JP2011063759A - Composite particle production method, composite particle, and cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for simply making substitute particles closer in texture to polyamide resin particles and to thereby improve texture in a cosmetic. <P>SOLUTION: There is provided, e.g., a method for producing composite particles composed of seed particles and coating layers formed on their surfaces and made from a material different from that of the seed particles, the method for producing the composite particles being characterized in that the composite particles surfaced with a polyamide resin are produced by practicing the step of making a slurry prepared by dispersing the seed particles in a polyamide resin solution prepared by dissolving a polyamide resin in an organic solvent and the step of depositing the polyamide resin from the polyamide resin solution on the surfaces of the seed particles contained in the slurry to form the coating layers thereon. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing composite particles, composite particles, and a cosmetic.

Conventionally, a polyamide resin is widely known under a trade name such as “nylon”, and its fiber is widely used as a material for underwear such as stockings because of its excellent texture to the skin.
Because of this excellent texture for human skin, spherical particles formed of polyamide resin are included in cosmetics. For example, fine spherical particles having an average particle diameter of about 100 μm or less are made of polyamide resin. It has been made to give a smooth feel to makeup cosmetics and the like.

However, the polyamide resin has an excellent texture, but its unit price is higher than that of a general resin. Therefore, studies have been made on particles replacing the polyamide resin particles for the purpose of cost reduction and the like.
However, until now no particles have been found that can provide a texture like polyamide resin particles, and no suitable materials for cosmetics or the like to be blended in place of polyamide resin particles have been found. .
For example, the following Patent Document 1 describes that acrylic ester resin particles have excellent flexibility and can be used for cosmetics, and a soft feel can be obtained. It is difficult to replace the polyamide resin particles with different ones.

JP 2000-186017 A

In response to the problem that it is difficult to obtain substitute particles for such polyamide resin particles, composite particles are prepared by using particles of other materials as seed particles and coating the surface of the seed particles with polyamide resin. Thus, it is conceivable to make the feel close to that of polyamide resin particles.
A method of using a polyamide resin solution in which a polyamide resin is dissolved in an organic solvent can be considered to coat each particle with a polyamide resin while preventing the particles from adhering to each other and forming aggregated particles. .
However, since the polyamide resin is only slightly soluble in a general organic solvent that can be used industrially, it is necessary to coat the polyamide resin on the seed particles with a sufficient thickness to exhibit the texture of the polyamide resin. It is considered that a lot of labor is required, and conventionally, such a method has not been studied.

That is, conventionally, it has been difficult to produce substitute particles that are closer to the texture of polyamide resin particles, and therefore it is difficult to impart an excellent texture to cosmetics.
This invention is made | formed in view of such a problem, and provides the method of producing simply the alternative particle close | similar to the texture of a polyamide resin particle, and aims at the improvement of the texture in cosmetics.

  As a result of intensive studies by the inventor regarding the above problems, the composite particles surprisingly have a texture similar to that of the polyamide resin even when the polyamide resin is coated in a very thin state. As a result, the present invention has been completed.

  That is, the present invention relating to the method for producing composite particles is a method for producing composite particles in which a coating layer made of a material different from the seed particles is provided on the surface of the seed particles, wherein the polyamide resin is dissolved in an organic solvent. Forming a slurry in which the seed particles are dispersed in the polyamide resin solution formed, and depositing the polyamide resin from the polyamide resin solution on the surface of the seed particles contained in the slurry to form the coating layer And producing the composite particles whose surfaces are coated with the polyamide resin.

  Further, the present invention relating to the composite particles is a composite particle in which the surface of the seed particles is provided with a coating layer made of a material different from the seed particles, and the coating layer is formed by coating the surface with a polyamide resin. And a step of preparing a slurry in which the seed particles are dispersed in a polyamide resin solution in which the polyamide resin is dissolved in an organic solvent, and the polyamide resin on the surface of the seed particles contained in the slurry. And a step of depositing a polyamide resin from the solution, and the coating layer is formed by the deposited polyamide resin.

  Furthermore, the present invention relating to a cosmetic is a cosmetic comprising a composite particle in which a coating layer made of a material different from the seed particle is provided on the surface of the seed particle, A composite particle in which the polyamide resin is coated to form the coating layer is used, and a slurry in which the seed particles are dispersed in a polyamide resin solution in which the polyamide resin is dissolved in an organic solvent is prepared. A composite particle in which the step and a step of depositing a polyamide resin from the polyamide resin solution on the surface of the seed particles contained in the slurry are performed, and the coating layer is formed by the deposited polyamide resin Is used.

