Catalyst particle, catalyst solution, catalyst composition and catalyst molded body

The present invention relates to catalyst particles, a catalyst solution, a catalyst composition and a catalyst molded product, specifically, a catalyst particle having a catalytic action, a catalyst solution, a catalyst composition and a catalyst molded product.

Conventionally, it has been known that oxides such as titanium oxide exhibit a photocatalytic effect.

For example, it is known that oxides such as titanium oxide, strontium titanate, and tungsten oxide decompose organic substances by their photocatalytic action (see, for example, Non-Patent Document 1).

<p><nplcit num="1"><text>Surface Science Vol.24, No.1, pp. 13-18, 2003</text></nplcit></p>

<p> However, depending on the use or purpose of the catalyst, a molded product may be formed from the catalyst resin composition after preparing the catalyst resin composition by blending the oxide proposed in Patent Document 1 with the resin.</p><p> However, in the above-mentioned molded product, since the resin is in contact with the oxide, there is a problem that the resin is easily deteriorated by the above-mentioned catalytic action of the oxide.</p><p> Further, at the time of preparing the above-mentioned resin composition, there is a problem that the oxide is easily aggregated in the resin, and therefore the transparency is lowered.</p><p> An object of the present invention is a catalyst particle having excellent dispersibility in a solvent and / or a resin, a catalyst solution in which the catalyst particles are dispersed in a solvent and having excellent transparency, and a catalyst composition in which deterioration of the resin is suppressed and excellent in transparency. And to provide a catalyst compact.</p>

<p> In order to achieve the above object, the catalyst particles of the present invention contain inorganic particles having a catalytic action and organic groups bonded to the surface of the inorganic particles, and the inorganic particles are caused by steric hindrance of the organic groups. It is characterized by having a shape that does not contact each other.</p><p> Further, the catalyst particles of the present invention preferably have a catalytic action on a gas and / or a liquid.</p><p> Further, the catalyst particles of the present invention preferably have a photocatalytic action on a gas and / or a liquid.</p><p> Further, in the catalyst particles of the present invention, it is preferable to disperse the primary particles in a solvent and / or a resin.</p><p> Further, it is preferable that the catalyst particles of the present invention contain a plurality of types of the organic groups different from each other.</p><p> Further, in the catalyst particles of the present invention, the organic group is bonded to the surface of the inorganic particle via a bonding group, and the bonding group contains a phosphoric acid group and / or a phosphoric acid ester group. Is preferable.</p><p> Further, in the catalyst particles of the present invention, it is preferable that the inorganic particles contain an oxide.</p><p> Further, in the catalyst particles of the present invention, the inorganic particles are TiO.₂, WO₃And SrTiO₃It is preferable to contain at least one oxide selected from the group consisting of Pt, Pd, Cu, CuO and RuO.₂It is preferable to further contain at least one inorganic substance selected from the group consisting of and NiO.</p><p> Further, in the catalyst particles of the present invention, it is preferable that the average value of the maximum length is 450 nm or less.</p><p> Further, the catalyst particles of the present invention are preferably obtained by surface-treating an inorganic substance and / or a complex thereof with an organic compound containing the organic group, and the inorganic substance and / or the complex at a high temperature. It is preferable to surface-treat the organic compound under high pressure water, or it is also preferable to surface-treat the inorganic substance and / or the complex in the organic compound at high temperature.</p><p> Further, the catalyst solution of the present invention is characterized by containing a solvent and the above-mentioned catalyst particles dispersed in the solvent.</p><p> Further, the catalyst composition of the present invention is characterized by containing a resin and the above-mentioned catalyst particles dispersed in the resin.</p><p> Further, the catalyst molded product of the present invention is characterized in that it is formed from the above-mentioned catalyst composition.</p><p> Further, the catalyst molded product of the present invention is preferably an optical film.</p>

<p> Since the catalyst particles of the present invention have a shape in which the inorganic particles do not come into contact with each other due to steric hindrance of the organic group, they are uniformly dispersed in the solvent and / or the resin.</p><p> Further, in the catalyst solution of the present invention in which the catalyst particles of the present invention are dispersed in a solvent, the catalyst particles are uniformly dispersed, so that the transparency can be improved.</p><p> Further, in the catalyst composition of the present invention in which the catalyst particles of the present invention are dispersed in a resin and the catalyst molded product of the present invention formed from the catalyst composition, the above-mentioned shape based on the steric hindrance of organic groups in the catalyst particles is inorganic. It becomes difficult for the particles to come into direct contact with the resin. Therefore, it is possible to exhibit a catalytic action on a gas or a liquid while suppressing deterioration of the resin in the catalyst composition and the catalyst molded product.</p><p> As a result, the catalyst composition of the present invention and the catalyst molded product of the present invention have various detoxification action, deodorant action, sterilization (or antibacterial or bactericidal) action, antifouling action, decomposition action, etc., while having excellent durability. It can exhibit catalytic action.</p><p> Furthermore, since the catalyst particles are uniformly dispersed in the catalyst composition of the present invention and the catalyst molded body of the present invention, transparency can be improved.</p><p> As a result, the catalyst molded product of the present invention can be used for various optical applications and various building material applications.</p>

<figref num="1">FIG. 1 shows the ultraviolet-visible absorption spectra at the start of light irradiation, the passage of 30 minutes, the passage of 1 hour, the passage of 2 hours, the passage of 3 hours, and the passage of 4 hours in Example 10.</figref><figref num="2">FIG. 2 shows UV-visible at each time of the start of light irradiation, the passage of 5 minutes, the passage of 10 minutes, the passage of 15 minutes, the passage of 30 minutes, the passage of 1 hour, and the passage of 2 hours in Example 66. The absorption spectrum is shown.</figref>

The catalyst particles of the present invention contain inorganic particles having a catalytic action and organic groups bonded to the surface of the inorganic particles.

The inorganic particles preferably have a photocatalytic action that catalyzes a gas and / or a liquid (described later) by absorbing light.

Such catalyst particles are obtained, for example, by surface-treating an inorganic substance and / or a complex thereof with an organic compound.

Examples of the inorganic substance include metals composed of metal elements such as typical elements and transition elements, for example, non-metals composed of non-metal elements such as boron and silicon, and inorganic compounds containing metal elements and / or non-metals.

Examples of metallic or non-metallic elements include boron (B) of group IIIB-silicon (Si) of group IVB-arsenic (As) of group VB in the long-period periodic table (IUPAC, 1989). With the boundary of Teruru (Te) of the genus VIB-Astatin (At) of the genus VIIB, these elements and the elements on the left and lower sides of the long-period periodic table from the boundary can be mentioned. For example, IIIA elements such as Sc, Y, IVA elements such as Ti, Zr, Hf, VA elements such as V, Nb, Ta, VIA elements such as Cr, Mo, W, etc. For example, elements of the genus VIA such as Mn, Re, for example, elements of the genus VIII such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, and elements of the genus IB such as Cu, Ag, Au, for example. , Zn, Cd, Hg and other IIB elements, such as B, Al, Ga, In, Tl and other IIIB elements, such as Si, Ge, Sn, Pb and other IVB elements, such as As, Sb, VB elements such as Bi, VIB elements such as Te, Po, VIIB elements such as At, lanthanide series elements such as La, Ce, Pr, Nd, etc., such as Ac, Th, U, etc. Actinium series elements and the like.

Examples of the inorganic compound include hydrogen compounds, hydroxides, nitrides, halides, oxides, carbonates, sulfates, nitrates, acetates, acid salts, sulfides, carbides, phosphorus compounds and the like. Further, the inorganic compound may be a composite compound, and examples thereof include an oxide nitride and a composite oxide.

Among the above-mentioned inorganic substances, preferably inorganic compounds are mentioned, and more preferably, for example, oxides, sulfates, nitrates, acetates, formic acids, composite oxides, and particularly preferably oxides are mentioned.

Examples of the oxide include a metal oxide, preferably titanium oxide (titanium dioxide, titanium (IV) oxide, titania: TiO).₂), Tungsten Trioxide (Tungsten Trioxide, Tungsten Trioxide (VI), WO₃), Cerium oxide (cerium dioxide, cerium oxide (IV), ceria: CeO₂), Zirconium oxide (Zirconium dioxide, Zirconium oxide (IV), Zirconia: ZrO₂), Tantalum Oxide (Tantalum Dioxide, Tantalum Oxide (IV), TaO₂) And so on.

The arrangement state of the atoms in the oxide is not particularly limited, and may be, for example, either crystalline or non-crystalline (amorphous).

The oxides can be used alone or in combination of two or more.

Sulfate is sulfate ion (SO)₄^2-) And a compound of a metal element cation (more specifically, sulfuric acid (H)₂SO₄) Is a compound in which a hydrogen atom is replaced with a metal), and examples of the metal element contained in the sulfate include an element belonging to the genus IVA, an element IB, preferably Ti and Cu.

Specifically, examples of the sulfate include preferably titanium sulfate, zirconium sulfate, hafnium sulfate, copper sulfate, silver sulfate and the like, and more preferably titanium sulfate and copper sulfate.

Sulfates can be used alone or in combination of two or more.

