JP2010241785A - Resin particle, method of manufacturing composite particle and cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin particle capable of easily coating the surface of an amorphous calcium phosphate and suitable as a core particle capable of restraining its dropping, and a method of manufacturing a composite particle suitable for forming a core/shell type composite particle excellent in the uniformity of its coating layer containing the amorphous calcium phosphate, and consequently a cosmetic excellent in the effect of inhibiting makeup-comes-off. <P>SOLUTION: The resin particle is formed by polymerization of a vinyl monomer and contains a component, either one of a phosphite diester having a specified structure or a partial ester of a phosphoric acid having a specific structure, and used as a core particle for forming a core/shell type composite particle by coating the amorphous calcium phosphate on its surface. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to resin particles obtained by polymerizing vinyl monomers, core-shell type composite particles, and cosmetics.

Calcium phosphates such as hydroxyapatite are excellent in the adsorption performance and light scattering performance of organic substances such as oil, and amorphous calcium phosphate is generally larger in specific surface area than crystalline hydroxyapatite, etc. Is excellent.
Conventionally, particles using these calcium phosphates, or composite particles in which a calcium phosphate component is supported on the surface of other particles are used in cosmetics and the like.
For example, in Patent Document 1 below, composite particles in which hydroxyapatite particles are adhered to the surface of the previous particles by mixing and compressing organic particles or inorganic particles and hydroxyapatite particles finer than these particles are mixed. It is described for use in cosmetics.

By the way, as a composite particle having a portion where components are different in one particle, a core-shell type composite particle formed of a substance having a different interior and surface is known.
This core-shell type composite particle is provided with a coating layer on the surface of the core particle to form an outer shell, and while exhibiting the function of the component of the coating layer, characteristics such as particle weight and flexibility, Since the particle shape can be adjusted by selecting the material and shape of the core particle, it is easy to adjust the particle according to the application.
For example, in cosmetics, it is required to prevent makeup collapse due to sebum and soft focus (blurring) by light scattering. Therefore, a coating layer that forms the outer shell of the core-shell type composite particles to be contained is formed with calcium phosphate. The above-mentioned demand can be satisfied.
Furthermore, when a soft and smooth feel is required because it is used in contact with the skin, such as foundations and eye shadows, the composite particles are softened (flexibility) by using a resin material to form the core particles. Furthermore, by adopting spherical resin particles and making the shape of the composite particles spherical, it is possible to impart a smooth feeling of use to the cosmetic.

Here, if the method of the above-mentioned patent document 1 is adopted and hydroxyapatite particles are supported on the surface of spherical organic particles, the hydroxyapatite particles are not only scattered on the surface, but the surface is covered with hydroxyapatite. It is difficult to form composite particles so as to be in the state of being.
Therefore, the composite particles obtained by such a method have a small area covered with hydroxyapatite, and not only do hydroxyapatite's light scattering performance and organic substance adsorption performance not fully exhibited, but also the hydroxyapatite supported on the surface falls off. Has the problem of being easy.

Such a problem is expected to be improved by coating the surface of the resin particles with calcium phosphate in the form of a film. However, sufficient studies have been made in the past to form core-shell type composite particles using amorphous calcium phosphate. Not.
For this reason, the present situation is that sufficient studies have not been made on the core particles that can be easily surface-coated with this amorphous calcium phosphate and that can realize strong support.

JP 63-27414 A

An object of the present invention is to provide resin particles that can be easily coated with amorphous calcium phosphate and that are suitable as core particles that can be prevented from falling off.
In addition, this provides a method for producing composite particles capable of producing core-shell type composite particles with excellent homogeneity of the coating layer made of amorphous calcium phosphate. Providing a fee is a further issue.

The resin particles according to the present invention for solving the above problems are obtained by polymerizing a vinyl monomer, and are diesters of phosphorous acid represented by the following general formula (1),
Or a partial ester of phosphoric acid represented by the following general formula (2) or (3),
(However, in the above general formulas (1) to (3), R ¹ and R ² are each independently one from 1 to 14 acyclic saturated or unsaturated hydrocarbons. Or a group represented by the following formula (4).
It is a resin particle containing any of the above components, and is characterized in that it is used as a core particle for forming a core-shell type composite particle by coating the surface with amorphous calcium phosphate.

In addition, the present invention relating to the method for producing composite particles is a composite particle in which a coating layer using amorphous calcium phosphate is formed on the surface of resin particles to be core particles in order to form core-shell composite particles. It is a production method, wherein a vinyl monomer is polymerized, and is a diester of phosphorous acid represented by the following general formula (1),
Or a partial ester of phosphoric acid represented by the following general formula (2) or (3),
(However, in the above general formulas (1) to (3), R ¹ and R ² are each independently one from 1 to 14 acyclic saturated or unsaturated hydrocarbons. Or a group represented by the following formula (4).
The resin particles containing any of the above components are used as the core particles, and by preparing an aqueous suspension containing the resin particles and a calcium phosphate component, amorphous calcium phosphate is precipitated on the surface of the resin particles, It is characterized by forming a coating layer.

Furthermore, the present invention relating to a cosmetic is a cosmetic comprising core-shell type composite particles in which a coating layer made of amorphous calcium phosphate is formed on the surface of resin particles serving as core particles. The composite particles are obtained by polymerizing a vinyl monomer and are diesters of phosphorous acid represented by the following general formula (1),
Or a partial ester of phosphoric acid represented by the following general formula (2) or (3),
(However, in the above general formulas (1) to (3), R ¹ and R ² are each independently one from 1 to 14 acyclic saturated or unsaturated hydrocarbons. Or a group represented by the following formula (4).
Resin particles containing any of the above components are used as the core particles, and amorphous calcium phosphate is deposited on the surface of the resin particles by preparing an aqueous suspension containing the resin particles and the calcium phosphate component. In this case, the coating layer is formed.

The resin particles of the present invention contain at least one or more components as shown in the above formulas (1) to (3).
Therefore, these components are present on the surface of the resin particles, and the affinity with calcium phosphate is improved in this portion, so that amorphous calcium phosphate can be firmly supported.
Moreover, for example, when a method of forming the coating layer by depositing amorphous calcium phosphate on the surface of the resin particles by preparing an aqueous suspension containing the resin particles and the calcium phosphate component is employed. Since the amorphous calcium phosphate is deposited starting from the location where the components shown in the above formulas (1) to (3) are present, the coating layer can be easily formed.
Furthermore, the components as shown in the above formulas (1) to (3) are usually dispersed on the surface of the resin particles, and these components can be the starting point for precipitation of amorphous calcium phosphate. An excellent coating layer can be formed.
The core-shell type composite particles obtained in this way will exhibit the characteristics of amorphous calcium phosphate more prominently, and by incorporating these composite particles, it is possible to suppress the collapse of makeup when using cosmetics. Can be.

That is, according to the present invention, it is possible to provide resin particles suitable as core particles that can be easily surface-coated with amorphous calcium phosphate and can suppress the dropping thereof.
In addition, according to the present invention, there can be provided a method for producing composite particles suitable for producing core-shell type composite particles excellent in homogeneity of a coating layer using amorphous calcium phosphate.
Furthermore, according to this invention, the cosmetics excellent in the suppression effect of makeup collapse can be provided.

The figure which shows the X-ray-diffraction pattern of an amorphous calcium phosphate and crystalline calcium phosphate. The figure which shows the composite particle of manufacture example 1 (SEM photograph, left: low magnification, right: high magnification). The figure which shows the composite particle of the manufacture example 2 (SEM photograph, left: low magnification, right: high magnification). The figure which shows the composite particle of manufacture example 4 (SEM photograph, left: low magnification, right: high magnification). The figure which shows the composite particle of manufacture example 5 (SEM photograph, left: low magnification, right: high magnification). The figure which shows the composite particle of the manufacture example 11 (SEM photograph, left: low magnification, right: high magnification). The figure which shows the composite particle of the manufacture example 12 (SEM photograph, left: low magnification, right: high magnification). The figure which shows the composite particle of manufacture example 13 (SEM photograph, left: low magnification, right: high magnification). The figure which shows the composite particle of manufacture example 14 (SEM photograph, left: low magnification, right: high magnification). The figure which shows the composite particle of the manufacture example 15 (SEM photograph, left: low magnification, right: high magnification). The front view which shows the light-scattering evaluation method.

As an embodiment according to the present invention, composite particles suitable as a component to be contained in a cosmetic will be described.
This composite particle is a core-shell type composite particle in which a coating layer is provided on the surface of a core particle to form an outer shell, and the coating layer is formed of amorphous calcium phosphate.

