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

Abstract

To provide a molded product comprising a water-soluble polysiloxane compound having an amino group and inorganic particles, which makes it possible to reduce a storage volume and can be redispersed in a dispersion medium to be used in the form of a dispersion liquid.SOLUTION: The present invention provides a molded product comprising a water-soluble polysiloxane compound having an amino group and inorganic particles, the compound being represented by formula (1) (but excluding organic titanate or organic zirconate) [R1 represents H, a C1-20 monovalent hydrocarbon group, or a monovalent hydrocarbon group having a carboxy group, represented by general formula (2) below (R3, R4, and R5 each independently represent H or a C1-20 monovalent hydrocarbon group, and a represents 0 or 1), R2 represents a C1-20 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].SELECTED DRAWING: None

Description

Technical Field

[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.

Background Art

[0002] Inorganic particles are used in various applications such as pigments, ultraviolet shielding materials, heat conduction fillers, fillers, photocatalysts, ceramic raw materials, and electronic devices, and are used by being blended into cosmetics, paints, resin compositions, and the like. At that time, depending on each application, the surface of the inorganic particles is treated with another inorganic compound or organic compound to improve the performance and functions of the inorganic particles.

[0003] For example, in Patent Document 1, a solid composition is proposed for the purpose of preparing an anticorrosive coating composition obtained by dehydrating an aqueous composition based on 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 on a hydroxyl functional group. Further, it is disclosed that this solid composition becomes the same composition as the aqueous composition before dehydration by rehydration.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

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

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

[0007] As a result of intensive studies to achieve the above object, the present inventors have found that a molded article containing a water-soluble polysiloxane compound having an amino group and inorganic particles can reduce the storage volume compared to a dispersion liquid containing them, so that the costs during storage and transportation can be reduced, and it can be redispersed in a dispersion medium during use and used as an inorganic particle dispersion liquid, and the obtained inorganic particle dispersion liquid can maintain a dispersed state for a long time, and thus the present invention has been completed.

[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), [Chemical Formula] [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), [Chemical Formula] [In formula (2), R 3 , R 4 and R 5 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and a represents 0 or 1.) R 2 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, m is a positive number that is 0 or less than 3, n is 0 or 1, and n + m is a positive number that is 0 or less than 3. 2. The molded article of 1, wherein the inorganic particles are inorganic oxide particles, 3. The molded article 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 molded article 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 with respect to 100 parts by mass of the inorganic particles, 5. An inorganic particle dispersion liquid comprising a mixture of the molded article of 1 and a dispersion medium, wherein the inorganic particles are dispersed in the dispersion medium, 6. A method for producing an inorganic particle dispersion liquid, which comprises mixing the molded article of 1 and a dispersion medium, 7. A method for producing the molded article of 1, which comprises mixing a solution containing the water-soluble polysiloxane compound having an amino group and the inorganic particles, and then molding the obtained mixture is provided.

Effects of the Invention

[0009] The molded article of the present invention can reduce the storage volume as compared with a dispersion liquid containing a water-soluble polysiloxane compound having an amino group and inorganic particles, and thus can reduce the costs during storage and transportation. In addition, the molded article of the present invention can be redispersed in a dispersion medium during use and used as an inorganic particle dispersion liquid. Furthermore, the obtained inorganic particle dispersion liquid containing the water-soluble polysiloxane compound having an amino group can maintain a dispersed state for a long time.

Modes for Carrying Out the Invention

[0010] Hereinafter, the present invention will be specifically described. 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] [Chemical formula]

[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, more preferably 1 to 5 carbon atoms, or a monovalent hydrocarbon group having a carboxy group represented by the following general formula (2).

[0013] [Chemical formula]

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

[0015] Incidentally, some or all of the hydrogen atoms of each of the above hydrocarbon groups may be substituted with other substituents. Specific examples of such substituents include alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, (iso)propoxy groups, and phenoxy groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; cyano groups, amino groups, acyl groups, alkoxycarbonyl groups having 1 to 5 carbon atoms, carboxy groups, alkylsilyl groups having 1 to 5 carbon atoms, alkoxysilyl groups having 1 to 5 carbon atoms, etc., and these may be used in combination. The substitution positions of these substituents are not particularly limited, nor is the number of substituents limited.