As described above, the present inventor has found that even when the surface of the seed particles is coated with the polyamide resin in a relatively thin state, the texture of the polyamide resin is greatly reflected in the tactile sensation.
It seems that such an effect is exhibited because the texture unique to the polyamide resin is greatly influenced by the presence of functional groups on the surface.
Therefore, for example, even if a coating layer having a thickness of several molecules to a thickness of about submicron is formed on the surface of the seed particles, the composite particles can be given a texture peculiar to the polyamide resin due to the presence of the functional groups.
That is, since a small amount of the polyamide resin may be deposited on the surface of the seed particles, the polyamide resin solution used for coating the seed particles with the polyamide resin is also a dilute solution in which the concentration of the polyamide resin is 10% by mass or less. Is sufficient, and composite particles having a texture like polyamide resin particles can be produced using an industrially easy-to-use solvent such as methanol.

As described above, according to the present invention, substitute particles closer to the texture of the polyamide resin particles can be easily produced, and substitute particles that can be used for the same applications as the polyamide resin particles can be obtained.
Therefore, the texture of cosmetics can be improved while using a substitute for polyamide resin particles.

The figure which shows the composite particle of manufacture example 2 (SEM photograph: Left low magnification photograph, Right high magnification photograph).

A preferred embodiment of the present invention will be described below.
The composite particles of the present embodiment are those in which a coating layer made of a material different from the seed particles is provided on the surface of the seed particles, and the coating layer is formed of a polyamide resin.
As will be described later, the coating layer includes a step of producing a slurry in which the seed particles are dispersed in a polyamide resin solution in which a polyamide resin is dissolved in an organic solvent, and a surface of the seed particles contained in the slurry. And a step of depositing a polyamide resin from the polyamide resin solution to form the coating layer, and the composite particles are separated from the polyamide resin solution by separating the particles on which the coating layer is formed. And then dried and manufactured.

The seed particles are not limited to materials such as organic materials and inorganic materials, but usually organic materials can be suitably used.
And in the point which gives smooth tactile sensation to cosmetics etc., it is preferable that it is a spherical particle which has an average particle diameter in the range of 0.5 micrometer or more and 30 micrometers or less.
Further, in terms of being able to reveal a soft feel to the composite particles, it is preferable to use resin particles obtained by using a crosslinked acrylate resin as seed particles.

The resin particles formed by this acrylic ester resin cross-linked product are usually those having a compressive strength of 3.5 kgf / mm ² or less, particularly in that the soft feel can be exhibited more significantly. Preferably has a compressive strength of 0.05 kgf / mm ² or more and 1.0 kgf / mm ² or less.
Further, 0.05 kgf / mm ² or more, and most preferably has a compressive strength of 0.6 kgf / mm ² or less.
The most preferable lower limit of the compressive strength is 0.05 kgf / mm ^2, and if it is less than this value, the feel of the resin particles is reflected in the feel of the cosmetic when it is contained in the cosmetic. This is because it is difficult to sufficiently improve the feeling of use such as elongation and smoothness.
Moreover, the upper limit of the compressive strength is set to the above value because when the value exceeds 0.6 kgf / mm ² , the feel of the seed particles starts to affect the feeling of use such as the soft feeling of the composite particles. This is because when the value exceeds 1.0 kgf / mm ² , the feel of the cosmetic containing the composite particles may be lowered.

The average particle size of the composite particles means a particle size measured by a Coulter counter method.
The compressive strength is a value measured using a micro compression tester HCTM200 manufactured by Shimadzu Corporation.
That is, when a compression test is performed on a single resin particle at a constant load speed up to a load of 1 gf, the value is calculated by the following formula from the load at the time of 10% deformation of the particle diameter and the particle diameter.

Compressive strength (kgf / mm ² ) = 2.8 × load (kgf) / {π × particle diameter (mm) × particle diameter (mm)}

Spherical acrylate resin particles suitable as seed particles are obtained by polymerizing a (meth) acrylate monomer by aqueous suspension polymerization, emulsion polymerization, seed polymerization or dispersion polymerization in the presence of a crosslinking agent. Obtainable.
In addition, the term “(meth) acryl” is used in this specification as a concept including both “acryl” and “methacryl”.

As this (meth) acrylic acid ester monomer, it is preferable to use an oil-soluble monomer.
Furthermore, it is preferable to use a (meth) acrylic acid ester monomer having 1 to 12 carbon atoms in the substituent that forms an ester bond with (meth) acrylic acid.
Specifically, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, Examples include methacrylic acid esters such as n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate.
In particular, it is preferable to use an acrylic ester having 1 to 8 carbon atoms, and it is preferable to contain this acrylic ester in the monomer in a proportion of 50 to 95% by mass.
In addition, the said (meth) acrylic acid ester-type monomer may be used either individually, or may be used in combination of multiple types.

