Molded product containing inorganic particles and water soluble polysiloxane compound having amino group, method for producing same, and inorganic particle dispersion liquid

Abstract

This molded product (not comprising an organic titanate or an organic zirconate) comprising inorganic particles and a water soluble polysiloxane compound which has an amino group and which is represented by formula (1) makes it possible to reducing a storage volume and can be redispersed in a dispersion medium to be used in the form of a dispersion liquid. [R1 represents a hydrogen atom, a C1-20 substituted or unsubstituted monovalent hydrocarbon group, or a monovalent hydrocarbon group which has a carboxy group represented by general formula (2) below (where R3, R4, and R5 each independently represent a hydrogen atom or a C1-20 substituted or unsubstituted monovalent hydrocarbon group, and a represents 0 or 1), R2 represents a C1-20 substituted or unsubstituted monovalent hydrocarbon group, m is 0 or a positive number less than 3, n is 0 or 1, and n+m is 0 or a positive number less than 3.]

Description

Molded article containing water-soluble polysiloxane compound having amino groups and inorganic particles, its manufacturing method, and inorganic particle dispersion

[0001] The present invention relates to a molded article containing a water-soluble polysiloxane compound having an amino group and inorganic particles, a method for producing the same, and an inorganic particle dispersion.

[0002] Inorganic particles are used in a variety of applications, such as pigments, ultraviolet shielding materials, thermally conductive fillers, packing materials, photocatalysts, ceramic raw materials, electronic devices, etc., and are also incorporated into cosmetics, paints, resin compositions, etc. In such applications, the surfaces of the inorganic particles are treated with other inorganic compounds or organic compounds depending on the application, thereby improving the performance, functions, etc. of the inorganic particles.

[0003] For example, Patent Document 1 proposes a solid composition for preparing an anticorrosion coating composition obtained by dehydrating an aqueous composition based on a particulate metal or a mixture of particulate metals, an organic titanate and / or an organic zirconate, and a silane having at least one hydrolyzable functional group in a hydroxyl functional group, and discloses that this solid composition, upon rehydration, has a composition similar to that of the aqueous composition before dehydration.

[0004] Special table 2021-504557 publication

[0005] The technology of Patent Document 1 makes it possible to reduce storage capacity, but the solid composition based on only a silicon precursor cannot be rehydrated, and it is essential to include an organic titanate and / or an organic zirconate.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a molded product containing a water-soluble polysiloxane compound having amino groups and inorganic particles, which can reduce the storage capacity and can be redispersed in a dispersion medium and used as a dispersion, a method for producing the same, and an inorganic particle dispersion.

[0007] As a result of extensive research to achieve the above-mentioned object, the inventors of the present invention have discovered that a molded product containing a water-soluble polysiloxane compound having amino groups and inorganic particles can have a smaller storage volume than a dispersion containing them, thereby reducing storage and transportation costs, and that the molded product can be redispersed in a dispersion medium at the time of use and used as an inorganic particle dispersion, and that the obtained inorganic particle dispersion can maintain a dispersed state for a long period of time, thereby completing the present invention.

[0008] That is, the present invention provides: 1. a molded article containing a water-soluble polysiloxane compound having an amino group represented by the following general formula (1) and inorganic particles (however, organic titanates and organic zirconates are not included); [In formula (1), R 1 represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having a carboxy group represented by the following general formula (2): (In formula (2), R 3 , R 4 and R 5 each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and a represents 0 or 1. 2 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, m is 0 or a positive number less than 3, n is 0 or 1, and n+m is 0 or a positive number less than 3.] 2. The shaped product of 1, wherein the inorganic particles are inorganic oxide particles, 3. The shaped product of 2, wherein the inorganic oxide particles are selected from the group consisting of titanium oxide, silicon oxide, zinc oxide, zirconium oxide, aluminum oxide, and zeolite, 4. The shaped product of 1 or 2, wherein the blending amount of the water-soluble polysiloxane compound having an amino group is 0.1 to 1000 parts by mass per 100 parts by mass of the inorganic particles, 5. An inorganic particle dispersion liquid consisting of a mixture of the shaped product of 1 and a dispersion medium, in which the inorganic particles are dispersed in the dispersion medium, 6. A method for producing an inorganic particle dispersion liquid, which comprises mixing the shaped product of 1 with a dispersion medium, 7. The method for producing a molded article according to claim 1 comprises mixing a solution containing the water-soluble polysiloxane compound having an amino group with the inorganic particles, and then molding the resulting mixture.

