JP2022148630A - Composite fine particle and production method of the same - Google Patents

Abstract

To provide composite fine particles which have excellent separation property of dye or the like by producing the composite fine particles consisting of inorganic fine particles coated with a polymer compound through one step without requiring any pretreatment step.SOLUTION: Composite fine particles comprise inorganic fine particles which are directly coated with a polymer compound having at least one selected from a group consisting of an amide bond, an imide bond and a nitrogen-containing heterocyclic aromatic ring in the main chain. A dye and/or metal ion adsorbent contain the composite fine particles in which the inorganic fine particles are coated with the polymer compound having at least one selected from the group consisting of the amide bond, the imide bond and the nitrogen-containing heterocyclic aromatic ring in the main chain.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to composite microparticles and a method for producing the same.

Composite materials that combine polymers and inorganic fine particles are widely used as highly functional materials that combine the various functions and properties of both. However, in compositing dissimilar materials with significantly different interfacial properties, control of the affinity and adhesiveness between interfaces has always been one of the important technical issues to be solved. has been considered. Composite materials come in various forms such as plate-like, powder-like, and fibrous-like forms, and powders (fine particles) are in high demand because they are excellent in moldability.

Typical composite techniques include (1) a method of treating inorganic fine particles with a silane coupling agent and then reacting them with a polymer (see, for example, Patent Documents 1 and 2); (monomers and low-molecular-weight compounds) are vapor-deposited or chemically modified, followed by polymer polymerization; (3) immersing inorganic fine particles in a pre-prepared polymer solution; A mechanical method of colliding high-molecular fine particles at high speed in the gas phase can be used.

JP-A-2007-254523 JP 2004-010664 A

However, the above methods (1) to (3) require more than two steps (pretreatment and compounding), requiring a lot of labor, time and cost.

In addition, since the silane coupling agent is used in the above method (1), another compound (third component) is mixed with the constituent material of the target composite fine particles, which may affect the characteristics. have a nature.

In addition, the above method (2) inevitably involves complicated processes such as reaction in vapor deposition or chemical modification, control of polymer polymerization reaction using reaction points in reactive compounds, and the like.

Moreover, in the method (3) above, some types of polymers do not dissolve in solvents, or the types of solvents are very limited. For example, most of the polyamide compounds polymerized by the method described in JP-A-2006-257345 are insoluble in most solvents.

On the other hand, since the method (4) is a mechanical composite, it does not require pretreatment in many cases, but it is difficult to control the surface morphology of the prepared composite fine particles and the amount of coating. However, since these controls are indispensable for imparting functionality (separability, etc.) and quality control, they are inevitably complicated steps.

As described above, the present invention can produce composite fine particles in which inorganic fine particles are coated with a polymer compound in one step without requiring a pretreatment step, and provides composite fine particles having excellent separation ability for dyes and the like. With the goal.

As a result of intensive research to solve the above problems, the present inventors have found that by polymerizing a plurality of monomers in a solution containing inorganic fine particles, inorganic fine particles can be obtained in one step without the need for a pretreatment step. It has been found that composite microparticles coated with a polymer compound can be produced, and composite microparticles excellent in the ability to separate dyes and the like can be provided. Based on such findings, the inventors have further studied and completed the present invention. That is, the present invention includes the following configurations.

Section 1. A composite fine particle, wherein an inorganic fine particle is directly coated with a polymer compound having at least one selected from the group consisting of an amide bond, an imide bond and a nitrogen-containing heteroaromatic ring on the main chain.

Section 2. Item 2. Item 1, wherein the polymer compound is at least one selected from the group consisting of a polyamide compound, a polyamideimide compound, a polyesteramide compound, a polyamideurethane compound, a polybenzoxazole compound, a polybenzimidazole compound and a polyimide compound. Composite microparticles.

Item 3. Item 3. The composite fine particle according to Item 1 or 2, wherein the inorganic fine particle does not have an organic functional group derived from a silane coupling agent on its surface.

Section 4. Item 4. The composite microparticles according to any one of items 1 to 3, which are dyes and/or metal ion adsorbents.

Item 5. Item 5. The composite fine particles according to any one of items 1 to 4, wherein the inorganic fine particles have an average particle size of 5 nm to 1 cm.

Item 6. Dye and/or metal ion adsorption, wherein the inorganic fine particles contain composite fine particles coated with a polymer compound having at least one selected from the group consisting of an amide bond, an imide bond and a nitrogen-containing heteroaromatic ring in the main chain. agent.

Item 7. Item 7. The dye and/or metal ion adsorbent according to Item 6, wherein the inorganic fine particles are directly coated with the polymer compound.

Item 8. Item 8. The dye and/or metal ion adsorbent according to Item 6 or 7, wherein the inorganic fine particles do not have an organic functional group derived from a silane coupling agent on the surface.

Item 9. Item 9. The dye and/or metal ion adsorbent according to any one of Items 6 to 8, wherein the inorganic fine particles have an average particle size of 5 nm to 1 cm.

Item 10. A method for producing the composite fine particles according to any one of Items 1 to 5 or the dye and/or metal ion adsorbent according to any one of Items 6 to 9,
A manufacturing method comprising the step of mixing a first solution obtained by dissolving an acid chloride compound in an organic solvent and a second solution obtained by dissolving a primary amine compound in an organic solvent in the presence of the inorganic fine particles. .

Item 11. Item 11. The production method according to Item 10, wherein the mixing step is further performed in the presence of a secondary amine compound and/or a tertiary amine compound.

Item 12. The mixing step is a step of adding the inorganic fine particles and the secondary amine and/or the tertiary amine compound to the second solution, then adding and mixing the first solution. 11. The manufacturing method according to 11.

Item 13. Item 13. The production method according to Item 11 or 12, wherein the secondary amine compound and/or the tertiary amine compound are soluble in both the first solution and the second solution.

According to the present invention, composite fine particles in which inorganic fine particles are coated with a polymer compound can be produced in one step without requiring a pretreatment step.

1 is an SEM image of composite fine particles obtained in Example 1. FIG. It is an SEM image of silica fine particles used as a raw material. 4 is an SEM image of composite fine particles obtained in Example 2. FIG. 4 is an SEM image of composite fine particles obtained in Example 3. FIG. 4 is an SEM image of composite fine particles obtained in Example 4. FIG. 4 is an SEM image of composite fine particles obtained in Example 5. FIG. It is an SEM image of alumina fine particles used as a raw material.

As used herein, "contain" is a concept that includes both "comprise," "consist essentially of," and "consist of."