  The acrylic ester resin particles include monomers copolymerizable with (meth) acrylic ester monomers, for example, vinyl groups such as styrene, p-methylstyrene, α-methylstyrene, and vinyl acetate. One or more other monomers having the above may be added.

Examples of the cross-linking agent include cross-linkable monomers. Examples of such cross-linkable monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Decaethylene glycol di (meth) acrylate, pentadecaethylene glycol di (meth) acrylate, pentacontactor ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, allyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, phthalate (Meth) acrylate monomers such as diethylene glycol di (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol diacrylate, polyester acrylate, urethane acrylate, divinylbenzene , Divinylnaphthalene and aromatic divinyl monomers which are derivatives thereof.
These may be used alone or in combination.

Among these crosslinking agents, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexane Since methacrylic acid ester-based crosslinking agents such as diol dimethacrylate and caprolactone-modified dipentaerythritol hexaacrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol diacrylate, and polyester acrylate have low skin irritation, this embodiment is used. It can be said that it is particularly suitable when such composite particles are used for cosmetic applications.
Moreover, it is preferable to use a crosslinking agent so that it may become 5 to 50 mass% in all the monomers.

These monomers and crosslinking agents may be used alone or used in combination of plural kinds, finally compressive strength 0.05 kgf / mm ² or more, 0.6 kgf / mm ² or less, preferably 0.1 kgf / Their composition and blending amount can be determined so as to be mm ² or more and 0.4 kgf / mm ² or less.
When forming the resin particles by aqueous suspension polymerization, a polymerization initiator, a dispersant, a surfactant, and the like are used as necessary.

  Examples of the polymerization initiator include oil-soluble peroxides such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, and t-butyl hydroperoxide. Examples thereof include oil-soluble azo compounds such as oxides, 2,2′-azobisisobutyronitrile, and 2,2′-azobis (2,4-dimethylvaleronitrile).

  Examples of the dispersant include poorly water-soluble inorganic salts such as calcium phosphate and magnesium pyrophosphate, and water-soluble polymers such as polyvinyl alcohol, methyl cellulose, and polyvinyl pyrrolidone. Further, surfactants include anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl phosphate ester salt, polyoxyethylene alkyl ether, polyoxyethylene Nonionic surfactants such as alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxysorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, amphoteric surfactants such as lauryl dimethylamine oxide, etc. Can be mentioned.

The above polymerization initiator, dispersant and surfactant may be used alone or in combination of two or more.
The addition rate of the polymerization initiator to all monomers is 0.1 to 1% by mass, the addition rate of the dispersing agent to all monomers is 0.5 to 10% by mass, and when using a surfactant, It is preferable to add at 0.01-0.2 mass%.

Examples of the polymerization reaction for producing such resin particles include a method in which the resin monomer phase and the aqueous phase are mixed and then heated while stirring.
The polymerization temperature is preferably 40 to 90 ° C., and the polymerization time is preferably 1 to 10 hours.
At this time, the average particle diameter of the resin particles can be appropriately determined by controlling the mixing conditions and stirring conditions of the monomer and water.
Control of mixing conditions and stirring conditions is, for example, using a homogenizer, an emulsifying disperser using a high shear applied to the gap between the rotating blades and the wall of the rotating blades, or using an ultrasonic disperser, It can be carried out by pressurizing a monomer aqueous solution through a ceramic microporous membrane and pressing it into a dispersion medium.
After the completion of the polymerization, the dispersing agent is decomposed with an acid or the like as required, and crosslinked (meth) acrylic acid ester resin particles can be obtained by filtration, washing, drying, pulverization, and classification.
In addition, you may utilize the method described in Unexamined-Japanese-Patent No. 3-37201 for manufacture of bridge | crosslinking (meth) acrylic-ester type resin particle itself.

Such a coating layer covering the surface of the seed particles includes a polycondensation reaction product of ε-caprolactam known as a trade name “nylon 6”, a polycondensation reaction product of undecane lactam known as “nylon 11”, “nylon 12 Can be formed by a polyamide resin such as a polycondensation product of lauryl lactam known as
Further, a copolycondensation reaction product of hexamethylenediamine and adipic acid known as the trade name “nylon 66”, a copolycondensation reaction product of hexamethylenediamine and sebacic acid known as “nylon 610”, “nylon 6T” A copolycondensation reaction product of hexamethylenediamine and terephthalic acid known as “Nylon 6I” and a copolycondensation reaction product of hexamethylenediamine and isophthalic acid known as “nylon 6I” can also be used for forming the coating layer.
Furthermore, a copolycondensation reaction product of nonanediamine and terephthalic acid known as trade name “nylon 9T”, a copolycondensation reaction product of methylpentadiamine and terephthalic acid known as “nylon M5T”, “nylon 612” Known copolycondensation polymers of caprolactam and lauryl lactam may also be employed as the forming material.