[0009] The molded product of the present invention can have a smaller storage volume than a dispersion containing a water-soluble polysiloxane compound having an amino group and inorganic particles, thereby reducing storage and transportation costs. Furthermore, the molded product of the present invention can be redispersed in a dispersion medium at the time of use and used as an inorganic particle dispersion. Furthermore, the resulting inorganic particle dispersion containing a water-soluble polysiloxane compound having an amino group can maintain a dispersed state for a long period of time.

[0010] The present invention will be described in detail below. The molded article of the present invention contains a water-soluble polysiloxane compound having an amino group represented by the following general formula (1) (hereinafter referred to as "compound (1)") and inorganic particles.

[0011]

[0012] In the above general formula (1), R 1 is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, or a monovalent hydrocarbon group having a carboxy group represented by the following general formula (2):

[0013]

[0014] R 1 Examples of the monovalent hydrocarbon group include linear, branched, or cyclic alkyl groups, alkenyl groups, aryl groups, and aralkyl groups. Specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, 1-propenyl, and 2-propenyl (allyl) groups; aryl groups such as phenyl, tolyl, and naphthyl groups; and aralkyl groups such as phenylmethyl and 2-phenylethyl groups. Among these, R 1As the alkyl group, a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 5 carbon atoms, or an alkenyl group is preferable, and from the viewpoint of easy availability of raw materials in particular, a hydrogen atom, an unsubstituted linear or branched alkyl group having 1 to 3 carbon atoms, or an alkenyl group is more preferable, and a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is even more preferable.

[0015] Some or all of the hydrogen atoms in each of the hydrocarbon groups may be substituted with other substituents, and specific examples of these substituents include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, (iso)propoxy, and phenoxy; halogen atoms, such as fluorine, chlorine, bromine, and iodine; cyano, amino, acyl, alkoxycarbonyl groups having 1 to 5 carbon atoms, carboxy, alkylsilyl groups having 1 to 5 carbon atoms, and alkoxysilyl groups having 1 to 5 carbon atoms, and these can also be used in combination. There are no particular limitations on the substitution positions of these substituents, and there are no particular limitations on the number of substituents.

[0016] In the above general formula (2), R 3 , R 4 and R 5 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. 3 , R 4 and R 5 The monovalent hydrocarbon group of R 1 In the above general formula (2), a is 0 or 1, and preferably 1.

[0017] Specific examples of the monovalent hydrocarbon group having a carboxy group represented by the general formula (2) above include carboxyalkyl groups such as carboxymethyl, 1-carboxyethyl, 1-carboxy-1-methylethyl, 2-carboxyethyl, 2-carboxy-1-methylethyl, 2-carboxy-2-methylethyl, 2-carboxy-1-phenylethyl, and 2-carboxy-2-phenylethyl groups; and dicarboxyalkyl groups such as 1,2-dicarboxyethyl and 2,3-dicarboxypropyl groups. By introducing a monovalent hydrocarbon group having a carboxy group represented by the general formula (2), the dispersion in which the molded product is redispersed can maintain a dispersed state for a long period of time.

[0018] Among these, from the viewpoint of easy availability of raw materials, a carboxymethyl group, a 2-carboxyethyl group, a 2-carboxy-1-methylethyl group, a 2-carboxy-2-methylethyl group, and a 2,3-dicarboxypropyl group are preferred.

[0019] In the above general formula (1), R 2 R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. 2 The monovalent hydrocarbon group of R 1 Examples of the monovalent hydrocarbon groups include the same groups as those exemplified above.

[0020] Among these, R 2 As the monovalent hydrocarbon group, a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms; or an alkenyl group is preferable, and from the viewpoint of easy availability of raw materials in particular, an unsubstituted linear or branched alkyl group having 1 to 3 carbon atoms; or an alkenyl group is more preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is even more preferable.

