JP2818328B2 - Method for producing porous spherical apatite particles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing porous spherical apatite particles used for, for example, cosmetic raw materials.

[0002]

2. Description of the Related Art Apatite has a general chemical formula of M ₁₀ (ZO ₄ )
A substance group represented by ₆ X ₂ , wherein M is Ca, P
b, Ba, Sr, Cd, Zn, Ni, Mg, Na, K,
Fe, at least one from among the elements of Al, as _{ZO 4, PO 4, AsO 4} , VO 4, SiO 4 or C
O ₃ and X are composed of at least one of the elements or atomic groups of F, OH, Cl, Br and O.

[0003] Hydroxyapatite, which is a kind of apatite, is represented by the chemical formula Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , which is processed into substantially spherical particles having a particle size of about 10 μm using a spray dryer or the like. Because the surface is porous, not only is it good for "slip" and "glue" on the skin, but it is also non-toxic and has the property of adsorbing fats and oils. It is used.

Conventionally, the porous spherical hydroxyapatite particles as described above have been obtained as aggregates of hydroxyapatite fine particles. For example, a slurry composed of hydroxyapatite fine particles of 0.1 μm or less is spray-dried. It is manufactured by spherical granulation and drying using.

However, porous spherical apatite particles are
Since it is manufactured by spherical granulation using a spray dryer, there has been a problem that its particle size distribution is hard to be sharp.

Therefore, since the function of hydroxyapatite is exerted on the surface of the particles, resin particles whose particle size distribution is easily controlled are used as nuclei, and the surfaces of the nuclei are coated with fine particles of hydroxyapatite. Thus, a method for obtaining porous spherical apatite particles has been devised.

As the resin used in the above-mentioned method, polymethyl methacrylate (hereinafter referred to as PMMA) which has been conventionally used as a raw material for dental materials, bone fillers, cosmetics and the like and has high safety is used. As the coating method, a dry method such as a mechanochemical method or a high-speed airflow impact method (hybridization) is used.

[0008]

However, in the above-mentioned conventional method, dents are formed on the surface of resin particles serving as nuclei, and hydroxyapatite particles are attached to the resin particles as in the case of composite toe. The shape of the porous spherical apatite particles tends to be irregular and irregular.

Therefore, when such porous spherical apatite particles are used as a raw material for cosmetics such as a foundation substrate, "slip" or "paste" on the skin of the cosmetics is required.
However, it is difficult to say that it is sufficient.

Accordingly, an object of the present invention is to provide a method for producing porous spherical apatite particles having a shape close to a true sphere and a sharp particle size distribution in order to improve "slip" and "glue" on the skin. It is to provide.

[0011]

Method for producing a porous spherical apatite particles of the present invention, in order to solve the problems] In order to solve the above problem, by supplying the slurry and the resin particles of apatite particles in high-speed air stream, the resin While the particles are dispersed, the surface of the resin particles is coated with the apatite fine particles to obtain porous spherical apatite particles.

The apatite in the apatite fine particles is
A substance group represented by the general chemical formula M ₁₀ (ZO ₄ ) ₆ X ₂ , wherein M is Ca, Pb, Ba, Sr, Cd, Zn,
Ni, Mg, Na, K, Fe, and at least one from among the elements of Al, as _{ZO 4, PO 4, AsO 4} , VO
₄ , SiO ₄ or CO ₃ and X as F, OH, C
It is composed of at least one of l, Br and O elements or atomic groups.

The apatite fine particles preferably have a particle size of 0.1 μm or less in order to produce porous spherical apatite particles having a large specific surface area.

The resin is not particularly limited as long as it is excellent in moldability and strength and is non-toxic. For example, polymethyl methacrylate (hereinafter referred to as PMMA) can be used.

The average particle size and particle size distribution of the resin particles can be changed according to the desired average particle size and particle size distribution of the porous spherical apatite particles.

The concentration of the slurry is 1 to 90% by weight.
However, when the slurry concentration exceeds 30% by weight, the viscosity becomes considerably high, so that uneven stirring is easily performed and it is difficult to obtain a uniform slurry. On the other hand, when the slurry concentration is less than 3% by weight, the yield of the porous spherical apatite particles becomes small,
The concentration range of the slurry is preferably 3 to 30% by weight.

As the dispersant, various dispersants for dispersing apatite fine particles and resin particles can be used. Specific examples include polyacrylate, nitrohumate, and the like.
Lignin sulfonate, styrene-maleic anhydride copolymer, and the like are not limited thereto.

