JPH07196314A - Tube-shaped synthetic inorganic fine particles - Google Patents

Abstract

(57) [Summary] [Structure] A tubular synthesis which has a needle-like and / or columnar shape, has a hollow space inside, and satisfies the physical properties of the following formulas (a) to (e). Inorganic fine particles. (A) 0.1 ≦ DS1 ≦ 1000 (μm), (b) 0.
05 ≦ DS2 ≦ 100 (μm), (c) 0.02 ≦ DS
3 ≦ 95 (μm), (d) DS1 / DS2 ≧ 2, (e)
0.05 ≦ DS3 / DS2 ≦ 0.95 DS1 is the major axis of the tubular synthetic inorganic fine particles measured by electron micrograph, DS2 is the same outer diameter (minor axis), DS
3 is an average particle diameter (μm) having the same inner diameter, DS1 / DS2 is an aspect ratio of the long diameter and the short diameter of the fine particles, and DS3 / DS2 is a value showing a ratio of the inner diameter and the outer diameter of the fine particles. [Effect] It is useful as a carrier such as a catalyst, an adsorbent, a sustained-release material, a filler for plastics, and an anti-blocking agent for fibers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel tubular synthetic inorganic fine particle, more specifically, a needle-like and / or specific particle size
Alternatively, the present invention relates to fine tubular synthetic inorganic fine particles having a columnar shape and having a hollow space having an inner diameter of a specific particle size therein. The tubular synthetic inorganic fine particles of the present invention include, for example, catalyst carriers, pharmaceutical carriers, agrochemical carriers, microbial carriers, biological carriers, peroxide carriers, plant growth agents, olefin absorbents, ultraviolet absorbents, adsorbents, sustained release agents, Liquid absorbents, ceramic raw materials, various carriers, filter agents, filter aids, microbial rearing, biomaterials, desiccants, fragrances, other carriers or their raw materials, plastic / rubber / paint / ink / sealing materials and papermaking fillers, It is useful as an antiblocking agent for fibers and films. Further, by combining the above various uses, it is possible to develop new uses.

[0002]

2. Description of the Related Art Conventionally, as a porous body of synthetic inorganic material,
Synthetic zeolite, silica gel, alumina gel, Fluorite R (trade name, Tokuyama Soda), spherical calcium phosphate and the like are known. However, there is no report on fine tubular synthetic inorganic fine particles having fine voids of a specific particle size.
Synthetic zeolite, silica gel, alumina gel and the like are used for various carriers because of their high specific surface areas. The high specific surface area is due to the extremely fine pores. However, synthetic zeolite, silica gel, alumina gel and the like have the drawback of poor retention. That is, since most of the pores are too small, less than 0.02 μm, they are easily adsorbed but easily released, and the ability of the adsorbed substances to be released little by little over a long period of time as a carrier of a sustained release body is poor. In addition, it is difficult to apply porous materials as filtering agents and filter aids because the pores are too small, and it is also possible to adsorb and sustained-release liquids with high surface tension, poorly wettable substances, high-viscosity substances and polymer substances. Have difficulty.

A commercially available product having pores of 0.02 μm or more is, for example, fluorite. Fluorite is a gyrolite-type calcium silicate having a petal-like crystal structure and has communicating holes, and is a crushed product or a molded product having an irregular shape. Although it has the advantage that the amount of liquid absorbed is high, it has the drawback that the release rate is extremely fast and it does not function as a sustained release agent for a long period of time. When used as a filler for papermaking, paints, plastics, etc., it is necessary to grind and classify to adjust the particle size required for the filler, but the crushing destroys the petal-like shape. Therefore, there is a problem that the original physical properties cannot be maintained.

As spherical calcium phosphate
03809 is mentioned. This discloses a method for producing a spherical calcium phosphate-based porous body having a large specific surface area, which is useful for biomaterials and the like, and has a uniform particle size and pore size. There is no description about fine tubular synthetic inorganic fine particles having a hollow and / or columnar shape and having a hollow space of a specific particle size inside. Halloysite is a natural mineral having an acicular shape and a space inside. Halloysite contains needle-like particles having a space inside, but since it is a natural product, it not only contains a large number of unusable impurities, but also has a nonuniform particle size and shape.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks, and its purpose is to have a needle-like and / or columnar shape having a specific particle size, and a fine particle having a specific particle size inside. It is an object of the present invention to provide fine synthetic inorganic fine particles having various hollow spaces.

[0006]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention have obtained a finely-synthesized compound having a needle-like and / or columnar shape having a specific particle size and having a fine hollow space having a specific particle size inside. The inventors have found that the inorganic fine particles are useful for the above-mentioned various uses, and have completed the present invention. That is, needle-like and /
Alternatively, the present invention provides a tubular synthetic inorganic fine particle having a columnar shape, having a hollow space inside, and satisfying the physical properties of the following formulas (a) to (e). (A) 0.1 ≦ DS1 ≦ 1000 (μm) (b) 0.05 ≦ DS2 ≦ 100 (μm) (c) 0.02 ≦ DS3 ≦ 95 (μm) (d) DS1 / DS2 ≧ 2 (e) 0.05 ≦ DS3 / DS2 ≦ 0.95 However, DS1: average particle diameter (μm) of major axis of tubular synthetic inorganic fine particles measured by an electron micrograph. DS2: Average particle diameter (μm) of the outer diameter (minor diameter) of the tubular synthetic inorganic fine particles measured by an electron micrograph. DS3: Average particle diameter (μm) of the inner diameter of the tubular synthetic inorganic fine particles measured by an electron micrograph. DS1 / DS2: A value representing the aspect ratio of the long diameter and the short diameter of the tubular synthetic inorganic fine particles. DS3 / DS2: A value representing the ratio of the inner diameter to the outer diameter of the tubular synthetic inorganic fine particles.

The present invention will be described in detail below. The tubular synthetic inorganic fine particles according to the present invention are characterized in that they are needle-like and / or columnar shaped particles having a specific particle size, and are fine tubular synthetic inorganic particles having a hollow space having a specific particle size inside. That is, the tubular synthetic inorganic fine particles of the present invention have a larger apparent specific surface area than the spherical, cubic, and amorphous particles. Further, by having a hollow space inside, the apparent specific surface area is larger than that of the conventional needle-like and / or columnar shape. Various useful substances can be retained in the hollow space, and conversely, harmful and useless substances can be captured and removed. Furthermore, by utilizing the shape and the hollow space of a specific particle size inside, it is possible not only to selectively retain, capture and remove a substance of a specific particle size, but also to control the retention time, etc. is there. Its fields of application include catalyst carriers, pharmaceutical carriers, agricultural chemical carriers, microbial carriers,
Biological carrier, peroxide carrier, plant growth agent, olefin absorbent, ultraviolet absorbent, adsorbent, sustained release agent, liquid absorbent, ceramic raw material, various carriers, filter agent, filter aid, microorganism breeding, biomaterial, drying Examples include agents, fragrances, other carriers or raw materials thereof. Expected applications include plastics, rubber, paints, inks, sealants, papermaking, textiles and films.

When the tubular synthetic inorganic fine particles of the present invention are used as a filler in plastics, rubbers and paints, they are fine particles and are needle-like and / or columnar in shape, and are advantageous over other shapes such as large surface area. Not only
The organic substance enters the hollow space inside, resulting in extremely good affinity. Plastics, rubbers, paints, inks, sealing materials and paper compositions filled with tubular synthetic inorganic fine particles have good physical properties because they have good affinity. Furthermore, catalyst carriers, pharmaceutical carriers, agrochemical carriers, microbial carriers, biological carriers, peroxide carriers, plant growth agents, olefin absorbers, ultraviolet absorbers, adsorbents, sustained-release bodies to which the above-mentioned tubular synthetic inorganic fine particles are applied. , Liquid absorbents, ceramic raw materials, various carriers, filter agents, filter aids, microbial rearing, biomaterials, desiccants, fragrances, and other carrier compositions for plastics, rubbers, paints, inks, sealing materials and paper compositions By filling, a composite effect and / or a synergistic effect can be expected.

[0009] Plastic fibers and films are exposed to friction and wear when they are actually used because they have a drawing step in the manufacturing process, in which antiblocking property is important in their manufacturing processes and fields of use. At this time, if the affinity of the added inorganic anti-blocking agent and the plastic is poor, the added inorganic anti-blocking agent is released and trouble occurs, the tubular synthetic particles of the present invention are fine particles, and external Has a needle-like shape and / or a columnar shape, which is not only advantageous over other shapes, but also the organic substance enters the hollow space inside, resulting in extremely good affinity, and thus as a blocking inhibitor. It is useful. It is also useful as a filter agent, a filter aid, and a filler for papermaking due to the effect of having a needle-like shape and / or a columnar shape and the effect of having a hollow space inside.