Although it is possible to use phenol, cresol, or the like as a solvent for dissolving such a polyamide resin, methanol is used in consideration of the risk of residual solvent being generated in the composite particles and being brought into cosmetics. It is preferable.
This methanol can be used as a solvent for dissolving the polyamide resin in a heated (hot methanol) state.
The polyamide resin solution obtained by dissolving the polyamide resin in an organic solvent such as methanol may contain other components as necessary.
The preferred thickness of the coating layer formed by this polyamide resin solution depends on the material of the seed particles. For example, the coating layer formed on the surface of the seed particles such as crosslinked (meth) acrylate resin particles is 0 The thickness is preferably 0.05 μm or more and 0.5 μm or less.
The thickness of the coating layer is preferably within the above-mentioned range. If the thickness is thinner than the lower limit, it may be difficult to make the composite particles exhibit the texture of the polyamide resin. However, on the other hand, even if the thickness exceeds the upper limit value, the labor required is increased, and it is difficult to further improve the texture of the polyamide resin.

As a method for producing composite particles by forming such a coating layer on the surface of the seed particles, a step of preparing a slurry in which the seed particles are dispersed in a polyamide resin solution in which a polyamide resin is dissolved in an organic solvent. (Hereinafter also referred to as “slurry preparation process”), a process of depositing a polyamide resin from the polyamide resin solution on the surface of the seed particles to form the coating layer (hereinafter also referred to as “precipitation process”), and a coating layer is formed. And a step of drying the particles after separating them from the polyamide resin solution (hereinafter also referred to as “filtration / drying step”).
Below, each process is demonstrated.

In preparing a polyamide resin solution by dissolving a polyamide resin in an organic solvent, if a polyamide resin solution having a high concentration of the polyamide resin is prepared, the viscosity of the polyamide resin solution increases. For example, in the filtration and drying step, There is a risk of deteriorating the workability of the filtering work.
Therefore, the polyamide resin solution prepared in this step preferably has a polyamide resin concentration of 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less. preferable.
By using such a dilute solution, it is possible to carry out the filtration operation with good working efficiency in the filtration / drying step.
Moreover, it can suppress that particles adhere and form an aggregate after filtration.

As the organic solvent for preparing the dilute solution of the polyamide resin, methanol can be suitably used as described above.
When using this methanol, it is usually preferable to heat the methanol to a temperature equal to or higher than its boiling point (64.7 ° C.) in order to exhibit a certain degree of solution property to the polyamide resin.
Therefore, it is preferable to carry out the slurry production process using a pressure vessel so that the polyamide resin solution can be produced in a pressurized state.

  The slurry preparation step may be a procedure in which a polyamide resin solution is prepared in advance and seed particles are dispersed in the polyamide resin solution to prepare a slurry. Alternatively, after the seed particles are dispersed in methanol, a polyamide is prepared. It is possible to add a resin and dissolve it by heating so that the preparation of the polyamide resin solution and the preparation of the slurry are performed simultaneously.

(Precipitation process)
In order to precipitate the polyamide resin on the surface of the seed particles contained in the slurry, the solubility of the polyamide resin in the polyamide resin solution may be reduced. In the case where the above hot methanol is used as a solvent. Can precipitate the polyamide resin on the surface of the seed particles by lowering the temperature of the polyamide resin solution.
Specifically, when the temperature of the polyamide resin solution (slurry) in the slurry preparation step is a temperature equal to or higher than the boiling point of methanol, for example, 100 to 120 ° C., and the concentration of the polyamide resin is 0.5 to 5 mass%. For example, by reducing the temperature of the slurry to about 50 ° C. below the boiling point, the polyamide resin can be deposited on the surface of the seed particles, and a coating layer can be formed.
Further, instead of or in addition to such a method, a solvent having a high compatibility with the organic solvent used for the preparation of the polyamide resin solution and having a lower solubility in the polyamide resin than the organic solvent is used as the polyamide. A method of adding to the resin solution can also be employed as a method for depositing the polyamide resin.
For example, it is possible to form a coating layer by depositing polyamide resin on the surface of seed particles by adding water (water vapor) to a slurry in which hot methanol is used as an organic solvent.