[0021] In the above general formula (1), m is a positive number of 0 or less than 3, preferably a positive number of 0 or less than 2, and more preferably a positive number of 0 or less than 1. n is 0 or 1, and preferably 0. n+m is a positive number of 0 or less than 3, preferably a positive number of 0 or less than 2, and more preferably a positive number of 0 or less than 1.

[0022] Specific examples of the compound (1) include 3-aminopropyl silanetriol polymer, 3-aminopropyl methyl silanediol polymer, N-methyl-3-aminopropyl silanetriol polymer, N-methyl-3-aminopropyl methyl silanediol polymer, N-(2-aminoethyl)-3-aminopropyl silanetriol polymer, N-(2-aminoethyl)-3-aminopropyl methyl silanediol polymer, N-carboxymethyl-3-aminopropyl silanetriol polymer, and N-carboxymethyl-3-aminopropyl Methyl silanediol polymer, N-(1-carboxy)ethyl-3-aminopropyl silanetriol polymer, N-(1-carboxy)ethyl-3-aminopropyl methyl silanediol polymer, N-(1-carboxy-1-methyl)ethyl-3-aminopropyl silanetriol polymer, N-(1-carboxy-1-methyl)ethyl-3-aminopropyl methyl silanediol polymer, N-(2-carboxy)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy)ethyl-3-aminopropyl methyl silane Diol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropyl methyl silanediol polymer, N-(2-carboxy-2-methyl)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy-2-methyl)ethyl-3-aminopropyl methyl silanediol polymer, N-(2-carboxy-1-phenyl)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy-1-phenyl)ethyl-3-aminopropyl silanetriol polymer )ethyl-3-aminopropylmethylsilanediol polymer, N-(2-carboxy-2-phenyl)ethyl-3-aminopropylsilanetriol polymer, N-(2-carboxy-2-phenyl)ethyl-3-aminopropylmethylsilanediol polymer, N-(1,2-dicarboxy)ethyl-3-aminopropylsilanetriol polymer, N-(1,2-dicarboxy)ethyl-3-aminopropylmethylsilanediol polymer, N-(2,3-dicarboxy)propyl-3-aminopropylsilanetriol polymer, N-(2,3-dicarboxy)propyl-3-aminopropylmethylsilanediol polymer, etc.

[0023] Among these, particularly preferred are aminopropyl silanetriol polymers having no carboxy group, such as 3-aminopropyl silanetriol polymer and N-(2-aminoethyl)-3-aminopropyl silanetriol polymer; N-carboxymethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy)ethyl-3-aminopropylmethyl silanediol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropyl silanetriol polymer, and N-(2-carboxy-2-methyl)ethyl-3-aminopropyl silanetriol. aminopropyl silanetriol polymers having one carboxy group such as N-(1,2-dicarboxy)ethyl-3-aminopropyl silanetriol polymer; and aminopropyl silanetriol polymers having two carboxy groups such as N-(1,2-dicarboxy)ethyl-3-aminopropyl silanetriol polymer and N-(2,3-dicarboxy)propyl-3-aminopropyl silanetriol polymer, and more preferred are N-(2-carboxy)ethyl-3-aminopropyl silanetriol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropyl silanetriol polymer, and N-(2-carboxy-2-methyl)ethyl-3-aminopropyl silanetriol polymer.

[0024] The compound (1) contained in the molded product of the present invention can be dissolved again in a solvent such as water after molding, and therefore can be redispersed even without containing the organic titanate and organic zirconate described in Patent Document 1.

[0025] Compound (1) can be obtained, for example, by mixing a silane compound having an amino acid ester-containing group represented by the following general formula (3) (hereinafter referred to as “compound (3)”) with water to carry out a hydrolysis reaction, and then drying the mixture under normal pressure or reduced pressure as necessary.

[0026] (In the formula, R 2 and n have the same meaning as above.)