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

[0017] Specific examples of the monovalent hydrocarbon group having a carboxy group represented by the above general formula (2) 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, 2-carboxy-2-phenylethyl groups; dicarboxyalkyl groups such as 1,2-dicarboxyethyl, 2,3-dicarboxypropyl groups, etc. By introducing a monovalent hydrocarbon group having a carboxy group represented by the general formula (2), a dispersion liquid obtained by redispersing the molded article can maintain a dispersed state over a long period of time.

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

[0019] In the general formula (1) above, R 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. R 2 As the monovalent hydrocarbon group of R 1 groups similar to the monovalent hydrocarbon groups exemplified by R

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

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

[0022] Specific examples of the above compound (1) include 3-aminopropylsilanetriol polymer, 3-aminopropylmethylsilanediol polymer, N-methyl-3-aminopropylsilanetriol polymer, N-methyl-3-aminopropylmethylsilanediol polymer, N-(2-aminoethyl)-3-aminopropylsilanetriol polymer, N-(2-aminoethyl)-3-aminopropylmethylsilanediol polymer, N-carboxymethyl-3-aminopropylsilanetriol polymer, N-carboxymethyl-3-aminopropylmethylsilanediol polymer, N-(1-carboxy)ethyl-3-aminopropylsilanetriol polymer, N-(1-carboxy)ethyl-3-aminopropylmethylsilanediol polymer, N-(1-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer, N-(1-carboxy-1-methyl)ethyl-3-aminopropylmethylsilanediol polymer, N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer, N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropylmethylsilanediol polymer, N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer, N-(2-carboxy-2-methyl)ethyl-3-aminopropylmethylsilanediol polymer, N-(2-carboxy-1-phenyl)ethyl-3-aminopropylsilanetriol polymer, N-(2-carboxy-1-phenyl)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,Examples thereof include 3-(dicarboxy)propyl-3-aminopropylmethylsilanediol polymer and the like.

[0023] Among these, in particular, aminopropylsilanetriol polymers having no carboxy group such as 3-aminopropylsilanetriol polymer and N-(2-aminoethyl)-3-aminopropylsilanetriol polymer; N-carboxymethyl-3-aminopropylsilanetriol polymer, N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer, N-(2-carboxy)ethyl-3-aminopropylmethylsilanediol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer, N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer and other aminopropylsilanetriol polymers having one carboxy group; N-(1,2-dicarboxy)ethyl-3-aminopropylsilanetriol polymer, N-(2,3-dicarboxy)propyl-3-aminopropylsilanetriol polymer and other aminopropylsilanetriol polymers having two carboxy groups are preferred, and N-(2-carboxy)ethyl-3-aminopropylsilanetriol polymer, N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol polymer, N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol polymer are more preferred.

[0024] Since the compound (1) contained in the molded article of the present invention can be dissolved again in a solvent such as water after molding, it can be redispersed without containing the organic titanates and organic zirconates described in Patent Document 1.

[0025] The 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 under normal pressure or reduced pressure as necessary.

[0026] [Chemical formula] (wherein, R 2 and n represent the same meanings as described above.)

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

[0028]

Chemical formula

[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, more preferably 1 to 5 carbon atoms, or a triorganosilyl group represented by the following general formula (5). -SiR 9 R 10 R 11 ···(5)

[0030] In the above general formula (4), examples of the monovalent hydrocarbon group of R 8 include the same groups as the monovalent hydrocarbon groups exemplified by 1 In the above general formula (5), R 9 10 11 9 10 11 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the monovalent hydrocarbon group of 9 10 11 include the same groups as those of R 11 Examples of the monovalent hydrocarbon group of1 Groups similar to the monovalent hydrocarbon group exemplified above can be mentioned.

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

[0033] Specific examples of the above 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, 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-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-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-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-aminopropylmethyldimethoxysilaneN-(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, N-[2,3-bis(methoxycarbonyl)]propyl-3-aminopropylmethyldimethoxysilane, etc. can be mentioned.

[0034] Among these, in particular, 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, N-(2-trimethylsiloxycarbonyl)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, N-[2,3-bis(methoxycarbonyl)]propyl-3-aminopropyltrimethoxysilane are preferred.