As used herein, the term “amorphous calcium phosphate” is tricalcium phosphate containing crystal water represented by the general formula “Ca ₃ (PO ₄ ) ₂ .nH ₂ O”, In particular, the crystal structure is intended to be amorphous.
And, since the crystal structure is amorphous, amorphous calcium phosphate contains a large amount of water of crystallization, so that the pattern of the powder X-ray diffraction method is higher than that of crystalline calcium phosphate as shown in FIG. It can be confirmed from the broad.
The identification of Ca ₃ (PO ₄ ) ₂ .nH ₂ O is JCPDS card no. This can be confirmed by pattern fitting with 18-0303.
Ca ₃ (PO ₄ ) ₂ .nH ₂ O (JCPDS card No. 18-0303) has three X-ray diffraction peaks when 2θ of the X-ray diffraction pattern is in the range of 31 to 35 degrees, Since crystalline hydroxyapatite (JCPDS card No. 09-0432) has four X-ray diffraction peaks, it is possible to discriminate amorphous calcium phosphate from crystalline apatite by X-ray diffraction measurement.

The coating layer formed on the surface of the resin particles of this embodiment is formed by amorphous calcium phosphate because amorphous calcium phosphate has a stronger cohesive force in an aqueous medium than crystalline calcium phosphate. This is because the resin particles are agglomerated so as to enclose the resin particles, and a firm coating layer can be formed after dehydration and drying.
On the other hand, when crystalline hydroxyapatite or tricalcium phosphate is used, it is difficult to sufficiently coat the resin particles as the core because the cohesive force in the aqueous medium is weak.
Moreover, since amorphous calcium phosphate is superior to crystalline hydroxyapatite and tertiary calcium phosphate in adsorbing sebum components, it can be said that it is suitable for forming composite particles to be contained in cosmetics. The reason why the coating layer to be formed on the surface of the particles is formed of amorphous calcium phosphate is that an effect of preventing the cosmetic breakup due to the adsorption of sebum is expected.

In addition, as long as the calcium of the said amorphous calcium phosphate does not impair the effect of this invention remarkably, for example, barium, strontium, zinc, magnesium, sodium, potassium, iron, aluminum, titanium, etc. May be dissolved, or may be partially ion-exchanged or substituted. For example, a part of “PO ₄ ” may be “VO ₄ ”, “SiO ₄ ”, “CO ₄ ”, etc. It may be substituted with one kind of atomic group.
Furthermore, calcium phosphate may be combined with one or more metal oxides to form a coating layer.
The metal oxide is not particularly limited, and examples thereof include titanium oxide, zinc oxide, and cerium oxide.

  In addition, the term “core-shell type” in the present specification does not intend only that the outer shell that covers the surface of the core particle without gaps is formed by a coating layer, but a film-like core. It is used in the meaning including even a coating layer covering the surface of the particle is formed only in part.

The core particle of the present embodiment for forming the outer shell by this coating layer is a spherical resin particle formed such that the vinyl monomer is polymerized to have an average particle diameter in the range of 5 to 50 μm. It is.
Moreover, the resin particles may be a diester of phosphorous acid represented by the following general formula (1),
Or a partial ester of phosphoric acid represented by the following general formula (2) or (3),
(However, in the above general formulas (1) to (3), R ¹ and R ² are each independently one from 1 to 14 acyclic saturated or unsaturated hydrocarbons. Or a group represented by the following formula (4).
Any of these components is contained.

Examples of the vinyl monomer include styrene monomers such as styrene and α-methylstyrene, acrylate monomers such as methyl acrylate and butyl acrylate, methyl methacrylate, and butyl methacrylate. Such methacrylic acid ester monomers are mentioned.
These can be used alone or in combination to form resin particles. In addition to the above, monomers that can be copolymerized with the monomers exemplified above can also be used to form resin particles.

In order to form resin particles with such a monomer, a conventionally known method such as suspension polymerization or emulsion polymerization can be employed, and among these, a spherical shape having an average particle diameter of 5 to 50 μm is obtained. Thus, it is preferable to employ suspension polymerization in an aqueous medium as a method of forming the resin particles.
In order to accelerate the polymerization of the vinyl monomer during such polymerization, it is also possible to use a polymerization initiator, and as the polymerization initiator, a conventional polymerization initiator for suspension polymerization of the vinyl monomer can be used. A polymerization initiator soluble in the vinyl monomer used can be employed.
Examples of such a polymerization initiator include peroxides such as benzoyl peroxide and dicumyl peroxide, and azo compounds such as azobisisobutyronitrile.

  In addition, about the average particle diameter of the resin particle, for example, according to “Reference MANUAL FORTHE COULTER MULTISIZER (1987)” issued by Coulter Electronics Limited using a precision particle size distribution measuring device such as “Coulter Multisizer II” manufactured by Beckman Coulter, Inc. , And performing calibration using a 50 μm aperture.

In addition, either the phosphite ester or the partial ester of phosphoric acid represented by the general formulas (1) to (3) can be contained in the resin particles in suspension polymerization.
In addition, phosphorous acid is shown by following Structural formula (5).

That is, it has two hydroxyl groups that can form an ester bond by dehydration condensation reaction or the like.
The phosphite is a compound represented by the general formula (1), in which all of the two hydroxyl groups are esterified by reaction with alcohols.
That is, phosphite means only complete ester of phosphorous acid and does not contain partial ester.
Then, R ¹ and R ² in the general formula (1) represents a monovalent group obtained by removing one hydrogen atom from 1 to 14 amino, acyclic, saturated or unsaturated hydrocarbon carbon atoms.
R ¹ and R ² may be the same as or different from each other.
Examples of R ¹ and R ² include branched or unbranched alkyl groups, alkenyl groups, and alkynyl groups.
A suitable example of this phosphite is dibutyl hydrogen phosphite.

The partial ester of phosphoric acid used in the present invention is a partial ester of phosphoric acid represented by “H ₃ PO ₄ ”.
In addition, phosphorous acid is shown by following Structural formula (6).

That is, it has three hydroxyl groups that can form an ester bond by dehydration condensation reaction or the like.
This partial ester of phosphoric acid is esterified by reacting only one or two of the three hydroxyl groups with alcohols or the like, and is represented by the general formula (2) or (3). It is a compound represented.
Here, R ¹ and R ² are the same as those in the general formula (1) described above, and the complete ester of phosphoric acid is excluded from the compound represented by (2) or (3).
Suitable examples of the partial ester of phosphoric acid include caprolactone EO-modified phosphate dimethacrylate, monoisodecyl phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate and the like.

Here, as caprolactone EO-modified phosphoric dimethacrylate, (n = 1, a = 1, b = 2) and (n = 1, a = 2, b =) of the compound represented by the following structural formula (7) What is marketed as a brand name "PM-21" from Nippon Kayaku Co., Ltd. which is a mixture with 1) can be used.

The above-mentioned phosphorous acid ester or partial ester of phosphoric acid (hereinafter collectively referred to as “esters”) acts as a vinyl monomer dispersant in suspension polymerization in an aqueous medium. It is in a state of being taken into the particles after the polymerization.
The esters used for forming the resin particles may be used alone or in combination of one or more thereof, and one or more selected from phosphites and a portion of phosphoric acid One or more selected from esters can also be mixed and used.

Along with these esters, an inorganic compound powder can be used as a dispersant in suspension polymerization.
In particular, it is preferable to use magnesium pyrophosphate powder.
By carrying out suspension polymerization in an aqueous medium containing these esters and magnesium pyrophosphate powder, spherical resin particles having a uniform particle size can be easily obtained, which is useful for producing composite particles suitable for cosmetics. Resin particles can be obtained.
In suspension polymerization using these etesuls and magnesium pyrophosphate powder, a polymer (resin particles) can be obtained while suppressing the coalescence of vinyl monomers.
Therefore, the polymerization can be completed in a state close to the initial dispersion state of the vinyl monomer in the aqueous medium, the proportion of the vinyl monomer in the aqueous medium, the amount of the dispersant used, the stirring speed, etc. The size of the resin particles can be adjusted to some extent by adjusting the dispersion state of the vinyl monomer in the initial stage of polymerization.
Usually, if it is in the range of 1-100 micrometers, the resin particle of the magnitude | size uniform by this adjustment can be obtained.

In addition, as for the magnesium pyrophosphate powder, these inorganic compounds are preferably used as any fine powder having an average particle diameter of 0.01 to 10 μm, and in particular, have an average particle diameter of 0.01 to 1 μm. It is preferable to use it as a fine powder.
Other than this magnesium pyrophosphate powder, for example, particles of inorganic polymer substances such as barium carbonate, calcium carbonate, calcium phosphate, calcium sulfate and the like that are sparingly soluble in water, talc, bentonite, silicic acid, diatomaceous earth, clay, etc. Can be used together.

  These are preferably used as fine powders having an average particle diameter of 0.01 to 10 μm, particularly as fine powders having an average particle diameter of 0.01 to 1 μm, like the magnesium pyrophosphate powder. It is preferable.