[0027] In the above general formula (3), R 6 R is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, or a monovalent hydrocarbon group having an alkoxycarbonyl group represented by the following general formula (4): 6 The monovalent hydrocarbon group of R 1 Examples of the monovalent hydrocarbon groups include the same groups as those exemplified above.

[0028] (In the formula, R 3 ~R 5 and a have the same meaning as above.)

[0029] In the above general formula (4), R 8 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, or a triorganosilyl group represented by the following general formula (5): 9 R 10 R 11 ...(5)

[0030] In the above general formula (4), R 8 The monovalent hydrocarbon group of R 1 In the above general formula (5), R 9 , R 10 and R 11 R each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. 9 , R 10 and R 11 The monovalent hydrocarbon group of R 1 Examples of the monovalent hydrocarbon groups include the same groups as those exemplified above.

[0031] Among these, R 9 , R 10 and R 11As the alkyl group, an unsubstituted linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; an alkenyl group; or an aryl group is preferable, and from the viewpoint of easy availability of raw materials in particular, an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms; or an alkenyl group is more preferable, and a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group is even more preferable.

[0032] Specific examples of the triorganosilyl group represented by the general formula (5) include trimethylsilyl, ethyldimethylsilyl, diethylmethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl, hexyldimethylsilyl, octyldimethylsilyl, decyldimethylsilyl, octadecyldimethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, triphenylsilyl, tert-butyldiphenylsilyl, etc. Among these, from the viewpoint of easy availability of raw materials, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl, and tert-butyldiphenylsilyl are more preferred, and trimethylsilyl and triisopropylsilyl are even more preferred.

[0033] Specific examples of the compound (3) include 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N-methyl-3-aminopropyldimethoxymethylsilane, N-methyl-3-aminopropyldiethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N -(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldiethoxymethylsilane, N-(methoxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(methoxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(methoxycarbonyl)methyl-3-aminopropyltriethoxysilane, N-(methoxycarbonyl)methyl-3-aminopropylmethyldiethoxysilane, N-(ethoxycarbonyl)methyl-3-aminopropyltrimethoxysilane Silane, N-(ethoxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(ethoxycarbonyl)methyl-3-aminopropyltriethoxysilane, N-(ethoxycarbonyl)methyl-3-aminopropylmethyldiethoxysilane, N-(trimethylsiloxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(trimethylsiloxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(trimethylsiloxycarbonyl)methyl-3-aminopropyltriethoxysilane, N-(trimethylsiloxycarbonyl)methyl N-(triethylsiloxycarbonyl)methyl-3-aminopropylmethyldiethoxysilane, N-(triethylsiloxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(triethylsiloxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(triisopropylsiloxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(triisopropylsiloxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(1-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane,N-(1-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(1-methoxycarbonyl-1-methyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-methoxycarbonyl-1-methyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropyltriethoxysilane , N-(2-methoxycarbonyl)ethyl-3-aminopropylmethyldiethoxysilane, N-(2-ethoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-ethoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-ethoxycarbonyl)ethyl-3-aminopropyltriethoxysilane, N-(2-ethoxycarbonyl)ethyl-3-aminopropylmethyldiethoxysilane, N-(2-trimethylsiloxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-to N-(2-trimethylsiloxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-trimethylsiloxycarbonyl)ethyl-3-aminopropyltriethoxysilane, N-(2-trimethylsiloxycarbonyl)ethyl-3-aminopropylmethyldiethoxysilane, N-(2-triethylsiloxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-triethylsiloxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-triisopropylsiloxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane aminopropyltrimethoxysilane, N-(2-triisopropylsiloxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl-2-phenyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl-2-phenyl)ethyl-3-aminopropylmethyldimethoxysilane,Examples of such silane include N-(1-methyl-2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-methyl-2-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(1-phenyl-2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-phenyl-2-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-[1,2-bis(methoxycarbonyl)]ethyl-3-aminopropyltrimethoxysilane, N-[1,2-bis(methoxycarbonyl)]ethyl-3-aminopropylmethyldimethoxysilane, N-[2,3-bis(methoxycarbonyl)]propyl-3-aminopropyltrimethoxysilane, and N-[2,3-bis(methoxycarbonyl)]propyl-3-aminopropylmethyldimethoxysilane.