Nitrate is nitrate ion (NO)₃^-) And a compound of a metal element cation (more specifically, nitric acid (HNO)₃) Is a compound in which a hydrogen atom is replaced with a metal), and examples of the metal element contained in the nitrate include a genus VIII element, and preferably Pd and Pt.

Specifically, as the nitrate, preferably, iron nitrate, cobalt nitrate, nickel nitrate, ruthenium nitrate, rhodium nitrate, palladium nitrate, osmium nitrate, iridium nitrate and the like can be mentioned, and palladium sulfate and platinum sulfate are more preferable. Can be mentioned.

Nitrate can be used alone or in combination of two or more.

Acetate is acetate ion (CH)₃COO^-) And a cation of a metal element (more specifically, a compound in which the hydrogen atom of the carboxyl group (-COOH) in acetic acid is replaced with a metal), and examples of the metal element contained in the acetate include, for example. , VIII element, preferably Ni.

Specifically, the acetate salt is preferably nickel acetate.

Acetate can be used alone or in combination of two or more.

Formate is formic acid ion (HCOO)^-) And a cation of a metal element (more specifically, a compound in which a hydrogen atom of a carboxyl group (-COOH) in formic acid is replaced with a metal), and examples of the metal element contained in formic acid include, for example. , IB element, preferably Cu.

Specifically, the formic acid salt is preferably copper formate.

The formic acid salt can be used alone or in combination of two or more.

The composite oxide is a compound of oxygen and a plurality of elements, and the plurality of elements are selected from at least an element other than oxygen in the above-mentioned oxide, a group I element, and a group II element. There are two or more combinations.

Examples of the element I include alkali metals such as Li, Na, K, Rb, and Cs. Examples of Group II elements include alkaline earth metals such as Be, Mg, Ca, Sr, Ba, and Ra.

As a combination of a plurality of elements, for example, a combination of a group II element and an IVB group element, a combination of a group II element and a group VIII element, a combination of a group II element and an IVA group element, and a combination of a group II element and a group II element. Combinations that include at least Group II elements, such as combinations with VA elements, such as combinations of Group I and IVA elements, combinations of Group I elements, IVA elements, and lanthanide series elements, Group I. Examples include combinations containing at least Group I elements, such as combinations of elements and VA genus elements, such as combinations of VA genus elements and IIB genus elements.

Examples of the composite oxide containing at least a Group II element include an alkaline earth metal salt of titanate, an alkaline earth metal salt of zirconic acid, an alkaline earth metal salt of iron acid, an alkaline earth metal salt of silicate, and an alkali niobate. Examples include earth metal salts.

Examples of the composite oxide containing at least a Group I element include an alkali metal titanate salt, an alkali metal zirconate salt, an alkali metal vanadium salt, and an alkali metal niobate salt.

Examples of the composite oxide containing a VA element and an IIB element include a niobium acid metal salt and the like.

Preferred examples of the composite oxide oxide include alkaline earth metal titanate, alkali metal titanate, alkaline earth niobate metal salt, alkali metal niobate, and metal niobate.

Examples of the alkaline earth metal salt of titanate include beryllium titanate (BeTiO).₃), Magnesium Titanate (MgTiO₃), Calcium titanate (CaTiO)₃), Strontium titanate (SrTiO)₃), Barium titanate (BaTiO₃), Barium tetratitanate (BaTi)₄O₉), Radium Titanate (RaTiO)₃) And so on.

Examples of the alkali metal titanate salt include sodium hexatitanate (Na).₂Ti₆O₁₃), Potassium titanate (K)₂La₂Ti₃O₁₀) And so on.

Examples of the alkaline earth metal salt of niobate include strontium niobate (Sr).₂Nb₂O₇) And so on.

Examples of the niobate alkali metal salt include potassium niobate (K).₄Nb₆O₁₇) And so on.

Examples of the niobate metal salt include zinc niobate (ZnNb).₂O₆) And so on.

The composite oxide can be used alone or in combination of two or more.

The complex contains a central atom and / or a central ion and a ligand that coordinates with it.

Examples of the central atom include metal elements similar to those described above, preferably IVA group elements, VIII group elements, IVB group elements, and more preferably Ti, Zr, Fe, Ni, Ru, Sn and the like. Can be mentioned.

Examples of the central ion include the above-mentioned cations of metal elements.

Examples of the ligand include a coordination compound such as carboxylic acid, hydroxycarboxylic acid, and acetylacetone, and examples thereof include a cation of the above-mentioned coordination compound and a coordination ion such as a hydroxide ion.

Examples of the carboxylic acid include dicarboxylic acids such as oxalic acid, succinic acid, and phthalic acid.

Examples of the hydroxycarboxylic acid include monohydroxymonocarboxylic acids such as 2-hydroxyoctanoic acid, lactic acid and glycolic acid (specifically, α-monohydroxycarboxylic acid), and monohydroxydicarboxylic acids such as malic acid. For example, a monohydroxytricarboxylic acid such as citric acid can be mentioned.

The coordination number is, for example, 1 to 6, preferably 1 to 3.

The complex can be prepared and obtained from the above-mentioned metal elements and ligands.

The above-mentioned inorganic substances (specifically, oxides, composite oxides) and complexes can also be formed (prepared) as salts and / or hydrates. Examples of the salt include salts with cations such as ammonium ions.

In addition, the above-mentioned inorganic substances and complexes can be used alone or in combination of two or more.

When an inorganic substance and / or a complex is used in combination, such a combination includes, for example, a combination of a plurality of types of inorganic substances (first combination), for example, a combination of an inorganic substance and a complex (second combination). Be done.

The first combination includes, for example, a combination of a plurality of types of inorganic substances, and specifically, for example, a combination of an oxide (first inorganic substance) and a metal, a sulfate, a nitrate, and an acid salt is selected. The combination with at least one kind of inorganic substance (second inorganic substance) is mentioned.

More specifically, as the first combination, for example, a combination of a metal oxide and a metal (general VIII element), a combination of a metal oxide and a sulfate, and a combination of a metal oxide and an acid salt can be mentioned. Specifically, 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.

The second combination includes, for example, a combination of a complex having a ligand of hydroxycarboxylic acid and a metal, for example, a combination of a complex having a ligand of hydroxycarboxylic acid, a hydroxide and an acetate. For example, a combination of a complex in which the ligand is a hydroxycarboxylic acid, a hydroxide, and a complex in which the ligand is acetylacetone can be mentioned.

Specifically, as a second combination, for example, a combination of a titanium complex in which the central atom is titanium and the ligand is 2-hydroxyoctanoic acid and platinum, for example, the central atom is titanium and the ligand is A combination of a titanium complex in which is 2-hydroxyoctanoic acid, strontium hydroxide, and nickel acetate, for example, a titanium complex in which the central atom is titanium and the ligand is 2-hydroxyoctanoic acid, and strontium hydroxide. And a combination with a ruthenium complex in which the central atom is ruthenium and the ligand is acetylacetone.

The organic compound is, for example, an organic group-introducing compound that introduces (places) an organic group on the surface of the inorganic particle, and specifically includes a bonding group that can be bonded to the surface of the inorganic particle and an organic group. I'm out. That is, the organic group is bonded to the surface of the inorganic particles via the bonding group.

The bonding group is appropriately selected according to the type of inorganic particles, and is, for example, a phosphoric acid group (-PO (OH)).₂, Phosphono group), phosphoric acid ester group (phosphonic acid ester group), carboxyl group, carboxylic acid ester group (carboxyester group), amino group, sulfo group, hydroxyl group, thiol group, epoxy group, isocyanate group, nitro group, Examples thereof include functional groups such as an azo group, a silyloxy group, an imino group, an aldehyde group (acyl group), a nitrile group and a vinyl group (polymerizable group). Preferred examples include a phosphoric acid group, a phosphoric acid ester group, a carboxyl group, an amino group, a sulfo group, a hydroxyl group, a thiol group, an epoxy group, an azo group, a vinyl group and the like, and more preferably, a phosphoric acid group and a phosphoric acid. Examples thereof include an ester group, a carboxyl group, an amino group and a hydroxyl group.

The phosphoric acid ester group is, for example, an alkyl ester group of phosphoric acid (specifically, orthophosphoric acid), that is, an alkoxyphosphonyl, and is represented by the following formula (1).

-PO (OR)_nH_2-n (1) (In the formula, R is an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 or 2.) In the above formula (1), the alkyl group represented by R is preferably methyl or ethyl.

n is preferably 2.

Examples of the phosphoric acid ester group include phosphoric acid dimethyl ester (dimethoxyphosphonyl: -PO (OCH).₃)₂), Phosphate diethyl ester (diethoxyphosphonyl: -PO (OC)₂H₅)₂), Dipropyl ester phosphate (dipropoxyphosphonyl: -PO (OC)₃H₇)₂) And other phosphoric acid dialkyl esters, such as phosphoric acid monomethyl ester (monomethoxyphosphonyl: -PO (OCH)₃) H, Phosphate Monoethyl Ester (Monoethoxyphosphonyl: -PO (O)₂CH₅) H), Phosphate monopropyl ester (monopropoxyphosphonyl: -PO (O)₃CH₇) H) and the like, such as phosphoric acid monoalkyl esters. Preferably, a phosphoric acid dialkyl ester is used.