It has been experimentally confirmed that the sphericity of the obtained porous spherical apatite particles can be improved by adding even a small amount of the above-mentioned dispersant to the mixture. The amount of impurities in the porous spherical apatite particles will also increase with this,
The added amount of the dispersant is preferably 10% by weight or less.

[0019]

According to the above method, the slurry of apatite fine particles is
The resin and the resin particles are supplied into a high-speed airflow, and the apatite fine particles and the resin particles are slid in the airflow to generate static electricity having different polarities on the apatite fine particles and the resin particles. At times, aggregation of resin particles and apatite fine particles is reduced.

Therefore, the surface of the resin particles can be coated with the apatite fine particles in the air stream while dispersing the resin particles to avoid agglomeration, so that the surface of one resin particle is uniformly coated with the apatite fine particles. Porous spherical apatite particles can be obtained.

Therefore, by appropriately selecting the shape and particle size distribution of the resin particles, the obtained porous spherical apatite particles can have a sharp particle size distribution and a substantially spherical shape.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 which is one embodiment of the present invention will be described below with reference to FIG. [Example 1] First, the preparation of the hydroxyapatite fine particles will be described.
Phosphoric acid aqueous solution diluted 2 to 4 times is dropped until near H11, and then a phosphoric acid aqueous solution diluted about 5 times or more is dropped to adjust the pH to 10 to 9, and appropriately diluted with ion exchanged water. As a result, an HAp slurry (having a concentration of 20% by weight) in which fine particles of hydroxyapatite (hereinafter, referred to as HAp) having a particle size of 0.1 μm or less were suspended was obtained. HAp here is Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ .

Next, a method for producing the porous spherical apatite particles will be described. First, a predetermined amount of water is added to the above-mentioned HAp slurry and the mixture is stirred with a stirring motor to obtain a HAp preparation. Polymethyl methacrylate having a desired average particle size and particle size distribution (hereinafter, referred to as
PMMA), resin particles (manufactured by Sekisui Chemical Co., Ltd., trade name: Techpolymer MB-8C) and water are added in predetermined amounts, respectively, and as shown in FIG. 1, HAp particles (apatite fine particles) 1, PMMA particles (Resin particles) 2
A mixed solution (mixture) 4 containing was prepared.

Also, a predetermined amount of a binder solution prepared by adjusting the ratio (weight ratio) of solid content [Methylcellulose binder EB-43PS (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) to water] to 1/60 is added. Solution 4 was also prepared. The respective mixing ratios and operating conditions described below are shown in Table 1.

[0025]

[Table 1]

However, the units of the blending amounts of PMMA, HAp slurry, water and binder are expressed in grams, the unit of liquid supply is expressed in grams / hour, and the unit of drying temperature is expressed in ° C.

Each mixed solution 4 prepared at various mixing ratios was
The metering pump 5 supplies a predetermined supply amount to a liquid coating nozzle 7 of a coating machine (model DC-08, manufactured by Nisshin Engineering) 6 and a high speed generated in the liquid coating nozzle 7 by compressed air from a compressor 8. Each was supplied into the airflow.

The mixed solution 4 in the high-speed airflow is coated while being dispersed by the high-speed airflow and sprayed into the drying chamber 9, and then the porous spherical apatite particles 10 coated while being dispersed are discharged from the liquid coating nozzle 7. Riding on the discharged high-speed airflow, it descends down the center of the drying chamber 9, and then rises while being dried by hot air heated by the heater 11 blowing upward from the lower part of the drying chamber 9. , And collected by the filter 13 through the cyclone 12.

Here, the porous spherical apatite particles 10
For recovery, the filter 13 was used instead of the cyclone 12. Table 1 shows the mixing ratios of PMMA, HAp slurry, water and / or binder, and the operating conditions described above for coating the porous spherical apatite particles 10.

On the other hand, the HAPM particles 1
When the A particles 2 increases, since PMMA particles 2 tend to aggregate, as a dispersing agent 3, H ⁺ ions acrylic acid N
A mixed solution 4 was prepared by further adding an acrylic-NH ₄ dispersant having a molecular weight of about 10,000 (D-134, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) substituted with H ₄ ⁺ ions to a predetermined concentration. By operating in the same manner as described above, the porous spherical apatite particles 10
I got Table 2 shows the mixing ratio of each of the mixed solutions 4.

As the other dispersant for the above-mentioned dispersant 3, various dispersants for dispersing apatite fine particles and resin particles can be used. Specific examples include polyacrylate, nitrohumate, and the like. Lignin sulfonate,
There is a styrene-maleic anhydride copolymer and the like, but not limited thereto.