[0035] Examples of the mixing method of compound (3) and water include a method of adding compound (3) to water or a method of adding water to compound (3). The water used in the above mixing is preferably 1.5 to 10,000 moles, more preferably 1.5 to 1,000 moles, and even more preferably 1.5 to 100 moles per mole of the above compound (3). If the amount of water used is small, sufficient hydrolysis does not occur and the product does not become solid. Conversely, if the amount of water used is large, the energy required for drying increases and the efficiency deteriorates.

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

[0037] During mixing, a solvent other than water can be used if necessary. Examples of the solvents 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 metal and alloy particles such as aluminum, manganese, nickel, titanium, or zinc; and 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 combination of two or more. Among these, inorganic oxide particles and their mixtures are particularly preferred, single inorganic oxide particles are more preferred, and aluminum oxide, titanium oxide, silicon oxide, and zirconium oxide are even more preferred.

[0039] From the viewpoints of moldability and economy, the compounding amount of compound (1) 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 with respect to 100 parts by mass of the inorganic particles.

[0040] Next, the method for producing the molded article will be described. The molded article of the present invention is obtained by mixing a solution containing compound (1) with inorganic particles and then molding the resulting composition. As the solution containing compound (1), the solution of compound (1) obtained by reaction may be used as it is, a solution to which another solvent is added may be used, or after the solution of compound (1) is once dried, it may be dissolved again in water or another solvent to form a solution for use.

[0041] The method of mixing the solution containing compound (1) with the inorganic particles is not particularly limited, but devices such as known mixers, dispersers, stirrers, etc. can be used. Examples of such devices include mixing and dispersing mills, homodispersers, mortar mixers, rolls, paint shakers, homogenizers, rotating and revolving mixers, etc. Among these, from the viewpoint of uniformity after mixing, homodispersers, homogenizers, and rotating and revolving mixers are preferred, and homodispersers and rotating and revolving mixers are more preferred.

[0042] The method of molding the liquid, clay-like or cream-like mixture of the solution containing compound (1) and the inorganic particles obtained by the above mixing is not particularly limited, but in addition to injection molding, extrusion molding, compression molding, press molding, and hand lay-up molding, it may also be molded by placing it 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 article may be used as it is, or the solvent may be distilled off by drying if necessary. The drying method of the molded article is not particularly limited, and examples include freeze drying, zeodration, fluidized bed drying, tray drying, vacuum evaporation, spray drying, etc. These methods may be performed alone or in combination of two or more. Among these, from the viewpoint of maintaining moldability, freeze drying, fluidized bed drying, tray drying, and vacuum evaporation are preferred. Also, the pressure and temperature at that time are not particularly limited, but it is normal pressure or reduced pressure, preferably -100 to 200 °C, more preferably 0 to 200 °C, and even more preferably 50 to 200 °C. If there is no problem with molding, drying may be performed before molding. The shape of the molded product of the present invention is not particularly limited, and examples include granular, tablet, capsule, spherical, elliptical, plate, cylindrical, prismatic, polyhedral, tubular, cubic shapes, etc.

[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 with a dispersion medium. In the molded product, since the surface of the inorganic particles is surface-treated with the compound (1), the molded product easily disintegrates in the dispersion medium, and furthermore, the inorganic particles in the obtained dispersion do not settle and can maintain a dispersed state for a long time. As the dispersion medium, in addition to water, a solvent other than water used when mixing a solution containing the compound (1) and 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.

Examples

[0045] Hereinafter, the present invention will be specifically described 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-aminopropylsilane triol 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 to distill off methanol and water generated by hydrolysis. Water was added to adjust the concentration so that the concentration of the resulting aqueous solution became 50% by mass, whereby 76.8 g of an aqueous solution containing N-(2-carboxy)ethyl-3-aminopropylsilanetriol and its condensate was obtained.

[0047] [Synthesis Example 2] Synthesis of aqueous solution containing N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol and its condensate 40.0 g of water was charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 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 to distill off methanol and water generated by hydrolysis. Water was added to adjust the concentration so that the concentration of the resulting aqueous solution became 50% by mass, whereby 26.6 g of an aqueous solution containing N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol and its condensate was obtained.

[0048] [Synthesis Example 3] Synthesis of aqueous solution containing N-(2-carboxy-2-methyl)ethyl-3-aminopropylsilanetriol and its condensate 40.0 g of water was charged into a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 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 to distill off methanol and water generated by hydrolysis. Water was added to adjust the concentration so that the concentration of the resulting aqueous solution became 50% by mass, whereby 30.6 g of an aqueous solution containing N-(2-carboxy-1-methyl)ethyl-3-aminopropylsilanetriol and its condensate was obtained.