These dispersants are preferably used in an amount of 0.01 to 0.4% by weight based on the vinyl monomer with respect to the total amount of esters used.
Among these, it is especially preferable to set it as either 0.03 to 0.2 weight%.
It is preferable that the amount of the ester used is selected from such a range. When the ester is used in an amount exceeding 0.4% by weight, the aqueous phase and the oil phase are mixed and dispersed in suspension polymerization. This is because when the monomer droplets are formed, the particles are excessively atomized, making it difficult to make the composite particles have a size suitable for cosmetic use.
Conversely, when the ester content is less than 0.01% by weight, the effect of suppressing the coalescence of vinyl monomer droplets dispersed in the polymerization process is poor and coarse resin particles are formed. This is because there is a risk of being carried out.
Furthermore, the esters are components for improving the affinity between the resin particles and the amorphous calcium phosphate, and are also components that serve as starting points for precipitation when deposited on the surface of the resin particles by the slurry containing the calcium phosphate component. .
For this reason, when the amount of the ester is less than 0.01% by weight, the homogeneity of the coating layer by amorphous calcium phosphate may be impaired, or peeling from the resin particle surface may easily occur.

Moreover, it is preferable that the addition amount of an inorganic compound fine powder shall be either 0.1-20 weight% with respect to a vinyl-type monomer.
Among these, it is particularly preferable to set it to any one of 0.5 to 10% by weight.
It is preferable that the amount of the inorganic compound powder used is selected from the above range. If the inorganic compound powder is used in excess of 20% by weight, the viscosity of the suspension polymerization solution is excessively increased. This is because turbid polymerization becomes difficult.
On the other hand, when the amount is less than 0.1% by weight, the effect of suppressing the coalescence of vinyl monomer droplets is poor, and coarse resin particles may be formed.

  Although not described in detail here, it is possible to contain, for example, a coloring component other than the above-exemplified components in the formation of the resin particles and the coating layer, and the coating layer formed of amorphous calcium phosphate can be further added. It is also possible to form a colored layer or the like on the outside.

  Next, a manufacturing method of resin core particles and a manufacturing method of manufacturing core-shell type composite particles using resin particles obtained by the manufacturing method as core particles will be described.

(Method for producing resin particles)
As a method for producing resin particles in the present embodiment, it is preferable to perform suspension polymerization using the components exemplified above.
There are no particular restrictions on the mixing order of the components at this time, but the mixing order is preferably as follows.
That is,
(Step 1-1)
First, an inorganic compound powder such as magnesium pyrophosphate powder and a surfactant or the like are dissolved in water in advance as required.
(Step 1-2)
On the other hand, a mixed solution is prepared by mixing esters, a polymerization initiator, and a vinyl monomer.
(Process 2)
Thereafter, the inorganic compound powder dispersion water prepared in (1-1) and the mixed liquid prepared in (1-2) are mixed and stirred to suspend the droplets of vinyl monomer dispersed in an aqueous medium. Make a liquid.

  In (Step 2), when the size of the particles (droplets) of the vinyl polymer is observed while adjusting the stirring speed of the stirrer or homomixer, the size of the particles becomes a desired size. Thus, by keeping the stirring speed constant and then continuing stirring at the same speed, resin particles having a desired size can be easily obtained.

In order to produce a polymerization reaction in this suspension and to produce resin particles, it is preferable to use an autoclave as a reaction vessel.
The autoclave is preferably equipped with a stirrer and equipped with a jacket so that it can be heated and cooled.
And it is preferable to heat at the temperature of 50-100 degreeC at the initial stage of superposition | polymerization, and to maintain the temperature of this range after that, and to continue stirring continuously during superposition | polymerization period.
And while maintaining the heating temperature and stirring, the vinyl monomer is polymerized with the passage of time, and usually the polymerization is completed within a few hours to obtain a polymer (resin particles). .
During this time, since the coalescence of the dispersed vinyl monomer particles can be suppressed, resin particles having a desired particle diameter can be obtained.
Whether or not coalescence has occurred can be easily determined by taking a part of the obtained polymer particles and observing them under a microscope, and whether or not many particles having an irregular shape are mixed.

Further, at the time of polymerization of this vinyl monomer, the esters are taken in and resin particles are formed.
More specifically, before polymerization, the esters are present in a relatively large amount near the interface (particle surface) between the droplets formed in the aqueous medium by the vinyl monomer and the aqueous medium. Along with the polymerization reaction of the monomer, a part thereof, particularly a hydrocarbon part or a part related to the formula (4) is plunged into the inside of the particle, and a part is reacted with the vinyl monomer And is taken into the resin particles.
These esters have high affinity with calcium phosphate, and the location where the esters are present is likely to be the starting point for precipitation of amorphous calcium phosphate.
Moreover, since a large amount of esters are dispersed and present on the surface of the resin particles, amorphous calcium phosphate is easily precipitated in a homogeneous state, and a uniform and strong coating layer is formed.
In addition, since the coating layer is uniform, the composite particles are easily formed into the same spherical shape as the resin particles, and the formation of spherical composite particles having a uniform coating layer suitable for cosmetics is easily performed. It will be.

(Composite particle manufacturing method)
Then, the preparation method of the composite particle using this resin particle is demonstrated.
A method for forming a coating layer of amorphous calcium phosphate on the surface of the resin particles is not particularly limited, but in order to form a homogeneous coating layer, an aqueous suspension containing the resin particles and the calcium phosphate component is used. It is important to form a coating layer by preparing a liquid and precipitating amorphous calcium phosphate on the surface of the resin particles.

Examples of a method for producing such composite particles include a method of performing the following steps.
That is,
(Process A)
An alkaline solution in which a calcium salt such as calcium hydroxide is dispersed in water is prepared.
(Process B)
The resin particles produced by the previous production method are dispersed in the alkaline solution produced in this (Step A) to produce a resin particle dispersion.
(Process C)
Phosphoric acid is added to the resin particle dispersion prepared in (Step B) to form a calcium phosphate component together with the calcium content of the previous calcium hydroxide, and the resin particles are dispersed in an aqueous suspension containing the calcium phosphate component. The coating layer is formed by precipitating calcium phosphate on the surface.

At this time, since the pH of the liquid containing the calcium phosphate component is acidic, particularly when it is in a state of less than pH 5.0, calcium hydrogen phosphate may be formed. Therefore, the pH of the aqueous suspension in the formation of the coating layer with calcium phosphate Is preferably maintained at 5.0 or more.
In particular, it is preferable to adjust the addition amount of phosphoric acid so that the pH becomes any value of 6.5 to 10.5.
Moreover, since the temperature of the aqueous suspension rises due to the reaction heat by adding phosphoric acid, for example, formation of the coating layer while cooling the aqueous suspension to a temperature of 50 ° C. or lower It is preferable to carry out.
By carrying out this cooling, the step of adding phosphoric acid can be divided into a plurality of times, eliminating the need to wait for natural cooling each time, and making the composite particle production method more efficient.

In addition, in the precipitation of amorphous calcium phosphate in this (Step C), the esters contained in the resin particles tend to be the starting point for the precipitation of amorphous calcium phosphate, and the starting point (ester that is advantageous for the precipitation of the amorphous calcium phosphate) Therefore, a uniform coating layer is formed in which the precipitation rate of the amorphous calcium phosphate on the surface of the resin particles hardly occurs.
In addition, the adhesiveness between the coating layer and the resin particles is also good, and the amorphous calcium phosphate is prevented from falling off from the surface of the composite particles.

The amount of amorphous calcium phosphate supported on the resin particles can be adjusted mainly by the ratio of the resin particles and the calcium phosphate component in (Step C).
If the content of the calcium phosphate component is too small at this time, the thickness of the coating layer cannot be ensured sufficiently, and the resulting composite particles do not fully exhibit the light scattering property and organic matter adsorption property of amorphous calcium phosphate. On the other hand, even if the calcium phosphate component is excessively contained, a large amount of single particles of amorphous calcium phosphate may be formed.

  From this point of view, although depending on the size of the resin particle, etc., for example, if it is a resin particle having an average particle diameter of 1 to 10 μm, 5 parts by weight per 100 parts by weight of the resin particle It is preferable to contain the calcium phosphate component in the aqueous suspension in a proportion of not less than parts by weight, and it is more preferable to include the calcium phosphate component in the aqueous suspension in a proportion of not less than 7 parts by weight.

(Process D)
After the coating layer is formed on the surface with a predetermined thickness, the core-shell type composite particles can be powdered by dehydrating and drying the aqueous suspension.
In this dehydration drying, the cohesive force of the amorphous calcium phosphate forming the coating layer is increased, the surface is more firmly supported, and the dropping is suppressed.

The composite particles before drying are in a softer state than the coating layer after drying because the coating layer is swollen with water.
Therefore, for example, in the case where a dehydrated cake is produced by filtering the aqueous suspension with a dehydrator, the coating contains a certain amount of water rather than the composite particle powder obtained by crushing the dehydrated cake after drying. The composite particle powder obtained by drying while carrying out stirring or the like from a state where the layer is somewhat difficult is in a state in which surface unevenness is reduced.