Further, in this specification, when a numerical range is indicated by "A to B", it means from A to B.

1. Composite fine particles (first aspect)
In the composite microparticles of the present invention, inorganic microparticles are directly coated with a polymer compound having at least one selected from the group consisting of amide bonds, imide bonds and nitrogen-containing heteroaromatic rings on the main chain.

In other words, in the fine composite particles of the present invention, it is preferable that the inorganic fine particles do not have organic functional groups resulting from pretreatment with a silane coupling agent or the like on the surface. Therefore, the physical properties of the fine composite particles are not affected by the introduction of the silane coupling agent, and quality control can be easily performed.

(1-1) Inorganic Fine Particles The material of the inorganic fine particles used in the present invention is not limited, and can be widely selected according to the use of the final product. Examples include silica, alumina, glass, magnesia, zirconia, titania, ceria, zeolite, calcium oxide, and hydroxyapatite. These inorganic fine particles can be used alone or in combination of two or more.

Among them, silica, alumina, zeolite, and the like are preferable from the viewpoint of easy production of composite fine particles in which inorganic fine particles are coated with a polymer compound in one step by the production method described below.

As described above, the inorganic fine particles used in the present invention preferably do not have organic functional groups derived from silane coupling agents on their surfaces.

Such an organic functional group is usually imparted when pretreated with a silane coupling agent. preferable.

Silane coupling agents include, for example, vinyl-based, epoxy-based, styryl-based, methacryloxy-based, acryloxy-based, amino-based, ureido-based, chloropropyl-based, mercapto-based, sulfide-based, isocyanate-based, and the like. propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2 -aminoethyl)-3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane and the like.

Therefore, the organic functional groups derived from the silane coupling agent that the inorganic fine particles do not have on the surface include, for example, a vinyl group, an epoxy group, a styrene group, a methacryloyl group, an acryloxy group, an amino group, a ureido group, and a chloropropyl group. , a mercapto group, a sulfide group, an isocyanate group, and the like.

The shape of the inorganic fine particles is not limited, and may be spherical, plate-like, film-like, needle-like, fibrous, flaky, scale-like, etc., and can be appropriately determined according to the use of the final product. For example, when spherical, the average particle size of the inorganic fine particles is preferably about 5 nm to 1 cm, more preferably about 10 nm to 1 mm. In addition, the average particle size of the inorganic fine particles is measured by a particle size distribution analyzer.

(1-2) Polymer compound The polymer compound has at least one selected from the group consisting of an amide bond, an imide bond and a nitrogen-containing heteroaromatic ring (imidazole ring, oxazole ring, thiazole ring, etc.) in the main chain. There is no particular limitation as long as it is present, and examples thereof include polyamide compounds, polyamideimide compounds, polyesteramide compounds, polyamideurethane compounds, polybenzoxazole compounds, polybenzimidazole compounds, and polyimide compounds.

Known or commercially available products can be used for these polymer compounds.

When the production method of the present invention described later is used, the acid chloride described later and the primary amine compound are polymerized to obtain a polyamide compound, a polyesteramide compound, a polyamide urethane compound, etc. on the inorganic fine particles. many. Thus, after obtaining a polyamide compound, imidation can be performed by a conventional method to obtain a polyamideimide compound, a polyimide compound, and the like. Further, after obtaining a polyamide compound, a polybenzoxazole compound, a polybenzimidazole compound, or the like can be obtained by subjecting the polyamide compound to a ring closure reaction by a conventional method. Either case constitutes the present invention.

(1-3) Composite Fine Particles In the composite fine particles of the present invention, the inorganic fine particles described above are directly coated with the polymer compound described above. That is, the inorganic fine particles are coated with the polymer compound without interposing other layers such as organic functional groups derived from the silane coupling agent.

Therefore, the physical properties of the fine composite particles are not affected by the introduction of the silane coupling agent, and quality control can be easily performed.

In the composite fine particles of the present invention, the coating amount of the polymer compound is not particularly limited. From the viewpoint of easily adsorbing metal ions, the coating amount of the polymer compound measured by heat treatment at 1000 ° C. (in air) is 0.1 to 80% by mass, with the total amount of the composite fine particles of the present invention being 100% by mass. is preferred, and 0.1 to 70% by mass is more preferred.

The shape of the composite fine particles of the present invention is not limited, and may be spherical, plate-like, film-like, needle-like, fibrous, flaky, scale-like, etc., and can be appropriately determined according to the use of the final product. For example, when spherical, the average particle size of the fine composite particles of the present invention is preferably about 5 nm to 1 cm, more preferably about 10 nm to 1 mm. The average particle size of the fine composite particles of the present invention is measured using a particle size distribution analyzer.

Such composite fine particles of the present invention can adsorb dyes and metal ions when placed in, for example, a dye solution or a solution containing metal ions, and can be used as a dye and/or metal ion adsorbent. It is possible to

In this case, the target dye is not particularly limited, and examples thereof include rhodamine B, rhodamine 6G, acid red 87, acid red 289, acid red 92, sulforhodamine B, sunset yellow FCF, amaranth, fast green FCF, Examples include indigo carmine, methylene blue, brilliant cresyl blue, neutral red, reactive blue 4, congo red, crystal violet, methyl violet B, brilliant green, etc. Metal ions of interest are not particularly limited. Cr(VI), Fe(II), Co(II), Ni(II), Cu(II), As(V), Se(IV), Sr(II), Pd(II), Ag(I), Cd(II), La(III), Pt(IV), Au(III), Pb(II) and the like. The composite microparticles of the present invention can adsorb one or more of these.

2. Dye and/or metal ion adsorbent (second aspect)
In the dye and/or metal ion adsorbent of the present invention, inorganic fine particles are coated with a polymer compound having at least one selected from the group consisting of an amide bond, an imide bond and a nitrogen-containing heteroaromatic ring on the main chain. Contains composite microparticles.

(2-1) Inorganic Fine Particles The material of the inorganic fine particles used in the present invention is not limited, and can be widely selected according to the application of the final product. Examples include silica, alumina, glass, magnesia, zirconia, titania, ceria, zeolite, calcium oxide, and hydroxyapatite. These inorganic fine particles can be used alone or in combination of two or more.

Among them, silica, alumina, zeolite, and the like are preferable from the viewpoint of easy production of composite fine particles in which inorganic fine particles are coated with a polymer compound in one step by the production method described below.