The major axis of the tubular synthetic inorganic fine particles is 0.
It may be 1 μm or more and 1000 μm or less. 0.1 μm
Smaller particles are not preferable because particles agglomerate due to small particles themselves. The longer the better, the better,
If it is larger than 1000 μm, it tends to break during handling, which is not preferable. Preferably 0.1 μm or more and 500 μm or less,
It is more preferably 0.5 μm or more and 200 μm or less.
The outer diameter (minor diameter) of the tubular synthetic inorganic fine particles is 0.05.
It suffices if it is from 100 μm to 100 μm. If the particle size is smaller than 0.05 μm, the particles tend to aggregate, which is not preferable. 100
If it is larger than μm, it is easily broken during handling, which is not preferable. The thickness is preferably 0.05 μm or more and 20 μm or less, more preferably 0.1 μm or more and 10 μm or less.

The inner diameter of the tubular synthetic inorganic fine particles is 0.
It suffices if it is from 02 μm to 95 μm. Inner diameter is 0.0
When it is smaller than 2 μm, when it is used for the above purposes,
As a result, the adsorption rate as a carrier is slow, the pressure as a filtering agent / filter aid is high and the efficiency is poor, and the sustained release rate of the adsorbed / retained substance is delayed or the release rate is decreased, which is not preferable. If it is larger than 95 μm, it tends to be broken during handling, which is not preferable. Preferably 0.02 μm or more and 19 μm or less, more preferably 0.05 μm or more 9.
It is 5 μm or less.

The value of the ratio DS1 / DS2 of the major axis to the outer diameter (minor axis) of the tubular synthetic inorganic fine particles may be 2 or more. The larger this value is, the longer the tubular synthetic inorganic fine particles become in shape, The apparent specific surface area and the external space formed by the particles become larger, and not only the internal cavity space length becomes longer, but also the internal apparent specific surface area becomes higher, and as a result, physical adsorption becomes more The larger the size, the higher the retention capacity and the affinity, which is preferable. If this value is smaller than 2, the apparent specific surface area becomes small, which is not preferable. In addition, it cannot be said to be tubular synthetic inorganic fine particles. It is preferably 3 or more, more preferably 5 or more.

The value of the ratio DS4 / DS3 of the inner diameter to the outer diameter of the tubular synthetic inorganic fine particles may be from 0.05 to 0.95. The larger the value, the more the hollow synthetic inorganic fine particles have a hollow space. A large proportion is preferable, but a larger proportion than 0.95 is not preferable because it easily breaks during handling. If this value is smaller than 0.05, the ratio of the hollow space to the tubular synthetic inorganic fine particles becomes small, which is not preferable.

When the surface of the tubular synthetic inorganic fine particles has fine protrusions and / or fine pores, it has a high specific surface area and is physically adsorbed to have a high retention capacity, affinity, etc. It is more preferable because it tends to increase. In addition, 0.02 is formed on the surface of the tubular synthetic inorganic fine particles.
It is more preferable to have one or more pores with a size of μm or more.
The pore distribution of the tubular synthetic inorganic fine particles is preferably represented by the following formula (f). When the pore diameter is smaller than 0.02 μm even if the specific surface area is high, when it is used for the above-mentioned application, as a result, it is easily adsorbed but easily released, and is adsorbed for a long time as a sustained-release carrier. Poor ability to release objects in small amounts. Further, it is difficult to apply the porosity as a filtering agent and a filter aid, and it is also difficult to adsorb and sustainedly release a liquid having a high surface tension, a substance having poor wettability, a highly viscous substance and a polymer substance. (F) V1 ≦ V2 V1 and V2 are obtained by the pore distribution measured by the mercury intrusion method. V1: Pore volume (%) with a diameter of less than 0.02 μm V2: Pore volume (%) with a diameter of 0.02 μm or more For measurement, it is preferable to use electron microscope observation together.

When the tubular synthetic inorganic fine particles are used for the above-mentioned various uses, especially for various carriers and filtering agents, it is preferable that the specific surface area is high. The specific surface area Sw measured by the nitrogen adsorption BET method is 10 m ² / g or more. Yes, preferably 20
It is at least m ² / g, more preferably at least 50 m ² / g. Even if the specific surface area is extremely high, such as silica gel, it is sufficient that the formula (f) described above is satisfied.

The substance constituting the tubular synthetic inorganic fine particles may be an inorganic substance which is insoluble or hardly soluble in water, lower alcohol and solvent. When it is soluble, it is not preferable because it is soluble in the solvent used, the water vapor in the atmosphere, the lower alcohol, and the solvent when it is used industrially. For example, as the substance that constitutes the tubular synthetic inorganic fine particles, phosphate, fluoride, silicate, sulfate, perovskite salt (M
TiO ₃ , M = divalent metal salt), oxalates, carbonates and hydroxides of alkaline earth metal salts, phosphates, silicates and hydroxides of aluminium salts, silicic acid and silicic acid hydrates. It is mainly composed of at least one member selected from the group consisting of

The alkaline earth metal is preferably calcium, magnesium, strontium, barium or beryllium, more preferably calcium, magnesium,
It is barium. For example, calcium monohydrogen phosphate, tricalcium phosphate, hydroxyapatite [Ca ₃ (PO ₄ ) ₅
OH)], amorphous calcium phosphate, fluoroapatite [Ca ₃ (PO ₄ ) ₅ F], calcium pyrophosphate, calcium metaphosphate, calcium fluoride, calcium silicate, calcium calcium silicate, calcium fluorosilicate, calcium sulfite, sulfuric acid. Calcium, calcium titanate, calcium oxalate, calcium carbonate (calcite, vaterite, aragonite), calcium magnesium carbonate, calcium hydroxide, magnesium hydrogen phosphate,
Magnesium phosphate, magnesium pyrophosphate, magnesium silicate, magnesium sulfite, magnesium titanate,
Magnesium oxalate, magnesium carbonate, magnesium hydroxide, barium monohydrogen phosphate, barium phosphate, barium pyrophosphate, barium silicate, barium fluorosilicate, barium sulfate, barium sulfite, barium titanate, barium oxalate, barium carbonate, strontium hydrogen phosphate. , Strontium phosphate, strontium silicate, strontium sulfate, strontium titanate, strontium oxalate, strontium carbonate, beryllium phosphate, beryllium hydroxide, aluminum phosphate, aluminum silicate, magnesium aluminum silicate, sodium aluminosilicate, aluminum fluoride, aluminum hydroxide, Examples thereof include silicic acid and silicic acid hydrate.

Examples of the application will be given below to describe suitable substances constituting the tubular synthetic inorganic fine particles, but these are merely examples and the present invention is not limited thereto. For applications requiring affinity with living organisms such as bioreactors, calcium phosphate is preferable,
Hydroxyapatite is preferable. When using it as a nutritional supplement, it is sufficient to select a substance containing the target element.For example, when calcium is required, calcium salt is used. For calcium and phosphorus nutritional enhancement, calcium phosphate is selected from the calcium salt and magnesium. If it is necessary to use magnesium salt, magnesium salt may be selected. When sterilization and antibacterial effects are required, it is preferable that trace amounts of substances having sterilization and antibacterial effects such as copper, silver and platinum are mixed and / or applied and treated. When drying and dehumidifying and dehydrating effects are required, hydrated silicic acid, hydrated calcium silicate, hydrated aluminum silicate and the like are preferable. As a toothpaste abrasive, calcium phosphate,
Calcium fluorophosphate, calcium silicate, silicic acid hydrate and the like are preferable. When used for breeding microorganisms, those which do not harm the microorganisms may be selected. As the gas adsorbent, silicate or phosphate may be mainly added and other components may be appropriately added. As the peroxide carrier and sustained release agent, an alkaline substance is preferable, and hydroxyapatite, tricalcium phosphate, magnesium carbonate, etc. or a substance containing a part thereof is preferable, and it is also possible to treat them with other substances. Further, it is more preferable to treat and modify the alkaline substance. When heat resistance is required, phosphate,
Silicate is preferable, and hydroxyapatite Ca ₃ (PO ₄ ) ₅ OH and fluoroapatite Ca ₃ (PO ₄ ) are more preferable.
₅ F is preferred.