[0049] [Synthesis Example 4] Synthesis of Aqueous Solution Containing N-Carboxymethyl-3-aminopropylsilanetriol and Its Condensate Into a flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 35.1 g of water and 0.2 g of acetic acid were charged, and 20.0 g (0.065 mol) of N-methoxycarbonylmethyl-3-aminopropyltrimethoxysilane was added. The obtained reaction solution was distilled under normal pressure to distill off methanol and water generated by hydrolysis. Water was added to adjust the concentration so that the concentration of the obtained aqueous solution became 50% by mass, and 24.3 g of an aqueous solution containing N-carboxymethyl-3-aminopropylsilanetriol and its condensate was obtained.

[0050] [2] Production of Molded Article Containing Water-Soluble Polysiloxane Compound Having Amino Group 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 Corporation), and 1.0 g of water were put into a sample tube, and using a rotation-revolution mixer (ARE-310 manufactured by Shinki Co., Ltd.), the revolution speed was set to 2000 rpm and the rotation speed was set to 800 rpm, and kneaded for 3 minutes. 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 article 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 article 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 article 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] An aqueous solution obtained in Synthesis Example 1 and 3.0 g of an aqueous solution (concentration: 30% by mass) containing 3-aminopropylsilanetriol and its condensate were used instead of the water added in Example 1-1, and a molded article was obtained in the same manner as in Example 1-1.

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

[0056] [Example 1-7] Instead of the titanium oxide in Example 1-1, 2.0 g of silicon oxide (BET specific surface area: 49 m 2 / g) was used, and a molded article was obtained in the same manner as in Example 1-1.

[0057] [Example 1-8] Instead of the titanium oxide in Example 1-1, 2.0 g of silicon oxide (BET specific surface area: 49 m 2 / g) was used, and instead of the aqueous solution obtained in Synthesis Example 1, 2.0 g of the aqueous solution obtained in Synthesis Example 3 was used, and a molded article was obtained in the same manner as in Example 1-1.

[0058] [Comparative Example 1-1] Instead of the aqueous solution obtained in Synthesis Example 1, 2.0 g of water was used, and a molded article was obtained in the same manner as in Example 1-1. The molded article was brittle and easily crumbled when taken out of the mold.

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

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

[0061] [3] Production 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 dispersibility of the titanium oxide particles was good, and the dispersed state was maintained for 12 hours or more after shaking.

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

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

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

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

[0066] [Example 2-6] When water was added to the molded product obtained in Example 1-6 so that the concentration became 10% by mass, the molded product easily disintegrated, and a uniform dispersion was obtained by shaking. The dispersibility of the titanium oxide particles was medium, 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 became 1% by mass, the molded product easily disintegrated, and a uniform dispersion was obtained by shaking. The dispersibility of the silicon oxide particles was good, 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 became 1% by mass, the molded product easily disintegrated, and a uniform dispersion was obtained by shaking. The dispersibility of the silicon oxide particles was good, and the dispersed state was maintained for 24 hours or more after shaking.

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

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

[0071] [Comparative Example 2-3] When water was added to the molded product obtained in Comparative Example 1-3 so that the concentration became 1% by mass, the molded product did not disintegrate, and the molded product 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, an organic titanate and an organic zirconate are not included). 【Chemical 1】 [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). 【Chemical 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.) R 2 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, m is a positive number of 0 or less than 3, n is 0 or 1, and n + m is a positive number of 0 or less than 3.

2. The molded article according to Claim 1, wherein the inorganic particles are inorganic oxide particles.

3. The molded article according to Claim 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 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 with respect to 100 parts by mass of the inorganic particles.

5. An inorganic particle dispersion liquid comprising a mixture of the molded article according to Claim 1 and a dispersion medium, wherein the inorganic particles are dispersed in the dispersion medium.

6. A method for producing an inorganic particle dispersion liquid, comprising mixing the molded article according to Claim 1 and a dispersion medium.

7. A method for producing the molded article according to Claim 1, comprising mixing a solution containing the water-soluble polysiloxane compound having an amino group and the inorganic particles, and then molding the obtained mixture.

Images