The inorganic fine particles used in the present invention do not exclude having an organic functional group derived from a silane coupling agent on the surface. From the viewpoint of easy quality control, it is preferred that the surface does not have an organic functional group derived from a silane coupling agent.

Such an organic functional group is usually imparted when pretreated with a silane coupling agent. preferable.

Silane coupling agents include, for example, vinyl-based, epoxy-based, styryl-based, methacryloxy-based, acryloxy-based, amino-based, ureido-based, chloropropyl-based, mercapto-based, sulfide-based, isocyanate-based, and the like. propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2 -aminoethyl)-3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane and the like.

For this reason, the organic functional group derived from the silane coupling agent that the inorganic fine particles preferably do not have on the surface includes, for example, a vinyl group, an epoxy group, a styrene group, a methacryloyl group, an acryloxy group, an amino group, a ureido group, chloropropyl group, mercapto group, sulfide group, isocyanate group and the like.

The shape of the inorganic fine particles is not limited, and may be spherical, plate-like, film-like, needle-like, fibrous, flaky, scale-like, etc., and can be appropriately determined according to the use of the final product. For example, when spherical, the average particle size of the inorganic fine particles is preferably about 5 nm to 1 cm, more preferably about 10 nm to 1 mm. In addition, the average particle size of the inorganic fine particles is measured by a particle size distribution analyzer.

(2-2) Polymer compound The polymer compound has at least one selected from the group consisting of an amide bond, an imide bond and a nitrogen-containing heteroaromatic ring (imidazole ring, oxazole ring, thiazole ring, etc.) in the main chain. There is no particular limitation as long as it is present, and examples thereof include polyamide compounds, polyamideimide compounds, polyesteramide compounds, polyamideurethane compounds, polybenzoxazole compounds, polybenzimidazole compounds, and polyimide compounds.

Known or commercially available products can be used for these polymer compounds.

When the production method of the present invention described later is used, the acid chloride described later and the primary amine compound are polymerized to obtain a polyamide compound, a polyesteramide compound, a polyamide urethane compound, etc. on the inorganic fine particles. many. Thus, after obtaining a polyamide compound, imidation can be performed by a conventional method to obtain a polyamideimide compound, a polyimide compound, and the like. Further, after obtaining a polyamide compound, a polybenzoxazole compound, a polybenzimidazole compound, or the like can be obtained by subjecting the polyamide compound to a ring closure reaction by a conventional method. Either case constitutes the present invention.

(2-3) Dye and/or metal ion adsorbent In the dye and/or metal ion adsorbent of the present invention, the coating amount of the polymer compound is not particularly limited, but the pretreatment step is not required. , From the viewpoint that inorganic fine particles are easily coated with a polymer compound in one step and that dyes and metal ions are easily adsorbed, the coating amount of the polymer compound measured by heat treatment at 1000 ° C. (in air) is The total amount of the dye and/or metal ion adsorbent of the invention is preferably 0.1 to 80% by mass, more preferably 0.1 to 70% by mass, based on 100% by mass.

The shape of the dye and/or metal ion adsorbent of the present invention is not limited, and may be spherical, plate-like, film-like, needle-like, fibrous, flake-like, scale-like, etc., and is appropriately determined according to the application of the final product. can do. For example, when spherical, the average particle size of the dye and/or metal ion adsorbent of the present invention is preferably about 5 nm to 1 cm, more preferably about 10 nm to 1 mm. The average particle size of the dye and/or metal ion adsorbent of the present invention is measured by a particle size distribution analyzer.

Such a dye and/or metal ion adsorbent of the present invention can adsorb dyes and metal ions, for example, when placed in a dye solution or a solution containing metal ions.

In this case, the target dye is not particularly limited, and examples thereof include rhodamine B, rhodamine 6G, acid red 87, acid red 289, acid red 92, sulforhodamine B, sunset yellow FCF, amaranth, fast green FCF, Examples include indigo carmine, methylene blue, brilliant cresyl blue, neutral red, reactive blue 4, congo red, crystal violet, methyl violet B, brilliant green, etc. Metal ions of interest are not particularly limited. Cr(VI), Fe(II), Co(II), Ni(II), Cu(II), As(V), Se(IV), Sr(II), Pd(II), Ag(I), Cd(II), La(III), Pt(IV), Au(III), Pb(II) and the like. The dye and/or metal ion adsorbent of the present invention can adsorb one or more of these.

3. Production method The production method of the present invention is a method of producing the composite fine particles of the present invention or the dye and/or metal ion adsorbent of the present invention, comprising:
A step of mixing a first solution obtained by dissolving an acid chloride compound in an organic solvent and a second solution obtained by dissolving a primary amine compound in an organic solvent in the presence of inorganic fine particles. In addition, it is easy to coat the inorganic fine particles with the polymer compound, and small pieces of the polymer compound that are not combined (small pieces of the polymer compound that are not coated on the inorganic fine particles, waste, etc.) are less likely to be generated, and only composite fine particles are produced. From the viewpoint of easily obtaining It is preferably done in the presence.

That is, in the present invention, the acid chloride compound and the primary amine compound are each prepared as separate solutions.

(3-1) First Solution The acid chloride compound used in the first solution is not particularly limited, and for example, the same compounds used in conventional polymer compound synthesis can be used.

Examples of the acid chloride compound include acid dichloride compounds, acid trichloride compounds, acid tetrachloride compounds, and the like. In general, acid dichloride compounds and acid trichloride compounds can be preferably used. Examples of acid chloride compounds include fats such as oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, fumaric acid dichloride, glutaric acid dichloride, adipic acid dichloride, muconic acid dichloride, sebacic acid dichloride, nonanoic acid dichloride, and undecanoic acid dichloride. Group acid dichloride compounds; 1,2-cyclopropanedicarboxylic acid dichloride, 1,3-cyclobutanedicarboxylic acid dichloride, 1,3-cyclopentanedicarboxylic acid dichloride, 1,3-cyclohexanedicarboxylic acid dichloride, 1,4-cyclohexanedicarboxylic acid Alicyclic acid dichloride compounds such as dichloride; Dicarboxylic acid dichloride, 1,4-anthraquinonedicarboxylic acid dichloride, 2,5-biphenyldicarboxylic acid dichloride, 1,5-biphenylenedicarboxylic acid dichloride, 4,4'-biphenyldicarbonyl chloride, 4,4'-methylene dibenzoic acid dichloride, 4,4'-isopropylidene dibenzoic acid dichloride, 4,4'-bibenzyldicarboxylic acid dichloride, 4,4'-stilbenedicarboxylic acid dichloride, 4,4'-trandicarboxylic acid dichloride, 4,4'- carbonyl dibenzoic acid dichloride, 4,4'-oxybibenzoic acid dichloride, 4,4'-sulfonyl dibenzoic acid dichloride, 4,4'-dithiodibenzoic acid dichloride, p-phenylene diacetic acid dichloride, 3,3' - aromatic acid dichloride compounds such as p-phenylenedipropionic acid dichloride; acid trichloride compounds such as 1,3,5-benzenetricarbonyltrichloride; These acid chloride compounds can be used alone or in combination of two or more.