The method for producing the tubular inorganic fine particles of the present invention will be exemplified, but the present invention is not limited by the exemplified production method. For example, a needle-shaped and / or columnar particle composed of the substance X is used as a core, the surface of which is covered with a substance Y different from the core, and the substance Y-treated substance X (the substance Y is a needle-shaped and / or columnar particle) is coated. The coated material X) is prepared. Examples include a method of preparing a hollow space inside by removing all or part of the substance X serving as the core of the substance Y-treated substance X that is the prepared needle-shaped and / or columnar particles. Further, the substance Y coated by the above method is the substance X and the additive substance Z.
It is preferably produced by a reaction with
The acicular and / or columnar particles to be the core have the following formula (l)
Those satisfying the physical properties of (n) are preferable. (L) 0.1 ≦ DS4 <1000 (μm) (m) 0.05 ≦ DS5 <100 (μm) (n) DS4 / DS5 ≧ 2 However, DS4: average of major axis of core particles measured by electron micrograph Particle size (μm). DS5: Average minor particle diameter (μm) of core particles measured by electron micrograph. DS4 / DS5: A value representing the aspect ratio of the major axis and the minor axis of the core particles. Preferably, those satisfying the physical properties of the following formulas (o) to (q) are preferable. (O) 0.1 ≦ DS4 <500 (μm) (p) 0.05 ≦ DS5 <20 (μm) (q) DS4 / DS5 ≧ 3 More preferably, the physical properties of the following formulas (r) to (t) It is better to satisfy. (R) 0.5 ≦ DS4 <200 (μm) (s) 0.1 ≦ DS5 <10 (μm) (t) DS4 / DS5 ≧ 5 The substance X is particularly limited as long as it is acicular and / or columnar particles. Not a thing. The substance Y may be an inorganic substance that is insoluble or hardly soluble in water and / or a solvent different from the substance X,
For example, the substance Y is a phosphate, a fluoride, a silicate, a sulfate, a perovskite salt (MTiO ₃ , M = divalent metal salt), an oxalate, a carbonate, and an alkaline earth metal salt of a hydroxide, Aluminium salts, which are phosphates, silicates and hydroxides,
It is mainly composed of at least one selected from the group consisting of silicic acid and silicic acid hydrate. The alkaline earth metal is preferably calcium, magnesium, strontium, barium or beryllium, more preferably calcium, magnesium or barium. The substance Z is not particularly limited as long as it reacts with the substance X to become the substance Y.

A method of coating the substance Y on the acicular and / or columnar particles composed of the substance X which is the core will be described below. It is also possible to combine these. Further, the coating method is not limited to these methods. (Y1) The core particles are dispersed in water and / or a solvent to prepare a water and / or solvent suspension of the core particles. A method of coating a substance Y on the surface of a core particle by adding a substance as a raw material of the substance Y to the suspension and performing a precipitation reaction to generate the substance Y. Examples of the precipitation reaction include solution reaction, hydrolysis reaction and gas-liquid reaction. (Y2) The core particles are dispersed in water and / or a solvent to prepare a water and / or solvent suspension of the core particles. A method in which a water and / or solvent suspension of fine particles of substance Y is added to the suspension and the fine particles of substance Y are precipitated on the surface of the core particles to coat the surface of the core particles with the substance Y. Examples of the precipitation reaction include solution reaction, hydrolysis reaction and gas-liquid reaction. (Y3) The core particles are dispersed in water and / or a solvent to prepare a water and / or solvent suspension of the core particles. The substance Z is added to the suspension, and the substance Z and the substance X are reacted with each other to obtain the substance Y.
Is carried out to form a substance Y on the surface of the core particle.
The method of coating. Examples of the precipitation reaction include solution reaction, hydrolysis reaction and gas-liquid reaction. (Y4) A method of adsorbing and / or adhering the substance Z on the surface of the core particle by a wet or dry method and sintering the mixture to react the substance Z and the substance X to coat the surface of the core particle with the substance Y. As a method of adsorbing and / or adhering, for example, in a wet method, an adsorbing method using a particle size and / or a potential difference and an adhering method using an organic polymer are used, and in a dry method, methanochemical (impact force, stirring force Utilization) An adsorption method utilizing a reaction and an attachment method utilizing an organic substance can be mentioned. For example, using acicular and / or columnar particles of a divalent metal compound such as alkaline earth metal as a core, ultrafine titanium oxide is adhered to the core particle surface by the above method or a similar method, and then alkaline earth metal A perovskite-type compound is synthesized by sintering a divalent metal compound such as a metal and ultrafine titanium oxide, and needle-shaped and / or columnar particles of a perovskite-type compound-treated divalent metal compound such as an alkaline earth metal are prepared. be able to. By combining (Y5) (Y1) to (Y4), repeating the same method, or both operations, the substance Y1,
A method of coating a substance different from Y2 ... Or the same substance. When the tubular synthetic inorganic fine particles are synthesized from the coated particles prepared by this method, it is possible to synthesize the tubular synthetic inorganic fine particles having a peculiar layered structure composed of specific different thicknesses and substances.

A method for removing all or a part of the substance X serving as the core of the substance Y-treated substance X which is acicular and / or columnar particles will be described below, but the present invention is not limited to these methods. (X1) A substance that is soluble in an organic acid and / or an inorganic acid is selected as the substance X, and an inorganic substance that is insoluble or hardly soluble in the organic acid and / or the inorganic acid is selected as the substance Y. Then, the substance Y-treated substance X, which is needle-shaped and / or columnar particles, is treated with an organic acid and / or an inorganic acid in water and / or a solvent to dissolve and remove the substance X serving as a core.
It is preferable to use a buffer during dissolution. (X2) A substance that is soluble in a specific organic acid and / or an inorganic acid is selected as the substance X, and a substance Y is insoluble in a specific organic acid and / or an inorganic acid in which the substance X is soluble or A substance X which is a core by selecting a poorly soluble inorganic substance and treating the substance Y which is needle-like and / or columnar particles in water and / or a solvent with an organic acid and / or an inorganic acid How to dissolve and remove. It is preferable to use a buffer during dissolution. (X3) A similar method except that the “organic acid and / or inorganic acid” is changed to “water and / or solvent” by the method described in (X1). (X4) In the method described in (X2), "a specific organic acid and / or
Or the same method except that "inorganic acid" is changed to "specific aqueous solution and / or solvent". (X5) "Soluble" by the method described in (X1) to (X4)
Is changed to "degradable", "insoluble or sparingly soluble" is changed to "not decomposed or difficult to decompose", and "dissolved and removed" is changed to "decomposed and removed". (X6) A substance that is needle-shaped and / or columnar particles is selected as the substance X, a substance that thermally decomposes at a specific temperature is selected, and an inorganic substance that does not thermally decompose at a specific temperature that the substance X decomposes is selected as the substance Y. A method of thermally decomposing and removing the substance X to be the core by heat-treating the Y treated substance X at a specific temperature. (X7) “Pyrolysis at a specific temperature” by the method described in (X6)
The same method except that is changed to "specific temperature under specific atmosphere". (X8) At least 1 selected from (X1) to (X7)
By controlling the dissolution, decomposition and / or thermal decomposition of the core substance X by adjusting the conditions for the dissolution, decomposition and / or thermal decomposition by two methods A method of obtaining a specific dissolution, decomposition and / or thermal decomposition rate. As a result, the substance X serving as the core remains in an amount that is not dissolved, decomposed and / or thermally decomposed, and tubular synthetic inorganic fine particles in which different substances X and Y are layered are prepared.

[0022]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. Example 1 Preparation of Inorganic Fine Particles A1 Calcium carbonate of acicular aragonite type crystals having a major axis of 2 μm and a minor axis of 0.3 μm was dispersed in water to prepare an aqueous suspension of acicular calcium carbonate. While stirring this aqueous suspension, a 25% by weight aqueous solution of orthophosphoric acid was added dropwise to calcium carbonate and then aged with stirring to obtain hydroxyapatite-treated calcium carbonate. The resulting hydroxyapatite-treated calcium carbonate was treated with a mixed solution of acetic acid and glycine (amino acid) to dissolve and remove the calcium carbonate in the inside, thereby preparing inorganic fine particles A1 composed of hydroxyapatite. A small amount of sodium chloride and calcium chloride was added as a buffer to the mixed solution used for dissolution. Example 2 Preparation of Inorganic Fine Particles A2 When preparing the inorganic fine particles A1, “after dropping an aqueous solution of 25% orthophosphoric acid in a weight ratio to calcium carbonate was added”, “10 in a weight ratio to calcium carbonate was used.
%, Orthophosphoric acid aqueous solution was added dropwise, and then the inorganic fine particles A2 composed of hydroxyapatite were prepared in the same manner except that the content was changed to "." Example 3 Preparation of Inorganic Fine Particles A3 When preparing the inorganic fine particles A1, “after dropping a 25% by weight aqueous solution of orthophosphoric acid to calcium carbonate,” was added to “5% by weight of calcium carbonate.
Inorganic fine particles A3 composed of hydroxyapatite were prepared in the same manner except that the aqueous solution of orthophosphoric acid was added dropwise, and the procedure was changed to. Example 4 Preparation of Inorganic Fine Particles A4 When preparing the inorganic fine particles A1, “after dropping an aqueous solution of 25% orthophosphoric acid in a weight ratio to calcium carbonate was added”, “50 in a weight ratio to calcium carbonate.
%, Orthophosphoric acid aqueous solution was added dropwise, and then the inorganic fine particles A4 composed of hydroxyapatite were prepared in the same manner except that the content was changed to "." Example 5 Preparation of Inorganic Fine Particles A5 When preparing the inorganic fine particles A1, “a needle-shaped aragonite-type calcium carbonate having a major axis of 2 μm and a minor axis of 0.3 μm” was used as “a major axis of 20 μm and a minor axis of 0.6 μm. Inorganic fine particles A5 composed of hydroxyapatite were prepared in the same manner except that the shape was changed to "aragonite-type calcium carbonate having a shape."