The bonding group is appropriately selected according to the above-mentioned inorganic particles. Specifically, when the inorganic particles contain titanium oxide, for example, a phosphoric acid group and / or a phosphoric acid ester group is selected and inorganic. If the particles contain tungonic acid (discussed below), for example, an amino group is selected, and if the inorganic particles contain strontium titanate, for example, a carboxylic acid, a phosphate group and / or phosphorus. The acid ester group is selected.

One or more of these bonding groups are contained in the organic compound. Specifically, the linking group is attached to the terminal or side chain of the organic group.

The organic group includes, for example, a hydrocarbon group such as an aliphatic group, an alicyclic group, an aromatic aliphatic group, and an aromatic group.

Examples of the aliphatic group include a saturated aliphatic group and an unsaturated aliphatic group.

Examples of the saturated aliphatic group include an alkyl group having 1 to 20 carbon atoms.

Alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 3,3, Linear or branched alkyl groups with 1 to 20 carbon atoms such as 5-trimethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecil, icosyl, etc. Paraffin hydrocarbon group) and the like. Preferred are linear or branched alkyl groups having 1 to 12 carbon atoms.

Examples of the unsaturated aliphatic group include an alkenyl group having 2 to 20 carbon atoms and an alkynyl group.

Examples of the alkenyl group include alkenyl groups (olefin hydrocarbons) having 2 to 20 carbon atoms such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl (oleyl), and icosenyl. Hydrogen group).

Examples of the alkynyl group include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, and other alkynyl groups having 2 to 20 carbon atoms. Hydrocarbon groups).

Examples of the alicyclic group include a cycloalkyl group having 4 to 20 carbon atoms and a cycloalkenylalkylene group having 7 to 20 carbon atoms.

Examples of the cycloalkyl group include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl and the like.

Examples of the cycloalkenylalkylene group include norbornene decyl (norbornene decyl, bicyclo [2.2.1] hepta-2-enyl-decyl) and the like.

Examples of the aromatic aliphatic group include aralkyl groups having 7 to 20 carbon atoms such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl and diphenylmethyl.

Examples of the aromatic group include aryl groups having 6 to 20 carbon atoms such as phenyl, xsilyl, naphthyl, and biphenyl.

The organic group described above is a hydrophobic group for imparting hydrophobicity to the surface of the inorganic particles.

Therefore, the above-mentioned organic compound containing a hydrophobic group is provided as a hydrophobic organic compound for treating inorganic particles in a hydrophobic manner.

When such a hydrophobic organic compound is a phosphate group, specifically, it contains a saturated aliphatic group such as methylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, and decylphosphonic acid. Examples thereof include aliphatic group-containing phosphonic acids such as phosphonic acid (saturated phosphonic acid). Examples of the hydrophobic organic compound include an alicyclic group-containing phosphonic acid (alicyclic phosphonic acid) such as cyclohexanephosphonic acid, and an aromatic aliphatic group-containing phosphonic acid (aromatic) such as 6-phenylhexylphosphonic acid. (Adipose phosphonic acid), for example, aromatic group-containing phosphonic acid (aromatic phosphonic acid) such as phenylphosphonic acid and toluenephosphonic acid can be mentioned.

When the binding group is a phosphoric acid ester group as the hydrophobic organic compound, specifically, a saturated aliphatic group such as hexylphosphonic acid diethyl ester, octylphosphonic acid diethyl ester, and decylphosphonic acid diethyl ester. Examples thereof include an aliphatic group-containing phosphonic acid ester such as a group-containing phosphonic acid ester (saturated phosphonic acid dialkyl ester). Examples of the hydrophobic organic compound include an alicyclic group-containing phosphonic acid alkyl ester such as cyclohexanephosphonic acid diethyl ester (alicyclic phosphonic acid dialkyl ester), and an aroma such as 6-phenylhexylphosphonic acid diethyl ester. An aliphatic group-containing phosphonic acid ester (aromatic aliphatic phosphonic acid dialkyl ester), for example, an aromatic group-containing phosphonic acid alkyl ester (aromatic phosphonic acid dialkyl ester) such as phenylphosphonic acid diethyl ester and toluenephosphonic acid diethyl ester Can be mentioned.

When the binding group is a carboxyl group as the hydrophobic organic compound, specifically, for example, an aliphatic group-containing carboxylic acid (fatty acid) such as hexanoic acid, octanoic acid, or decanoic acid, for example, 6- Examples thereof include aromatic aliphatic group-containing carboxylic acids such as phenylhexanoic acid.

Further, as the hydrophobic organic compound, when the binding group is an amino group, specific examples thereof include aliphatic group-containing amines such as hexylamine, octylamine and decylamine.

On the other hand, the organic compound can also be provided as a hydrophilized organic compound for hydrophilically treating the inorganic particles. In that case, the organic group in the hydrophilized organic compound is the above-mentioned hydrocarbon group and the hydrophilic group bonded thereto. And have.

That is, the hydrophilic group is bonded to the terminal (the end (one end) opposite to the terminal (one end) bonded to the binding group) or the side chain of the above-mentioned hydrocarbon group in the hydrophilized organic compound.

Hydrophilic groups are polar functional groups (ie, polar groups), such as phosphate groups, phosphate ester groups, hydroxyl groups, carboxyl groups, amino groups, sulfo groups, carbonyl groups, cyano groups, nitro groups. , An aldehyde group, a thiol group and the like.

Preferred examples of the hydrophilic group include a phosphoric acid group, a phosphoric acid ester group, a hydroxyl group, a carboxyl group, a carboxylic acid ester group (carboxyester group), an amino group and a sulfo group. More preferably, a phosphoric acid group and a phosphoric acid ester group can be mentioned.

One or more of these hydrophilic groups are contained in the hydrophilized organic compound. When a plurality of hydrophilic groups are contained in the hydrophilized organic compound, for example, a combination of an amino group and a sulfo group can be mentioned.

Examples of the organic group containing a phosphoric acid group (phosphate group-containing organic group) include phosphonosaturated aliphatic groups (phosphonoaliphatic groups) such as 3-phosphonopropyl, 6-phosphonohexyl and 10-phosphonodecyl. , 6-Phononoarophatic groups such as phosphonophenylhexyl and the like.

Examples of the organic group containing a phosphoric acid ester group (phosphate ester group-containing organic group) include 3- (diethoxy-phosphonyl) propyl, 6- (diethoxy-phosphonyl) hexyl, and 10- (diethoxy-phosphonyl) decyl. Examples thereof include alkoxyphosphonyl hydrocarbon groups such as alkoxyphosphonyl saturated aliphatic groups (alkoxyphosphonyl aliphatic groups), for example, alkoxyphosphonyl aromatic aliphatic groups such as 6- (diethoxy-phosphonyl) phenylhexyl.

Examples of the organic group containing a hydroxyl group (hydroxy group-containing organic group) include a hydroxy aliphatic group such as 10-hydroxydecyl.

Examples of the organic group containing a carboxyl group (carboxyl group-containing organic group) include 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 7-carboxyheptyl, and 8-carboxyl. Examples thereof include a carboxy saturated aliphatic group (carboxy aliphatic group) such as carboxy octyl, 9-carboxynonyl and 10-carboxydecyl.

Examples of the organic group containing a carboxylic acid ester group (carboxyester group-containing organic group) include 2- (methoxy-carbonyl) ethyl, 3- (methoxy-carbonyl) propyl, 4- (methoxy-carbonyl) butyl, and 5-. (Methoxy-carbonyl) pentyl, 6- (methoxy-carbonyl) hexyl, 7- (methoxy-carbonyl) heptyl, 8- (methoxy-carbonyl) octyl, 9- (methoxy-carbonyl) nonyl, 10- (methoxy-carbonyl) Examples include carboxyester aliphatic groups such as decyl.

Examples of the organic group containing an amino group and a sulfo group (organic group having both an amino group / sulfo group) include an amino / sulfo aliphatic group such as 2-amino-3-sulfopropyl.

Specifically, 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, and an amino group-containing organic compound. Examples thereof include 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.

Preferred examples thereof include a phosphate group-containing organic compound, a phosphate ester group-containing organic compound, a hydroxyl group-containing organic compound, and a carboxy ester group-containing organic compound.

The phosphoric acid group-containing organic compound includes a case where the bonding group is a phosphoric acid group and the polar group is a carboxyl group (more specifically, when the phosphoric acid group is bonded to inorganic particles containing titanium oxide). For example, monophosphonocarboxylic acid is mentioned, and specific examples thereof include 3-phosphonopropionic acid, 6-phosphonohexanoic acid, 10-phosphonodecanoic acid, 6-phosphonophenylhexanoic acid and the like.

The phosphate ester group-containing organic compound includes a case where the bonding group is a phosphoric acid ester group and a polar group carboxyester group (more specifically, a case where the phosphoric acid ester group is bonded to inorganic particles containing titanium oxide. ) Examples include 3- (diethoxy-phosphonyl) propionic acid ethyl ester, 6- (diethoxy-phosphonyl) hexanoic acid ethyl ester, 10- (diethoxy-phosphonyl) decanoic acid ethyl ester and the like. The above-mentioned phosphate ester group-containing organic compound is also a carboxy ester group-containing organic compound.