For example, in the step of depositing amorphous calcium phosphate on the surface of resin particles, amorphous calcium phosphate is precipitated relatively uniformly by the action of esters, but some irregularities may be formed on the surface of the composite particles. is there.
In addition to the amorphous calcium phosphate that forms a coating layer and precipitates on the surface of the resin particles, there are also those that precipitate alone as finer particles than the resin particles. When the turbid liquid is filtered, the single particles of the amorphous calcium phosphate may be attached to the surface of the composite particles.

Therefore, when the dehydrated cake separated by filtration is left to dry in a state as it is or after being crushed to some extent, the surface irregularities and the protrusions due to the adhesion of amorphous calcium phosphate particles are dried composite particles Will remain.
On the other hand, by carrying out a drying step with stirring on the composite particles in a state where the coating layer immediately after being filtered by the dehydrator is soft, the drying progresses and the coating layer changes to a hard state. In the meantime, collisions and rubbing of the composite particles are generated, and the unevenness of the surface formed on the composite particles immediately after the process of filtering is averaged, or the non-adhesive particles attached to the surface are averaged. It can be changed to a flat surface state by, for example, incorporating fine particles of crystalline calcium phosphate alone into the coating layer.

  Since such composite particles have a smooth surface, they are particularly suitable for cosmetics. For example, when they are used as ingredients in makeup cosmetics, the makeup cosmetics are stretched on the skin. This can reduce the feeling of squeaking and makes the user feel a smooth feel.

Although depending on the size of the composite particles and the thickness of the coating layer, the water content in the dehydrated cake state is generally 15 to 70% by weight.
On the other hand, in order to obtain a dry powder having a flat surface state as described above, it is preferable to dry the whole with stirring until at least the water content is reduced to 5% by weight or less. More preferably, the stirring is continued until the content falls to 2% by weight or less.
If rapid drying is performed at this time, the surface of the composite particles may be dried without being sufficiently flattened. On the other hand, excessively slow drying may increase the working time. It becomes.
From this, it is preferable that the time required for the dehydrated cake having a water content of 15 to 70% by weight to have a water content of 5% by weight or less is approximately 5 to 20 hours.

  In order to carry out such a drying step with stirring, for example, it can be carried out using a stirring dryer or the like.

As described above, by using resin particles containing esters, it is possible to easily perform surface coating of amorphous calcium phosphate, and to form a uniform coating layer easily with the amorphous calcium phosphate. be able to.
Moreover, composite particles in which the removal of amorphous calcium phosphate from the surface is suppressed can be obtained by using the resin particles.

  Normally, amorphous calcium phosphate alone has a very strong cohesive force and is difficult to handle. However, the use of composite particles coated with resin particles reduces the aggregation and facilitates handling, while the resin particles are also easy to handle. However, by itself, there is a problem that it is easy to generate dust. However, by forming the coating layer with amorphous calcium phosphate, the occurrence of such a problem is suppressed and handling becomes easy.

  And by making the composite particles into a spherical shape reflecting the shape of the resin particles, the soft feeling is exhibited, and the light scattering property and the organic matter adsorbing property of amorphous calcium phosphate are exhibited. It is suitable as a component to be blended.

  In the case where the composite particles are used in cosmetics, the composite particles can be blended into the cosmetics as they are, and can also be subjected to surface treatment and contained in the cosmetics. Examples of the surface treatment include silicone and acrylic silicone. And treatment with materials conventionally used in cosmetics such as metal soap, lecithin, amino acids, collagen, coupling agents, and fluorine compounds.

  Other cosmetic ingredients include titanium oxide, zinc oxide, bengara, yellow iron oxide, black iron oxide, ultramarine, cerium oxide, talc, mica (muscovite, phlogopite, sauroite, biotite, lithia Mica, synthetic mica), sericite, kaolin, bentonite, clay, silicic acid, anhydrous silicic acid, magnesium silicate, zinc stearate, fluorinated phlogopite, synthetic talc, barium sulfate, magnesium sulfate, calcium sulfate, boron nitride , Inorganic powders such as bismuth oxychloride, alumina, zirconium oxide, magnesium oxide, chromium oxide, calamine, magnesium carbonate and their composites, silicone powder, silicone elastic powder, polyurethane powder, cellulose powder, polyamide powder, acrylic Resin powder, starch, polyethylene powder and their composites The organic powders such, can be optionally added one or two or more thereof.

  For cosmetics, liquid paraffin, squalane, ester oil, diglyceride, triglyceride, perfluoropolyether, petrolatum, lanolin, ceresin, carnauba wax, solid paraffin, fatty acid, polyhydric alcohol, silicone resin, fluororesin In addition, one or more acrylic resins and vinyl pyrrolidone can be blended as necessary.

  In addition, in cosmetics in which the composite particles of the present embodiment are blended, as functional ingredients, pigments, pH adjusters, humectants, thickeners, surfactants, dispersants, stabilizers, colorants, antiseptics An agent, an antioxidant, an ultraviolet absorber, a fragrance and the like can be appropriately blended within a range that does not significantly impair the effects of the present invention.

  Examples of such cosmetic dosage forms include emulsified foundations, powder foundations, oily foundations, solid emulsified foundations, eye shadows, teak colors, body powders, perfume powders, baby powders, face powders, lipsticks, milky lotions, beauty lotions. , Lotions, beauty creams, sunscreen lotions and the like.

In addition, in this specification, although this invention was demonstrated based on the said illustration, this invention is not limited to the said illustration.
For example, the application of composite particles is not limited to cosmetics, but can be used in other applications such as paints. The manufacturing method adopts resin particle manufacturing methods such as emulsion polymerization regardless of suspension polymerization. Thus, it is possible to produce resin particles having a larger particle size and to make the composite particles finer.
Furthermore, the shape of the resin particles and composite particles is not limited to a spherical shape.
That is, the resin particles and composite particles of the present invention may have an indefinite shape, and the shape is not limited.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.

(Production Example 1 of Composite Particle)
(Production of resin particles)
A dispersion in which 60 g of magnesium pyrophosphate powder was dispersed in 3000 g of water as a dispersant was placed in a 5-liter stainless beaker.
Separately, 50 g of ethylene glycol dimethacrylate and 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to 950 g of methyl methacrylate, and further caprolactone EO-modified phosphoric dimethacrylate (Nippon Kasei) as esters. Yakuhin Co., Ltd., trade name “PM-21”) was added so as to have a ratio of 500 ppm / monomer to prepare a monomer solution.
This monomer solution is put into the above stainless steel beaker and dispersed by a special machine “desktop TK homomixer” (rotation speed: 6000 rpm), and then placed in a jacketed 5 liter autoclave with a stirrer. The mixture was stirred while maintaining the temperature at 50 ° C., and suspension polymerization was carried out for 6 hours.
Thereafter, the temperature was raised to 105 ° C., and stirring was continued for 2 hours to prepare a slurry containing resin particles.
Next, the mixture was cooled, 6N hydrochloric acid was added until the pH of the slurry was 1 or less, and magnesium pyrophosphate was dissolved, followed by filtration and washing.
The average particle diameter of the obtained resin particles was 8.5 μm.

(Formation of coating layer)
The prepared resin particles were dispersed in ion-exchanged water, and 80 g of calcium hydroxide was added to a total amount of 3.5 liters, followed by stirring well to prepare a resin particle dispersion. The pH of the resin particle dispersion at this time was 13.0.
After cooling the resin particle dispersion to a temperature of 20 ° C. or lower, orthophosphoric acid diluted to a concentration of 10% was gradually added until the pH reached 10.5 to prepare an aqueous suspension containing a calcium phosphate component.
In addition, while adding orthophosphoric acid, it adjusted so that the temperature of a resin particle dispersion might not exceed 40 degreeC, and the rotation speed of stirring was adjusted suitably according to the viscosity change of the resin particle dispersion.
Stirring was continued for 2 hours after the dropping of orthophosphoric acid was completed to deposit amorphous calcium phosphate on the surface of the resin particles, and then the aqueous suspension was filtered and dried to obtain composite particles.
Since the composite particles after drying were in an aggregated state, they were crushed with a commercially available mixer and then passed through a 200-mesh sieve to obtain composite particles of Production Example 1.