[0034] Among these, particularly preferred are 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(methoxycarbonyl)methyl-3-aminopropyltrimethoxysilane, N-(methoxycarbonyl)methyl-3-aminopropylmethyldimethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl)ethyl-3-aminopropylmethyldimethoxysilane, N-(2-ethoxycarbonyl)ethyl-3-aminopropyltriethoxysilane, and N-(2-trimethylsiloxycarbonyl). N-(1-phenyl-2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-[1,2-bis(methoxycarbonyl)]ethyl-3-aminopropyltrimethoxysilane, N-(2-triisopropylsiloxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-methyl-2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-(1-phenyl-2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane, N-[1,2-bis(methoxycarbonyl)]ethyl-3-aminopropyltrimethoxysilane, and N-[2,3-bis(methoxycarbonyl)]propyl-3-aminopropyltrimethoxysilane are preferred.

[0035] Examples of methods for mixing compound (3) with water include adding compound (3) to water and adding water to compound (3). The amount of water used in the above mixing is preferably 1.5 to 10,000 mol, more preferably 1.5 to 1,000 mol, and even more preferably 1.5 to 100 mol per mol of compound (3). If too little water is used, hydrolysis will not occur sufficiently and the product will not become solid. Conversely, if too much water is used, the energy required for drying will increase, resulting in poor efficiency.

[0036] The temperature and pressure during the mixing are not particularly limited, but are preferably 0 to 120°C, more preferably 10 to 60°C, under normal pressure. The reaction time is also not particularly limited, but is preferably 1 to 40 hours, more preferably 1 to 20 hours. Furthermore, a catalyst is not particularly required, but an acid such as hydrochloric acid, sulfuric acid, or acetic acid; or a base such as sodium hydroxide, potassium hydroxide, or sodium carbonate may be added.

[0037] During mixing, a solvent other than water can also be used if necessary. Examples of the solvent that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, octane, isooctane, benzene, toluene, xylene, mesitylene, and tetralin; alcohol solvents such as methanol, ethanol, isopropanol, and tert-butanol; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

[0038] The inorganic particles used in the present invention include particles of metals such as aluminum, manganese, nickel, titanium, and zinc, and alloys thereof; inorganic oxide particles such as titanium oxide, silicon oxide, zinc oxide, zirconium oxide, aluminum oxide, iron oxide, manganese oxide, nickel oxide, and zeolite. These inorganic particles may be used alone or in a mixture of two or more. Among these, inorganic oxide particles and mixtures thereof are particularly preferred, with single inorganic oxide particles being more preferred, and aluminum oxide, titanium oxide, silicon oxide, and zirconium oxide being even more preferred.

[0039] From the viewpoints of moldability and economy, the amount of compound (1) to be blended is preferably 0.1 to 1,000 parts by mass, more preferably 1 to 500 parts by mass, even more preferably 5 to 300 parts by mass, and still more preferably 10 to 100 parts by mass, per 100 parts by mass of the inorganic particles.

[0040] Next, a method for producing the molded article will be described. The molded article of the present invention can be obtained by mixing a solution containing compound (1) with inorganic particles and then molding the resulting composition. The solution containing compound (1) may be a solution of compound (1) obtained by reaction, which can be used as is, or a solution to which another solvent has been added, or a solution obtained by drying a solution of compound (1) and then dissolving it in water or another solvent to obtain a solution.

[0041] The method for mixing the solution containing compound (1) with the inorganic particles is not particularly limited, and known devices such as mixers, dispersers, and stirrers can be used. Examples of such devices include a mixing / dispersion mill, a homodisper, a mortar mixer, a roll, a paint shaker, a homogenizer, and a planetary centrifugal mixer. Among these, from the viewpoint of uniformity after mixing, a homodisper, a homogenizer, and a planetary centrifugal mixer are particularly preferred, and a homodisper and a planetary centrifugal mixer are more preferred.

[0042] The method for molding the mixture of the liquid, clay-like, or cream-like solution containing the compound (1) and the inorganic particles obtained by the above mixing is not particularly limited, but may be injection molding, extrusion molding, compression molding, press molding, hand lay-up molding, or molding in a predetermined mold. Among these, injection molding, extrusion molding, and compression molding are particularly preferred, and compression molding is more preferred.