An acid chloride compound having a functional group can also be used as the acid chloride compound.

The functional group is not particularly limited as long as it can impart a desired function on the surface of the obtained fine particles. For example, hydroxyl group (-OH), carboxyl group (-COOH), amino group (-NH ₂ ), alkenyl group (group having -CH=CH-), alkynyl group (group having -C≡C-), vinyl ether group (group having -CH=CH-O-), amide group (-CONH ₂ ), nitrile group (-C≡N), isocyanate group (-N=C=O), nitro group (-NO ₂ ), In addition to functional groups such as a sulfone group (--SO ₃ H), a thiol group (--SH), and a crown ether group, halogenated alkyl groups such as --CF ₃ , --CCl ₃ , and --CBr ₃ may be mentioned. can. The acid chloride compound used as a raw material has a group —COCl. subsumed in

These functional groups may be contained singly or in combination of two or more. When one acid chloride compound has two or more functional groups, these functional groups may be the same or different from each other. In the present invention, these functional groups can be appropriately imparted to the fine particle surface depending on the desired physical properties of the composite fine particles to be obtained, the application of the final product, and the like.

When an acid chloride compound having a functional group is used, the acid chloride compound described above and having the above functional group can be used. Examples include 4,4′-(2,2-hexafluoroisopropylidene)diphthalic acid dichloride, 4-nitrophthalic acid dichloride, 3-nitrophthalic acid dichloride, 4-methylphthalic acid dichloride, tetrachlorophthalic acid dichloride and the like. . Acid dichlorides, acid trichlorides, and the like of acid chloride compounds that can be used in the polyamideimide described later and that have the functional groups described above can also be used as the acid chloride compound (raw material) of the present invention. In addition, 1,3,5-benzenetricarbonyltrichloride and the like, which can be used for synthesizing polyesteramide compounds, can also be used as the acid chloride compound (raw material) of the present invention.

In the present invention, an acid chloride compound having a functional group and an acid chloride compound having no functional group can be used in combination. This makes it possible to arbitrarily control the properties of the obtained composite microparticles. In this case, the ratio of the two can be appropriately set according to the type of functional group, the desired amount of functional group to be imparted, and the like.

Also, the acid chloride compound can be appropriately selected according to the desired properties of the composite fine particles to be obtained. For example, as an acid chloride compound, an aromatic acid dichloride (especially at least one of terephthalic acid dichloride, 4,4'-biphenyldicarbonyl chloride and isophthalic acid dichloride) or an aromatic acid trichloride (especially 1,3,5-benzenetrichloride) Carbonyl trichloride) makes it easy to uniformly coat the inorganic fine particles with the polyamide compound.

In the present invention, the polymer compound also includes a polyamideimide compound. Therefore, as the acid chloride compound, those used in conventional polyamideimide synthesis can be used. For example, trimellitic acid chloride, pyromellitic acid chloride, oxydiphthalic acid chloride, biphenyl-3,4,3′,4′-tetracarboxylic acid chloride, benzophenone-3,4,3′,4′-tetracarboxylic acid chloride, diethylpyromellitate diacyl chloride, diphenylsulfone-3,4,3′,4′-tetracarboxylic acid chloride, 4,4′-(2,2-hexafluoroisopropylidene)phthaloyl chloride, m(p)-phenyl Acid chlorides such as -3,4,3′,4′-tetracarboxylic acid chloride, cyclobutane-1,2,3,4-tetracarboxylic acid chloride, 1-carboxymethyl-2,3-5cyclopentanetricarboxylic acid chloride compounds can be used. These acid chloride compounds may be acid dichlorides, acid trichlorides or acid tetrachlorides.

Further, when precipitating a polyamideimide compound, in addition to the acid chloride compound, as anhydrides of carboxylic acids, trimellitic dianhydride, pyromellitic dianhydride, oxydiphthalic dianhydride, biphenyl-3, 4,3′,4′-tetracarboxylic dianhydride, benzophenone-3,4,3′,4′-tetracarboxylic dianhydride, diethylpyromellitate diacylic dianhydride, diphenylsulfone-3,4 ,3′,4′-tetracarboxylic dianhydride, 4,4′-(2,2-hexafluoroisopropylidene)diphthalic dianhydride, m(p)-phenyl-3,4,3′,4 '-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3-5cyclopentanetricarboxylic dianhydride, and the like can be used.

The organic solvent used in the first solution is not particularly limited as long as it substantially dissolves the acid chloride compound and does not dissolve the resulting polymer compound and fine composite particles. Secondary amine compounds or tertiary compounds such as, for example, acetone, dioxane, ethyl acetate, methyl acetate, dimethylacetamide, dimethylformamide, acetophenone, acetylacetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, toluene, xylene, tetrahydrofuran, etc. Solvents in which the amine compound is soluble can be mentioned, and solvents containing at least one of these can be used. In the first solution, among these, a solvent containing at least one of acetone, dioxane, ethyl acetate, dimethylacetamide and dimethylformamide is preferred. Depending on the type of acid chloride compound used, it may not dissolve immediately in a solvent such as acetone. Alternatively, it can be dissolved in acetone or the like after being dissolved in a secondary amine compound or a tertiary amine compound in advance.

The concentration of the acid chloride compound in the first solution may be appropriately set according to the type of acid chloride compound used, the concentration of the second solution, etc., but is usually preferably about 0.001 to 0.2 mol/liter. About 0.0025 to 0.1 mol/liter is more preferable. When the concentration of the acid chloride compound in the first solution is within this range, small pieces of the uncomplexed polymer compound (small pieces of the polymer compound not coated on the inorganic fine particles, scraps, etc.) are less likely to be generated, Only composite fine particles are easily obtained.