Example 6 Preparation of Inorganic Fine Particles A6 When the inorganic fine particles A1 were prepared, “a needle-shaped aragonite-type calcium carbonate having a major axis of 2 μm and a minor axis of 0.3 μm” was added to “a major axis of 50 μm and a minor axis of 1 μm. Inorganic fine particles A6 composed of hydroxyapatite were prepared in the same manner except that the needle-shaped calcium carbonate of aragonite type crystal was changed. Example 7 Preparation of Inorganic Fine Particles A7 When preparing the inorganic fine particles A1, the “argonite type calcium carbonate having a needle-like shape with a long diameter of 2 μm and a short diameter of 0.3 μm” was added to the “long diameter of 100 μm, a short diameter of 2 μm. Inorganic fine particles A7 composed of hydroxyapatite were prepared in the same manner except that "aragonite type calcium carbonate" was used. Example 8 Preparation of Inorganic Fine Particles A8 When preparing the inorganic fine particles A1, “acicular aragonite-type calcium carbonate having a long diameter of 2 μm and a short diameter of 0.3 μm” was added to the “long diameter of 200 μm, a short diameter of 4 μm. Inorganic fine particles A8 composed of hydroxyapatite were prepared in the same manner, except that "aragonite-type crystal calcium carbonate" was used. Example 9 Preparation of Inorganic Fine Particles A9 When the inorganic fine particles A1 were prepared, “acicular aragonite-type calcium carbonate having a major axis of 2 μm and a minor axis of 0.3 μm” was used as “major axis 0.5 μm, minor axis 0.1 μm. Inorganic fine particles A9 composed of hydroxyapatite were prepared in the same manner except that the columnar shape of the calcium carbonate of the calcite type crystal was changed. Example 10 Preparation of Inorganic Fine Particles A10 A columnar calcium sulfate having a major axis of 800 μm and a minor axis of 50 μm was dispersed in water to prepare an aqueous suspension of calcium sulfate. While stirring this aqueous suspension, an aqueous solution of sodium phosphate and calcium chloride in an amount of 25% by weight with respect to calcium sulfate as a weight ratio of hydroxyapatite was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium sulfate. By treating the obtained hydroxyapatite-treated calcium sulfate with an organic acid and / or an inorganic acid, the internal calcium carbonate was dissolved and removed to prepare inorganic fine particles A10 composed of hydroxyapatite.

Example 11 Preparation of Inorganic Fine Particles A11 When preparing the inorganic fine particles A5, "dissolve and remove internal calcium carbonate" is "50% of internal calcium carbonate.
In the same way, except that the
Inorganic fine particles A11 composed of hydroxyapatite were prepared. Example 12 Preparation of Inorganic Fine Particles A12 When preparing the inorganic fine particles A1, “agitating and aging to obtain hydroxyapatite-treated calcium carbonate.” Was designated as “phosphoric acid 1”.
Calcium hydrogen-treated calcium carbonate was used. Inorganic fine particles A12 composed of calcium monohydrogen phosphate were prepared in the same manner except that the content was changed to "." Example 13 Preparation of Inorganic Fine Particles A13 Needle-shaped aragonite type calcium carbonate having a major axis of 2 μm and a minor axis of 0.3 μm was dispersed in methanol to prepare a methanol suspension of acicular calcium carbonate. While stirring the methanol suspension, a 25% by weight methanol solution of orthophosphoric acid was added dropwise to calcium carbonate to obtain amorphous calcium phosphate-treated calcium carbonate. The obtained calcium carbonate treated calcium carbonate was removed by dissolving the internal calcium carbonate with an organic acid and / or an inorganic acid to prepare inorganic fine particles A13 composed of amorphous calcium phosphate. Example 14 Preparation of Inorganic Fine Particles A14 The inorganic fine particles A12 were heated and dehydrated to prepare inorganic fine particles A14 composed of calcium pyrophosphate. Example 15 Preparation of Inorganic Fine Particles A15 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate”. After adding dropwise an aqueous solution of orthophosphoric acid and sodium fluoride in an amount that gives 25% by weight of fluoroapatite with respect to calcium carbonate, the mixture is aged with stirring to obtain calcium fluoride-treated calcium carbonate. " Thus, an inorganic fine particle A15 composed of calcium fluoride was prepared.

Example 16 Preparation of Inorganic Fine Particles A16 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate. In the same manner as described below, except that "the calcium carbonate-treated calcium carbonate was aged by stirring and aging after adding an aqueous solution of 25% by weight of sodium fluoride to the calcium carbonate in weight ratio." The constituted inorganic fine particle A16 was prepared. Example 17 Preparation of Inorganic Fine Particles A17 When the inorganic fine particles A1 were prepared, “a hydroxyapatite-treated calcium carbonate was prepared by dropping an aqueous solution of 25% by weight of orthophosphoric acid relative to calcium carbonate and aging with stirring.” After adding dropwise an aqueous solution of sodium silicate and calcium chloride in an amount of 25% by weight calcium silicate to calcium carbonate, the mixture was aged with stirring to obtain calcium silicate-treated calcium carbonate. ” Inorganic fine particles A17 composed of calcium silicate were prepared. Example 18 Preparation of Inorganic Fine Particles A18 When preparing the inorganic fine particles A17, “acicular aragonite-type crystal calcium carbonate having a long diameter of 2 μm and a short diameter of 0.3 μm” was added to the “long diameter of 50 μm and a short diameter of 1 μm. Inorganic fine particles A18 composed of calcium silicate were prepared in the same manner except that the aragonite-type crystal calcium carbonate was modified. Example 19 Preparation of Inorganic Fine Particles A19 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and then aged with stirring to obtain hydroxyapatite-treated calcium carbonate.” After adding dropwise an aqueous solution of sodium silicate, magnesium chloride and calcium chloride in an amount of 25% by weight magnesium silicate to calcium carbonate, the mixture was aged with stirring to obtain calcium calcium silicate treated calcium carbonate. " In the same manner, inorganic fine particles A19 composed of magnesium calcium silicate were prepared. Example 20 Preparation of Inorganic Fine Particles A20 When the inorganic fine particles A1 were prepared, “a hydroxyapatite-treated calcium carbonate was prepared by dropping an aqueous solution of 25% by weight orthophosphoric acid relative to calcium carbonate and then aging with stirring”. After adding dropwise an aqueous solution of sodium silicate, sodium fluoride and calcium chloride in an amount of 25% by weight calcium fluorosilicate to calcium carbonate, the mixture was aged with stirring to obtain calcium fluorosilicate-treated calcium carbonate. " In the same manner as below, the inorganic fine particles A composed of calcium fluorosilicate
20 was prepared.

Example 21 Preparation of Inorganic Fine Particles A21 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate. "Depth of 25% by weight of calcium carbonate ultrafine titanium oxide powder suspension with respect to calcium carbonate was added dropwise to the mixture, followed by stirring, aging, dehydration, drying and sintering to obtain calcium titanate-treated calcium oxide. . "
Inorganic fine particles A21 composed of calcium titanate were prepared in the same manner except that the above was changed to. Example 22 Preparation of Inorganic Fine Particles A22 When the inorganic fine particles A1 were prepared, “a hydroxyapatite-treated calcium carbonate was prepared by dropping an aqueous solution of orthophosphoric acid in a weight ratio of 25% to calcium carbonate and aging with stirring.” After adding an aqueous solution of oxalic acid at a weight ratio of 25% to calcium carbonate, the mixture was aged with stirring to obtain calcium oxalate-treated calcium oxide. " Fine particles A22 were prepared. Example 23 Preparation of Inorganic Fine Particles A23 Columnar calcium sulfate having a major axis of 30 μm and a minor axis of 2 μm was dispersed in an aqueous solution to prepare an aqueous suspension of columnar calcium sulfate. While stirring this aqueous suspension, sodium hexametaphosphate and sodium sulfate were added, and then calcium carbonate and sodium carbonate in an amount to give 25% by weight of calcium carbonate to calcium sulfate were added to the calcium carbonate-treated sulfuric acid. It was calcium. By treating the obtained calcium carbonate-treated calcium sulfate with ammonium chloride, the internal calcium sulfate was dissolved and removed to prepare inorganic fine particles A23 composed of calcium carbonate. Example 24 Preparation of Inorganic Fine Particles A24 When the inorganic fine particles A23 were prepared, “calcium carbonate-treated sulfuric acid was added by adding an aqueous solution of calcium chloride and sodium carbonate in an amount of 25% by weight calcium carbonate to calcium sulfate. "Calcium calcium." Was added as "calcium magnesium carbonate-treated calcium sulfate by adding an aqueous solution of calcium chloride, magnesium chloride and sodium carbonate in an amount of 25% by weight calcium magnesium carbonate to calcium sulfate." Inorganic fine particles A24 composed of calcium magnesium carbonate were prepared in the same manner except that the above was changed to. Example 25 Preparation of Inorganic Fine Particles A25 When the inorganic fine particles A1 were prepared, “a hydroxyapatite-treated calcium carbonate was prepared by dropping an aqueous solution of orthophosphoric acid in a weight ratio of 25% to calcium carbonate and aging with stirring.” An aqueous solution of sodium hydrogen phosphate and magnesium chloride in an amount of 25% by weight magnesium monohydrogen phosphate is added dropwise to calcium carbonate,
Calcium carbonate treated with monohydrogen phosphate was used. "
Inorganic fine particles A25 composed of magnesium monohydrogen phosphate were prepared in the same manner except that the above was changed to.