[0043] The obtained molded product may be used as is, or, if necessary, the solvent may be removed by drying. The method for drying the molded product is not particularly limited, but examples thereof include freeze-drying, zeodration, fluidized-bed drying, tray drying, vacuum evaporation, and spray drying. These methods may be used alone or in combination of two or more. Among these, freeze-drying, fluidized-bed drying, tray drying, and vacuum evaporation are particularly preferred from the viewpoint of maintaining moldability. The pressure and temperature used are not particularly limited, but are preferably atmospheric pressure or reduced pressure, preferably −100 to 200°C, more preferably 0 to 200°C, and even more preferably 50 to 200°C. Drying may be performed before molding, provided that it does not interfere with molding. The shape of the molded product of the present invention is not particularly limited, but examples include granules, tablets, capsules, spheres, ellipses, plates, cylinders, prisms, polyhedrons, tubes, and cubes.

[0044] Next, the inorganic particle dispersion will be described. The inorganic particle dispersion of the present invention is obtained by redispersing the molded product formed as described above in a dispersion medium. Since the surfaces of the inorganic particles in the molded product are surface-treated with compound (1), the molded product easily disintegrates in the dispersion medium, and the inorganic particles in the resulting dispersion do not settle and can maintain a dispersed state for a long period of time. As the dispersion medium, in addition to water, a solvent other than water used when mixing the solution containing compound (1) and the inorganic particles can be used, but a dispersion medium containing water is preferred. The concentration of the dispersion is not particularly limited, but is preferably 0.01 to 70% by mass, more preferably 0.1 to 50% by mass, and even more preferably 0.5 to 30% by mass.

[0045] The present invention will be specifically explained below by showing synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[0046] [1] Preparation of a solution containing a water-soluble polysiloxane compound having an amino group [Synthesis Example 1] Synthesis of an aqueous solution containing N-(2-carboxy)ethyl-3-aminopropylsilanetriol and its condensate 79.7 g of water was charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, and 53.1 g (0.2 mol) of N-(2-methoxycarbonyl)ethyl-3-aminopropyltrimethoxysilane was added. The resulting reaction solution was distilled under atmospheric pressure, and the methanol and water produced by hydrolysis were distilled off. Water was added to adjust the concentration of the resulting aqueous solution to 50% by mass, yielding 76.8 g of an aqueous solution containing N-(2-carboxy)ethyl-3-aminopropylsilanetriol and its condensate.

[0047] Synthesis Example 2 Synthesis of an aqueous solution containing N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol and its condensate A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 40.0 g of water, and 20.0 g (0.072 mol) of N-(2-methoxycarbonyl-1-methyl)ethyl-3-aminopropyltrimethoxysilane was added. The resulting reaction solution was distilled under atmospheric pressure, and the methanol and water produced by hydrolysis were distilled off. Water was added to adjust the concentration of the resulting aqueous solution to 50% by mass, yielding 26.6 g of an aqueous solution containing N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol and its condensate.

[0048] Synthesis Example 3 Synthesis of an aqueous solution containing N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol and its condensate A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 40.0 g of water, and 20.0 g (0.072 mol) of N-(2-methoxycarbonyl-2-methyl)ethyl-3-aminopropyltrimethoxysilane was added. The resulting reaction solution was distilled under atmospheric pressure, and the methanol and water produced by hydrolysis were distilled off. Water was added to adjust the concentration of the resulting aqueous solution to 50% by mass, yielding 30.6 g of an aqueous solution containing N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol and its condensate.

[0049] Synthesis Example 4 Synthesis of an aqueous solution containing N-carboxymethyl-3-aminopropylsilanetriol and its condensate 35.1 g of water and 0.2 g of acetic acid were charged into a flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 20.0 g (0.065 mol) of N-methoxycarbonylmethyl-3-aminopropyltrimethoxysilane was added. The resulting reaction solution was distilled under atmospheric pressure, and the methanol and water produced by hydrolysis were distilled off. Water was added to adjust the concentration of the resulting aqueous solution to 50% by mass, yielding 24.3 g of an aqueous solution containing N-carboxymethyl-3-aminopropylsilanetriol and its condensate.