(3-2) Second Solution The primary amine compound used in the second solution is not particularly limited, and examples thereof include those used in the synthesis of known polymer compounds. For example, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 1,4' -bis(4-aminophenoxy)benzene, 1,3'-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, o-phenylenediamine, m-phenylenediamine, p-phenylene Diamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,4-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-methylene-bis(2-chloroaniline) , 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminodiphenyl sulfide, 2,6′-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4 -diaminoanthraquinone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminobibenzyl, R(+)-2,2'-diamino-1, 1'-binaphthalene, S(+)-2,2'-diamino-1,1'-binaphthalene, 1,3-bis(4-aminophenoxy)alkane, 1,4-bis(4-aminophenoxy)alkane, 1,5-bis(4-aminophenoxy)alkanes such as 1,n-bis(4-aminophenoxy)alkanes (n is 3 to 10), 1,2-bis[2-(4-aminophenoxy)ethoxy ] Aromatic diamine compounds such as ethane and 9,9-bis(4-aminophenyl)fluorene; 1,2-diaminomethane, 1,4-diaminobutane, tetramethylenediamine, 1,5-diaminopentane, 1,6 -diaminohexane, 1,8-diaminooctane, 1,10-diaminododecane, 1,11-diaminoundecane and other aliphatic diamine compounds; 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis(4-amino In addition to alicyclic diamine compounds such as cyclohexyl)methane and 4,4'-diaminodicyclohexylmethane, 3,4-diaminopyridine, 1,4-diamino-2-butanone and the like can also be used. These can be used alone or in combination of two or more.

In addition to the diamine compound, other amine compounds (monoamine compounds, polyvalent amine compounds, etc.) can also be used in the present invention. These can change the properties of the resulting composite fine particles of the present invention.

A primary amine compound having a functional group can also be used as the primary amine compound.

The functional group is not particularly limited as long as it can impart a desired function on the surface of the obtained fine particles. For example, hydroxyl group (-OH), carboxyl group (-COOH), amino group (-NH ₂ ), alkenyl group (group having -CH=CH-), alkynyl group (group having -C≡C-), vinyl ether group (group having -CH=CH-O-), amide group (-CONH ₂ ), nitrile group (-C≡N), isocyanate group (-N=C=O), nitro group (-NO ₂ ), In addition to functional groups such as a sulfone group (--SO ₃ H), a thiol group (--SH), and a crown ether group, halogenated alkyl groups such as --CF ₃ , --CCl ₃ , and --CBr ₃ may be mentioned. can. The primary amine compound used as a raw material has a group —NH ₂ . Included in the functional groups.

These functional groups may be contained singly or in combination of two or more. When one primary amine compound has two or more functional groups, these functional groups may be the same or different from each other. In the present invention, these functional groups can be appropriately imparted to the fine particle surface depending on the desired physical properties of the composite fine particles to be obtained, the application of the final product, and the like.

When a primary amine compound having a functional group is used, the primary amine compound having the functional group described above can be used. For example, 1,3-diamino-2-propyl alcohol, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2 '-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 4,4'-diaminooctafluorobiphenyl, 2,5-diaminobenzotrifluoride, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,3'-diaminobenzidine, 2,4,6-triaminopyrimidine, 4,4'-diamino-3,3'-dihydroxybiphenyl, 2,4-diamino-6-hydroxy Pyrimidine, 4,4'-diamino-3,3'-dimethyldiphenylmethane and the like can be used. In particular, when 3,5-diaminobenzoic acid, 4,4′-diamino-3,3′-dihydroxybiphenyl or the like is used, it is easy to uniformly coat the inorganic fine particles with a polymer compound such as a polyamide compound, and dyes and metal ions are easily coated. It is preferable because the separation performance of the like is improved.

In the present invention, a primary amine compound having a functional group and a primary amine compound having no functional group can be used in combination. This makes it possible to change the properties and the like of the obtained composite fine particles. In this case, the ratio of the two can be appropriately set according to the type of functional group, the desired amount of functional group to be imparted, and the like.

The organic solvent used in the second solution is not particularly limited as long as it substantially dissolves the primary amine compound and does not dissolve the resulting polymer compound and fine composite particles. For example, primary amine compounds such as acetone, dioxane, ethyl acetate, methyl acetate, dimethylacetamide, dimethylformamide, acetophenone, acetylacetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, toluene, xylene, tetrahydrofuran are soluble. Solvents include, and solvents containing at least one of these can be used. In the second solution, among these, a solvent containing at least one of acetone, dioxane, ethyl acetate, dimethylacetamide and dimethylformamide is preferred. When a mixed solvent is used in which a plurality of these solvents are used together, the polarity of the reaction solvent can be optimized, and the inorganic fine particles are easily coated with a polymer compound to form a composite. Depending on the type of primary amine compound used, it may not dissolve immediately in a solvent such as acetone. It may be dissolved in acetone or the like after being dissolved in the primary amine compound.

The solvent for the second solution may be the same as the solvent for the first solution, or may be different as long as they are compatible with each other.

The concentration of the primary amine compound in the second solution may be appropriately set according to the type of diamine compound used, the concentration of the first solution, etc., but is usually preferably about 0.001 to 0.2 mol/liter. , 0.0025 to 0.1 mol/liter is more preferable. If the concentration of the primary amine compound in the second solution is within such a range, small pieces of the polymer compound that are not combined (small pieces of the polymer compound that are not coated on the inorganic fine particles, scraps, etc.) are generated. It is difficult to obtain only composite microparticles.

(3-3) Secondary amine compound and/or tertiary amine compound In the mixing step of the present invention, as described above, it is easy to coat the inorganic fine particles with the polymer compound, and small pieces of the polymer compound that are not complexed. (small pieces of polymer compound not coated on the inorganic fine particles, scraps, etc.) etc. are unlikely to be generated, and only composite fine particles are easily obtained, the mixing step includes a secondary amine compound and / or a tertiary It is preferable to carry out in the presence of an amine compound, that is, in the presence of inorganic fine particles and a secondary amine compound and/or a tertiary amine compound.

The secondary amine compound and the tertiary amine compound are not particularly limited, but compounds that are soluble in both the first solution and the second solution are preferred. In addition, it may be a liquid (that is, an organic solvent) or a solid.

For example, the secondary amine compound is preferably at least one selected from heterocyclic secondary amines, alicyclic secondary amines, aliphatic secondary amines and aromatic secondary amines. As the tertiary amine compound, at least one of heterocyclic tertiary amines, alicyclic tertiary amines, aliphatic tertiary amines and aromatic tertiary amines can be preferably exemplified.

More specifically, heterocyclic secondary amine compounds include, for example, piperidine, pyrrole, pyrrolidine, piperazine, 3-pyrroline and the like. These heterocyclic secondary amine compounds can be used alone or in combination of two or more.