Example 26 Preparation of Inorganic Fine Particles A26 When preparing the inorganic fine particles A1, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate. The same applies to the following except that "is changed to" a magnesium phosphate-treated calcium carbonate obtained by adding dropwise an aqueous solution of sodium phosphate and magnesium chloride in an amount of 25% magnesium phosphate in weight ratio with respect to calcium carbonate, and aging with stirring ". Then, the inorganic fine particles A26 composed of magnesium phosphate were prepared. Example 27 Preparation of Inorganic Fine Particles A27 The inorganic fine particles A25 were heated and dehydrated to prepare inorganic fine particles A27 composed of magnesium pyrophosphate. Example 28 Preparation of Inorganic Fine Particles A28 When the inorganic fine particles A1 were prepared, “a 25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate”. After adding dropwise an aqueous solution of sodium silicate and magnesium chloride in an amount of 25% by weight magnesium silicate to calcium carbonate, the mixture was aged with stirring to give magnesium silicate-treated calcium carbonate. ” Inorganic fine particles A28 composed of magnesium silicate were prepared. Example 29 Preparation of Inorganic Fine Particles A29 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate”. After adding dropwise an aqueous solution of sodium silicate, sodium fluoride and magnesium chloride in an amount of 25% magnesium fluorosilicate by weight relative to calcium carbonate, the mixture was aged with stirring to give calcium fluorosilicate-treated calcium carbonate. " In the same manner as above, inorganic fine particles A29 composed of magnesium fluorosilicate were prepared. Example 30 Preparation of Inorganic Fine Particles A30 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate.” 25% magnesium titanate as a weight ratio to calcium carbonate
An aqueous suspension of ultrafine titanium oxide made of SA, an aqueous solution of magnesium chloride and sodium hydroxide was added dropwise, followed by aging with stirring,
Dehydration, drying and sintering were performed to obtain magnesium titanate-treated calcium oxide. Inorganic fine particles A30 composed of magnesium titanate were prepared in the same manner as described above except that the content was changed to "."

Example 31 Preparation of Inorganic Fine Particles A31 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate. "Is changed to" a magnesium oxalate-treated calcium oxide is obtained by dripping an amount of sodium oxalate and an aqueous solution of magnesium chloride, which are magnesium oxalate having a weight ratio of 25% with respect to calcium carbonate, and aging with stirring. " In the same manner, inorganic fine particles A31 composed of magnesium oxalate were prepared. Example 32 Preparation of Inorganic Fine Particles A32 When preparing the inorganic fine particles A23, “calcium carbonate-treated calcium sulfate was added by adding calcium chloride and sodium carbonate in an amount of 25% by weight calcium carbonate to calcium sulfate. Was carried out in the same manner as described above except that "the magnesium carbonate-treated calcium sulfate was added by adding magnesium chloride and sodium carbonate in an amount of 25% magnesium carbonate in weight ratio to calcium sulfate." Inorganic fine particles A32 composed of magnesium carbonate were prepared. Example 33 Preparation of Inorganic Fine Particles A33 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate”. An aqueous solution of sodium hydrogen phosphate and barium chloride having a weight ratio of 25% barium monohydrogen phosphate to calcium carbonate was added dropwise to obtain barium monohydrogen phosphate-treated calcium carbonate. ” Then, the inorganic fine particles A33 composed of barium monohydrogen phosphate were prepared. Example 34 Preparation of Inorganic Fine Particles A34 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate.” After adding dropwise an aqueous solution of sodium phosphate and barium chloride in an amount of 25% by weight barium phosphate to calcium carbonate, the mixture was aged with stirring to obtain barium phosphate-treated calcium carbonate. ” Inorganic fine particles A3 composed of barium phosphate
4 was prepared. Example 35 Preparation of Inorganic Fine Particles A35 The inorganic fine particles A33 were heated and dehydrated to prepare inorganic fine particles A35 composed of barium pyrophosphate.

Example 36 Preparation of Inorganic Fine Particles A36 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate. The same shall apply to the following except that "the barium silicate-treated calcium carbonate is added by dripping an aqueous solution of sodium silicate and barium chloride in an amount of 25% by weight barium silicate with respect to calcium carbonate, and aging with stirring." Inorganic fine particles A3 composed of barium silicate
6 was prepared. Example 37 Preparation of Inorganic Fine Particles A37 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and then aged with stirring to obtain hydroxyapatite-treated calcium carbonate.” After adding dropwise an aqueous solution of sodium silicate, sodium fluoride and barium chloride in an amount of 25% by weight of barium fluorosilicate to calcium carbonate, the mixture was aged with stirring to give barium fluorosilicate-treated calcium carbonate. " In the same manner, inorganic fine particles A37 composed of barium fluorosilicate were prepared. Example 38 Preparation of Inorganic Fine Particles A38 When preparing the inorganic fine particles A13, “25% by weight methanol solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate”. Except for changing to "the barium sulfate-treated calcium carbonate was added by dripping a methanol solution of sodium sulfate and barium chloride in an amount that produces 25% by weight barium sulfate with respect to calcium carbonate, and aged with stirring." Thus, inorganic fine particles A38 composed of barium sulfate were prepared. Example 39 Preparation of Inorganic Fine Particles A39 When the inorganic fine particles A38 were prepared, “acicular aragonite-type calcium carbonate having a long diameter of 2 μm and a short diameter of 0.3 μm” was added to the “long diameter of 100 μm and a short diameter of 2 μm. Inorganic fine particles A39 composed of barium sulfate were prepared in the same manner except that the content was changed to "aragonite-type crystal calcium carbonate." Example 40 Preparation of Inorganic Fine Particles A40 When the inorganic fine particles A38 were prepared, “acicular aragonite-type calcium carbonate having a major axis of 2 μm and a minor axis of 0.3 μm” was used as “major axis 0.5 μm, minor axis 0.1 μm. Inorganic fine particles A40 composed of barium sulfate were prepared in the same manner except that the “aragonite-type crystal calcium carbonate having a needle-like shape” was changed.

Example 41 Preparation of Inorganic Fine Particles A41 When preparing the inorganic fine particles A38, “sodium sulfate” was used.
Inorganic fine particles A41 composed of barium sulfite were prepared in the same manner as described above except that was changed to "sodium sulfite". Example 42 Preparation of Inorganic Fine Particles A42 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate.” 25% by weight of barium titanate based on calcium carbonate DEGUSSA
An aqueous suspension of ultrafine titanium oxide made of barium chloride and an aqueous solution of barium chloride and sodium hydroxide were added dropwise, and then stirring and aging, dehydration, drying and sintering were performed to obtain barium titanate-treated calcium oxide. Inorganic fine particles A42 composed of barium titanate were prepared in the same manner as described above except that the content was changed to "." Example 43 Preparation of Inorganic Fine Particles A43 When the inorganic fine particles A1 were prepared, “a hydroxyapatite-treated calcium carbonate was prepared by dropwise addition of a 25% by weight aqueous solution of orthophosphoric acid to calcium carbonate, followed by aging with stirring”. After adding dropwise an amount of sodium oxalate and an aqueous solution of barium chloride to obtain 25% by weight of barium oxalate with respect to calcium carbonate, the mixture was aged with stirring to obtain barium oxalate-treated calcium oxide. ” Thus, inorganic fine particles A43 composed of barium oxalate were prepared. Example 44 Preparation of Inorganic Fine Particles A44 When preparing the inorganic fine particles A38, “a methanol solution of sodium sulfate and barium chloride in an amount to give 25% by weight of barium sulfate as a weight ratio with respect to calcium carbonate was dropped, and then aged with stirring to obtain sulfuric acid. "It was barium-treated calcium carbonate."
% Of sodium carbonate and barium chloride in methanol were added dropwise and aged with stirring to obtain barium sulfate-treated calcium carbonate. Inorganic fine particles A composed of barium carbonate in the same manner as above except that
44 was prepared. Example 45 Preparation of Inorganic Fine Particles A45 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and then aged with stirring to obtain hydroxyapatite-treated calcium carbonate.” An aqueous solution of sodium hydrogen phosphate and strontium chloride in an amount of 25% strontium monohydrogen phosphate as a weight ratio with respect to calcium carbonate was added dropwise to obtain strontium monohydrogen phosphate-treated calcium carbonate. " Then, an inorganic fine particle A45 composed of strontium monohydrogen phosphate was prepared.