(Production Example 2)
(Production of resin particles)
A dispersion in which 60 g of magnesium pyrophosphate powder was dispersed in 3000 g of water as a dispersant was placed in a 5-liter stainless beaker.
Separately, 50 g of ethylene glycol dimethacrylate and 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to 950 g of methyl methacrylate, and further caprolactone EO-modified phosphoric dimethacrylate (Nippon Kasei) as esters. Yakuhin Co., Ltd., trade name “PM-21”) was added so as to have a ratio of 500 ppm / monomer to prepare a monomer solution.
This monomer solution is put into the above stainless steel beaker, dispersed with a “desktop TK homomixer” (rotation speed: 6000 rpm) manufactured by Tokushu Kika, and then put into a jacketed 5 liter autoclave with a stirrer. The mixture was stirred while maintaining the temperature at 50 ° C., and suspension polymerization was carried out for 6 hours.
Thereafter, the temperature was raised to 105 ° C., and stirring was continued for 2 hours to prepare a slurry containing resin particles.
Next, the mixture was cooled, 6N hydrochloric acid was added until the pH of the slurry became 1 or less, and magnesium pyrophosphate was dissolved, followed by filtration and washing.
The average particle diameter of the obtained resin particles was 8.5 μm.

(Formation of coating layer)
3 liters of ion-exchanged water was collected in a 5 liter poly beaker, 80 g of calcium hydroxide was added, and the mixture was stirred well. The pH of the liquid at this time was 13.0.
After cooling this liquid to a temperature of 20 ° C. or lower, orthophosphoric acid diluted to a concentration of 7.5% was gradually added until the pH reached 10.5 to prepare a liquid containing a calcium phosphate component.
In addition, while adding orthophosphoric acid, it adjusted so that liquid temperature might not exceed 40 degreeC, and the rotation speed of stirring was adjusted suitably according to the viscosity change of the liquid.
Stirring was continued for 2 hours after completion of the dropping of orthophosphoric acid.
The resin particles prepared previously are added to the calcium phosphate slurry thus obtained to prepare an aqueous suspension containing the calcium phosphate component and the resin particles, and the aqueous suspension is stirred for 2 hours to obtain the surface of the resin particles. After depositing amorphous calcium phosphate, the mixture was filtered and dried to obtain composite particles.
Since the composite particles after drying were in an aggregated state, they were pulverized with a commercially available mixer and then passed through a 200-mesh sieve to obtain composite particles of Production Example 2.

(Production Example 3)
(Production of resin particles)
A dispersion in which 60 g of magnesium pyrophosphate powder was dispersed in 3000 g of water as a dispersant was placed in a 5-liter stainless beaker.
Separately, 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is added to 1000 g of methyl methacrylate, and caprolactone EO-modified phosphate dimethacrylate (trade name “Nippon Kayaku Co., Ltd. PM-21 ") was added at a ratio of 500 ppm / monomer to prepare a monomer solution.
This monomer solution is put into the above stainless steel beaker and dispersed by a special machine “desktop TK homomixer” (rotation speed: 6000 rpm), and then placed in a jacketed 5 liter autoclave with a stirrer. The mixture was stirred while maintaining the temperature at 50 ° C., and suspension polymerization was carried out for 6 hours.
Thereafter, the temperature was raised to 105 ° C., and stirring was continued for 2 hours to prepare a slurry containing resin particles.
Next, the mixture was cooled, 6N hydrochloric acid was added until the pH of the slurry became 1 or less, and magnesium pyrophosphate was dissolved, followed by filtration and washing.
The average particle diameter of the obtained resin particles was 4.5 μm.

(Formation of coating layer)
The prepared resin particles were dispersed in ion-exchanged water, and 80 g of calcium hydroxide was added to a total amount of 3.5 liters, followed by stirring well to prepare a resin particle dispersion. The pH of the resin particle dispersion at this time was 13.0.
After cooling the resin particle dispersion to a temperature of 20 ° C. or lower, orthophosphoric acid diluted to a concentration of 10% was gradually added until the pH reached 10.5 to prepare an aqueous suspension containing a calcium phosphate component.
In addition, while adding orthophosphoric acid, it adjusted so that the temperature of a resin particle dispersion might not exceed 40 degreeC, and the rotation speed of stirring was adjusted suitably according to the viscosity change of the resin particle dispersion.
Stirring was continued for 2 hours after the dropping of orthophosphoric acid was completed to deposit amorphous calcium phosphate on the surface of the resin particles, and then the aqueous suspension was filtered and dried to obtain composite particles.
Since the composite particles after drying were in an agglomerated state, they were crushed with a commercially available mixer and then passed through a 200-mesh sieve to obtain composite particles of Production Example 3.

(Production Example 4)
(Production of resin particles)
A dispersion in which 60 g of magnesium pyrophosphate was dispersed in 3000 g of water as a dispersant was placed in a 5 liter stainless beaker.
Separately, 600 g of butyl acrylate, 200 g of 2-ethylhexyl acrylate, 200 g of ethylene glycol dimethacrylate, and 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, and caprolactone EO-modified phosphorus was further added as an ester. A monomer solution was prepared by adding acid dimethacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “PM-21”) to a ratio of 500 ppm / monomer.
This monomer solution is put into the above stainless steel beaker and dispersed by a special machine “desktop TK homomixer” (rotation speed: 6000 rpm), and then placed in a jacketed 5 liter autoclave with a stirrer. The mixture was stirred while maintaining the temperature at 50 ° C., and suspension polymerization was carried out for 6 hours.
Thereafter, the temperature was raised to 105 ° C., and stirring was continued for 2 hours to prepare a slurry containing resin particles.
Next, the mixture was cooled, 6N hydrochloric acid was added until the pH of the slurry became 1 or less, and magnesium pyrophosphate was dissolved, followed by filtration and washing.
The average particle diameter of the obtained resin particles was 7.8 μm.

(Formation of coating layer)
The prepared resin particles were dispersed in ion-exchanged water, and 80 g of calcium hydroxide was added to a total amount of 3.5 liters, followed by stirring well to prepare a resin particle dispersion. The pH of the resin particle dispersion at this time was 13.0.
After cooling the resin particle dispersion to a temperature of 20 ° C. or lower, orthophosphoric acid diluted to a concentration of 10% was gradually added until the pH reached 10.5 to prepare an aqueous suspension containing a calcium phosphate component.
In addition, while adding orthophosphoric acid, it adjusted so that the temperature of a resin particle dispersion might not exceed 40 degreeC, and the rotation speed of stirring was adjusted suitably according to the viscosity change of the resin particle dispersion.
Stirring was continued for 2 hours after the dropping of orthophosphoric acid was completed. After the amorphous calcium phosphate was precipitated on the surface of the resin particles, the aqueous suspension was filtered and dried to obtain composite particles.
Since the composite particles after drying were in an aggregated state, they were crushed with a commercially available mixer and then passed through a 200-mesh sieve to obtain composite particles of Production Example 4.

(Production Example 5)
(Production of resin particles)
A dispersion in which 60 g of magnesium pyrophosphate was dispersed in 3000 g of water as a dispersant was placed in a 5 liter stainless beaker.
Separately, 300 g of methyl methacrylate, 200 g of ethylene glycol dimethacrylate, 500 g of ethyl acetate and 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, and caprolactone EO-modified diphosphate diphosphate was further added as an ester. A monomer solution was prepared by adding methacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “PM-21”) to a ratio of 500 ppm / monomer.
This monomer solution is put into the above stainless steel beaker and dispersed by a special machine “desktop TK homomixer” (rotation speed: 6000 rpm), and then placed in a jacketed 5 liter autoclave with a stirrer. The mixture was stirred while maintaining the temperature at 50 ° C., and suspension polymerization was carried out for 6 hours.
Thereafter, the temperature was raised to 70 ° C., and stirring was continued for 2 hours to prepare a slurry containing resin particles.
Next, the slurry was distilled, and ethyl acetate was distilled off, followed by cooling. 6N hydrochloric acid was added until the pH of the slurry became 1 or less to dissolve magnesium pyrophosphate.
Further, this was filtered and washed.
The obtained particles were porous, the average particle diameter was 7.2 μm, and the specific surface area after drying was 90 m ² / g.

(Formation of coating layer)
The prepared resin particles were dispersed in ion-exchanged water, and 80 g of calcium hydroxide was added to a total amount of 3.5 liters, followed by stirring well to prepare a resin particle dispersion. The pH of the resin particle dispersion at this time was 13.0.
After cooling the resin particle dispersion to a temperature of 20 ° C. or lower, orthophosphoric acid diluted to a concentration of 10% was gradually added until the pH reached 10.5 to prepare an aqueous suspension containing a calcium phosphate component.
In addition, while adding orthophosphoric acid, it adjusted so that the temperature of a slurry might not exceed 40 degreeC, and the rotation speed of stirring was adjusted suitably according to the viscosity change of the slurry.
Stirring was continued for 2 hours after the dropping of orthophosphoric acid was completed to deposit amorphous calcium phosphate on the surface of the resin particles, and then the aqueous suspension was filtered and dried to obtain composite particles.
Since the composite particles after drying were in an aggregated state, they were crushed with a commercially available mixer and then passed through a 200-mesh sieve to obtain composite particles of Production Example 5.