Heterocyclic tertiary amines include, for example, pyridine, quinoline, isoquinoline, pyrazine, N,N'-dimethylpiperazine, pyrimidine, pyridazine, 1,2-dimethylimidazole, 1-methylimidazole and the like. These heterocyclic tertiary amine compounds can be used alone or in combination of two or more.

Heterocyclic amine compounds having both secondary and tertiary amino groups in the same molecule can also be used in the present invention. Heterocyclic amine compounds having both a secondary amino group and a tertiary amino group in the same molecule include, for example, imidazole, pyrazole, purine and the like. These heterocyclic amine compounds belong to both heterocyclic secondary amine compounds and heterocyclic tertiary amine compounds.

Alicyclic secondary amine compounds include, for example, 2-azabicyclo[2.2.2]octane (isoquinuclidine), 3,7-diazabicyclo[3.3.1]nonane (bispidine), 9-azabicyclo[3 .3.1]nonane (granatanin), 2,5-diazabicyclo[2.2.1]heptane, cyclohexylamine and the like. These alicyclic secondary amine compounds can be used alone or in combination of two or more.

Alicyclic tertiary amine compounds include, for example, 1,4-diazabicyclo[2.2.2]octane (triethylenediamine), 1-azabicyclo[2.2.2]octane (quinuclidine), 1-azabicyclo[ 3.2.2]nonane (homoquinuclidine), 9-methyl-9-azabicyclo[3.3.1]nonane (granatane), N,N-dimethyl-cyclohexylamine, N,N-diethyl-cyclohexylamine and the like. be done. These alicyclic tertiary amine compounds can be used alone or in combination of two or more.

Examples of fatty secondary amine compounds include ethylmethylamine, diethylamine, di-iso-amylamine, di-n-amylamine, dibenzylamine, 2-(N-methylamino)heptane and the like. These aliphatic secondary amine compounds can be used alone or in combination of two or more.

Examples of aliphatic tertiary amine compounds include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, N-ethyl-diamylamine, N , N,N′,N′-tetramethylethylenediamine, N,N,N′,N″,N″-pentamethyldiethylenetriamine, N,N,N′,N″,N″-pentamethyldipropylenetriamine, etc. mentioned. These fatty tertiary amine compounds can be used alone or in combination of two or more.

Examples of aromatic secondary amine compounds include N-methylaniline, N-isobutylaniline, N-ethylaniline, diphenylamine and the like. These aromatic secondary amine compounds can be used alone or in combination of two or more.

Examples of aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N-ethyl-N-methylaniline, triphenyleneamine, and benzyldimethylamine. These aromatic tertiary amine compounds can be used alone or in combination of two or more.

Among these, heterocyclic tertiary amines and/or alicyclic tertiary amines are preferable, and pyridine and/or triethylenediamine are particularly preferable, from the viewpoint of easily obtaining composite fine particles having a high degree of polymerization of the polymer compound. .

(3-4) Mixing step In the present invention, the above acid chloride compound is dissolved in an organic solvent in the presence of the above inorganic fine particles and optionally the above secondary amine compound and/or tertiary amine compound. and a second solution obtained by dissolving the above primary amine compound in an organic solvent are mixed.

The mixing ratio of the first solution and the second solution can be appropriately changed depending on the types of the acid chloride compound and the primary amine compound, the concentration of each solution, etc., but usually the acid chloride compound:primary amine compound=1: They can be mixed in a ratio of 0.5 to 2 (molar ratio), preferably 1:0.5 to 1.5 (molar ratio).

Organic solvents other than the secondary amine compound and the tertiary amine compound may be contained in the presence of the secondary amine compound and/or the tertiary amine compound used in the mixing step. Other organic solvents include, for example, those detailed for the first solution and the second solution.

Moreover, when the secondary amine compound and the tertiary amine compound are solid, a solution obtained by dissolving them in a solvent such as the above acetone may be used. Alternatively, solids may be dissolved directly in the first solution or the second solution.

A secondary amine compound and/or a tertiary amine compound can be added to the first solution and/or the second solution immediately before mixing the first solution and the second solution, but the reactivity of the acid chloride may decrease. It is preferable to add to the second solution from the viewpoint of easy prevention. That is, it is preferable to add the inorganic fine particles and the secondary amine and/or the tertiary amine compound to the second solution, then add the first solution and mix.

The amount of secondary amine compound and/or tertiary amine compound added depends on the type of acid chloride compound and primary amine compound used, the concentrations of the first and second solutions, and the desired (average ) It may be appropriately set according to the particle size, etc., but usually, when the secondary amine compound or tertiary amine compound is an organic solvent, about 1 to 100 mL per 100 mL of the first solution or second solution is preferred, and about 1 to 50 mL is more preferred. When the secondary amine compound or tertiary amine compound is solid, it is usually preferably about 0.00002 to 0.01 mol, and about 0.0001 to 0.005 mol, per 100 mL of the first solution or second solution. more preferred.

In the mixing step, it is particularly preferable to precipitate the polymer compound such as polyamide while stirring to produce the composite microparticles. Stirring can be carried out by a known stirring method (stirring device). In the present invention, the mixture may be stirred by ultrasonic waves, or by conventional methods such as a magnetic stirrer. Stirring with ultrasonic waves accelerates polymer polymerization and shortens the reaction time. A known ultrasonic device (for example, an ultrasonic cleaner) and operating conditions can be used as they are for stirring by ultrasonic waves. The frequency of the ultrasonic wave may be appropriately set according to the desired (average) particle size, etc., and is usually about 28 to 1000 kHz, preferably about 28 to 100 kHz.

The temperature in the mixing step is not particularly limited, and is usually about 0 to 100°C, preferably about 0 to 40°C. When the mixed solution is cooled to reduce the reaction rate, small pieces of uncomplexed polymer compounds (small pieces of polymer compounds not coated on inorganic fine particles, waste, etc.) are less likely to be generated, and only composite fine particles are produced. is easily obtained, the temperature in the mixing step is preferably about room temperature (25°C) or lower, particularly about 0 to 20°C. In addition, stirring can be performed until precipitation of polyamide is substantially completed.

The composite microparticles obtained in the mixing step can be recovered by solid-liquid separation according to a known method such as centrifugation.