(Filtering and drying process)
In the precipitation step, the composite particles are formed in a slurry state. Therefore, in order to obtain the composite particles according to the present embodiment in a dry powder state, the slurry is usually filtered and filtered. It is necessary to dry the composite particles.
In this filtration / drying step, it can be carried out using a general apparatus for separating and drying the particulate matter from the slurry, and a dehydrated cake with composite particles is produced by a filtration / dehydration apparatus such as a filter press, Examples include a method of drying the dehydrated cake with a dryer such as an oven.
Further, if necessary, the filtered composite particles may be dried after adding one or more “washing-dehydration” cycles.

As described above, the composite particles of the present embodiment can be produced by a simple method, and substitute particles for polyamide resin particles can be produced at a low cost from the viewpoints of material costs and production costs.
In addition, the flexibility of the particles can be adjusted by adjusting the material used to form the seed particles while approximating the texture of the surface to that of the polyamide resin particles.
In addition, if necessary, it is also possible to make the composite particles have a shape other than a sphere by using seed particles other than a sphere.

In addition, when this composite particle is used as a compounding agent for external preparations such as cosmetics and external medicines, it is usually preferable to have a spherical shape, and an oil agent, a silicone compound, a fluorine compound, etc. for adjusting the texture. The surface treatment of the composite particles may be performed with the surface treatment agent.
Generally, the polyamide resin is excellent in oil resistance, and the composite particles according to this embodiment are subjected to surface treatment with various oil agents because the coating layer is formed of the polyamide resin excellent in oil resistance. obtain.

By subjecting the composite particles to surface treatment, it becomes possible to improve water repellency and oil repellency.
Therefore, when the composite particles of the present embodiment are surface-treated and blended in cosmetics, even if they are used for a long time because they are difficult to get wet with water, sweat, sebum, etc. It is possible to provide cosmetics that are less likely to cause odors.

  The oil agent may be any of those usually used in cosmetics, for example, hydrocarbon oils such as liquid paraffin, squalane, petrolatum, paraffin wax, lauric acid, myristic acid, palmitic acid, stearic acid, olein Acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, synthetic fatty acids and higher fatty acids, glyceryl trioctanoate, propylene glycol dicaprate, cetyl ethyl hexanoate, isocetyl stearate, beeswax, Wax wax, lanolin, carnauba wax, candelilla wax and other waxes, flaxseed oil, cottonseed oil, castor oil, egg yolk oil, coconut oil and other oils, metal stearates such as zinc stearate and zinc laurate, cetyl alcohol, stearyl alcohol , Oleil alcohol Higher alcohols, etc. and the like.

  The method of treating the composite particles with an oil agent is not particularly limited, but for example, a dry method in which an oil agent is added to the composite particles and stirred with a mixer or the like, or a component constituting a polyamide resin and seed particles, etc. On the other hand, it is possible to use a wet method in which an oil agent is dissolved in an appropriate solvent that hardly influences, and composite particles are added thereto, mixed and stirred, and then the solvent is removed under reduced pressure or by heating to remove the solvent.

The silicone compound may be any one that is usually used in cosmetics, for example, dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, acrylic-silicone graft polymer, Organic silicone resin partially cross-linked organopolysiloxane polymer and the like can be mentioned.
The method for treating the composite particles with the silicone compound is not particularly limited. For example, the dry method or the wet method described above can be used.
Moreover, the method of baking-processing as needed, and the method of adding a reaction catalyst etc. suitably in the case of the reactive silicone compound are employable.

The fluorine compound may be any compound as long as it is usually used in cosmetics, for example, perfluoroalkyl group-containing esters, perfluoroalkylsilanes, perfluoropolyethers, and polymers having perfluoro groups. Examples include coalescence.
The method for treating the composite particles with the fluorine compound is not particularly limited, and for example, the dry method or the wet method described above can be used.
Moreover, you may employ | adopt the method of baking, as needed, and the method of adding a reaction catalyst etc. suitably in the case of the fluorine compound which has reactivity.

These surface treatment agents can be used by appropriately selecting one kind or two or more kinds.
Moreover, although the addition amount of these surface treating agents changes also with the particle diameter etc. of composite particle, 0.01-50 mass% with respect to composite particle, especially 0.1-10 mass% is preferable.
If the blending amount of the surface treatment agent is less than 0.01% by mass, water repellency and oil repellency may not be sufficiently obtained. If it exceeds 50% by mass, a remarkable effect corresponding to the increase in the amount of addition may be achieved. There is a risk of not being recognized or agglomeration.