Example 46 Preparation of Inorganic Fine Particles A46 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate. The same shall apply to the following, except that "the strontium phosphate-treated calcium carbonate is added by dripping an aqueous solution of sodium phosphate and strontium chloride in an amount of 25% strontium phosphate as a weight ratio with respect to calcium carbonate, and aging with stirring." Then, an inorganic fine particle A46 composed of strontium phosphate was prepared. Example 47 Preparation of Inorganic Fine Particles A47 When the inorganic fine particles A1 were prepared, “a hydroxyapatite-treated calcium carbonate was prepared by dropping an aqueous solution of orthophosphoric acid in a weight ratio of 25% with respect to calcium carbonate and aging with stirring.” After adding dropwise an aqueous solution of sodium silicate and strontium chloride in an amount of 25% strontium silicate by weight relative to calcium carbonate, the mixture was aged with stirring to obtain strontium silicate-treated calcium carbonate. ” Inorganic fine particles A47 composed of strontium silicate were prepared. Example 48 Preparation of Inorganic Fine Particles A48 When preparing the inorganic fine particles A1, “a hydroxyapatite-treated calcium carbonate was prepared by dropwise addition of a 25% by weight aqueous solution of orthophosphoric acid to calcium carbonate, followed by aging with stirring”. After adding dropwise an aqueous solution of sodium silicate, sodium fluoride, and strontium chloride in an amount to give 25% by weight of strontium fluorosilicate to calcium carbonate, the mixture was aged with stirring to obtain strontium fluorosilicate-treated calcium carbonate. " In the same manner as above, inorganic fine particles A48 composed of strontium fluorosilicate were prepared. Example 49 Preparation of Inorganic Fine Particles A49 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate”. After dropping an aqueous solution of sodium sulfate and strontium chloride in an amount of 25% strontium sulfate by weight relative to calcium carbonate, the mixture is aged with stirring to obtain strontium sulfate-treated calcium carbonate. ” Inorganic fine particles A49 composed of strontium sulfate were prepared. Example 50 Preparation of Inorganic Fine Particles A50 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to give hydroxyapatite-treated calcium carbonate”. 25% by weight of strontium titanate relative to calcium carbonate
An aqueous suspension of ultrafine titanium oxide made of SSA, an aqueous solution of strontium chloride and sodium hydroxide was added dropwise, and then aging with stirring, dehydration, drying and sintering were performed to obtain strontium titanate-treated calcium oxide. Inorganic fine particles A50 composed of strontium titanate were prepared in the same manner as described below except that the content was changed to "."

Example 51 Preparation of Inorganic Fine Particles A51 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate. "Is changed to" a strontium oxalate-treated calcium oxide by dripping an aqueous solution of sodium oxalate and an aqueous solution of strontium chloride to obtain 25% strontium oxalate as a weight ratio with respect to calcium carbonate, and aging with stirring. " In the same manner, inorganic fine particles A51 composed of strontium oxalate were prepared. Example 52 Preparation of Inorganic Fine Particles A52 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate”. After adding dropwise an amount of sodium carbonate, strontium chloride and an aqueous solution of sodium sulfate which gives 25% by weight of strontium carbonate to calcium carbonate, the mixture is aged with stirring to give strontium carbonate-treated calcium oxide. " As a result, inorganic fine particles A52 composed of strontium carbonate were prepared. Example 53 Preparation of Inorganic Fine Particles A53 When the inorganic fine particles A1 were prepared, “a hydroxyapatite-treated calcium carbonate was prepared by dropping an aqueous solution of orthophosphoric acid in a weight ratio of 25% to calcium carbonate, followed by aging with stirring”. After adding dropwise an aqueous solution of sodium phosphate and beryllium chloride in an amount of 25% beryllium phosphate by weight ratio to calcium carbonate, the mixture was aged with stirring to obtain beryllium phosphate-treated calcium carbonate. ” Inorganic fine particles A53 composed of beryllium phosphate were prepared. Example 54 Preparation of Inorganic Fine Particles A54 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and then aged with stirring to obtain hydroxyapatite-treated calcium carbonate.” After adding dropwise an aqueous solution of sodium phosphate and ammonium sulfate in an amount of 25% by weight of aluminum phosphate with respect to calcium carbonate, the mixture was aged with stirring to give aluminum phosphate-treated calcium carbonate. ” Inorganic fine particles A54 composed of aluminum were prepared. Example 55 Preparation of Inorganic Fine Particles A55 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate”. After adding dropwise an aqueous solution of sodium silicate and ammonium sulfate in an amount of 25% by weight of aluminum silicate to calcium carbonate, the mixture was aged with stirring to give aluminum silicate-treated calcium carbonate. ” Inorganic fine particles A55 composed of aluminum were prepared.

Example 56 Preparation of Inorganic Fine Particles A56 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and aged with stirring to obtain hydroxyapatite-treated calcium carbonate. “A drop of an aqueous solution of active silicate gel and sodium aluminate in an amount of 25% aluminum silicate by weight ratio to calcium carbonate was added, and the mixture was aged with stirring to give sodium aluminosilicate-treated calcium carbonate.”
Sodium aluminosilicate (Na ₂ O ・ 2SiO ₂・ Al ₂ O ₃・ nH ₂ O +
Inorganic fine particles A56 composed of mH ₂ O and A type zeolite were prepared. Example 57 Preparation of Inorganic Fine Particles A57 When the inorganic fine particles A56 were prepared, “acicular aragonite-type calcium carbonate having a long diameter of 2 μm and a short diameter of 0.3 μm” was added to the “long diameter of 100 μm and a short diameter of 2 μm. It is other than to change the aragonite type calcium carbonate crystals "are all in the same way, sodium aluminosilicate _{(Na 2 O · 2SiO 2 ·} Al 2 O 3 · nH 2 O + mH
₂ O, A type zeolite equivalent)
57 was prepared. Example 58 Preparation of Inorganic Fine Particles A58 When the inorganic fine particles A1 were prepared, “25% by weight aqueous solution of orthophosphoric acid relative to calcium carbonate was added dropwise and then aged with stirring to obtain hydroxyapatite-treated calcium carbonate.” An aqueous solution of sodium silicate having a weight ratio of 25% silicic acid to calcium carbonate was added dropwise, and ammonium chloride was further added, followed by aging with stirring to obtain silicic acid (SiO ₂ · nH ₂ O) -treated calcium carbonate. ”
Silicic acid (SiO ₂ · n
Inorganic fine particles A58 composed of H ₂ O) were prepared.

With respect to the inorganic fine particles A1 to A58 obtained in the above Examples 1 to 58, the main structural substances were identified by X-ray diffraction and / or chemical analysis. The results are shown in Tables 1 to 3. Also, electron micrograph, nitrogen adsorption BET
Tables 4 and 5 show the results of the measurement of specific surface area by the method and the pore distribution measurement by the mercury intrusion method. Each of the inorganic fine particles A1 to A58 was a tubular synthetic inorganic fine particle having a needle-like and / or columnar shape with a specific particle size and having a hollow space with a specific particle size. However, the symbols in Tables 4 and 5 have the following contents. DS1: The long-sided average particle diameter (μm) of the tubular synthetic inorganic fine particles measured by an electron micrograph. DS2: Average particle diameter (μm) of the outer diameter (minor diameter) of the tubular synthetic inorganic fine particles measured by an electron micrograph. DS3: Average particle diameter (μm) of the inner diameter of the tubular synthetic inorganic fine particles measured by an electron micrograph. DS1 / DS2: A value representing the aspect ratio of the long diameter and the short diameter of the tubular synthetic inorganic fine particles. DS3 / DS2: A value representing the ratio of the inner diameter to the outer diameter of the tubular synthetic inorganic fine particles. SW: Measured value (m ² / g) determined by the nitrogen adsorption BET method V1 and V2 are determined by the pore distribution measured by the mercury porosimetry method V1: Pore volume (%) less than 0.02 μm in diameter V2 : Pore volume (%) with a diameter of 0.02 μm or more The instruments used for various analyzes and measurements in the examples are described below. X-ray diffraction: Geigerflex R, Rigaku Denki Co., Ltd.
AD-IA electron microscope: Hitachi Ltd. scanning electron microscope S-5
10 and specific surface area by nitrogen adsorption BET method: Shibata Scientific Instruments Co., Ltd. Rapid surface area measuring instrument SA-1000 Pore distribution by mercury injection method: Micromeritics porosimeter pore size 9320

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Application Example] Table 6 shows the contents of the particles B1 to B11 used in the application comparative example, and Table 7 shows the physical properties thereof.

