle-containing resin molded article is formed so as to have a bicontinuous structure.
  • the particle-containing resin composition obtained by any of the above-described preparation methods has a configuration that does not allow the inorganic particles to contact with each other by steric hindrance of the organic group, and therefore coagulation of the inorganic particles is prevented.
  • a particle-containing resin molded article is formed from the particle-containing resin composition prepared above.
  • the particle-containing resin composition is applied to, for example, a substrate to form a coating, and the coating is dried, whereby a particle-containing resin molded article as a film (particle-containing resin film) is molded. After that, the film is peeled off from the substrate.
  • the substrate is made of a material that is not dissolved in an extraction liquid, which will be described later.
  • Specific examples include polyester films such as a polyethylene terephthalate film (PET); olefin films such as a polyethylene film and a polypropylene film; polyvinyl chloride films; polyimide films; polyamide films such as a nylon film; and synthetic resin films such as a rayon film.
  • Other examples of the substrate include paper substrates such as fine quality paper, Japanese paper, kraft paper, glassine paper, synthetic paper and top-coat paper.
  • other examples of the substrate include a glass plate, a copper plate, an aluminum plate, and an inorganic substrate such as stainless steel (SUS).
  • the thickness of the substrate is, for example, 2 to 1500 ⁇ m.
  • the particle-containing resin composition is applied by using, for example, a known application method such as spin coating or bar coating. Simultaneously with or immediately after application of the particle-containing resin composition, the solvent is removed by volatilization. If necessary, the solvent can be dried by application of heat after application of the particle-containing resin composition.
  • the thickness of the obtained film can be set as appropriate according to the use and purpose, and the thickness is, for example, 0.1 to 2000 ⁇ m, preferably 0.2 to 1000 ⁇ m and more preferably 0.3 to 500 ⁇ m.
  • the particle-containing resin molded article as a film can also be molded by a melt molding method in which the particle-containing resin composition is extruded by an extruding machine or the like.
  • the particle-containing resin molded article can also be molded as a block (mass) by injecting the particle-containing resin composition into a metal mold or the like and thereafter subjecting the resultant to, for example, heat molding such as heat pressing,
  • the organic-inorganic composite particles are dispersed as primary particles in the resin in the case where the organic-inorganic composite particles are blended at a low concentration.
  • the organic-inorganic composite particles are prevented from coagulating and forming secondary particles.
  • the particle-containing resin molded article has a phase separated structure formed of a resin phase composed of resin and a particle phase composed of organic-inorganic composite particles.
  • the particle phase is phase-separated from the resin phase.
  • the phase separated structure can be, for example, a two-phase separated structure (sea-island structure) in which the particle phase is dispersed in the resin phase.
  • the phase separated structure can be, for example, a bicontinuous phase separated structure in which the particle phase is three-dimensionally continuous.
  • the organic-inorganic composite particles in the particle phase can be extracted continuously (described later).
  • phase separated structure examples include a honeycomb structure, a columnar structure and the like.
  • the organic-inorganic composite particles are removed from the particle-containing resin molded article, whereby the resin molded article of the present invention can be obtained.
  • an extraction method is used in which an extraction solvent is brought into contact with the particle-containing resin molded article.
  • the particle-containing resin molded article is immersed in an extraction liquid.
  • the extraction liquid can be, for example, a solvent that dissolves organic-inorganic composite particles and permeates through resin without corroding (damaging) the resin.
  • a solvent that dissolves organic-inorganic composite particles and permeates through resin without corroding (damaging) the resin.
  • examples of such a solvent include an acid and an alkali.
  • the acid examples include inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, carbonic acid and phosphoric acid; organic acids such as formic acid and acetic acid; and the like.
  • alkali examples include inorganic alkalis such as sodium hydroxide, potassium hydroxide; and organic alkalis such as ammonia.
  • An acid is preferable, and an inorganic acid is more preferable.
  • the extraction liquid can be, for example, diluted with a diluent such as water, an alcohol (ethanol or the like), an aliphatic hydrocarbon (hexane or the like), and the concentration of the extraction liquid is, for example, 1 mass % or greater and less than 100 mass % of the total mass of the extraction liquid and the diluent.