Furthermore, the composite particles of the present embodiment can be colored particles by adding a coloring pigment to the seed particles or the material for forming the coating layer.
Examples of the coloring pigment include titanium oxide, zinc oxide, zirconium oxide, magnesium oxide, iron oxide, iron hydroxide, chromium oxide, chromium hydroxide, ultramarine, bitumen, manganese violet, ultraviolet, titanium black, carbon black, Aluminum powder, mica titanium, bismuth oxychloride, iron oxide treated mica titanium, bituminized mica titanium, carmine treated mica titanium, silica, calcium carbonate, magnesium carbonate, barium sulfate, barium silicate, calcium silicate, magnesium silicate, calcium phosphate , Hydroxyapatite, Zeolite, Alumina, Talc, Mica, Bentonite, Kaolin, Sericite and other inorganic pigments, Tartrazine, Sunset erotic FCF, Brilliant blue FCF, etc. Aluminum lake, Zirconium lake, Bali Mureki, to Lyndon pink CN, Lithol Rubine BCA, Lake Red CBA, phthalocyanine blue, and organic pigments of permanent orange, and the like.
These color pigments may be used alone or in combination of two or more.

The content of the color pigment in the composite particles is preferably 1 to 70% by mass in the total mass.
If the content is less than 1% by mass, the content is too small, and the effect of blending the color pigment becomes extremely thin, which is not preferable.
On the other hand, when the content exceeds 70% by mass, the amount of the color pigment is too large, which may make it difficult to produce composite particles.

The dispersion method of the color pigment is not particularly limited, but using carboxylic acid, sulfonic acid, sulfate ester, phosphate ester, and phosphonic acid, and salts thereof, or coupling agents such as silane, titanate, and aluminate. An example is a method in which the surface of the pigment is hydrophobized and then added to a polymerization system for producing seed particles.
The addition amount of the pigment surface treatment agent to the pigment is preferably 0.1 to 30% by mass.
The color pigment dispersing apparatus is not particularly limited as long as it can impart sufficient dispersion energy to the dispersion system.
Examples thereof include a ball mill, a sand mill, an ultrasonic disperser, and a homogenizer.

By incorporating the composite particles thus obtained in the range of 1 to 40% by mass, an excellent texture can be given to external preparations such as cosmetics and external medicines.
That is, it is possible to give an excellent texture as if the polyamide resin particles are added.
Cosmetics that exhibit such effects include soaps, body shampoos, facial cleansing creams, scrub facial cleansing cosmetics, lotions, creams, emulsions, packs, funniests, foundations, lipsticks, lip balms, Blusher, eyebrow cosmetics, nail polish cosmetics, hair washing cosmetics, hair dyes, hair styling, aromatic cosmetics, toothpaste, bath preparation, antiperspirant, sunscreen products, suntan products, body powder, baby powder, etc. Examples include shave creams, pre-shave lotions, after-shave lotions, and body lotions.

Moreover, what is expected to be effective as an external medicine is not particularly limited as long as it is applied to the skin.
Specific examples include pharmaceutical creams, ointments, pharmaceutical emulsions, and pharmaceutical lotions.
In these external preparations, if the blending amount is less than 1% by mass, the amount of resin particles is too small and the added effect is not clearly recognized.
On the other hand, if it exceeds 40% by mass, even if the addition amount is increased further, a significant effect corresponding to the increase in the addition amount is not recognized, which is not preferable.

Moreover, the component generally used for the external preparation can be mix | blended according to the objective.
Examples of such components include water, lower alcohols, fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, moisturizers, surfactants, polymer compounds, coloring material raw materials, Perfumes, antiseptics / bactericides, antioxidants, UV absorbers, and special ingredients.

  The fats and waxes include avocado oil, almond oil, olive oil, cacao butter, beef tallow, sesame butter, wheat germ oil, safflower oil, shea butter, turtle oil, persimmon oil, persic oil, castor oil, grape oil, macadamia nut oil , Mink oil, egg yolk oil, owl, palm oil, rosehip oil, hydrogenated oil, silicone oil, orange luffy oil, carnauba wax, candelilla wax, whale wax, jojoba oil, montan wax, beeswax, lanolin and the like.

  Examples of the hydrocarbon include liquid paraffin, petrolatum, paraffin, ceresin, microcrystalline wax, squalane and the like. Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, and synthetic fatty acid.

  Examples of the higher alcohol include lauryl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, octyl decanol, isostearyl alcohol, jojoba alcohol, decyltetra A decanol etc. are mentioned.