When a polyamideimide compound as a polymer compound is to be precipitated on the inorganic fine particles, an acid chloride compound used in polyamideimide synthesis such as trimellitic acid chloride is used, and the acid chloride present in the fine particles obtained in the mixing step is A carboxyl group and an amide group can be condensed and imidized. The imidization method is not particularly limited, but in the present invention, (i) dispersing in an organic solvent and heating (usually 130° C. or higher, preferably at a temperature of about 130 to 250° C.) A method of imidization (thermal ring closure), (ii) a method of imidization by a chemical reaction in an organic solvent (chemical ring closure), or (iii) heating in a nitrogen atmosphere (usually 300 ° C. or higher, preferably about 350 to 450 ° C. can be heated at a temperature of) to imidize (thermal ring closure).

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the embodiments.

For the ultrasonic agitation in the examples, an ultrasonic cleaner "three-frequency ultrasonic cleaner VS-100 III" was used.

Each evaluation in the present invention was measured as follows.

(1) Morphology The morphology was observed with a scanning electron microscope (SEM) (“SU8230” manufactured by Hitachi, Ltd.).

(2) Separation ability (dye)
Using an ultraviolet-visible spectrometer (manufactured by JASCO Corp.), the absorbance of the aqueous solution before and after adsorption was measured. After baseline correction of the obtained spectrum, the absorbance at 554 nm was read and used as the concentration of the aqueous solution. The adsorption removal rate was calculated using the following formula.
Adsorption removal rate (%) = (C0-C48H)/C0 x 100
C0: initial concentration (solution concentration before adsorption)
C48H: concentration after 48 hours (solution concentration after adsorption).

(Metal ions)
Using an inductively coupled plasma atomic emission spectrometer (manufactured by Thermo Fisher Scientific Co., Ltd.), the metal ion concentrations of the aqueous solutions before and after adsorption were measured. The adsorption removal rate was calculated using the following formula.
Adsorption removal rate (%) = (C0-C24H)/C0 x 100
C0: initial concentration (metal concentration before adsorption)
C24H: Concentration after 24 hours (metal ion concentration after adsorption).

Example 1: Composite fine particles obtained by depositing polyamide directly on the silica surface As the first solution, 50 mL solution of 0.0005 mol of 1,3,5-benzenetricarbonyltrichloride dissolved in acetone, and as the second solution, 3,5 A 50 mL solution was prepared by dissolving diaminobenzoic acid in a mixed solvent of acetone and dimethylacetamide (composition ratio=6:4 (volume ratio)).

After that, 0.125 g of silica fine particles (average particle size 5 μm) and 3 mL of pyridine were added to the second solution, and after stirring, the first solution was also mixed, subjected to ultrasonic waves at a frequency of 28 kHz for 30 minutes, and further stirred at room temperature with a magnetic stirrer. and stirred for 24 hours to react.

The product was observed with a scanning electron microscope (SEM), and it was confirmed that the obtained composite fine particles (Fig. 1) had the same shape as the silica fine particles (Fig. 2).

Further, it was confirmed by infrared spectroscopic analysis that a band derived from polyamide together with silica was obtained, and that the coating amount of polyamide was 3.6% by mass of the total weight of the fine composite particles by heat treatment at 1000° C. (in air).

Comparative Example 1: Silica Silica fine particles (average particle diameter 5 μm) (FIG. 2) were used as fine particles of Comparative Example 1.

Example 2: Composite fine particles obtained by depositing polyamide directly on the silica surface As the first solution, 50 mL solution of 0.0005 mol of 1,3,5-benzenetricarbonyltrichloride dissolved in acetone, and as the second solution, m-phenylene A 50 mL solution was prepared by dissolving diamine in a mixed solvent of acetone and dimethylacetamide (composition ratio=6:4 (volume ratio)).

After that, 0.125 g of silica fine particles (average particle size 5 μm) and 3 mL of pyridine were added to the second solution, and after stirring, the first solution was also mixed, subjected to ultrasonic waves at a frequency of 28 kHz for 30 minutes, and further stirred at room temperature with a magnetic stirrer. and stirred for 24 hours to react.

The product was observed with a scanning electron microscope (SEM), and it was confirmed that the obtained composite fine particles (Fig. 3) had the same shape as the silica fine particles (Fig. 2).

Further, it was confirmed by infrared spectroscopic analysis that a band derived from polyamide together with silica was obtained, and that the coating amount of polyamide was 4.3% by mass of the total weight of the fine composite particles by heat treatment at 1000° C. (in air).

Example 3: A 50 mL solution of 0.0005 mol of 1,3,5-benzenetricarbonyltrichloride dissolved in acetone as the first solution of composite fine particles in which polyesteramide is directly precipitated on the silica surface, and 4, as the second solution. A 50 mL solution was prepared by dissolving 4′-diamino-3,3′-dihydroxybiphenyl in a mixed solvent of acetone and dimethylacetamide (composition ratio=2:8 (volume ratio)).

After that, 0.125 g of silica fine particles (average particle size 5 μm) and 3 mL of pyridine were added to the second solution, and after stirring, the first solution was also mixed, subjected to ultrasonic waves at a frequency of 28 kHz for 30 minutes, and further stirred at room temperature with a magnetic stirrer. and stirred for 24 hours to react.

The product was observed with a scanning electron microscope (SEM), and it was confirmed that the obtained composite fine particles (Fig. 4) had the same shape as the silica fine particles (Fig. 2).

Further, it was confirmed by infrared spectroscopic analysis that a band derived from polyamide together with silica was obtained, and that the coating amount of polyamide was 1.4% by mass of the total weight of the fine composite particles by heat treatment at 1000° C. (in air).

Example 4: Composite fine particles obtained by depositing polyamide directly on the silica surface As the first solution, 50 mL solution of 0.0005 mol of 1,3,5-benzenetricarbonyltrichloride dissolved in acetone, and as the second solution, 3,5 A 50 mL solution was prepared by dissolving diaminobenzoic acid in a mixed solvent of acetone and dimethylacetamide (composition ratio=6:4 (volume ratio)).

After that, 0.125 g of silica fine particles (average particle diameter 5 μm) was added to the second solution, and after stirring, the first solution was also mixed and subjected to ultrasonic waves at a frequency of 28 kHz for 30 minutes, followed by a magnetic stirrer at room temperature for 24 hours. Stir and react.

The product was observed with a scanning electron microscope (SEM), and it was confirmed that the obtained composite fine particles (Fig. 5) had the same shape as the silica fine particles (Fig. 2).

It was also confirmed by infrared spectroscopic analysis that a band originating from polyamide together with silica was found, and that the coating amount of polyamide was 3.9% by mass of the total weight of the fine composite particles by heat treatment at 1000° C. (in air).