  • a diluent such as water, an alcohol (ethanol or the like), an aliphatic hydrocarbon (hexane or the like
  • concentration of the extraction liquid is, for example, 1 mass % or greater and less than 100 mass % of the total mass of the extraction liquid and the diluent.
  • the organic-inorganic composite particles can be dissolved.
  • a solvent is preferably used particularly when in the particle-containing resin molded article, the organic-inorganic composite particles are blended at a low concentration and the organic-inorganic composite particles are dispersed as primary particles in the resin. In this case, the solvent permeates through the resin and also dissolves the organic-inorganic composite particles dispersed as primary particles in the resin.
  • the extraction liquid can be a dispersing medium that disperses organic-inorganic composite particles, does not corrode (damage) resin and does not permeate through resin.
  • the dispersing medium include the same dispersing media as the solvents used in the washing step described above. Specific examples include water, an aqueous pH adjusting solution, a hydroxyl group-containing aliphatic hydrocarbon, a carbonyl group-containing aliphatic hydrocarbon, an aliphatic hydrocarbon, a halogenated aliphatic hydrocarbon, a halogenated aromatic hydrocarbon, an ether, an aromatic hydrocarbon and the like.
  • the dispersing medium is preferably an aliphatic hydro carbon.
  • the organic-inorganic composite particles are blended at a high concentration in the particle-containing resin molded article and the particle phase composed of the organic-inorganic composite particles is three-dimensionally continuous and exposed at the surface of the particle-containing resin molded article, so that the organic-inorganic composite particles can be dispersed (extracted) into the dispersing medium by continuously withdrawing the organic-inorganic composite particles from the exposed surface.
  • the extraction temperature is, for example, 0 to 150° C. and preferably 10 to 100° C. If the extraction temperature is below the above range, the extraction time exceeds the desired limit, which will be described next, and the producing cost may increase. If, on the other hand, the extraction temperature exceeds the above range, the resin may be degraded or the producing cost may increase.
  • the extraction time is, for example, 30 seconds to 5 hours and preferably 1 minute to 3 hours.
  • the extraction efficiency will be low. If the extraction time exceeds the above range, the producing cost may increase.
  • micropores are formed in the particle-containing resin molded article.
  • micropores are formed as openings (gaps) separated by the resin around the organic-inorganic composite particles.
  • micropore size of micropores are substantially the same outer shape and dimension as those of the organic-inorganic composite particles that have been removed from the resin.
  • the organic-inorganic composite particles are blended in the resin at a relatively low concentration and the organic-inorganic composite particles are dispersed as primary particles, the micropores are formed as independent pores (closed-cells) dispersed uniformly in the resin.
  • a resin molded article in which micropores are formed or in other words, a porous molded article can be obtained.
  • the resin molded article is formed as a film, a porous film is obtained.
  • the resin molded article can be used in, for example, optical applications including optical films such as a low-refractive film and an antireflective film, as well as electrical and electronic applications including electrical and electronic substrates such as a low-dielectric substrate.
  • the resin molded article has independent pores (micropores) formed by removing the organic-inorganic composite particles having an average particle size within the above range, and it is thus possible to further enhance clarity.
  • the refractive index of the low-refractive film for light having a wavelength of 633 nm is reduced to, for example, 99% or less of the refractive index of the resin for light having a wavelength of 633 nm, preferably reduced to 95% or less, more preferably reduced to 90% or less.
  • the refractive index is, for example, 1 to 3, preferably 1.05 to 2.5 and more preferably 1.1 to 2.
  • the reflectivity of the antireflective film for light having a wavelength of 550 nm is reduced to, for example, 99% or less of the reflectivity of the resin for light having a wavelength of 550 nm, and preferably reduced to 95% or less.
  • the reflectivity of the antireflective film for light having a wavelength of 550 nm is, for example, 9% or less, preferably 1 to 8% and more preferably 1.5 to 7%.
  • the dielectric constant of the low-dielectric substrate is reduced to, for example, 99% or less of the dielectric constant of the resin, preferably reduced to 95% or less, and more preferably reduced to 90% or less.
  • the dielectric constant of the low-dielectric substrate is, for example, 1 to 1000, preferably 1.2 to 100, and more preferably 1.5 to 100.