[0041]

[Table 6]

Among the particles B1 to B11 in Table 5, those not commercially available were prepared as follows. B3 Spherical hydroxyapatite 1 Mix calcium nitrate, diammonium ethylenediaminetetraacetate, diammonium hydrogen phosphate and aqueous ammonia,
Then add a small amount of hydrogen peroxide water, dehydrate the obtained particles,
It was washed with water and dried to obtain spherical hydroxyapatite 1 of about 50 μm. B4 Spherical hydroxyapatite 2 An orthophosphoric acid aqueous solution was added to a calcium hydroxide aqueous suspension to synthesize hydroxyapatite, and an aqueous suspension prepared by mixing sodium alginate with this was added dropwise to the calcium chloride aqueous suspension. Is dehydrated, washed with water and dried for about 3500
A spherical hydroxyapatite 2 having a size of μm was obtained. B10 Needle-like aragonite-type calcium carbonate 5% to calcium hydroxide in an aqueous solution of calcium hydroxide
% Orthophosphoric acid was added, carbon dioxide gas having a concentration of 20% was conducted at 40 ° C. while stirring, and a long diameter of 5 μm and a short diameter of 0.
4 μm of acicular aragonite type calcium carbonate was obtained.

[0043]

[Table 7]

Application Examples 1 to 58 Using 10 g of the inorganic fine particles A1 to A58, which are the tubular synthetic inorganic fine particles obtained in Examples 1 to 58, as a carrier, they were immersed in a 10% carbon tetrachloride solution of naphthalene, and then tetrachlorinated. Naphthalene (pesticide) -adsorbed inorganic fine particles A1 to A58, which are vaporized carbon and adsorbed 2 g of naphthalene, sustained-release bodies A1 to A58
Was prepared. The sustained release product was placed in a constant temperature bath at 40 ° C., the residual rate of naphthalene was measured over time, and its sustained release property was examined. The results are shown in Tables 8 to 10. It became clear that the tubular synthetic inorganic fine particles of the present invention are excellent as sustained-release carrier.

Application Comparative Examples 1 to 11 In the same manner as in Application Examples 1 to 58, except that the inorganic fine particles A1 to A58, which are tubular synthetic inorganic fine particles, are changed to the particles B1 to B11 shown in Table 6, the naphthalene adsorption particles B1 are similarly processed. ~
A sustained-release form of B11 was prepared, and the sustained-release property of naphthalene over time was examined for the sustained-release form. The results are shown in Table 11. In Comparative Application Examples 1 to 11, the sustained release property was remarkably poor as compared with the Applied Example.

[0046]

[Table 8]

[0047]

[Table 9]

[0048]

[Table 10]

[0049]

[Table 11]

Application Examples 59 to 116 Using 10 g of the inorganic fine particles A1 to A58, which are the tubular synthetic inorganic fine particles obtained in Examples 1 to 58, as a carrier, 5 g of a 40% aqueous solution of tannic acid was sprayed and adsorbed. Tannic acid adsorbing inorganic fine particles A adsorbing 2 g of tannic acid
A sustained release product of 1 to A58 was prepared. In order to test the deodorizing power of this sustained release body, nitrogen gas was supplied from one of the air-washing bottles (volume: 300 ml) containing 10% ammonia water 150 (50 ml).
While flowing at 0 ml / min, a column packed with the sustained-release material was attached to the other outlet, and ammonia passing through the column was introduced into a hydrochloric acid aqueous solution having a pH of 4 to reduce the adsorption capacity of the adsorbent. The persistence of the deodorizing power was investigated by determining the adsorption time until the pH became 10 or more until the ammonia was not adsorbed, and the results are shown in Tables 12 to 1
4 shows. Application Examples 59 to 116 showed good results, and it became clear that the tubular synthetic inorganic fine particles of the present invention are excellent as a deodorant carrier.

Application Comparative Examples 12 to 22 In the same manner as in Application Examples 59 to 116, except that the inorganic fine particles A1 to A58, which are tubular synthetic inorganic fine particles, are changed to the particles B1 to B11 in Table 6, the tannic acid adsorbing particles are similarly prepared. B
1 to B11 sustained-release preparations were prepared, and the deodorizing power was examined for their durability.
The results are shown in Table 15.

[0052]

[Table 12]

[0053]

[Table 13]

[0054]

[Table 14]

[0055]

[Table 15]

Application Examples 117 to 174 1 g of the inorganic fine particles A1 to A58, which are the tubular synthetic inorganic fine particles obtained in Examples 1 to 58, are used as a carrier.
Chlorine peroxide (having antibacterial, sterilizing, sterilizing and degrading ability) adsorbing inorganic fine particles A1 to A58, which was sprayed with a 0% stabilized chlorine peroxide solution to adsorb 2 g of chlorine peroxide. An asparagus was prepared. The sustained-release body was allowed to stand at room temperature, the residual rate was measured over time, and the sustained-release property was examined.
~ 19. The application examples 117 to 174 are good with respect to the application comparative examples 21 to 30 described below, and the tubular synthetic inorganic fine particles of the present invention are a sustained release carrier, an antibacterial agent carrier, a disinfectant carrier, and a bactericide carrier. It was also clarified that it is an excellent carrier for sustained-release peroxides.

Application Comparative Examples 23 to 33 In Application Examples 117 to 174, the inorganic fine particles A1 to A58, which are tubular synthetic inorganic fine particles, are replaced with the particles B1 to B11 in Table 6.
In the same manner as described below except that the chlorine peroxide adsorbent particles B1 to B11 were prepared in the same manner as described above, the chlorine peroxide adsorbing ability and the time-dependent sustained release property of the sustained release material were examined, and the results are shown in Table 2.
It shows in 0.

[0058]

[Table 16]

[0059]

[Table 17]

[0060]

[Table 18]

[0061]

[Table 19]

[0062]

[Table 20]

Application Examples 175 to 232 Using 10 g of the inorganic fine particles A1 to A58, which are the tubular synthetic inorganic fine particles obtained in Examples 1 to 58, as a carrier, 5
% Alkyl alkylaminoaminoglycine hydrochloride aqueous solution 2 g
Was then impregnated to prepare a sustained-release body of alkylpolyaminoethylglycine hydrochloride (antifungal agent) -adsorbed inorganic fine particles A1 to A58. The sustained release product was placed in a 500 ml glass container, a filter paper was laid on the glass container, and a piece of bread having a side of 3 cm was placed on the glass container, and the bread was left in a dark place with a humidity of 60%. Observe the condition, investigate its sustained release and anti-emergent properties,
The results are shown in Tables 21-23. 175-23 of application examples
2 is good with respect to the application comparative examples 31-40 described below. It was clarified that the tubular synthetic inorganic fine particles of the present invention are excellent as a sustained release carrier and an antifungal agent sustained release carrier.

Application Comparative Examples 34 to 44 In Application Examples 175 to 232, the inorganic fine particles A1 to A58, which are tubular synthetic inorganic fine particles, are replaced with the particles B1 to B11 in Table 6.
Alkylpolyaminoethylglycine hydrochloride (antifungal agent) adsorbent particles B1 to B11 are similarly used except that the above is changed to
Was prepared, and the sustained-release property and antifungal property of the sustained-release product were examined, and the results are shown in Table 24.

[0065]

[Table 21]

[0066]

[Table 22]

[0067]

[Table 23]

[0068]

[Table 24]

Application Examples 233 to 238 Inorganic fine particles A1, A9, A28, which are the tubular synthetic inorganic fine particles of Examples 1, 9, 28, 39, 46 and 56,
A38, A46 and A56 were dispersed in ethylene glycol with an ultrasonic disperser to obtain an ethylene glycol dispersion of inorganic fine particles A having a concentration of 1%. 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol and 0.09 part by weight of magnesium acetate tetrahydrate are placed in a reaction vessel,
While heating and raising the temperature, the generated methanol was distilled off to terminate the transesterification reaction. After that, the inorganic fine particles A
The ethylene glycol dispersion of 1, A9, A28, A38, A46 and A56 was used as the solid content of the inorganic fine particles A.
3 parts by weight, 0.03 parts by weight of phosphoric acid and 0.04 parts by weight of antimony oxide are added and polycondensation reaction is carried out for 4 hours.
Inorganic fine particles A1, A9, A28, A38, A46 and A
Polyethylene terephthalate A1, A containing 56
9, A28, A38, A46 and A56 were obtained. Polyethylene terephthalate A1, A9, A28, A38, A
46 and A56 are dried by a conventional method and melt-extruded at 290 ° C. to obtain an amorphous sheet, and the sheet flow direction (longitudinal direction)
At 110 ° C. by 3.5 times, at 110 ° C. by 3.5 times, and at 130 ° C. by 1.08 times in the longitudinal direction.
Inorganic fine particles A1, A9, A28, A38, A4 of the examples were used as antiblocking agents by heat treatment at 0 ° C. for 3 seconds.
Polyethylene terephthalate films A1, A9 and A56 containing 6 and A56 and having a thickness of 15 μm were obtained. The film properties are shown in Table 25. From the results in Table 25, it was clarified that the tubular synthetic inorganic fine particles of the present invention are excellent as antiblocking agents and plastic fillers.