  Examples of the sterol include cholesterol, dihydrocholesterol, phytocholesterol and the like. Fatty acid esters include ethyl linoleate, isopropyl myristate, lanolin fatty acid isopropyl, hexyl laurate, myristyl myristate, cetyl myristate, octadodecyl myristate, decyl oleate, octadodecyl oleate, hexadecyl dimethyloctanoate, isooctanoic acid Cetyl, decyl palmitate, glyceryl trimyristate, glycerin tri (capryl / capric acid), propylene glycol dioleate, glyceryl triisostearate, glycerin triisooctanoate, cetyl lactate, myristyl lactate, diisostearyl malate and cholesteryl isostearate And cyclic alcohol fatty acid esters such as cholesteryl hydroxystearate.

  Examples of the metal soap include zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc undecylenate and the like. Examples of the humectant include glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium DL-pyrrolidone carboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerin, xylit, and maltitol.

  Examples of the surfactant include anionic surfactants such as higher fatty acid soap, higher alcohol sulfate, N-acyl glutamate, and phosphate ester salts, and cationic surfactants such as amine salts and quaternary ammonium salts, Amphoteric surfactants such as betaine type, amino acid type, imidazoline type and lecithin, nonionic surfactants such as fatty acid monoglyceride, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, ethylene oxide condensate Agents.

  Examples of the polymer compound include gum arabic, tragacanth gum, guar gum, locust bean gum, karaya gum, iris moss, quince seed, gelatin, shellac, rosin, casein and other natural polymer compounds, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose Semi-synthetic polymer compounds such as sodium alginate, ester gum, nitrocellulose, hydroxypropylcellulose, crystalline cellulose, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil, nylon Particles, polymethyl methacrylate particles, crosslinked polystyrene particles, silicone particles, urethane particles, polyester Ren particles, synthetic polymer compounds such as resin particles of the silica particles and the like.

  Examples of the coloring material raw materials include iron oxide, ultramarine, conger, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide, talc, kaolin, mica, calcium carbonate, magnesium carbonate, mica, aluminum silicate. , Barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, hydroxyapatite, ceramic powder and other inorganic pigments, azo, nitro, nitroso, xanthene And tar dyes such as quinoline, quinoline, anthraquinoline, indigo, triphenylmethane, phthalocyanine, and pyrene.

Here, the powder material such as the polymer compound or the color material material may be subjected to surface treatment in advance.
A conventionally known surface treatment technique can be used as the surface treatment method.
For example, oil treatment with hydrocarbon oil, ester oil, lanolin, etc., silicone treatment with dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, perfluoroalkyl group-containing ester, perfluoroalkylsilane, perfluoropolyether , Fluorine compound treatment with a polymer having a perfluoroalkyl group, silane coupling agent treatment with 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, isopropyltriisostearoyl titanate, isopropyltris ( Dioctylpyrophosphate) Titanium coupling agent treatment with titanate, metal soap treatment, amino acid treatment with acylglutamic acid, etc., lecithin with hydrogenated egg yolk lecithin, etc. Treatment, collagen treatment, polyethylene process, moisture retention treatment, an inorganic compound treatment, and processing methods such as mechanochemical treatment.

  Examples of the fragrances include natural fragrances such as lavender oil, peppermint oil, and lime oil, and synthetic fragrances such as ethyl phenyl acetate, geraniol, and p-tert-butylcyclohexyl acetate. Examples of the antiseptic / bactericidal agent include methyl paraben, ethyl paraben, propyl paraben, benzalkonium, benzethonium and the like.

  Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, tocopherol and the like. Ultraviolet absorbers include inorganic absorbents such as fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide, fine particle iron oxide, fine particle zirconium oxide, benzoic acid-based, paraaminobenzoic acid-based, anthranilic acid-based, salicylic acid-based And organic absorbents such as cinnamic acid, benzophenone and dibenzoylmethane.

  Examples of the special ingredients include hormones such as estradiol, estrone, ethinylestradiol, cortisone, hydrocortisone, prednisone, vitamins such as vitamin A, vitamin B, vitamin C, vitamin E, citric acid, tartaric acid, lactic acid, aluminum chloride, Skin astringents such as aluminum sulfate / potassium sulfate, allantochlorohydroxyaluminum, zinc paraphenolsulfonate, zinc sulfate, cantalis tincture, pepper tincture, ginger tincture, assembly extract, garlic extract, hinokitiol, carpronium chloride, pentadecanoic acid glyceride, Examples thereof include hair growth promoters such as vitamin E, estrogen, and photosensitizer, and whitening agents such as magnesium phosphate-L-ascorbate and kojic acid.

  In the present embodiment, the present invention has been described with reference to the method for producing composite particles, composite particles, and cosmetics as described above, but the method for producing composite particles of the present invention, composite particles, And cosmetics are not limited to said illustration.