Further, as the phosphoric acid ester group-containing organic compound, when the bonding group is a phosphoric acid ester group and the polar group is a hydroxyl group (more specifically, the phosphoric acid ester group is bonded to inorganic particles containing titanium oxide. For example, a compound having a phosphoric acid ester group / hydroxyl group such as 10- (diethoxy-phosphonyl) decanol can be mentioned. The compound having a phosphate ester group / hydroxyl group is also a hydroxyl group-containing compound.

Moreover, the above-mentioned organic groups may be the same or different from each other.

When the organic groups are different, that is, when the organic group contains a plurality of organic groups of different types, the organic groups include a plurality of cognate organic groups and / or a plurality of different groups of organic groups.

Examples of the homologous organic group include a combination of a plurality of aliphatic groups, a combination of a plurality of phosphonoaliphatic groups, a combination of a plurality of alkoxyphosphonyl aliphatic groups, a combination of a plurality of carboxy aliphatic groups, and the like. Examples thereof include a plurality of carboxyester aliphatic groups.

Examples of the combination of a plurality of aliphatic groups include a combination of a saturated aliphatic group having less than 10 carbon atoms and a saturated aliphatic group having 10 or more carbon atoms, and specifically, a combination of octyl and decyl and methyl. And a combination of decyl. Further, as a combination of a plurality of aliphatic groups, for example, a combination of a saturated aliphatic group having less than 7 carbon atoms and a saturated aliphatic group having 7 or more carbon atoms can be mentioned. Specifically, a combination of methyl and octyl, Examples include hexyl and decyl combinations and hexyl and octyl combinations. Further, a combination of a saturated aliphatic group having less than 5 carbon atoms and a saturated aliphatic group having 5 or more carbon atoms can be mentioned, and a specific combination of methyl and hexyl can be mentioned.

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, and specifically, 3-phosphonopropyl and Examples include the combination of 6-phosphonohexyl.

Examples of the combination of the 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. Examples include a combination of 3- (diethoxy-phosphonyl) propyl and 6- (diethoxy-phosphonyl) hexyl, a combination of 3- (diethoxy-phosphonyl) propyl and 10- (diethoxy-phosphonyl) decyl.

Examples of the combination of the plurality of carboxyaliphatic groups include a combination of a carboxyaliphatic group having less than 5 carbon atoms and a carboxyaliphatic group having 5 or more carbon atoms, and specifically, 2-carboxyethyl and 5 -Combination of carboxypropyl can be mentioned.

Examples of the combination of the plurality of carboxyester aliphatic groups include a combination of a carboxyester aliphatic group having less than 7 carbon atoms and a carboxyester aliphatic group having 7 or more carbon atoms, and specifically, 2-( Examples include a combination of methoxy-carbonyl) ethyl and 5- (methoxy-carbonyl) heptyl, a combination of 2- (methoxy-carbonyl) ethyl and 9- (methoxy-carbonyl) nonyl.

If the organic group contains a plurality of cognate organic groups, the organic group contains a plurality of organic groups having different sizes (length or / and size, that is, the number of carbon atoms). Therefore, between adjacent large-sized organic groups, resin molecules enter into the voids (pockets) formed corresponding to the small-sized organic groups, and the interaction between the large-sized organic groups and the resin molecules occurs. Can be improved. As a result, the dispersibility of the catalyst particles can be improved.

Examples of organic groups of different groups include aliphatic groups, alicyclic groups, aromatic aliphatic groups, aromatic groups, phosphono aliphatic groups, phosphono aromatic aliphatic groups, alkoxyphosphonyl aliphatic groups, and alkoxyphosphonyl aromatic groups. At least two different groups selected from the group consisting of aliphatic groups, hydroxy aliphatic groups, carboxy aliphatic groups, carboxy aromatic aliphatic groups, carboxy aromatic groups, carboxy ester aliphatic groups and amino / sulfo aliphatic groups. Combinations can be mentioned.

As the organic groups of different groups, preferably a combination of an aliphatic group and an aromatic aliphatic group, a combination of an aliphatic group and a carboxy aliphatic group, a combination of an aliphatic group and a carboxyester aliphatic group, a carboxy aliphatic group and a carboxy group. Examples include combinations of ester aliphatic groups.

Examples of the combination of the aliphatic group and the aromatic aliphatic group include a combination of a saturated aliphatic group having 6 to 12 carbon atoms and an aromatic aliphatic group having 7 to 15 carbon atoms, and specifically, octyl and phenyl. Examples include hexyl combinations.

Examples of the combination of the aliphatic group and the carboxy aliphatic group include a combination of an aliphatic group having less than 6 carbon atoms and a carboxy aliphatic group having less than 6 carbon atoms, and specifically, methyl and 2-carboxyethyl. , Combinations of methyl and 5-carboxypentyl. In addition, a combination of an aliphatic group having 6 or more carbon atoms and a carboxy aliphatic group having less than 6 carbon atoms is also mentioned, and specific examples thereof include a combination of octyl and 2-carboxyethyl, and a combination of octyl and 5-carboxypentyl. Be done.

Examples of the combination of the aliphatic group and the carboxyester aliphatic group include a combination of an aliphatic group having less than 6 carbon atoms and a carboxyester aliphatic group having less than 6 carbon atoms, and specifically, methyl and 2- ( Examples include a combination of methoxy-carbonyl) ethyl.

In addition, examples of the combination of the aliphatic group and the carboxyester aliphatic group include a combination of an aliphatic group having less than 6 carbon atoms and a carboxyester aliphatic group having 6 or more carbon atoms, and specifically, methyl and 9 Examples include the combination of-(methoxy-carbonyl) nonyl.

Further, examples of the combination of the aliphatic group and the carboxyester aliphatic group include a combination of an aliphatic group having 7 or more carbon atoms and a carboxyester aliphatic group having 7 or more carbon atoms, and specifically, octyl and 9 Examples include the combination of-(methoxy-carbonyl) nonyl, decyl and the combination of 9- (methoxy-carbonyl) nonyl.

Examples of the combination of the aliphatic group and the carboxyester aliphatic group include a combination of an aliphatic group having 6 or more carbon atoms and a carboxyester aliphatic group having less than 6 carbon atoms, and specifically, decyl and 2- ( Examples include a combination of methoxy-carbonyl) ethyl.

Examples of the combination of the carboxy aliphatic group and the carboxy ester aliphatic group include a combination of a carboxy aliphatic group having less than 5 carbon atoms and a carboxy ester aliphatic group having 6 or more carbon atoms. Examples include combinations of carboxyethyl and 9- (methoxy-carbonyl) nonyl.

If the organic group contains a plurality of organic groups of different groups, the organic group is a resin component having excellent compatibility with the organic group of each group when the resin is prepared as a mixture of a plurality of resin components. Excellent compatibility with resin molecules can be exhibited. Therefore, the interaction between the organic group and the resin molecule of the resin component can be improved. As a result, the dispersibility of the catalyst particles can be improved.

The above-mentioned organic group exists on the surface of the inorganic particles in the catalyst particles. Specifically, the organic group extends from the surface of the inorganic particle toward the outside of the inorganic particle via a bonding group.

The catalyst particles described above are produced by subjecting an inorganic substance and / or a complex and an organic compound to a reaction treatment, preferably a high temperature treatment.

The high temperature treatment is carried out in a solvent. Examples of the solvent include water, for example, the above-mentioned organic compounds.

Specifically, the inorganic substance and / or the complex is surface-treated with an organic compound under high temperature and high pressure water (hydrothermal synthesis: hydrothermal reaction), or the inorganic substance and / or the complex is surface-treated in the high temperature organic compound. By surface treatment, catalyst particles are obtained. That is, catalyst particles are obtained by surface-treating the surface of an inorganic substance and / or a complex (inorganic particles formed by) with the above-mentioned organic compound containing an organic group.

In hydrothermal synthesis, for example, the above-mentioned inorganic substance and an organic compound are reacted at high temperature and high pressure in the presence of water (first hydrothermal synthesis).

Preferred examples of the inorganic substance used for the first hydrothermal synthesis include oxides, sulfates, nitrates, formic acids, hydroxides and metals.

The inorganic substances used for the first hydrothermal synthesis can be used alone or in combination. When an inorganic substance is used in combination, the first combination described above is adopted.

To carry out the first hydrothermal synthesis, first, the reaction system is prepared under high temperature and high pressure by putting inorganic substances, organic compounds and water into a pressure-resistant airtight container and heating them.

The blending ratio of each component is, for example, 1 to 1500 parts by mass, preferably 5 to 500 parts by mass, more preferably 5 to 250 parts by mass, and water is added to 100 parts by mass of the inorganic substance. For example, 50 to 8000 parts by mass, preferably 80 to 6600 parts by mass, and more preferably 100 to 4500 parts by mass.

Since the density of the organic compound is usually 0.8 to 1.1 g / mL, the blending ratio of the organic compound is, for example, 1 to 1500 mL, preferably 5 to 500 mL, more preferably 5 to 500 mL with respect to 100 g of the inorganic substance. , 5 ~ 250 mL.

Further, the number of blended organic compounds may be set to, for example, 0.01 to 1000 mol, preferably 0.02 to 50 mol, and more preferably 0.1 to 10 mol with respect to 1 mol of the inorganic substance.