  • the particle-containing resin molded article in the case where the particle-containing resin molded article has a phase separated structure formed of a particle phase and a resin phase, more specifically, a bicontinuous phase separated structure in which the particle phase is three-dimensionally continuous, the micropores are formed as communicating pores in the resin.
  • the resin molded article has communicating pores (micropores) formed by removing the organic-inorganic composite particles, and thus has excellent mechanical strength and can be widely used as a porous film (porous molded article) having paths (passages) formed by communicating pores extending in the thickness direction (front-back surface direction) in various applications such as a sizing filter, a molecular separation membrane, an adsorptive separation filter and an electrolyte membrane.
  • the organic-inorganic composite particles can be partially left by adjusting the conditions therefor.
  • the extraction time is set to, for example, 80% or less, preferably 65% or less and more preferably 50% or less of the extraction time when the organic-inorganic composite particles are fully extracted.
  • the extraction time is, for example, less than 60 minutes, preferably 30 minutes or less, and for example, 1 second or greater.
  • the proportion of remaining organic-inorganic composite particles increases toward one side of the resin molded article, specifically, increases from the surface of the resin molded article toward the interior (inside). In other words, the proportion of existing micropores in the resin molded article increases from the interior to the surface of the resin molded article.
  • the concentration distribution in the thickness direction of the micropores is in a range of, for example, 0 to 90 volume %, preferably a range of 0 to 60 volume % and more preferably a range of 0 to 40 volume %.
  • the concentration of micropores in the surface of the porous film is 90 volume % (preferably 65 volume %)
  • the concentration of micropores in the center portion in the thickness direction of the porous film is 0 volume %
  • a concentration gradient is formed therebetween.
  • the substrate is laminated on one side of the film, and the resultant (laminate) can be immersed in an extraction liquid. After that, the laminate is removed from the extraction liquid and dried. Then, the film is peeled off from the substrate.
  • the concentration distribution in the thickness direction of micropores is in a range of, for example, 0 to 90 volume %, preferably a range of 0 to 65 volume % and more preferably a range of 0 to 40 volume %.
  • the concentration of micropores in the surface of the porous film is 90 volume % (preferably 65 volume %)
  • the concentration of micropores in the back surface of the porous film is 0 volume %
  • a concentration gradient is formed in the thickness direction.
  • the porous film (resin molded article) can be used as a refractive-index distribution optical film, a dielectric distribution substrate or the like because the organic-inorganic composite particles are partially left and the proportion of existing micropores varies in the thickness direction of the porous film.
  • the titanium complex of the present invention contains a titanium atom as a central atom and a hydroxycarboxylic acid having a total of 7 or more carbon atoms as a ligand.
  • the hydroxycarboxylic acid is an organic compound that has a total of 7 or more carbon atoms and contains a carboxyl group and a hydroxyl group, and it can be, for example, a saturated or unsaturated hydroxycarboxylic acid having a total of 7 or more carbon atoms such as hydroxyalkanoic acid, hydroxyalkenoic acid or hydroxyalkynoic acid.
  • the total number of carbon atoms of such a hydroxycarboxylic acid is preferably 8 or greater, for example, 16 or less, and preferably 13 or less.
  • the number of carboxyl groups contained in the hydroxycarboxylic acid is, for example, 1 to 3 and preferably 1, and the number of hydroxyl groups is, for example, 1 to 3 and preferably 1.
  • hydroxycarboxylic acids listed above a hydroxymonocarboxylic acid and a monohydroxycarboxylic acid are preferable, and a monohydroxymonocarboxylic acid is preferable.
  • monohydroxymonoalkanoic acids having a total of 7 to 13 carbon atoms such as a 2-hydroxyalkanoic acid ( ⁇ -hydroxyalkanoic acid) and a 3-hydroxyalkanoic acid ( ⁇ -hydroxyalkanoic acid) are particularly preferable.
  • Specific examples include 2-hydroxyoctanoic acid and 3-hydroxydecanoic acid.
  • Such monohydroxymonoalkanoic acids having a total of 7 to 13 carbon atoms can be used as a ligand constituting a titanium complex. Furthermore, titanium complexes containing such a monohydroxymonoalkanoic acid as a ligand can enhance heat resistance (180° C. or higher) as compared to titanium complexes containing a hydroxycarboxylic acid having a total of 6 or fewer carbon atoms as a ligand.