Application Comparative Examples 45 to 52 Blocking was performed in the same manner as in Application Examples 233 to 238 except that the tubular synthetic inorganic fine particles were changed to the particles B1, B3, B5, B8, B9, B10 and B11 in Table 6. Particles B1, B3, B5, B8, B9, B1 as inhibitors
0 and B11 polyethylene terephthalate films B1, B3, B5, B8, B9 and B10 having a thickness of 15 μm
Got The film properties are shown in Table 25.

[0071]

[Table 25]

Sliding property: A film is wound around a fixed hard chrome fixing pin having a diameter of 6 mm at a rotation angle of 135 °, a load of 53 g (T2) is applied, and a speed is 1 m / min.
The film is run with a load of 53 g and the resistance at the opposite end (T1, g). Abrasion resistance: A film is wound around a fixed hard chrome fixing pin with a diameter of 6 mm and brought into contact at an angle of 135 degrees, and the speed is 10
The film was run for 1000 m at m / min and a tension of 200 g, and the amount of worn white powder attached to the pins was visually evaluated.

Application Examples 239 to 245 1: 1 mixture of Examples 1, 5, 1 and 5 28, 38, 46
And 56, which are tube-shaped synthetic inorganic fine particles, which are 1: 1 mixture of inorganic fine particles A1, A5, A1 and A5, A28, A3
1 g of 8, A46 and A56 was dispersed in 99 g of water with an ultrasonic disperser to prepare 100 g of A28, A38, A46 and A56, a 1: 1 mixture of water dispersions A1, A5, A1 and A5. The glass vacuum holder KGS-47 (manufactured by Toyo Advantic, 100 mesh stainless support screen, effective filtration area 9.6 cm ² ) was used for No. 2 pieces of filter paper (manufactured by Toyo Advantic) were set, moistened with water, and 1: 1 mixture of the water dispersions A1, A5, A1 and A5, and 100 g of A28, A38, A46 and A56 were mixed.
Filtration was performed under a reduced pressure of 00 mmHg, and No. 2 Inorganic particles A1, A5, 1: 1 mixture of A1 and A5 on filter paper, A2
8, A38, A46 and A56 were precoated with 1 g.
This was subjected to a filtration test with 100 ml of a 0.5 μm concentration of 0.3 μm latex sphere dispersion, and the particle scavenging performance (the higher the scavenging efficiency, the better, further 100 %, The better.) Was measured and the results are shown in Table 26. From the results in Table 26, it became clear that the tubular synthetic inorganic fine particles of the present invention are useful as a filter aid.

Application Comparative Examples 52 to 58 In Application Examples 239 to 245, the same procedure as in Example 6 was repeated except that the tubular synthetic inorganic fine particles were changed to the particles B1, B3, B5, B8, B9, B10 and B11 shown in Table 6. Tests were carried out and the properties as filter aids are shown in Table 26.

[0075]

[Table 26]

Application Examples 246 to 251 Inorganic fine particles A1, A5, A28, which are the tubular synthetic inorganic fine particles of Examples 1, 5, 28, 38, 46 and 56,
10 kg of A38, A46 and A56 was dispersed in warm water to prepare a warm water suspension, and 2 kg of stearic acid was emulsified with 0.4 kg of dodecylbenzenesulfonic acid and added to the warm water suspension,
After stirring, aging, dehydration, drying and finishing, stearic acid-treated inorganic fine particles A1, A5, A28, A38, A46
And A56. The stearic acid-treated inorganic fine particles 20
By weight, 80 parts by weight of polypropylene in a heat-melted state was added as a powder, and kneaded and dispersed to prepare polypropylene pellets containing 20% of the stearic acid-treated inorganic fine particles. A test piece was prepared from the pellet by an injection molding method, and the tensile strength of the normal portion and the tensile strength of the weld portion were measured, and the results are shown in Table 27. From the results shown in Table 27, it was clarified that when the tubular synthetic inorganic fine particles of the present invention were used as a filler in polypropylene, not only the ordinary portion but also the weld portion was high, and the filler was useful as a polypropylene filler. It is also considered to be useful as a filler for thermoplastics other than polypropylene.

Application Comparative Examples 59 to 65 In the same manner as in Application Examples 246 to 251, except that the tubular synthetic inorganic fine particles are changed to the particles B1, B3, B5, B8, B9, B10 and B11 shown in Table 6, the same procedure is performed. 20% particles
Content polypropylene pellets were prepared, a test piece was prepared from the pellets by an injection molding method, the tensile strength of the normal portion and the tensile strength of the weld portion were measured, and the results are shown in Table 27. Although B11 of Comparative Application Example 65 and similar talc have been conventionally used, they cannot be said to be satisfactory in physical properties. In particular, there is a problem that the strength of the weld portion is reduced.

[0078]

[Table 27]

[0079]

INDUSTRIAL APPLICABILITY As described above, the tubular synthetic inorganic particles of the present invention are used as a carrier for catalysts and drugs, adsorbents and sustained-release materials, plastics, rubbers, paints, inks, sealing materials, and fillers for papermaking. It is useful as an anti-blocking agent in fibers, films and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B01D 53/86 ZAB C01B 25/32 Z C01F 11/18 H 9040-4G M 9040-4G 11/22 9040-4G 11/46 A 9040-4G B 9040-4G 11/48 9040-4G // B01D 53/28 C02F 3/10 ZAB Z C09K 3/00 L

Claims (10)

[Claims] 1. A needle-shaped and / or columnar shape having a hollow space inside, and the following formulas (a) to (e):
Tube-shaped synthetic inorganic fine particles satisfying the above physical properties. (A) 0.1 ≦ DS1 ≦ 1000 (μm) (b) 0.05 ≦ DS2 ≦ 100 (μm) (c) 0.02 ≦ DS3 ≦ 95 (μm) (d) DS1 / DS2 ≧ 2 (e) 0.05 ≦ DS3 / DS2 ≦ 0.95 However, DS1: average particle diameter (μm) of major axis of tubular synthetic inorganic fine particles measured by an electron micrograph. DS2: Average particle diameter (μm) of the outer diameter (minor diameter) of the tubular synthetic inorganic fine particles measured by an electron micrograph. DS3: Average particle diameter (μm) of the inner diameter of the tubular synthetic inorganic fine particles measured by an electron micrograph. DS1 / DS2: A value representing the aspect ratio of the long diameter and the short diameter of the tubular synthetic inorganic fine particles. DS3 / DS2: A value representing the ratio of the inner diameter to the outer diameter of the tubular synthetic inorganic fine particles. 2. The tubular synthetic inorganic fine particles according to claim 1, further having fine protrusions and / or fine pores on the surface thereof and satisfying the physical properties of the following formula (f) together. (F) V1 ≦ V2 V1 and V2 are obtained by the pore distribution measured by the mercury intrusion method. V1: Pore volume of less than 0.02 μm diameter (%) V2: Pore volume of 0.02 μm or more diameter (%) 3. The synthetic inorganic fine particles are phosphates, fluorides, silicates, sulfates, carbonates, perovskite salts (MTi).
O ₃ , M = divalent metal), oxalates and hydroxides of alkaline earth metal salts, phosphates, silicates and hydroxides of aluminium salts, silicic acid and silicic acid hydrates. A composition mainly comprising at least one selected from the above.
Or the tubular synthetic inorganic fine particles according to 2. 4. The tubular synthetic inorganic fine particles according to claim 3, wherein the alkaline earth metal is at least one selected from the group consisting of calcium, magnesium, barium, strontium and beryllium. 5. The tubular synthetic inorganic fine particles according to claim 1, which are mainly composed of hydroxyapatite and / or fluoroapatite. 6. The method according to claim 1, further satisfying the following expression (g).
5. The tubular synthetic inorganic fine particles according to 5 above. (G) DS1 / DS2 ≧ 3 7. The method according to claim 1, further satisfying the following expression (h).
5. The tubular synthetic inorganic fine particles according to 5 above. (H) DS1 / DS2 ≧ 5 8. The tubular synthetic inorganic fine particles according to claim 1, which further satisfy the following physical properties of the formula (i). (I) Sw ≧ 10 m ² / g Sw: specific surface area (m ² / m ² measured by nitrogen adsorption BET method)
g) 9. The tubular synthetic inorganic fine particles according to claim 1, which further satisfy the following physical properties of the formula (j). (J) Sw ≧ 20 m ² / g Sw: Specific surface area measured by nitrogen adsorption BET method (m ² /
g) 10. The tubular synthetic inorganic fine particles according to claim 1, which further satisfy the following physical properties of the formula (k). (K) Sw ≧ 50 m ² / g Sw: Specific surface area (m ² / m ² measured by nitrogen adsorption BET method)
g)