Example 5: Composite fine particles obtained by depositing polyamide directly on the alumina surface As the first solution, 50 mL solution of 0.0005 mol of 1,3,5-benzenetricarbonyltrichloride dissolved in acetone, and as the second solution, 3,5 A 50 mL solution was prepared by dissolving diaminobenzoic acid in a mixed solvent of acetone and dimethylacetamide (composition ratio=6:4 (volume ratio)).

After that, 0.125 g of silica fine particles (average particle size 5 μm) and 3 mL of pyridine were added to the second solution, and after stirring, the first solution was also mixed, subjected to ultrasonic waves at a frequency of 28 kHz for 30 minutes, and further stirred at room temperature with a magnetic stirrer. and stirred for 24 hours to react.

The product was observed with a scanning electron microscope (SEM), and it was confirmed that the obtained composite fine particles (Fig. 6) had the same shape as the alumina fine particles (Fig. 7).

It was also confirmed by infrared spectroscopic analysis that a band derived from polyamide together with alumina, and that the coating amount of polyamide was 3.1% by mass of the total weight of the composite fine particles by heat treatment at 1000° C. (in air).

Comparative Example 2: Alumina Alumina fine particles (average particle size: 100 nm) (Fig. 7) were used as fine particles of Comparative Example 2.

Test Example 1: Resolution (Rhodamine 6G)
80 mg of the composite fine particles obtained in Example 1 were dispersed in 160 mL of a 3.5 mg/L rhodamine 6G aqueous solution (pH 7), and the solution was stirred with a magnetic stirrer at room temperature for 48 hours. The adsorption removal rate of Rhodamine 6G was 99%.

On the other hand, the adsorption removal rate of uncoated silica fine particles (Comparative Example 1) was 47%, indicating a remarkable coating effect.

Test Example 2: Resolution (Rhodamine B)
80 mg of the composite fine particles obtained in Example 2 were dispersed in 160 mL of a 3.5 mg/L Rhodamine B aqueous solution (pH 7), and the solution was stirred with a magnetic stirrer at room temperature for 48 hours. The adsorption removal rate of Rhodamine B was 85%.

On the other hand, the adsorption removal rate of uncoated silica fine particles (Comparative Example 1) was 15%, indicating a remarkable coating effect.

Test Example 3: Resolution (Rhodamine B)
80 mg of the composite fine particles obtained in Example 3 were dispersed in 160 mL of a 3.5 mg/L Rhodamine B aqueous solution (pH 7), and the solution was stirred with a magnetic stirrer at room temperature for 48 hours. The adsorption removal rate of Rhodamine B was 77%.

On the other hand, the adsorption removal rate of uncoated silica fine particles (Comparative Example 1) was 15%, indicating a remarkable coating effect.

Test Example 4: Resolution (Rhodamine 6G)
80 mg of the composite fine particles obtained in Example 4 were dispersed in 160 mL of a 3.5 mg/L rhodamine 6G aqueous solution (pH 7), and the solution was stirred with a magnetic stirrer at room temperature for 48 hours. The adsorption removal rate of Rhodamine 6G was 100%.

On the other hand, the adsorption removal rate of uncoated silica fine particles (Comparative Example 1) was 47%, indicating a remarkable coating effect.

Test Example 5: Resolution (Rhodamine B)
80 mg of the composite fine particles obtained in Example 5 were dispersed in 160 mL of a 3.5 mg/L Rhodamine B aqueous solution (pH 7), and the solution was stirred with a magnetic stirrer at room temperature for 48 hours. The adsorption removal rate of Rhodamine B was 73%.

On the other hand, the adsorption removal rate of uncoated alumina fine particles (Comparative Example 2) was 36%, indicating a remarkable coating effect.

Test Example 6: Resolution (copper ion)
80 mg of the composite fine particles obtained in Example 1 were dispersed in 40 mL of a 10 ppm copper nitrate aqueous solution (pH 5.5), and the solution was stirred in a constant temperature shaking water bath at 30°C for 24 hours. As a result, the adsorption removal rate of copper ions was 19%.

On the other hand, the adsorption removal rate of uncoated silica fine particles (Comparative Example 1) was 0%, indicating a remarkable coating effect.

Claims (13)

A composite fine particle, wherein an inorganic fine particle is directly coated with a polymer compound having at least one selected from the group consisting of an amide bond, an imide bond and a nitrogen-containing heteroaromatic ring on the main chain. 2. The polymer compound according to claim 1, which is at least one selected from the group consisting of polyamide compounds, polyamideimide compounds, polyesteramide compounds, polyamideurethane compounds, polybenzoxazole compounds, polybenzimidazole compounds and polyimide compounds. of composite microparticles. 3. The fine composite particles according to claim 1, wherein the inorganic fine particles do not have an organic functional group derived from a silane coupling agent on the surface. 4. The fine composite particles according to any one of claims 1 to 3, which are dyes and/or metal ion adsorbents. The fine composite particles according to any one of claims 1 to 4, wherein the inorganic fine particles have an average particle size of 5 nm to 1 cm. Dye and/or metal ion adsorption, wherein the inorganic fine particles contain composite fine particles coated with a polymer compound having at least one selected from the group consisting of amide bonds, imide bonds and nitrogen-containing heteroaromatic rings in the main chain. agent. 7. The dye and/or metal ion adsorbent according to claim 6, wherein said inorganic fine particles are directly coated with said polymer compound. 8. The dye and/or metal ion adsorbent according to claim 6 or 7, wherein the inorganic fine particles do not have an organic functional group derived from a silane coupling agent on the surface. The dye and/or metal ion adsorbent according to any one of claims 6 to 8, wherein the inorganic fine particles have an average particle size of 5 nm to 1 cm. A method for producing the composite fine particles according to any one of claims 1 to 5 or the dye and/or metal ion adsorbent according to any one of claims 6 to 9,
A manufacturing method comprising the step of mixing a first solution obtained by dissolving an acid chloride compound in an organic solvent and a second solution obtained by dissolving a primary amine compound in an organic solvent in the presence of the inorganic fine particles. . 11. The production method according to claim 10, wherein said mixing step is further carried out in the presence of a secondary amine compound and/or a tertiary amine compound. The mixing step is a step of adding the inorganic fine particles and the secondary amine and/or the tertiary amine compound to the second solution, then adding and mixing the first solution. Item 12. The manufacturing method according to item 11. 13. The production method according to claim 11 or 12, wherein said secondary amine compound and/or tertiary amine compound is soluble in both said first solution and said second solution.

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