  • Such a titanium complex is prepared by reacting a hydroxycarboxylic acid having a total of 7 or more carbon atoms with a titanium atom.
  • the substance containing a titanium atom is not particularly limited, and can be, for example, titanium particles, titanium powders or the like.
  • the size (average particle size) of titanium particles or titanium powders is not particularly limited.
  • the titanium particles can be, for example, commercially available titanium particles (available from Wako Pure Chemical Industries, Ltd.).
  • the hydrogen peroxide solution is a solution in which hydrogen peroxide (H 2 O 2 ) is dissolved in water, and has a concentration of, for example, 10 to 50 volume % and preferably 20 to 40 volume %.
  • aqueous alkali solutions can be used singly or in combination.
  • the pH of the mixed solution is, for example, 6 or greater, preferably 7 to 14 and more preferably 9 to 14.
  • the proportion of the substance containing a titanium atom is, for example, 0.5 to 5 g and preferably 1 to 3 g per 100 mL of the hydrogen peroxide solution, and is, for example, 0.5 to 5 g and preferably 1 to 2 g per 100 mL of the mixed solution.
  • Stirring conditions are as follows: the temperature is, for example, ⁇ 15 to 80° C., preferably ⁇ 10 to 50° C. and more preferably ⁇ 5 to 25° C.; and the time is, for example, 0.1 to 24 hours, preferably 1 to 10 hours and more preferably 1 to 5 hours.
  • any one of the hydroxycarboxylic acids having a total of 7 or more carbon atoms is mixed with the aqueous solution of peroxotitanium complex so as to prepare a titanium complex-containing solution.
  • the solvent there is no particular limitation on the solvent as long as the hydroxycarboxylic acid can be dissolved.
  • examples include water, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and the like.
  • alcohols are preferable.
  • the concentration of the hydroxycarboxylic acid solution is, for example, 0.1 to 80 mass %, preferably 1 to 50 mass % and more preferably 5 to 30 mass %.
  • the proportion of hydroxycarboxylic acid is, for example, 1 to 6 mol, preferably 1 to 5 mol, and more preferably 1 to 4 mol per mol of the substance containing a titanium atom.
  • the proportion of hydroxycarboxylic acid is less than 1 mol per mol of the substance containing a titanium atom, a titanium complex cannot be formed due to the shortage of ligand, and so a by-product containing a ligand (hydroxycarboxylic acid) and titanium atoms that do not form the complex may be left, and the desired titanium oxide particles may not be obtained from the titanium complex containing the by-product. If, on the other hand, the proportion of hydroxycarboxylic acid exceeds 6 mol per mol of the substance containing a titanium atom, the amount of hydroxycarboxylic acid will be excessive and wasted, and thus it may be inappropriate in terms of cost.
  • Stirring conditions are as follows: the temperature is, for example, 0 to 80° C., preferably 5 to 70° C. and more preferably 10 to 60° C.; and the time is, for example, 0.1 to 24 hours, preferably 0.5 to 10 hours and more preferably 1 to 5 hours. After stirring, if necessary, the mixture is allowed to stand still for, for example, 10 to 40 hours.
  • a hydroxycarboxylic acid By mixing and stirring a hydroxycarboxylic acid and an aqueous solution of peroxotitanium complex as described above, the hydroxycarboxylic acid is reacted with the peroxotitanium complex contained in the aqueous solution of peroxotitanium complex, as a result of which a titanium complex is formed. Accordingly, a titanium complex-containing solution that contains a titanium complex is prepared.
  • the obtained titanium complex-containing solution is dried to prepare a titanium complex.
  • the drying method There is no particular limitation on the drying method, and known methods such as vacuum drying, spray drying and freeze drying can be used.
  • the solvent is dried by increasing the temperature with a drier or the like to prepare a titanium complex.
  • drying conditions There is no particular limitation on the drying conditions as long as the solvent can be removed.
  • the temperatures is, for example, 50 to 100° C. and preferably 60 to 90° C.