(Production Examples 6 to 10)
By adjusting the amount of calcium hydroxide and the amount of orthophosphoric acid used in forming the coating layer, the amount of the calcium phosphate component relative to 100 parts by weight of the resin particles in the aqueous suspension is 5.1 parts by weight (Production Example 6). 7.4 parts by weight (Production Example 7), 21.0 parts by weight (Production Example 8), 28.5 parts by weight (Production Example 9), and 34.7 parts by weight (Production Example 10) Except for the above, composite particles were produced in the same manner as in Production Example 1.
In addition, the quantity of the calcium phosphate component with respect to 100 parts by weight of the resin particles in the aqueous suspensions in Production Examples 1 to 5 is 9.6 parts by weight.

(Production Example 11)
(Production of resin particles)
A dispersion liquid in which 60 g of magnesium pyrophosphate and 0.75 sodium lauryl sulfate were dispersed in 3000 g of water as an inorganic compound was placed in a 5 liter stainless beaker.
Separately, 50 g of ethylene glycol dimethacrylate and 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to 950 g of methyl methacrylate to prepare a monomer solution.
That is, here, a monomer solution was prepared without using esters.
This monomer solution is put into the above stainless steel beaker and dispersed by a special machine “desktop TK homomixer” (rotation speed: 6000 rpm), and then placed in a jacketed 5 liter autoclave with a stirrer. The mixture was stirred while maintaining the temperature at 50 ° C. and subjected to suspension polymerization for 6 hours.
Thereafter, the temperature was raised to 105 ° C., and stirring was continued for 2 hours to prepare a slurry containing resin particles.
Next, the mixture was cooled, 6N hydrochloric acid was added until the pH of the slurry became 1 or less, and magnesium pyrophosphate was dissolved, followed by filtration and washing.
The average particle diameter of the obtained resin particles was 8.5 μm.

(Formation of coating layer)
The prepared resin particles were dispersed in ion-exchanged water, and 80 g of calcium hydroxide was added to a total amount of 3.5 liters, followed by stirring well to prepare a resin particle dispersion. The pH of the resin particle dispersion at this time was 13.0.
After cooling the resin particle dispersion to a temperature of 20 ° C. or lower, orthophosphoric acid diluted to a concentration of 10% was gradually added until the pH reached 10.5 to prepare an aqueous suspension containing a calcium phosphate component.
In addition, while adding orthophosphoric acid, it adjusted so that the temperature of a slurry might not exceed 40 degreeC, and the rotation speed of stirring was adjusted suitably according to the viscosity change of the slurry.
Stirring was continued for 2 hours after the dropping of orthophosphoric acid was completed to deposit amorphous calcium phosphate on the surface of the resin particles, and then the aqueous suspension was filtered and dried to obtain composite particles.
Since the composite particles after drying were in an aggregated state, they were crushed with a commercially available mixer and then passed through a 200-mesh sieve to obtain composite particles of Production Example 11.

(Production Example 12)
A slurry containing a calcium phosphate component was prepared by the method shown in Production Example 2.
The slurry was suction filtered, dried at 80 ° C., pulverized, and then finely pulverized with a jet mill to produce amorphous calcium phosphate powder.
On the other hand, resin particles were produced by the method for producing resin particles shown in Production Example 1, and 100 g of the resin particles dried and crushed and passed through an open 45 μm sieve was prepared. 10 g of powdered calcium phosphate powder was added and mixed with a commercially available mixer to produce composite particles, and composite particles of Production Example 12 were obtained.

(Production Example 13)
Composite particles were produced in the same manner as in Production Example 2 except that the calcium phosphate slurry used in Production Example 2 was replaced with a commercially available third calcium phosphate slurry (Taihei Chemical Co., Ltd., trade name “TCP-10U”). Composite particles were obtained.
The X-ray diffraction pattern of the calcium phosphate powder dried at 80 ° C. after suction filtration of the third calcium phosphate slurry was consistent with the X-ray diffraction pattern of hydroxyapatite.
Further, in Production Example 13, many single particles of calcium phosphate were observed together with the composite particles in which the coating layer of calcium phosphate was formed.

(Production Example 14)
The composite particles of Production Example 1 are produced by filtering an aqueous suspension and separating the powder after being dried in a shelf-type dryer. The composite particles were produced in the same manner as in Production Example 1 except that the composite particles separated from the aqueous suspension were filtered and then dried by stirring.
More specifically, the dehydrated cake obtained by filtration from the aqueous suspension is dried with stirring using a horizontal vacuum dryer manufactured by Gansu Kosan Co., Ltd., and the resulting composite particle powder is mixed into a mixer. After further pulverization, the mixture was passed through a 200-mesh sieve to obtain composite particles of Production Example 14.

  Specifically, the temperature of the horizontal vacuum dryer (the jacket temperature of the dryer) is 60 ° C., the rotation speed is 10 rpm, the peripheral speed is 7.85 m / min, and drying is performed for 18 hours. What was wt% was dried to a moisture content of 1.5 wt%.

(Production Example 15)
The composite particles of Production Example 4 are produced by filtering an aqueous suspension and separating the powder after being dried in a shelf dryer. The composite particles were produced in the same manner as in Production Example 4, except that the composite particles separated from the aqueous suspension were filtered and then dried with stirring.
More specifically, the dehydrated cake obtained by filtration from the aqueous suspension is dried with stirring using a horizontal vacuum dryer manufactured by Gansu Kosan Co., Ltd., and the resulting composite particle powder is mixed into a mixer. After further pulverizing, a 200-mesh sieve was passed through to obtain composite particles of Production Example 15.

  Specifically, the temperature of the horizontal vacuum dryer (the jacket temperature of the dryer) is 60 ° C., the rotation speed is 10 rpm, the peripheral speed is 7.85 m / min, and drying is performed for 16 hours. What was wt% was dried to a moisture content of 0.9 wt%.

(Evaluation)
The composite particles of Production Examples 1, 2, 4, 5, 11, 12, 13, 14, and 15 were observed with a scanning electron microscope (SEM), and the composite particles of Production Examples 1 to 13 (composite particles and calcium phosphate were used. Light scattering characteristics and oil absorption using oleic acid were measured for mixed particles with single particles).
Moreover, although it explains in full detail in the back | latter stage, with respect to the composite particle of manufacture example 1, 4, 14, 15, the sensory test regarding the touch was implemented.

(SEM observation)
SEM photographs of the composite particles of Production Examples 1, 2, 4, 5, 11, 12, 13, 14, and 15 are shown in FIGS. The photograph on the left is an image of composite particles taken at a low magnification, and the photograph on the right is taken at a higher magnification than the photograph on the left.
Among them, Production Examples 1, 2, 4, and 5 are those in which resin particles containing esters are used.
From FIG. 2 to FIG. 5 regarding these, it can be seen that a coating layer of amorphous calcium phosphate is uniformly formed on the surface.
This can be clearly grasped by comparison with Production Example 12 (FIG. 7) in which amorphous calcium phosphate powder and resin particles are mixed with a mixer. In Production Example 12, a coating layer is formed. In addition, the amorphous calcium phosphate powder is only slightly adhered to the surface, and many resin particles are exposed on the surface.
On the other hand, in Production Examples 1, 2, 4, and 5, the coating layer is formed on the surface, and since the shape is spherical like the resin particles, the coating layer is formed in a uniform film shape. You can see that
Although not specifically illustrated here, it was confirmed by SEM observation that composite particles similar to Production Examples 1, 2, 4, and 5 were obtained in Production Examples 3 and 6 to 10 as well. ing.
That is, in the method as in Production Example 12, it is difficult to form composite particles with a uniform coating layer, whereas according to the method as in Production Example 1, a coating using amorphous calcium phosphate is used. It can be seen that core-shell type composite particles having excellent layer homogeneity can be easily obtained.

  In addition, about the manufacture example 11 (FIG. 6) using the resin particle which does not contain ester, it is not as much as the manufacture example 12, but the manufacture example 1 of what partly shows the calcium phosphate which coat | covers the resin particle in a film form, 2, 4, and 5 (FIGS. 2 to 5) do not appear to be covered with amorphous calcium phosphate on one side.

Furthermore, in Production Example 13 (FIG. 8) in which crystalline calcium phosphate instead of amorphous calcium phosphate was precipitated on the surface while using resin particles containing esters, the surface was entirely covered with calcium phosphate. Although it is observed, it is not a uniform film-like coating layer as in Production Examples 1, 2, 4, 5 (FIGS. 2 to 5), but is made of fine particles of crystalline calcium phosphate. The powder adheres to the entire surface of the resin particles and is in a fuzzy state.
This is because esters are likely to be the starting point of precipitation not only for amorphous calcium phosphate but also for crystalline calcium phosphate, but crystalline calcium phosphate is precipitated due to its lower cohesive strength than amorphous calcium phosphate. This is considered to be because calcium phosphate became powdery instead of filmy.
These points are also supported by the light scattering evaluation results to be described later.