[0050] [2] Production of a molded article containing a water-soluble polysiloxane compound having amino groups and inorganic particles [Example 1-1] 2.0 g of the aqueous solution obtained in Synthesis Example 1, 5.0 g of titanium oxide (anatase type, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.0 g of water were placed in a sample tube and kneaded for 3 minutes using a planetary centrifugal mixer (ARE-310, manufactured by Thinky Corporation) at a revolution speed of 2000 rpm and a rotation speed of 800 rpm. The kneaded composition was transferred to a mold and dried at 110°C for 1 hour to obtain a molded article.

[0051] Example 1-2 A molded product was obtained in the same manner as in Example 1-1, except that 2.0 g of the aqueous solution obtained in Synthesis Example 2 was used instead of the aqueous solution obtained in Synthesis Example 1.

[0052] Example 1-3 A molded product was obtained in the same manner as in Example 1-1, except that 2.0 g of the aqueous solution obtained in Synthesis Example 3 was used instead of the aqueous solution obtained in Synthesis Example 1.

[0053] Example 1-4 A molded product was obtained in the same manner as in Example 1-1, except that 2.0 g of the aqueous solution obtained in Synthesis Example 4 was used instead of the aqueous solution obtained in Synthesis Example 1.

[0054] Example 1-5 A molded product was obtained in the same manner as in Example 1-1, except that 3.0 g of an aqueous solution (concentration: 30% by mass) containing 3-aminopropylsilanetriol and its condensate was used instead of the aqueous solution obtained in Synthesis Example 1 and the water added in Example 1-1.

[0055] Example 1-6 A molded product was obtained in the same manner as in Example 1-1, except that 3.0 g of an aqueous solution (concentration: 30% by mass) containing 3-(2-aminoethyl)aminopropylsilanetriol and its condensate was used instead of the aqueous solution obtained in Synthesis Example 1 and the water added in Example 1-1.

[0056] [Example 1-7] Instead of the titanium oxide of Example 1-1, silicon oxide (BET specific surface area 49 m 2 A molded product was obtained in the same manner as in Example 1-1, except that 2.0 g of PEG-140 / g was used.

[0057] [Example 1-8] Instead of the titanium oxide of Example 1-1, silicon oxide (BET specific surface area 49 m 2 A molded product was obtained in the same manner as in Example 1-1, except that 2.0 g of the aqueous solution obtained in Synthesis Example 3 was used instead of the aqueous solution obtained in Synthesis Example 1.

[0058] Comparative Example 1-1 A molded product was obtained in the same manner as in Example 1-1, except that 2.0 g of water was used instead of the aqueous solution obtained in Synthesis Example 1. The molded product was brittle and easily crumbled when removed from the mold.

[0059] Comparative Example 1-2 A molded product was obtained in the same manner as in Example 1-1, except that 3.0 g of an aqueous solution (concentration: 30% by mass) prepared by hydrolyzing γ-glycidoxypropyltriethoxysilane used in Patent Document 1 was used instead of the aqueous solution obtained in Synthesis Example 1 and the water added in Example 1-1.

[0060] [Comparative Example 1-3] Instead of titanium oxide in Example 1-1, silicon oxide (BET specific surface area 49 m 2 A molded product was obtained in the same manner as in Example 1-1, except that 2.0 g of a hydroxybenzoate (1.0 g / g) was used and 2.0 g of water was used instead of the aqueous solution obtained in Synthesis Example 1.

[0061] [3] Preparation of inorganic particle dispersion [Example 2-1] When water was added to the molded product obtained in Example 1-1 so that the concentration became 10% by mass, the molded product easily disintegrated, and a uniform dispersion was obtained by shaking. The titanium oxide particles had good dispersibility, and the dispersed state was maintained for 12 hours or more after shaking.