When the organic compound contains a plurality of (for example, two) organic groups of different types, specifically, the molar ratio of the organic compound containing one organic group to the organic compound containing the other organic group. Is, for example, 10: 90 to 99.9: 0.1, preferably 20: 80 to 99: 1.

Further, since the density of water is usually about 1 g / mL, the mixing ratio of water is, for example, 50 to 8000 mL, preferably 80 to 6600 mL, and more preferably 100 to 4500 mL with respect to 100 g of the inorganic substance. Is.

When an inorganic substance is used in combination, specifically, when the first combination described above is adopted, the first inorganic substance is blended in a larger amount than the second inorganic substance, and specifically, the first The mixing ratio of the second inorganic substance to 100 parts by mass of the inorganic substance is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and usually 0.01 parts by mass or more. In other words, the mixing ratio of the second inorganic substance to 1 mol of the first inorganic substance is, for example, 0.2 mol or less, preferably 0.1 mol or less, more preferably 0.05 mol or less, and usually 0.0001 mol or more.

Specifically, the reaction conditions in the hydrothermal reaction are such that the heating temperature is, for example, 100 to 600 ° C, 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. On the other hand, the reaction time when a continuous reactor is used is, for example, 1 minute or less.

In the above reaction, the obtained reactant mainly contains a precipitate that precipitates in water and a deposit that adheres to the inner wall of the closed container.

The precipitate is obtained, for example, by sedimentation separation in which the reactant is precipitated by gravity or centrifugal force field. Preferably, it is obtained as a precipitate of the reactants by centrifugal sedimentation (centrifugation), which is precipitated by a centrifugal force field.

In addition, the deposits are collected by, for example, a spatula.

The reaction product can also be recovered (separated) by adding a solvent to wash the unreacted organic compound (that is, dissolving the organic compound in the solvent) and then removing the solvent.

Examples of the solvent include alcohols such as methanol, ethanol, propanol and isopropanol (hydroxyl group-containing aliphatic hydrocarbons), and ketones such as acetone, methyl ethyl ketone, cyclohexanone and cyclopentanone (carbonyl group-containing aliphatic hydrocarbons). For example, aliphatic hydrocarbons such as pentane, hexane and heptane, for example halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and trichloroethane, for example halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, for example tetrahydrofuran and the like. Examples include ethers, for example, aromatic hydrocarbons such as benzene, toluene and xylene, for example, pH-adjusted aqueous solutions such as aqueous ammonia. Alcohol is preferably used.

The reaction product after washing is separated from the solvent (supernatant) by filtration, decantation, or the like, and recovered. Then, if necessary, the reactants are dried, for example by heating or airflow.

As a result, catalyst particles having inorganic particles and organic groups to be bonded to the surface thereof are obtained.

On the other hand, unlike the first hydrothermal synthesis described above, inorganic particles formed from an inorganic substance and / or a complex different from the charged raw material by hydrothermally synthesizing the inorganic substance and / or the complex (prepared raw material) and the organic compound. It is also possible to obtain catalyst particles containing (second hydrothermal synthesis).

Examples of the inorganic substances used for the second hydrothermal synthesis include hydroxides, sulfates, acetates, metals, and hydrates thereof.

In hydroxides, elements contained in hydroxides (hydroxyl ions (OH)^-) And the elements that make up the cation. ) Examples include the same elements as those that combine with oxygen in the above-mentioned oxides.

Specific examples of the hydroxide include strontium hydroxide (Sr (OH)).₂) And so on.

Examples of the complex used for the second hydrothermal synthesis include a titanium complex and the like.

As a hydrate used for the second hydrothermal synthesis, for example, tungstic acid (WO)₃ H₂O), ammonium paratungate pentahydrate ((NH)₄)₂WO₄ 5H₂O) and the like. The above-mentioned hydrate produces tungsten oxide by desorbing the hydrated water by the second hydrothermal synthesis.

Such inorganic substances and complexes (raw materials) can be used alone or in combination of two or more.

When the raw materials used for the second hydrothermal synthesis are used in combination, the above-mentioned first combination and second combination are adopted.

When the first combination is adopted and the second inorganic material is a metal, the second inorganic material does not change its chemical composition before and after the reaction (second hydrothermal synthesis).

As the first combination, the second inorganic substance to be subjected to the second hydrothermal synthesis specifically includes palladium, platinum and the like, which are used before and after the reaction (second hydrothermal synthesis). , No change in chemical composition.

Then, after the second hydrothermal synthesis, the metal or its oxide forming the second inorganic substance is supported on the first inorganic substance.

Supported is defined as a state in which the metal or oxide is substantially uniformly present inside and / or on the surface of the first inorganic material.

Specifically, the metal (copper) forming the sulfate (copper) is supported on the oxide (tungsten oxide) after the second hydrothermal synthesis. In addition, the VIII group elements (palladium and platinum) are supported on oxides (tungsten oxide) after the second hydrothermal synthesis. Further, the metal (copper) forming the formic acid salt (copper formate) is supported on tungsten oxide after the second hydrothermal synthesis.

The mixing ratio of each component in the second hydrothermal synthesis is, for example, 1 to 1500 parts by mass, preferably 5 to 500 parts by mass, and more preferably 5 for the organic compound with respect to 100 parts by mass of the inorganic substance and the complex. It is ~ 250 parts by mass, and 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 blending ratio of the organic compound is, for example, 0.9 to 1880 mL, preferably 4.5 to 630 mL, more preferably 4.5 to 320 mL with respect to 100 g of the inorganic substance and the complex, and the number of moles of the organic compound blended is the inorganic substance and the complex. It can also be set to, for example, 0.01 to 10000 mol, preferably 0.1 to 10 mol, per 1 mol of the complex.

The mixing ratio of water is, for example, 50 to 8000 mL, preferably 80 to 6600 mL, and more preferably 100 to 4500 mL with respect to 100 g of the inorganic substance and the complex.

When an inorganic substance and a complex are used in combination, the second combination described above is adopted, and more specifically, when a combination of a complex and an inorganic substance is adopted, the mixing ratio of the inorganic substance to 100 parts by mass of the complex is For example, it is 10 parts by mass or less, preferably 8 parts by mass or less, more preferably 5 parts by mass or less, and usually 0.001 parts by mass or more. In other words, the mixing ratio of the inorganic substance to 1 mol of the complex is, for example, 0.1 mol or less, preferably 0.08 mol or less, more preferably 0.05 mol or less, and usually 0.00001 mol or more.

When a plurality of complexes are used, specifically, when a combination of a titanium complex and a ruthenium complex is adopted, the mixing ratio of the ruthenium complex to 100 parts by mass of the titanium complex is, for example, 50 parts by mass or less. It is preferably 25 parts by mass or less, and usually 0.1 parts by mass or more. In other words, the blending ratio of the ruthenium complex to 1 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 more.

The reaction conditions in the second hydrothermal synthesis are the same as the reaction conditions in the first hydrothermal synthesis described above.

When a combination of titanium complex and platinum is adopted as the second combination, the titanium complex produces titanium oxide by the reaction (second hydrothermal synthesis), while platinum is produced before and after the reaction. , No change in chemical composition. When a combination of a titanium complex, strontium hydroxide, and nickel acetate is adopted as the second combination, the titanium complex and strontium hydroxide are combined with strontium titanate by a reaction (second hydrothermal synthesis). (SrTiO₃), And nickel acetate produces nickel oxide (NiO). Furthermore, when a combination of a titanium complex, strontium hydroxide, and ruthenium complex is adopted as the second combination, the titanium complex and strontium hydroxide are combined with strontium titanate by a reaction (second hydrothermal synthesis). (SrTiO₃) Is produced, and the ruthenium complex is ruthenium oxide (RuO).₂) Is generated.

As a result, catalyst particles having inorganic particles formed from an inorganic substance and a complex different from the charged inorganic raw material and organic groups bonded to the surface thereof are obtained.

Further, in the above-mentioned first hydrothermal synthesis and second hydrothermal synthesis formulations, a pH adjuster can be further added to each component in an appropriate ratio.

Examples of the pH adjuster include an aqueous ammonia solution and an aqueous sodium hydroxide solution.

For surface treatments in hot organic compounds, the organic compounds are blended with the inorganic and / or complex and heated, for example, under normal pressure. The organic compound is subjected to high temperature treatment while also serving as an organic group-introduced compound and a solvent for dispersing or dissolving an inorganic substance and / or a complex.

The blending ratio 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 with respect to 100 parts by mass of the inorganic substance and the complex. The volume-based mixing ratio of the organic compound is, for example, 1 to 10000 mL, preferably 10 to 5000 mL, and more preferably 20 to 1000 mL with respect to 100 g of the inorganic substance and the complex.

The heating temperature is, for example, a temperature exceeding 100 ° C, preferably 125 ° C or higher, 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. On the other hand, the reaction time when a continuous reactor is used is, for example, 1 minute or less.

Further, for example, the pressure can be increased by heating. The high pressure conditions are the same as the hydrothermal synthesis pressure described above.

Surface treatment in a high-temperature organic compound gives inorganic particles made of an oxide of a metal forming an inorganic substance and / or a complex, and catalyst particles having an organic group bonded to the surface thereof.