Further, when a small amount of each of the above dispersants is added to the mixed solution 4, the resulting porous spherical apatite particles 10
It is experimentally confirmed that the sphericity of the particles is improved. However, if the dispersant added to the mixed solution 4 increases too much, the amount of impurities in the porous spherical apatite particles 10 also increases. 10% by weight
The following is preferred.

[0033]

[Table 2]

However, the unit of the compounding amount of PMMA, HAp slurry, water and dispersant was expressed in grams.

When the coating state of each of the porous spherical apatite particles 10 obtained in Example 1 was observed with a scanning electron microscope, for example, as shown in the substitute photographs of FIGS. It was found that almost spherical spherical apatite particles in which apatite fine particles were clearly coated on one PMMA particle were obtained without aggregation. In addition, as shown in Table 1, porous spherical apatite particles can be obtained without adding a binder, but by adding a binder, the coating became stronger.

Next, a second embodiment which is another embodiment of the present invention.
Will be described. Example 2 A HAp slurry was prepared in the same manner as in Example 1 described above, and the concentration was adjusted to 20% by weight. The HAp slurry and P
MMA [Technopolymer MB-8C, trade name, manufactured by Sekisui Plastics Co., Ltd.] particles and a coating machine using a jet jet under the conditions shown in Table 3 [Freund Industrial Co., Ltd.]
Coatmizer].
The HAp slurry was used as a liquid spray, and the PMMA particles were used as a powder spray.

When the state of coating of the collected particles was observed with a scanning electron microscope, coated porous spherical apatite particles were observed as shown in FIG.

[0038]

[Table 3]

The unit of the air pressure is kg / cm ³ , and the unit of the feed amount is g / min.

As described above, according to the method of each of the above embodiments, by adding PMMA particles to the HAp slurry having a predetermined concentration and supplying the slurry to a dispacoat or coatmizer, the PMMA particles are hardly aggregated.
Porous spherical apatite particles in which apatite fine particles are uniformly coated on two PMMA particles can be stably obtained.

The dispersant was HAp slurry and PMMA.
By adding to the mixture with the particles, aggregation of the PMMA particles is prevented, and porous spherical apatite particles in which apatite fine particles are uniformly coated on one PMMA particle can be obtained more stably. Further, by adding a binder to the above mixture, the coating film of the apatite fine particles becomes stronger, and the strength of the obtained porous spherical apatite particles is also improved.

Therefore, usually, PMMA has good moldability and its average particle size and particle size distribution can be easily and arbitrarily manufactured within a predetermined range. Therefore, for example, a material having a sharp particle size distribution is selected. Then, porous spherical apatite particles having a sharp particle size distribution, which cannot be obtained with a granulated product of conventional apatite fine particles, can be easily and stably produced by the above method.

In addition, since it is extremely easy to shape the shape of PMMA into a substantially true sphere, the obtained porous spherical apatite particles are uniformly coated on one PMMA with apatite fine particles. It is extremely easy to make the obtained porous spherical apatite particles substantially spherical. Further, by adjusting the average particle size of PMMA to an arbitrary size, the average particle size of the obtained porous spherical apatite particles can be easily controlled.

Further, the porous spherical apatite particles obtained by the above method can have an extremely large specific surface area even if the apatite particles are unevenly distributed on the surface even if they have PMMA as a nucleus.

Therefore, even when such porous spherical apatite particles are used as a cosmetic material such as a foundation material, for example, free fatty acids, which are sebum waste products that have an adverse effect on the skin among human sebum components, can be effectively adsorbed. The ability to remove fats and oils can be maintained without practical problems.

Further, since PMMA, which is considerably less expensive than apatite fine particles, can be used as a nucleus, the above-mentioned method is also advantageous in that the obtained porous spherical apatite particles are inexpensive.
It has become economical.

As a result, the porous spherical apatite particles obtained by the above method have a sharp particle size distribution and can be made almost spherical in shape, so that they have good "slip" and "glue" on the skin. Therefore, it can be suitably used as a cosmetic raw material such as a cleansing cream and a foundation.

The porous spherical apatite particles are
Since it has sufficient biocompatibility, it can be suitably used as a dental material and a bone filler as a biomaterial. Furthermore, when the conventional HAp single particles are used as a filler for a medium-pressure chromatographic column for component separation, the HAp single particles are broken by pressure due to insufficient strength of the HAp single particles, and clogging easily occurs in the column. However, since the above configuration uses PMMA particles as base particles, the strength of the particles can be improved, so that the above configuration can be used as a filler for a medium-pressure chromatographic column for component separation.