  • the time is 0.1 to 48 hours, preferably 0.5 to 24 hours and more preferably 1 to 10 hours.
  • the coordination number of the titanium complex is, for example, 1 to 6 preferably 2 to 4 per titanium atom.
  • the coordination number can be analyzed with, for example, a mass spectrometer such as a matrix assisted laser desorption ionization (MALDI)— time-of-flight (TOF) mass spectrometer (MS), or the like
  • the yield of the titanium complex is, for example, 60 to 100 mol % and preferably 80 to 100 mol % relative to the substance containing a titanium atom used.
  • the titanium complex is subjected to thermal decomposition to produce titanium oxide particles.
  • the titanium complex is subjected to a high-temperature and high-pressure treatment (hydrothermal synthesis) in water to produce titanium oxide particles.
  • the titanium complex and water are introduced into a reactor.
  • the proportion of the titanium complex is, for example, 5 to 40 parts by mass, preferably 10 to 30 parts by mass per 100 parts by mass of water.
  • the reactor can be a known high-pressure reactor (autoclave) or continuous high-pressure reactor.
  • An example of such a high-pressure reactor is a commercially available high-pressure reactor (available from AKICO Corporation).
  • Another example of a continuous high-pressure reactor is a commercially available continuous high-pressure reactor (available from ITEC Co. Ltd.).
  • the reactor is brought to high-temperature and high-pressure conditions, whereby titanium oxide particles are produced (hydrothermal synthesis).
  • Reaction conditions for the hydrothermal synthesis are the same as those for the hydrothermal synthesis (first hydrothermal synthesis) illustrated in the third embodiment.
  • the reaction product obtained by the above hydrothermal synthesis includes a precipitate that mostly precipitates in water and a deposit that adheres to the inner wall of the airtight container.
  • the precipitate can be separated and recovered by using any of the methods.
  • the precipitate is obtained by, for example, sedimentation separation in which the reaction product is settled by gravity or a centrifugal field.
  • the precipitate is obtained as a precipitate of the reaction product by centrifugal sedimentation (centrifugal separation) in which the reaction product is settled by a centrifugal field.
  • the deposit is recovered by, for example, a scraper (spatula) or the like.
  • the reaction product can also be recovered (separated) by adding a solvent to wash away unreacted hydroxycarboxylic acid (or in other words, dissolving the hydroxycarboxylic acid in the solvent) and thereafter removing the solvent.
  • the solvent can be, for example, any of the solvents listed above.
  • an alcohol is preferable.
  • the washed reaction product is separated from the solvent (supernatant liquid) by, for example, filtration, decantation or the like, and recovered. After that, the reaction product is dried by, for example, application of heat, an air stream or the like if necessary.
  • the titanium oxide particles have a crystal structure of, for example, anatase (tetragonal crystal), rutile (tetragonal crystal) or brookite (orthorhombic crystal).
  • the crystal structure can be determined by electron diffraction such as XRD (X-ray diffraction) or TEM (transmission electron microscope).
  • the titanium oxide particles of the present invention are prepared by treating a titanium complex containing a hydroxyl carboxylic acid having a total of 7 or more carbon atoms as a ligand in hot high pressure water.
  • the ligand of the titanium complex is a hydroxyl carboxylic acid having a total of 7 or more carbon atoms, decomposition of the ligand is suppressed even in hot high pressure water, as a result of which coloring of the resulting titanium oxide particles can be reduced.
  • the applications of the titanium oxide particles of the present invention can be, for example, various industrial products, and optical applications and the like are preferable because coloring is reduced.
  • the first group of inventions will be described in further detail by showing Examples, Comparative Examples, Preparation Examples and Producing Examples corresponding to the first group of inventions, but the first group of inventions is not limited thereto.
  • Particles were loaded into a glass holder and subjected to X-ray diffractometry under the following conditions. After that, from the obtained peaks, the components of the primary particles were assigned by database search.
  • a sample was produced by dispersing particles on a sample stage and coating the particles with osmium. Next, the prepared sample was photographed with the following field emission-scanning electron microscope (FE-SEM).
  • FE-SEM field emission-scanning electron microscope
  • the lengthwise length (maximum length) LL and sideways length (minimum length) SL of each particle were measured, and then the lengthwise length LL and sideways length SL of the entire particles were calculated from the arithmetic mean of the measured values.