Further, the above-mentioned high-temperature treatment (surface treatment) can be carried out independently, or can be carried out in plurality from the viewpoint of improving the treatment efficiency.

As a method of carrying out a plurality of high-temperature treatments, for example, a method of repeating the above-mentioned first hydrothermal synthesis, a second hydrothermal synthesis, and a surface treatment in a high-temperature organic compound, or each of the above-mentioned treatments. Is adopted in combination. Preferably, a method of carrying out each of the above-mentioned treatments in combination is adopted. More preferably, after the second hydrothermal synthesis, a method of surface treatment in a high temperature organic compound is adopted.

Specifically, the titanium complex is treated at a high temperature in the above-mentioned phosphate ester group-containing organic compound (carboxyester group-containing organic compound), and an organic in which a carboxyaliphatic group is bonded to titanium oxide via a phosphate group. Obtain inorganic composite particles. Then, the obtained organic-inorganic composite particles are treated at a high temperature in alcohol to generate a carboxyester group-containing organic group from a carboxyaliphatic group in the organic group. That is, the carboxyl group bonded to the terminal of the aliphatic group is transesterified with an alcohol.

The shape of the catalyst particles (primary particles) thus obtained is not particularly limited, and may have, for example, anisotropy or isotropic, and has an average particle size (anisotropic) thereof. If so, the average value of the maximum length) is, 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 the viewpoint of transparency.

The average particle size of the catalyst particles will be described in detail in later examples, but measurement by dynamic light scattering (DLS) or image analysis by transmission electron microscope (TEM) or scanning electron microscope (SEM), Furthermore, it is calculated by a calculation using Scheller's equation based on X-ray diffraction (XRD) data.

If the average particle size exceeds the above range, the transparency of the catalyst solution, the catalyst resin composition and the catalyst molded product may decrease, and the catalyst may be crushed when mixed with the resin.

Further, if the average particle size is less than the above range, the ratio of the volume of the organic group to the surface of the catalyst particles becomes high, and the inorganic particles may not easily exhibit the catalytic action.

The catalyst particles thus obtained are less likely to aggregate in the dry state, and even if they apparently aggregate in the dry state, they aggregate (formation of secondary particles) in the catalyst composition and the catalyst molded body. Is prevented and dispersed almost uniformly in the resin.

Further, in the catalyst particles, the ratio of the surface area of the organic group to the surface area of the inorganic particle, that is, the surface coverage of the organic group in the catalyst particle (= (surface area of organic group / surface area of inorganic particle) × 100) is, for example, It is 30% or more, preferably 60% or more, and usually 200% or less.

In calculating the surface coverage, first, the shape of the inorganic particles is confirmed by a transmission electron microscope (TEM), the average particle size is calculated, and the specific surface area of the particles is calculated from the shape of the inorganic particles and the average particle size. calculate. In addition, the ratio of organic groups in the catalyst particles is calculated from the weight change when the catalyst particles are heated to 800 ° C by a differential thermal balance (TG-DTA). Then, the amount of organic groups in one particle is calculated from the molecular weight of the organic groups, the density of the particles, and the average volume. Then, the surface coverage is obtained from them.

Further, when the surface coverage is high and the organic groups of the catalyst particles are long enough to cancel the charge of the inorganic particles, the type of the solvent (medium) for dispersing the catalyst particles is the type of the organic group. Can be controlled (designed or managed) with.

Further, the catalyst particles obtained as described above can be wet-classified.

That is, a solvent is added to the catalyst particles, and after stirring them, they are allowed to stand, and then separated into a supernatant and a precipitate. The solvent depends on the type of organic group, but examples thereof include the same as above, preferably hydroxyl group-containing aliphatic hydrocarbon, carbonyl group-containing aliphatic hydrocarbon, aliphatic hydrocarbon, and halogenation. Examples include aliphatic hydrocarbons and pH-adjusted aqueous solutions.

After that, catalyst particles having a small average particle size can be obtained by recovering the finished product.

By wet classification, the average particle size of the obtained catalyst particles (primary 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.

Then, the catalyst particles obtained as described above can be dispersed in a solvent and a resin, respectively, and prepared as a catalyst solution and a catalyst composition, respectively.

The catalyst solution contains a solvent and the above-mentioned catalyst particles.

To prepare such a catalyst solution, the solvent and the catalyst particles are mixed and stirred to disperse the catalyst particles in the solvent.

The solvent is not particularly limited, and examples thereof include the solvent used in the above-mentioned washing, and further, in addition to these, an alicyclic hydrocarbon such as cyclopentane and cyclohexane, for example, an ester such as ethyl acetate. , For example, polyols such as ethylene glycol and glycerin, for example, nitrogen-containing compounds such as N-methylpyrrolidone, pyridine, acetonitrile and dimethylformamide, isostearyl acrylate, lauryl acrylate, isobolonyl acrylate, butyl acrylate, methacrylate, acrylic acid, Contains acrylic monomers such as tetrahydrofurfuryl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxyethyl acrylate, and acroylmorpholin, for example, vinyl groups such as styrene and ethylene. Examples include monomers, such as epoxy group-containing monomers such as bisphenol A type epoxy.

These solvents can be used alone or in combination of two or more. Preferred are halogenated aliphatic hydrocarbons.

The mixing ratio 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 with respect to 100 parts by mass of the catalyst solution.

In the catalyst solution thus obtained, the catalyst particles have a shape in which the inorganic particles do not come into contact with each other, so that the catalyst particles are uniformly dispersed as primary particles in the solvent. Therefore, the transparency of the catalyst solution can be improved.

Further, the catalyst composition contains a resin and the above-mentioned catalyst particles.

Examples of the resin include thermosetting resins and thermoplastic resins.

Examples of the thermosetting resin include polycarbonate resin, epoxy resin, thermosetting polyimide resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin, silicone resin, and thermosetting urethane resin.

Examples of the thermoplastic resin include olefin resin, acrylic resin, polystyrene resin, polyester resin, polyacrylonitrile resin, maleimide resin, polyvinyl acetate resin, ethylene / vinyl acetate copolymer, polyvinyl alcohol resin, polyamide resin, and polyvinyl chloride. Resin, polyacetal resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyether ether ketone resin, polyallylsulfone resin, thermoplastic polyimide resin, thermoplastic urethane resin, polyetherimide resin, polymethylpentene Examples thereof include resins, cellulose resins, liquid crystal polymers, and ionomers.

These resins can be used alone or in combination of two or more.

Further, the catalyst particles and the resin can be selected so that their solubility parameters (SP values) satisfy a predetermined relationship.

That is, the difference between the catalyst particles and the resin has a predetermined SP value (ΔSP, specifically, the solubility parameter of the resin (SP)._resinValue) and solubility parameter of catalyst particles (SP)_particleIt is selected so that it is the absolute value of the difference from the value).

Among the above-mentioned resins, when it is desired to impart excellent mechanical strength to the catalyst molded body molded from the catalyst composition, a highly oriented resin having high orientation is preferable, and specific examples are olefins. Examples thereof include resins, acrylic resins, polystyrene resins, polyester resins, polyvinyl alcohol resins, thermoplastic polyimide resins, polyetherimide resins, and liquid crystal polymers.

Examples of the olefin resin include cyclic olefin resins and chain olefin resins. Preferably, a cyclic olefin resin is used.

Examples of the cyclic olefin resin include polynorbornene, ethylene / norbornene copolymers, and derivatives thereof.

Examples of the chain olefin resin include polyethylene, polypropylene, and an ethylene / propylene copolymer.

Examples of the acrylic resin include polymethylmethacrylate and the like.

Examples of the polyester resin include polyarylate, polyethylene terephthalate, and polyethylene naphthalate.

The polyvinyl alcohol resin can be obtained, for example, by completely or partially saponifying a polyvinyl acetate resin obtained by polymerizing a vinyl monomer containing vinyl acetate as a main component by an appropriate method. The degree of saponification of the polyvinyl alcohol resin is, for example, 70 to 99.99 mol%, preferably 70 to 99.9 mol%.

Further, the above-mentioned resin has, for example, a hydrophilic group such as a carboxyl group and a hydroxyl group, for example, a hydrophobic group such as a hydrocarbon group.

Then, in order to prepare the catalyst composition, first, the above-mentioned solvent and the resin are mixed, and the resin is dissolved in the solvent to prepare a resin solution. Then, the resin solution and the catalyst particles are mixed and stirred to prepare a catalyst composition (first preparation method).

The blending ratio of the resin is, for example, 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 more with respect to 100 parts by mass of the resin solution. If the blending ratio of the resin exceeds the above range, the solubility of the resin may decrease.

The mixing ratio 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 with respect to 100 parts by mass of the solid content (resin) of the resin solution. .. The mixing ratio of the catalyst particles is, for example, 0.1 to 300 parts by mass, preferably 1 to 200 parts by mass, and more preferably 3 to 3 parts by mass with respect to 100 parts by mass of the total amount of the resin solution (total amount of resin and solvent). It is also 100 parts by mass.

Further, the catalyst composition can also be prepared by first preparing the above-mentioned catalyst solution, then mixing the catalyst solution and the resin, and stirring them (second preparation method).

In the catalyst solution, the catalyst particles are dispersed as primary particles in the solvent.