Further, when FIG. 2 and FIG. 9 (Production Examples 1 and 14) and FIG. 4 and FIG. 10 (Production Examples 4 and 15) are compared, these are only different in the drying method. In FIG. 9 where the photographing magnification is higher than that in FIG. 9 or in the photograph in FIG. 10 where the photographing magnification is higher than that in FIG. 4, it can be seen that the surface unevenness is not seen and a flat surface is formed.
That is, it can be seen that composite particles having excellent surface smoothness can be obtained by carrying out a drying step with stirring.

(Evaluation of light scattering properties)
For the composite particles obtained in Production Examples 1 to 13 and the resin particles produced in Production Example 1 (before depositing amorphous calcium phosphate), an automatic goniophotometer (Murakami Color Research Laboratory Co., Ltd.) The reflection light distribution at a reflection angle of −90 degrees to +90 degrees when irradiated with an incident angle of −45 degrees was measured using a product name “GP-200”).
Specifically, a double-sided tape cut into a square with a side of 5 cm centered on the black portion is adhered to a black-and-white concealment paper ("Test Chart 2803" manufactured by BYK-Gardner), and this double-sided tape affixing position The composite particles obtained in each production example were dropped using a bulk specific gravity measuring instrument (JIS K 5101 compliant product), and excess composite particles were removed by blowing compressed air onto the composite particles dropped on this double-sided tape. Then, the reflected light distribution was measured as a measurement sample.
Table 1 shows the ratio of the reflected light intensities (reflected light intensity ratio) at −25 degrees, 0 degrees, and +25 degrees when the reflected light intensity at +45 degrees is 100.
The incident angles of −25 degrees, 0 degrees, +25 degrees, −45 degrees, and the reference reflection angle of +45 degrees are as shown in FIG. 11, and incident light is incident from the direction of −45 degrees. In general, since light is reflected in the direction of +45 degrees, the light scattering becomes so strong that a strong reflection intensity is observed on the rear side, that is, on the −25 degrees side with respect to the reflection direction of the light. It can be said that it is excellent.

  As shown above, Production Example 11 using resin particles not containing esters, Production Example 12 in which the surface of the resin particles is hardly coated with calcium phosphate, and resin particles containing esters are not used. In Production Example 13 in which crystalline calcium phosphate was deposited on the surface instead of crystalline calcium phosphate, the reflected light intensity ratio at −25 degrees and 0 degrees was a low value, which was obtained in Production Examples 1 to 5 and the like. It can be seen that the coating of the resin particle surface with calcium phosphate is not sufficient as compared with the composite particles.

In addition, in Production Example 6 using resin particles containing esters, the reflected light intensity ratio of −25 degrees and 0 degrees is observed as a low value.
However, in Production Example 6, since resin particles containing esters that are the starting points for precipitation of calcium phosphate are used, Production Example 11 using resin particles containing no such esters or Unlike the production example 13 in which crystalline calcium phosphate having a weak cohesive force is precipitated, a relatively homogeneous coating layer is formed, but the amount of the calcium phosphate component is in the production examples 1 to 4 and the production example 11 As compared with “9.6 parts by weight” in the case of ˜13, only about “5.1 parts by weight” is contained in the aqueous suspension, so that the composite particles of Production Examples 1 to 4 are excellent. This is presumably because a sufficient coating layer is not formed to exert the light scattering property.

In other words, in Production Example 6, compared to Production Examples 11 to 13 (calcium phosphate addition amount: 9.6 parts by weight), although the amount of calcium phosphate is about half, light scattering properties equivalent to these are obtained. Therefore, it can be said that the composite particle manufacturing method of the present invention is more efficient than the conventional composite particle manufacturing method.
Even when the calcium phosphate component is contained in the aqueous suspension only in a small amount as in Production Example 6, the production conditions of the composite particles such as the precipitation time of calcium phosphate and the pH value of the aqueous suspension are finely adjusted. By doing so, it is considered that the amount of precipitation can be increased and the light scattering property can be improved, but in that case, high precision is required in the manufacturing operation of the composite particles.
Therefore, the aqueous suspension contains a calcium phosphate component at a ratio of 5 parts by weight or more with respect to 100 parts by weight of the resin particles in that core-shell type composite particles having excellent light scattering properties and the like can be easily produced. It is preferable that the calcium phosphate component is contained in the aqueous suspension at a ratio of 7 parts by weight or more, and 9.6 parts by weight or more is particularly preferable.

(Evaluation of oil absorption)
The oil absorption was measured for the composite particles obtained in Production Examples 1 to 13 and the resin particles produced in Production Example 1 (before the amorphous calcium phosphate was precipitated).
In the measurement, the oil absorption was measured using oleic acid which is the main component of sebum as an oil agent.
In the measurement, 1 g of the composite particles of each production example was precisely weighed on a glass plate, and then oleic acid was dropped using a burette having a capacity of 10 ml, and each time a sample was quickly kneaded with a stainless steel spatula.
By proceeding with this operation, the amount of oleic acid when the sample became one lump was determined, and this value was taken as the wet point (WP).
Further, oleic acid was dropped and kneaded repeatedly to determine the amount of oleic acid when the sample started to fluidize, and this value was defined as the pour point (FP).
By this evaluation, the difference between the values of the pour point and the wet point (FP-WP) was converted to 100 g of composite particles to obtain the oil absorption value (ml / 100 g).
The results are shown in Table 1 above. Moreover, the ratio of the oil absorption amount of the composite particle of each manufacture example when the oil absorption amount of the resin particle produced in manufacture example 1 was made into the reference value (1.0) was computed.
The values are also shown in Table 1.

As shown in this table, excellent oil absorbency is observed in the composite particles of Production Examples 11 and 12.
On the other hand, the composite particles of Production Example 13 show only a low oil absorption.
This is considered to be due to the difference in oil absorption performance between amorphous calcium phosphate and crystalline calcium phosphate.
Also, excellent oil absorbency was observed in the composite particles of Production Examples 11 and 12 because the surface of the resin particles was not supported with a sufficient amount of amorphous calcium phosphate, but amorphous calcium phosphate. This is probably because a large number of single particles are mixed.
That is, even though only a low value of light scattering is shown, a high value in oil absorption is shown because the amount of amorphous calcium phosphate coating the resin particles is small, constituting single particles It is recognized that this is evidence that a large amount of amorphous calcium phosphate is present.

  In addition, in Production Examples 6 and 7 in which the amount of the calcium phosphate component contained in the aqueous suspension was reduced compared to Production Examples 1 to 4, Production Example 11, and the like, the oil absorption value corresponding to the light scattering value was This also shows that in Production Examples 6 and 7, most of the calcium phosphate component is coated on the resin particles, and a uniform coating is formed.

(Evaluation of touch)
The composite particles obtained in Production Examples 14 and 15 were subjected to a sensory evaluation of the touch as compared with the composite particles of Production Examples 1 and 4 in which the drying method was changed.
In addition, particles having an average particle diameter of 11.3 μm (hydroxyapatite particles) obtained by granulating amorphous calcium phosphate into a spherical shape with a spray dryer were also used for evaluation.
The evaluation was performed by having 10 panelists perform the act of spreading each particle on the wrist, and the action of putting the fingers between the thumb and forefinger and rubbing these fingers, and sensory evaluation of the feel. Carried out by adding
The evaluation items were three items of “no feeling of squeaking”, “good slippery”, and “adhesion to skin”.
At this time, in each item, 9 or more out of 10 people evaluated “good” as “◎”, and 7 to 8 out of 10 people evaluated “good” as “◯”. A case where 5 to 6 people evaluated “good” was judged as “Δ”, and a case where 4 or less panelists evaluated as “good” was judged as “x”.
The results are shown in Table 2.
In addition, the measurement of the “reflected light intensity” was performed on the composite particles of Production Examples 14 and 15.
The obtained results are shown in Table 2 together with the results of the composite particles of Production Examples 1 and 4 above.

  From this, it can be seen that the composite particles of Production Examples 14 and 15 subjected to the drying step with stirring are excellent in surface smoothness and particularly excellent as a component to be contained in cosmetics.

(Cosmetics production example)
(1) Manufacture of powder foundation Powder foundation was produced by the mixing | blending shown to the following "blending (1)".
<Formulation (1)>
Composite particles of Production Example 1: 15 parts by weight Sericite: 21 parts by weight Mica mica: 51 parts by weight Red iron oxide: 0.6 parts by weight Yellow iron oxide: 1 part by weight Black iron oxide: 0.1 parts by weight 2-ethyl Cetyl hexanoate: 10 parts by weight Sorbitan sesquioleate: 1 part by weight Preservative: 0.2 part by weight Fragrance: 0.1 part by weight

In preparation, composite particles, sericite, muscovite, red iron oxide, yellow iron oxide and black iron oxide were mixed with a Henschel mixer, and this was mixed with cetyl 2-ethylhexanoate, sorbitan sesquioleate and preservative. Was added and mixed uniformly.
After adding a fragrance | flavor to this and mixing, it grind | pulverized and passed through the sieve.
This was compression molded into a metal pan to obtain a powder foundation.