  • a sample was produced by machining a resin molded article (including an optical film) with a cross section polisher (SM-08010, available from JEOL Ltd.). After that, the prepared sample was coated with osmium, and a cross section of the sample was observed with the following field emission-scanning electron microscope (FE-SEM).
  • FE-SEM field emission-scanning electron microscope
  • Particles were dispersed on a Cu mesh having a microgrid support film, and the particles were observed with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • TEM HF-2000, available from Hitachi High-Tech Manufacturing & Service Corporation
  • a particle dispersion was placed in a quartz cell, and particle size distribution was measured with the following particle size distribution measuring apparatus.
  • Particle size distribution measuring apparatus Zetasizer Nano-Zs, available from Marvern Instruments
  • Strontium hydroxide octahydrate available from Wako Pure Chemical Industries, Ltd. in an amount of 0.5 g
  • formic acid available from Wako Pure Chemical Industries, Ltd.
  • decanoic acid available from Wako Pure Chemical Industries, Ltd.
  • pure water in an amount of 2.032 mL
  • the high-pressure reactor was closed with a cover, heated to 400° C. in a shaking furnace (available from AKICO Corporation) so as to pressurize the inside of the high-pressure reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal synthesis.
  • a shaking furnace available from AKICO Corporation
  • the high-pressure reactor was plunged into cold water for quenching.
  • Example 1-1 The formulation of respective components and the evaluation results in Example 1-1 are presented in Table 1, and an image-processed FE-SEM micrograph in Example 1-1 is shown in FIG. 1 .
  • Strontium hydroxide octahydrate available from Wako Pure Chemical Industries, Ltd.
  • pure water in an amount of 2.355 mL were introduced into a 5 mL high-pressure reactor (available from AKICO Corporation).
  • the high-pressure reactor was closed with a cover, heated to 400° C. in a shaking furnace (available from AKICO Corporation) so as to pressurize the inside of the high-pressure reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal synthesis.
  • a shaking furnace available from AKICO Corporation
  • the high-pressure reactor was plunged into cold water for quenching.
  • Strontium hydroxide octahydrate available from Wako Pure Chemical Industries, Ltd.
  • formic acid available from Wako Pure Chemical Industries, Ltd.
  • pure water in an amount of 2.265 mL were introduced into a 5 mL high-pressure reactor (available from AKICO Corporation).
  • the high-pressure reactor was closed with a cover, heated to 400° C. in a shaking furnace (available from AKICO Corporation) so as to pressurize the inside of the high-pressure reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal synthesis.
  • a shaking furnace available from AKICO Corporation
  • the high-pressure reactor was plunged into cold water for quenching.
  • Comparative Example 1-2 The formulation of respective components and the evaluation results in Comparative Example 1-2 are presented in Table 1, and an image-processed FE-SEM micrograph in Comparative Example 1-2 is shown in FIG. 2 .
  • Strontium hydroxide octahydrate available from Wako Pure Chemical Industries, Ltd. in an amount of 0.5 g
  • formic acid available from Wako Pure Chemical Industries, Ltd.
  • oleic acid available from Wako Pure Chemical Industries, Ltd.
  • aqueous ammonia in an amount of 1.892 mL were introduced into a 5 mL high-pressure reactor (available from AKICO Corporation).
  • the amount of aqueous ammonia was adjusted such that the resulting reaction system had a pH of 10.
  • the high-pressure reactor was closed with a cover, heated to 400° C. in a shaking furnace (available from AKICO Corporation) so as to pressurize the inside of the high-pressure reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal synthesis.
  • a shaking furnace available from AKICO Corporation
  • the high-pressure reactor was plunged into cold water for quenching.
  • Example 1-17 The formulation of respective components and the evaluation results in Example 1-17 are presented in Table 2, and an image-processed TEM micrograph is shown in FIG. 3 .
  • the primary particles had an acicular shape with a sideways length SL of approximately 20 to 100 nm and a lengthwise length LL of approximately 60 to 280 nm with reference to FIG. 3 . It was also confirmed that the aspect ratio of the primary particles was 3 to 14 as a result of calculation from FIG. 3 .

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