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)
Spherical particles formed by cross-linked polymethylmethacrylate (PMMA) resin (manufactured by Sekisui Plastics Co., Ltd., trade name “MBX-8C”, average particle size 8 μm, compressive strength: 3.1 kgf / mm ² ) seed particles 100 g of the seed particles, 10 g of polyamide resin (manufactured by Ube Industries, nylon 12, model name “7115U”), and 1000 ml of methanol were placed in a 2 liter autoclave and heated to 110 ° C. with stirring. The polyamide resin was dissolved to prepare a slurry.
Thereafter, stirring was continued for 5 minutes at a temperature of 110 ° C., and then the slurry was cooled at a cooling rate of 100 ° C./h until the temperature of the slurry reached 50 ° C., thereby depositing a polyamide resin on the surface of the seed particles.
Then, after further natural cooling, when the temperature of the slurry reaches 40 ° C., the slurry is suction filtered using a Buchner funnel, the dewatered cake separated by filtration is dried and crushed, and a 45 μm sieve is obtained. Composite particles of Production Example 1 that were passed through and used for evaluation were produced.

(Production Example 2)
The seed particles are formed into spherical particles (made by Sekisui Plastics Co., Ltd., trade name “ACX-806C”, average particle diameter of 8 μm, compressive strength: 0.5 kgf / mm ² ) formed of a crosslinked acrylate resin. The composite particles of Production Example 2 were produced in the same manner as Production Example 1, except that the replacement was performed.

(Production Example 3)
The seed particles are porous spherical particles formed by cross-linked polymethyl methacrylate (PMMA) resin (manufactured by Sekisui Plastics Co., Ltd., trade name “MBP-8”, average particle size 8 μm, compressive strength: 0.9 kgf / Mm ² ) The composite particles of Production Example 3 were produced in the same manner as Production Example 1, except that the particle size was changed to / mm ² ).

(Evaluation)
Using the composite particles of Production Examples 1 to 3, and the polyamide resin particles, the seed particles of Production Example 1 (PMMA spherical particles), and the seed particles of Production Example 2 (acrylate resin particles) as a comparative control, the texture A sensory evaluation of was performed.
Specifically, ten panelists were allowed to 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 together, and sensory evaluation of the feel Carried out by adding
The evaluation items were four items of “feeling tight”, “adhesion to skin”, “softness”, and “slippery”.
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 4 to 6 people evaluated “good” was judged as “Δ”, and a case where there were 3 or less panelists evaluated as “good” was judged as “x”.
The results are shown in Table 1.

  From the above, it can be seen that according to the present invention, it is possible to obtain alternative particles having a texture approximate to that of the polyamide resin particles.

In addition, a mode that the composite particle produced by the manufacture example 2 was observed with the scanning electron microscope (SEM) is shown in FIG.
As also shown in this figure, it can be seen that the composite particles of Production Example 2 are spherical and can give an excellent feel when blended in cosmetics and the like.

Claims (6)

A method for producing composite particles in which a coating layer of a material different from the seed particles is provided on the surface of the seed particles,
Preparing a slurry in which the seed particles are dispersed in a polyamide resin solution in which the polyamide resin is dissolved in an organic solvent; and depositing the polyamide resin from the polyamide resin solution on a surface of the seed particles contained in the slurry And the step of forming the coating layer to produce composite particles having a surface coated with a polyamide resin.   The method for producing composite particles according to claim 1, wherein spherical resin particles formed of a crosslinked acrylic ester resin are used as the seed particles. A composite particle in which a coating layer of a material different from the seed particle is provided on the surface of the seed particle,
A step of preparing a slurry in which the seed particles are dispersed in a polyamide resin solution in which a polyamide resin is coated on a surface to form the coating layer and the polyamide resin is dissolved in an organic solvent; A composite particle comprising a step of depositing a polyamide resin from the polyamide resin solution on a surface of the seed particles contained, and the coating layer is formed by the deposited polyamide resin.   The composite particle according to claim 3, wherein the seed particle is a spherical resin particle formed of a cross-linked acrylic ester resin. A cosmetic material containing composite particles provided with a coating layer made of a material different from the seed particles on the surface of the seed particles,
As the composite particles, composite particles having a surface coated with a polyamide resin to form the coating layer are used, and the seed particles are dispersed in a polyamide resin solution in which the polyamide resin is dissolved in an organic solvent. And a step of depositing a polyamide resin from the polyamide resin solution on the surface of the seed particles contained in the slurry, and the coating layer is formed by the deposited polyamide resin. Cosmetics characterized by using formed composite particles.   The cosmetic according to claim 5, wherein the seed particles are spherical resin particles formed of a crosslinked acrylate resin.