The blending ratio of the 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 with respect to 100 parts by mass of the solid content (catalyst particles) of the catalyst solution. ..

Further, for example, the catalyst composition can be prepared by blending the solvent, the catalyst particles and the resin at once and stirring them (third preparation method).

The blending ratio of each component 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 with respect to 100 parts by mass of the total amount of the catalyst composition. Yes, the 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 more. The mixing ratio of the solvent is the balance of the catalyst composition excluding the catalyst particles and the resin.

Further, in order to prepare the catalyst composition, first, a resin solution and a catalyst solution can be prepared respectively, and then the resin solution and the catalyst solution can be mixed and stirred (fourth preparation method). ..

The blending ratio of the resin in the resin solution is the same as the blending ratio exemplified in the first preparation method described above.

The compounding ratio of the catalyst particles in the catalyst solution is the same as the compounding ratio exemplified in the above-mentioned method for preparing the catalyst solution.

The mixing ratio of the resin solution and the catalyst solution is based on the mass of the resin and the catalyst particles, for example, 99: 1 to 10:90, preferably 95: 5 to 20:80, and more preferably 90:10. Mix so that it is ~ 30: 70.

Furthermore, in order to prepare the catalyst composition, for example, the resin can be melted by heating and blended with the catalyst particles without blending a solvent (fifth preparation method).

The catalyst composition thus prepared is a melt of the catalyst composition containing no solvent.

When the resin is made of a thermoplastic resin, the heating temperature is the same as or higher than the melting temperature, and specifically, 200 to 350 ° C. When the resin is made of a thermosetting resin, the temperature at which the resin is in the B stage state is, for example, 85 to 140 ° C.

The mixing ratio of the resin and the catalyst particles is, for example, 99: 1 to 10:90, preferably 95: 5 to 20:80, and more preferably 90: 10 to 30:70 on a mass basis.

In the catalyst composition obtained by each of the above-mentioned preparation methods, the catalyst particles are uniformly dispersed in the resin. Specifically, in the catalyst composition, the catalyst particles are dispersed in the resin as primary particles (without substantially agglutinating).

Then, the obtained catalyst composition is applied onto, for example, a known support plate to prepare a coating film, and the coating film is dried to form a catalyst molded product as a film.

In the coating of the catalyst composition, for example, a known coating method such as a spin coater method or a bar coater method is used. In the application of this catalyst composition, the solvent is removed by volatilization at the same time as or immediately after the application. If necessary, the solvent can be dried by heating after coating.

The thickness of the obtained film is appropriately set according to the intended use and purpose, and is, for example, 0.1 to 2000 μm, preferably 0.1 to 1000 μm, and more preferably 0.1 to 500 μm.

The catalyst molded product can also be molded as a film by a melt molding method in which the above-mentioned catalyst composition is extruded by an extrusion molding machine or the like.

Further, the catalyst composition can be injected into a mold or the like, and then the catalyst molded body can be molded as a block (lump) by thermoforming such as a hot press.

The catalyst molded body is formed of a catalyst composition in which the catalyst particles are dispersed in the resin, and the above-mentioned shape based on the steric hindrance of the organic group in the catalyst particles makes it difficult for the inorganic particles to come into direct contact with the resin. Become. Therefore, the catalyst molded product can exhibit a catalytic action on a gas or a liquid while suppressing deterioration of the resin.

Specifically, the catalyst molded body absorbs 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. It can exhibit detoxification, deodorization, sterilization (or antibacterial or bactericidal) action, and decomposition action against poisons, odors (bad odors), bacteria, organic substances, etc. contained in gases such as. Furthermore, it can exhibit detoxification, sterilization, antifouling, and decomposition effects on poisons, bacteria, filth, organic substances, etc. contained in liquids such as water .

As a result, the catalyst molded body can be used as a catalyst molded body having various catalytic actions (photocatalytic action) such as detoxification action, deodorizing action, sterilization action, antifouling action, and decomposition action while having excellent durability. ..

Furthermore, since the catalyst particles are uniformly dispersed in this catalyst molded product, transparency can be improved.

As a result, this catalyst molded product can be used for various optical applications and various building material applications that require transparency.

Specifically, when the catalyst molded body is molded as a film, for example, a polarizing film, a retardation film, a brightness improving film, and a field of view used in an image display device such as a liquid crystal display or an organic electroluminescence device. It can be used as an optical film such as an angle enlargement film, a high refractive index film, and a light diffusing film.

When the catalyst molded body is molded as a film, for example, an ultraviolet absorbing film, an antifouling film, an antibacterial film, a deodorizing film, a superhydrophilic film, a sterilizing film, a detoxifying film, a chemical substance decomposition film, etc. It can also be used as a film for building materials (building).