(2) Production of emulsified foundation An emulsified foundation was prepared according to the formulation shown in "Composition (2)" below.
<Formulation (2)>
Composite particles of Production Example 1: 20.0 parts by weight Sericite: 6.0 parts by weight Titanium dioxide: 3.0 parts by weight Stearic acid: 2.0 parts by weight Cetyl alcohol: 0.3 parts by weight Liquid paraffin: 20.0 Part by weight Polyethylene (10 mol) monooleate: 1.0 part by weight Sorbitan trioleate: 1.0 part by weight Propylene glycol: 5.0 part by weight Polyethylene glycol 4000: 5.0 part by weight Triethanolamine: 1 0.0 parts by weight Bee gum: 0.5 parts by weight Purified water: 50.2 parts by weight Pigment: appropriate amount Fragrance: appropriate amount Preservative: appropriate amount

In preparation, first, composite particles, sericite, titanium dioxide and pigment were mixed with a kneader (powder part).
Separately from this “powder part”, polyethylene glycol, triethanolamine, propylene glycol and bee gum were added to purified water and dissolved by heating to prepare a solution.
The powder part prepared previously was added to this solution, and the powder was uniformly dispersed with a homomixer and kept at 70 ° C. (water phase component).
Next, the other components were mixed, dissolved by heating and kept at 70 ° C. (oil phase component).
The previous aqueous phase component was added to the oil phase component, pre-emulsified, and uniformly emulsified and dispersed with a homomixer, and then cooled while stirring to obtain an emulsified foundation.

(3) Manufacture of skin lotion A skin lotion was prepared by the blending shown in “Blend (3)” below.
<Formulation (3)>
Composite particles of Production Example 15: 10.0 parts by weight Stearic acid: 2.5 parts by weight Cetyl alcohol: 1.5 parts by weight Petrolatum: 5.0 parts by weight Liquid paraffin: 10.0 parts by weight Polyethylene (10 mol) monoolein Acid ester: 2.0 parts by weight Polyethylene glycol 1500: 3.0 parts by weight Triethanolamine: 1.0 part by weight Purified water: 64.5 parts by weight Perfume: 0.5 parts by weight Preservative: Appropriate amount

In preparation, first, stearic acid, cetyl alcohol, petrolatum, liquid paraffin and polyethylene monooleate are dissolved by heating, and composite particles are added thereto, mixed with a kneader, and kept at 70 ° C. (oil phase) component).
In addition, polyethylene glycol and triethanolamine were added to purified water, dissolved by heating, and kept at 70 ° C. (water phase component).
The oil phase component was added to the water phase component, pre-emulsified, and then uniformly emulsified with a homomixer, and cooled to 30 ° C. while stirring after the emulsification to obtain a cosmetic emulsion.

(4) Manufacture of lipstick A lipstick was prepared according to the formulation shown in “Composition (4)” below.
<Formulation (4)>
Composite particle of Production Example 14: 10.0 parts by weight Titanium dioxide: 3.0 parts by weight Red No. 202: 0.5 parts by weight Red No. 206: 2.0 parts by weight Red No. 223: 0.05 parts by weight Ceresin: 12 0.0 parts by weight Beeswax: 8.0 parts by weight Cetyl alcohol: 5.0 parts by weight Whale wax: 4.0 parts by weight Carbana wax: 1.0 parts by weight Liquid paraffin: 21.0 parts by weight Liquid lanolin: 20.0 parts by weight Butyl stearate ester: 11.45 parts by weight Sorbitan sesquioleate: 2.0 parts by weight Fragrance: appropriate amount Antioxidant: appropriate amount

In preparation, first, composite particles, titanium dioxide, red No. 202 and red No. 206 were added to a part of liquid paraffin and mixed well with a caller (pigment part).
Red No. 223 was dissolved in butyl stearate (dye part).
The other components were mixed and dissolved by heating, and then the pigment part and the dye part were added and dispersed uniformly with a homomixer.
After dispersion, it was poured into a mold and rapidly cooled to obtain a sticky lipstick.

  These “powder foundation”, “emulsification foundation”, “cosmetic milk liquid”, and “lipstick” did not easily cause makeup collapse and had excellent usability.

From the above, it can be seen that according to the present invention, it is possible to provide resin particles suitable for core particles that can be easily surface-coated with amorphous calcium phosphate and can suppress the falling off. .
In addition, according to the present invention, it can be seen that there can be provided a method for producing composite particles capable of producing core-shell type composite particles having excellent homogeneity of a coating layer using amorphous calcium phosphate.
Furthermore, according to this invention, it turns out that the cosmetics excellent in the suppression effect of makeup collapse can be provided.

Claims (10)

A vinyl-based monomer is polymerized, and is a diester of phosphorous acid represented by the following general formula (1),
Or a partial ester of phosphoric acid represented by the following general formula (2) or (3),
(However, in the above general formulas (1) to (3), R ¹ and R ² are each independently one from 1 to 14 acyclic saturated or unsaturated hydrocarbons. Or a group represented by the following formula (4).
Resin particles containing any of the components,
Resin particles characterized by being used as core particles for forming core-shell type composite particles by coating the surface with amorphous calcium phosphate.   Whether the polymerization of the vinyl monomer is suspension polymerization in an aqueous medium containing magnesium pyrophosphate powder, and whether the suspension polymerization is a diester of phosphorous acid or a partial ester of phosphoric acid. The resin particle according to claim 1, wherein the resin particles are carried out in a state in which any of the above is mixed with the vinyl monomer. In order to form core-shell type composite particles, a method for producing composite particles, in which a coating layer using amorphous calcium phosphate is formed on the surface of resin particles to be core particles,
A vinyl-based monomer is polymerized, and is a diester of phosphorous acid represented by the following general formula (1),
Or a partial ester of phosphoric acid represented by the following general formula (2) or (3),
(However, in the above general formulas (1) to (3), R ¹ and R ² are each independently one from 1 to 14 acyclic saturated or unsaturated hydrocarbons. Or a group represented by the following formula (4).
The resin particles containing any of the above components are used as the core particles, and by preparing an aqueous suspension containing the resin particles and a calcium phosphate component, amorphous calcium phosphate is precipitated on the surface of the resin particles, A method for producing composite particles, wherein a coating layer is formed.   The resin particles are polymerized in a state where either the diester of phosphorous acid or the partial ester of phosphoric acid is mixed with the vinyl monomer, and the polymerization is 4. The method for producing composite particles according to claim 3, wherein the polymerization is suspension polymerization in an aqueous medium containing magnesium pyrophosphate powder.   A resin particle dispersion containing the resin particles and calcium salt is prepared, and the aqueous suspension is prepared by adding phosphoric acid to the resin particle dispersion, and the pH of the aqueous suspension is The manufacturing method of the composite particle of Claim 3 or 4 which adds phosphoric acid so that it may become any value of 6.5-10.5, and deposits an amorphous calcium phosphate on the surface of the said resin particle.   6. The method according to claim 3, wherein the step of filtering the formed composite particles from the aqueous suspension and the step of drying the composite particles obtained by the filtering while stirring are performed. The manufacturing method of the composite particle of description. It is a cosmetic comprising core-shell type composite particles in which a coating layer made of amorphous calcium phosphate is formed on the surface of resin particles to be core particles,
The composite particles are obtained by polymerizing a vinyl monomer, and are diesters of phosphorous acid represented by the following general formula (1),
Or a partial ester of phosphoric acid represented by the following general formula (2) or (3),
(However, in the above general formulas (1) to (3), R ¹ and R ² are each independently one from 1 to 14 acyclic saturated or unsaturated hydrocarbons. Or a group represented by the following formula (4).
Resin particles containing any of the above components are used as the core particles, and amorphous calcium phosphate is deposited on the surface of the resin particles by preparing an aqueous suspension containing the resin particles and the calcium phosphate component. A cosmetic comprising the coating layer formed thereon.   The resin particles are polymerized in a state where either the diester of phosphorous acid or the partial ester of phosphoric acid is mixed with the vinyl monomer, and the polymerization is The cosmetic according to claim 7, wherein the cosmetic is suspension polymerization in an aqueous medium containing magnesium pyrophosphate powder.   In the composite particles, the aqueous suspension is prepared by adding phosphoric acid to the resin particle dispersion after the resin particle dispersion containing the resin particles and the calcium salt is prepared. Claims formed by adding phosphoric acid so that the pH of the suspension has a value of 6.5 to 10.5, and depositing amorphous calcium phosphate on the surface of the resin particles. Item 7. A cosmetic according to item 7 or 8.   The cosmetic according to any one of claims 7 to 9, wherein the composite particles are obtained by being filtered from the aqueous suspension and then dried with stirring.