[0062] [Example 2-2] When water was added to the formed product obtained in Example 1-2 so that the concentration became 10% by mass, the formed product easily disintegrated, and a uniform dispersion was obtained by shaking. The titanium oxide particles had good dispersibility, and the dispersed state was maintained for 12 hours or more after shaking.

[0063] [Example 2-3] When water was added to the formed product obtained in Example 1-3 so that the concentration became 10% by mass, the formed product easily disintegrated, and a uniform dispersion was obtained by shaking. The titanium oxide particles had good dispersibility, and the dispersed state was maintained for 12 hours or more after shaking.

[0064] [Example 2-4] When water was added to the formed product obtained in Example 1-4 so that the concentration became 10% by mass, the formed product easily disintegrated, and a uniform dispersion was obtained by shaking. The titanium oxide particles had good dispersibility, and the dispersed state was maintained for 12 hours or more after shaking.

[0065] [Example 2-5] When water was added to the formed product obtained in Example 1-5 so that the concentration became 10% by mass, the formed product easily disintegrated, and a uniform dispersion was obtained by shaking. The titanium oxide particles had moderate dispersibility, and the dispersed state was maintained for up to 5 hours after shaking.

[0066] [Example 2-6] When water was added to the formed product obtained in Example 1-6 so that the concentration became 10% by mass, the formed product easily disintegrated, and a uniform dispersion was obtained by shaking. The titanium oxide particles had moderate dispersibility, and the dispersed state was maintained for up to 5 hours after shaking.

[0067] [Example 2-7] When water was added to the molded product obtained in Example 1-7 so that the concentration was 1% by mass, the molded product easily disintegrated, and a uniform dispersion was obtained by shaking. The silicon oxide particles had good dispersibility, and the dispersed state was maintained for 24 hours or more after shaking.

[0068] [Example 2-8] When water was added to the molded product obtained in Example 1-8 so that the concentration was 1% by mass, the molded product easily disintegrated, and a uniform dispersion was obtained by shaking. The silicon oxide particles had good dispersibility, and the dispersed state was maintained for 24 hours or more after shaking.

[0069] [Comparative Example 2-1] When water was added to the shaped product obtained in Comparative Example 1-1 so that the concentration was 10% by mass, the shaped product easily disintegrated, and a uniform dispersion was obtained by shaking, but the titanium oxide particles settled out one hour after shaking.

[0070] Comparative Example 2-2 When water was added to the shaped product obtained in Comparative Example 1-2 so that the concentration of the shaped product became 10% by mass, the shaped product did not collapse, and remained at the bottom of the container even after shaking.

[0071] Comparative Example 2-3 When water was added to the formed product obtained in Comparative Example 1-3 so that the concentration became 1% by mass, the formed product did not collapse, and remained at the bottom of the container even after shaking.

Claims

1. A molded article containing a water-soluble polysiloxane compound having an amino group represented by the following general formula (1) and inorganic particles (however, organic titanates and organic zirconates are not included). [In formula (1), R 1 represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having a carboxy group represented by the following general formula (2): (In formula (2), R 3 , R 4 and R 5 each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and a represents 0 or 1. 2 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, m is 0 or a positive number less than 3, n is 0 or 1, and n+m is 0 or a positive number less than 3.

2. The molded article according to claim 1, wherein said inorganic particles are inorganic oxide particles.

3. The molded article according to claim 2, wherein said inorganic oxide particles are selected from the group consisting of titanium oxide, silicon oxide, zinc oxide, zirconium oxide, aluminum oxide and zeolite.

4. The molded article according to claim 1 or 2, wherein the blending amount of the water-soluble polysiloxane compound having an amino group is 0.1 to 1000 parts by mass per 100 parts by mass of the inorganic particles.

5. An inorganic particle dispersion comprising a mixture of the molded product according to claim 1 and a dispersion medium, in which the inorganic particles are dispersed.

6. A method for producing an inorganic particle dispersion, which comprises mixing the molded product according to claim 1 with a dispersion medium.

7. The method for producing a molded article according to claim 1, which comprises mixing a solution containing the water-soluble polysiloxane compound having an amino group with the inorganic particles, and then molding the resulting mixture.

Images