[0049]

Comparative Example Comparative example 1 which is a comparative example of the present invention will be described.
It is as follows. [Comparative Example 1] HAp slurry
Was prepared in the same manner as in Example 1, and the concentration was adjusted using water.
To 20% by weight. PM in the HAp slurry
MA [manufactured by Sekisui Plastics Co., Ltd., trade name Techpolymer M
B-8C] and stirred for 1 hour with a stirring motor
To obtain a mixture. Spray this mixture with a metering pump
Dryer (L-8, FOC-2 manufactured by Okawara Kako Kikai Co., Ltd.)
The mixture was supplied to an atomizer of 0) to perform granulation and drying.

The powder obtained by granulation and drying is cyclone
, And cannot be fully collected by cyclone
The fine powder was collected by a bag filter.

The supply of the liquid raw material by the above-mentioned metering pump is performed.
The feed rate was 1-3 kg / h. Spray dryer
Mouth temperature is controlled between 200 and 250 ° C and outlet temperature is below 100 ° C.
It is controlled so that it does not fall, and
The number of turns was set in the range of 10,000 to 37,000 rpm.

Each porous spherical apatite particle obtained here
The coating condition of the probe was observed with a scanning electron microscope.
As a result, as shown in the drawing substitute photograph of FIG.
Aggregation of PMMA was observed, and one PMMA particle
Porous spherical apata coated with fine particles of patite
Apatite fine particles in the aggregate of PMMA and PMMA
Mixed porous spherical apatite particles
I was

Next, Comparative Example 2 which is another comparative example of the present invention.
Will be described. [Comparative Example 2] A HAp slurry was prepared in the same manner as in Example 1 above,
The degree was adjusted to 20% by weight using water. That HAp sla
PMMA [Sekisui Plastics Co., Ltd.
Copolymer MB-8C], and further, a binder
To 20% by weight or less and add it to the stirring motor.
The mixture was further stirred for 1 hour to obtain a mixture. This mixture is
Under the same operating conditions as in Comparative Example 1, granulation and drying were performed.
Was. In addition, as said binder, two types of acrylic
Binder [Taiichi Kogyo Seiyaku Co., Ltd., trade name TB-1,
2], methylcellulose binder [Daiichi Kogyo Seiyaku
(Trade name: EB-43PS), carboxymethyl
Cellulosic binder [Daiichi Kogyo Seiyaku Co., Ltd., product
F-SA] was used alone or in combination of two or more.

Each porous spherical apatite particle obtained here
The coating condition of the probe was observed with a scanning electron microscope.
From the observation, it was found that the PMM was slightly similar to that in FIG.
Aggregation of A was observed and apatite was added to one PMMA particle.
Porous spherical apatite particles coated with fine particles
And apatite fine particles are coated on the aggregate of PMMA
And porous spherical apatite particles.

[0055]

As described above, the method for producing porous spherical apatite particles of the present invention comprises the steps of:
And the resin particles are supplied into the high-speed air stream, while dispersing the resin particles is a method to obtain a porous spherical apatite particles coated with the apatite particles on the surface of the resin particles.

Therefore, the apatite particles can be uniformly coated on the surface of the resin particles while dispersing the resin particles and avoiding agglomeration, so that the apatite particles can be uniformly coated on the surface of one resin particle. The obtained porous spherical apatite particles can be obtained.

Therefore, by appropriately selecting the shape and the particle size distribution of the resin particles, the obtained porous spherical apatite particles can have a sharp particle size distribution and a substantially spherical shape.

As a result, since the particle size distribution is sharp and the shape is almost a true sphere, the effect of stably producing porous spherical apatite particles having good “slip” and “glue” on skin can be obtained. Play.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a coating machine used in Example 1 in a method for producing porous spherical apatite particles of the present invention.

FIG. 2 is a photograph substituted for a drawing showing the particle structure of the porous spherical apatite particles obtained in Example 1 of the present invention.

FIG. 3 is a photograph as a drawing showing the particle structure of another porous spherical apatite particle obtained in Example 1 above.

FIG. 4 is a photograph substituted for a drawing showing the particle structure of the porous spherical apatite particles obtained in Example 2 of the present invention.

FIG. 5 is a photograph as a drawing showing the particle structure of the porous spherical apatite particles obtained in Example 4 of the present invention.

[Explanation of symbols]

 Reference Signs List 1 HAp particles (apatite fine particles) 2 PMMA particles (resin particles) 4 Mixed solution (mixture) 10 Porous spherical apatite particles

Claims (1)

(57) [Claims] 1. A supplies <br/> slurry and the resin particles of apatite particles in high-speed air stream, while dispersing the resin particles, porous spherical by coating the apatite particles on the surface of the resin particles A method for producing porous spherical apatite particles, characterized by obtaining apatite particles.