<p> The present invention will be described in more detail with reference to Preparation Examples, Examples, and Comparative Examples, but the present invention is not limited thereto.</p><p> The evaluation method of the catalyst particles, the catalyst solution and the film (catalyst molded product) will be described below. &lt;Evaluation method&gt; (1) X-ray diffraction method (XRD) The catalyst particles were filled in glass folders, and X-ray diffraction was performed under the following conditions. Then, from the obtained peak, the components of the inorganic compound were assigned by database search.</p><p> X-ray diffractometer: D8 DISCOVER with GADDS, made by Bruker AXS (Incident side optical system) X-ray source: CuKα (λ = 1.542Å), 45kV, 360mA Spectrometer (monochromator): Multilayer mirror Collimator diameter: 300 μm (Light receiving side optical system) Counter: 2D PSPC (Hi-STAR) Distance between catalyst particles and counter: 15 cm 2θ = 20, 50, 80 degrees, ω = 10, 25, 40 degrees, Phi = 0 degrees, Psi = 0 degrees Measurement time: 10 minutes -Attribution (semi-quantitative software): FPM EVA, manufactured by Bruker AXS (2) Fourier Transform Infrared Spectroscopy (FT-IR) The Fourier transform infrared spectrophotometric measurement of the catalyst particles was carried out by the KBr method using the following device.</p><p> Fourier Transform Infrared Spectrophotometer: FT / IR-470Plus, manufactured by JASCO (3) Measurement of average particle size A. DLS (Dynamic Light Scattering Method) Prepare a sample (catalyst solution, solid content concentration 1% by mass or less) by dispersing the catalyst particles in a solvent, and measure the average particle size of the catalyst particles in the sample with a dynamic light scattering photometer (model number "ZEN3600": manufactured by Sysmex). Measured at. B. SEM (Scanning Electron Microscope) The catalyst solution is dropped and dried on a sample table, and observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation, or JSM-7001F, manufactured by JEOL Ltd.) to determine the average particle size of the catalyst particles. Observed. C. TEM (Transmission Electron Microscope) A solvent-diluted sample (catalyst solution, solid content concentration of 1% by mass or less) is dropped onto a TEM grid (corodion film, carbon support film), dried, and transmitted electron microscope (TEM, H-7650, Hitachi). The average particle size of the catalyst particles was calculated by observing the catalyst particles with (High Technologies America) and analyzing the image. D. XRD By substituting the obtained data in the above (1) XRD into the following Scheller's equation (1), the average particle size of the catalyst particles was calculated.</p><p> D = Kλ / (βcosθ) (1) (In the formula, D is the average particle size of the crystal particle size, K is the Scheller constant, λ is the wavelength of the X-ray tube, β is the half width, and θ is the diffraction angle.) (4) Evaluation of catalysis A. Examples 1 to 78 and Comparative Examples 1 to 5 A 0.01 mass% (0.02 m mol / L) aqueous solution of Rhodamine B (molecular weight 479.01) was prepared.</p><p> Then, 0.01 g of the catalyst particles of Examples 1 to 78 and Comparative Examples 1 to 5 was added to a transparent 2 mL vial, and then 1 g of the prepared Rhodamine B aqueous solution was added.</p><p> After that, in a dark room, illuminate the vial with black light (ultraviolet rays with a wavelength of 365 nm) at 1 mW / cm.²Then, it was irradiated for 1 hour.</p><p> Then, the rhodamine B aqueous solution in the vial was analyzed by ultraviolet-visible absorption. Such analysis was performed by an ultraviolet-visible spectrophotometer (U-560, manufactured by JASCO Corporation).</p><p> Then, the presence or absence of catalytic action of the catalyst particles was evaluated according to the following evaluation criteria.</p><p> : The peak (wavelength 550 nm) derived from rhodamine B disappeared.</p><p> X: A peak (wavelength 550 nm) derived from rhodamine B remained.</p><p> 1 and 2 show the ultraviolet-visible absorption spectra of Examples 10 and 66 from the start of irradiation to the predetermined lapse of time, respectively.</p><p> B. Examples 79-94 and Comparative Examples 6-13 A 1 mol / L acetaldehyde aqueous solution was prepared.</p><p> Then, 0.1 g of the catalyst particles of Examples 1 to 78 and Comparative Examples 1 to 5 was added to a vial (10 mL), and then 100 μL of the prepared acetaldehyde aqueous solution was added by syringe. Then, a septum cap was attached to the mouth of the vial, and they were stirred well.</p><p> The vial was then irradiated with light from a 300 W xenon lamp (Cermax LX-300, manufactured by Perkin Elmer) for 30 minutes. By providing a cut-off filter (HOYA L42, manufactured by HOYA Corporation) on the xenon lamp, ultraviolet light (ultraviolet light having a wavelength of 420 nm or less) was shielded (shielded).</p><p> Then, in the vial, the CO produced by the decomposition of formaldehyde₂Concentration was measured by gas chromatography (HP5890 SeriesIIplus / HP5972, column: Ultra-1 (0.2 mmφ × 25 m, df = 0.33um), manufactured by Agilent).</p><p> Then, the presence or absence of catalytic action of the catalyst particles was evaluated according to the following evaluation criteria.</p><p> : CO₂The concentration was 10 ppm or more.</p><p> ×: CO₂The concentration was less than 10 ppm. (5) Evaluation of resin deterioration A white film (described later) in which catalyst particles were dispersed was heated in a dryer at 80 ° C. for 1 hour. After that, black light (ultraviolet rays with a wavelength of 365 nm) was applied to the film at an illuminance of 1 mW / cm.²Then, it was irradiated for 24 hours.</p><p> Then, the deterioration of the film was visually observed and evaluated according to the following evaluation criteria.</p><p> : The film was white.</p><p> X: The film was yellow.</p><p> &lt;Preparation of titanium complex&gt; Preparation Example 1 (Preparation of titanium complex whose ligand is 2-hydroxyoctanoic acid) To a 500 mL beaker, 100 mL of 30% by volume hydrogen peroxide solution and 25 mL of 25 wt% ammonia were added under ice cooling. Further, 1.5 g of titanium powder was added to them, and the mixture was stirred under ice-cooling for 3 hours until it was completely dissolved. Next, 15.5 g of 2-hydroxyoctanoic acid dissolved in 25 mL of ethanol was added and stirred. After all the components were dissolved, stirring was stopped and the mixture was allowed to stand for a whole day and night. Then, it was dried in a dryer at 75 ° C. for 3 hours to obtain a water-soluble titanium complex.</p><p> This titanium complex is provided as a complex (see Tables 1, 3 to 7 and 9) in Examples 8 to 17, 31 to 69, 78, 89 and Comparative Example 3 described later.</p><p> Preparation Example 2 (Preparation of titanium complex whose ligand is glycolic acid) A water-soluble titanium complex was obtained by the same treatment as in Preparation Example 1 except that 3.6 g of glycolic acid was added instead of 15.5 g of 2-hydroxyoctanoic acid.</p><p> This titanium complex is provided as a complex (see Table 2) in Example 21 described later.</p><p> Preparation Example 3 (Preparation of titanium complex whose ligand is citric acid) A water-soluble titanium complex was obtained by the same treatment as in Preparation Example 1 except that 9.1 g of citric acid was added instead of 15.5 g of 2-hydroxyoctanoic acid.</p><p> This titanium complex is provided as a complex (see Table 2) in Examples 18 to 20 described later.</p><p> Preparation Example 4 (Preparation of titanium complex whose ligand is malic acid) A water-soluble titanium complex was obtained by the same treatment as in Preparation Example 1 except that 6.3 g of malic acid was added instead of 15.5 g of 2-hydroxyoctanoic acid.</p><p> This titanium complex is provided as a complex (see Table 2) in Example 22 described later.</p><p> &lt;Preparation of catalyst particles&gt; Examples 1 to 94 and Comparative Examples 1 to 13 Each component (inorganic and / or complex, organic compound, pH regulator and water) was charged into a 5 mL high pressure reactor (manufactured by AKICO) according to the formulations shown in Tables 1-9.</p><p> Next, the lid of the high-pressure reactor was closed, and the reaction was carried out in a shaking-type heating furnace (manufactured by AKICO) according to the high-temperature treatment conditions shown in Tables 1 to 9.</p><p> Then, the high pressure reactor was put into cold water for rapid cooling.</p><p> Next, ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) is added and stirred, and then centrifuged at 12000 G for 20 minutes with a centrifuge (trade name: MX-301, manufactured by Tomy Seiko Industries, Ltd.) to form a precipitate (manufactured by Tommy Seiko). (Reactant) was separated from the supernatant (washing step). This cleaning operation was repeated 5 times.</p><p> Then, the ethanol in the precipitate was dried by heating at 80 ° C. to obtain catalyst particles.</p><p> Then, the obtained catalytic particles were evaluated for (1) XRD, (2) FT-IR, (3) average particle size, and (4) catalytic action, respectively.</p><p> As a result, in (1) XRD, the inorganic particles are TiO.₂(Examples 1 to 78 and Comparative Examples 1 to 5), WO₃(Examples 79 to 86 and Comparative Examples 6 to 13), SrTiO₃It was confirmed that it was (Examples 87 to 94).</p><p> In addition, (2) FT-IR confirmed that the organic groups listed in Tables 1 to 9 were present on the surface of the inorganic particles.</p><p> (3) In the measurement of the average particle size, as is clear from Tables 1 to 9, it can be seen that the average particle size of the catalyst particles of Examples 1 to 9 is 450 nm or less.</p><p> Further, in Examples 1 to 78 and Comparative Examples 1 to 5, the peak derived from rhodamine B disappeared, and in Examples 79 to 94 and Comparative Examples 6 to 13, CO was produced based on the decomposition of formaldehyde.₂It was found that the catalyst particles of Examples 1 to 94 and Comparative Examples 1 to 13 exhibited an organic substance decomposing action (photocatalytic action). &lt;Creation of catalyst molded product&gt; Polyarylate (polyarylate resin of Example 4 of JP2009-80440A) and chloroform were mixed and mixed uniformly to prepare a resin solution having a solid content concentration of 10% by mass.</p><p> Separately, the catalyst particles of each Example and each Comparative Example and chloroform were mixed and uniformly mixed to disperse the catalyst particles in chloroform to prepare a catalyst solution having a solid content concentration of 10% by mass. ..</p><p> Next, the resin solution and the catalyst solution are mixed so that the mixing ratio of the resin and the catalyst particles is 90:10 (mass number of resins: mass parts of catalyst particles) on a mass basis, and an ultrasonic disperser is installed. The catalyst particles were dispersed in the resin solution. As a result, a varnish having a transparent catalyst composition was prepared.</p><p> Then, the varnish of the obtained catalyst composition was applied onto the support plate by the spin coating method. Chloroform was almost volatilized during coating. Then, the applied catalyst composition is dried at 50 ° C. for 1 hour (first step drying), and then at 100 ° C. for 10 minutes (second step drying). , A film (catalyst molded body) containing catalyst particles was prepared.</p><p> Then, (5) resin deterioration was evaluated for the obtained film.</p><p> The results are shown in Tables 1-9.</p><p> As can be seen from Tables 1 to 9, in the evaluation of resin deterioration, it was found that the polyarylate resin forming the film was deteriorated because the film turned yellow in each comparative example.</p><p> On the other hand, in each example, it was found that the film was white or colorless and transparent and had no discoloration, and the deterioration of the polyarylate resin could be suppressed.</p><p> In the table, in the column of the compounding amount of the compounding formulation, the numerical value in parentheses shown in parentheses indicates the compounding volume mL, and the other numerical value, that is, the numerical value not shown in parentheses indicates the compounding mass g.</p><p> In the table, in the column of average particle size, the numerical value in parentheses indicated by [] indicates the average particle size calculated by TEM or SEM image analysis, and the numerical value in parentheses indicated by &lt;&gt; is the XRD data. The average particle size calculated by the calculation using Scheller's formula based on is shown, and the other numerical values, that is, the numerical values not shown in parentheses, indicate the average particle size measured by DLS.</p><p> The TiO used in Examples 1 to 7 and 30₂Will be described in detail below.</p><p> TiO of Example 1 and Example 2₂: Average particle size 7nm, trade name "CSB-M", manufactured by Sakai Chemical Industry Co., Ltd. TiO of Example 3 and Example 30₂: Average particle size 9nm, trade name "SSP-25", manufactured by Sakai Chemical Industry Co., Ltd. TiO of Example 4 and Example 5₂: Minor diameter 5 ~ 15nm, major diameter 30 ~ 90nm, trade name "TTO-V-3", manufactured by Ishihara Sangyo Co., Ltd. TiO of Example 6₂: Average particle size 30 ~ 50nm, "TTO-55 (A)", manufactured by Ishihara Sangyo Co., Ltd. TiO of Example 7₂: Average particle size 10 ~ 30nm, TTO-51 (A), manufactured by Ishihara Sangyo Co., Ltd.</p><p><tables num="1"><img file="JP2011235280A_D0001.tif" /></tables></p><p><tables num="2"><img file="JP2011235280A_D0002.tif" /></tables></p><p><tables num="3"><img file="JP2011235280A_D0003.tif" /></tables></p><p><tables num="4"><img file="JP2011235280A_D0004.tif" /></tables></p><p><tables num="5"><img file="JP2011235280A_D0005.tif" /></tables></p><p><tables num="6"><img file="JP2011235280A_D0006.tif" /></tables></p><p><tables num="7"><img file="JP2011235280A_D0007.tif" /></tables></p><p><tables num="8"><img file="JP2011235280A_D0008.tif" /></tables></p><p><tables num="9"><img file="JP2011235280A_D0009.tif" /></tables></p>