JP5029313B2 - Polycaproamide resin composite fine particles - Google Patents

Description

  The present invention relates to polycaproamide resin composite microparticles, and more particularly to polycaproamide resin composite microparticles that can improve contact feeling when used as a raw material for cosmetics and can impart UV-cutting performance.

  Fine particles composed of polyamide (nylon) resin have been used as a raw material for various cosmetics since they have good slipperiness with the skin, and various investigations have been made on their production methods.

  For example, Patent Document 1 discloses a method of obtaining fine particles of polylaurolactam (nylon 12) while polymerizing by heating and dissolving lauryl lactam in liquid paraffin, adding an alkaline catalyst, a co-catalyst, and the like and stirring with heating. Are listed. However, the fine particles of nylon 12 obtained by this method have a very smooth surface and a small amount of oil absorption, so that sufficient performance as a cosmetic raw material cannot be obtained. In addition, this method cannot control the surface form such as making the surface porous. If the conditions of the polymerization reaction are adjusted to make the surface of the nylon 12 fine particles porous, fine particles having a uniform particle size cannot be obtained, such as an increase in particle size or fusion of particles.

  Patent Document 2 describes a method for obtaining nylon 12 powder by reacting lauryl lactam in xylene. However, the fine particles obtained by this method have a smooth surface, and it is impossible to control the surface form such as making the surface porous. If an attempt is made to produce porous nylon fine particles by adjusting the polymerization reaction conditions, uniform fine particles cannot be obtained, for example, the particle size is increased or the particles are fused together.

  These methods are methods for forming particles at the same time as the polymerization reaction, but methods for producing fine particles using a once polymerized polyamide resin are also known. For example, Patent Document 3 describes a method in which fine particles of a polyamide resin are precipitated by dissolving a synthetic linear polyamide resin in a solvent at a high temperature and then cooling the solution. As a specific example, there is described a method of obtaining fine particles by dissolving polyhexamethylene adipamide (nylon 66) or polyhexamethylene sebacamide (nylon 610) in a glycol solvent and then cooling. Although it has been suggested that polycaproamide (nylon 6) fine particles are obtained by this method, there is no description that true spherical porous particles having a uniform particle size can be obtained, and the particle size and surface morphology are controlled. There is no mention of the possibility or conditions of this.

  Patent Document 4 describes a method for producing amorphous nylon resin fine particles by dissolving an amorphous nylon resin in a mixed solvent of ethylene glycol and morpholine or dimethylacetamide and then cooling. The particles obtained by this method are amorphous nylon fine particles, and there is no description that the production of nylon 6 resin fine particles can be true spherical porous particles having a uniform particle size. There is no description of the possibility or conditions of controlling the process.

  Patent Document 5 describes the use of fine particles made of nylon 12 resin having a smooth surface in cosmetics.

  Furthermore, a method of modifying the surface by fixing another fine particle on the surface of the fine particle is also known. For example, Patent Document 6 describes a method for producing composite particles by fixing other solid particles to the surface of solid particles using an impact-type impacting means, and softening, melting, and fixing the solid particles. Has been. Specifically, composite particles in which polymethylmethacrylate particles are fixed on the surface of nylon 12 particles are described. However, in this method, particles fixed on the surface remain as they are. The surface is not smooth and only those with many irregularities can be obtained. Therefore, the modification effect by other particles is insufficient.

  Patent Document 7 describes a method for producing composite particles by embedding or fixing other solid particles on the surface of the solid particles using an impact-type impacting means. Specifically, composite particles in which titanium dioxide particles are embedded on the surface of nylon 12 particles are described. However, in order to embed titanium dioxide particles on the smooth surface of nylon 12 particles, when trying to coat the surface with titanium dioxide, A large amount of titanium dioxide was required, and the surface of the nylon 12 particles could not be completely modified with titanium dioxide, and sufficient UV-cutting performance could not be imparted.

  Further, in Patent Document 8, other solid particles are embedded by embedding other solid particles in the recesses of the solid particles having irregularities, holes, and grooves on the surface, and softening, melting, and deforming the solid particles using an impact type means. Describes a method of producing composite particles by enclosing the particles. Specifically, composite particles are described in which acetylene black is wrapped around the porous surface of nylon 6 particles and further coated with nylon 6 thereon. However, once acetylene black is attached to the surface of the porous nylon 6 particles, the surface is coated with nylon 6 by applying thermal energy by impact, so that the surface of the obtained composite particles is smooth nylon 6 The advantage of the porous surface of nylon 6 is not utilized. The surface of the porous nylon 6 particles is simply smoothed, and there is little meaning to complex it.

  Therefore, composite fine particles in which the surface of the fine particles made of polyamide resin is coated with other fine particles are not used as composite fine particles having a uniform particle diameter and being porous and having a large oil absorption amount. Sometimes, there was a problem that the sense of contact was not always sufficient.

Japanese Examined Patent Publication No. 45-29832 Japanese Patent Publication No. 48-2949 US Pat. No. 2,639,278 JP-A-5-32795 JP-A-9-263523 Japanese Patent Laid-Open No. 62-140636 JP 62-83029 A Japanese Patent Laid-Open No. 62-298443

  An object of the present invention is a composite fine particle having a uniform particle diameter and a large oil absorption amount, which improves the touch feeling when used as a raw material for cosmetics, and can impart a UV-cutting performance. It is to provide fine particles.

The polycaproamide resin composite fine particles of the present invention that achieve the above object have a relative viscosity of 1.70 to 2.35, an average particle diameter of 5 to 20 μm, and an oil absorption of 100 to 200 mL / 100 g made of polycaproamide resin. A composite fine particle obtained by coating the surface of a certain fine particle with metal oxide fine particles, wherein the composite fine particle has an average particle diameter of 5 to 20 μm and an oil absorption of 70 to 200 mL / 100 g.

The polycaproamide resin composite fine particles of the present invention are formed by coating the surfaces of polycaproamide resin fine particles having a porous particle surface with metal oxide fine particles, and the composite fine particles have an average particle size of 5 to 20 μm. And the oil absorption is as large as 70 to 200 mL / 100 g. For this reason, when this polycaproamide resin composite fine particle is used as a raw material for cosmetics, it can improve the sense of contact with the skin as compared with conventional fine particles for cosmetics. Can be given.

The polycaproamide resin composite fine particles of the present invention are based on fine particles made of a polycaproamide resin, and the surface thereof is coated with metal oxide fine particles (hereinafter sometimes referred to as “other fine particles”). It is.

  The average particle size of the polycaproamide resin composite fine particles is in the range of 5 to 20 μm, preferably 5 to 17 μm, more preferably 5 to 15 μm from the viewpoint of contact feeling with the skin when used as a raw material for cosmetics. It is good to be in the range. When the average particle diameter of the composite fine particles is within this range, an excellent contact feeling can be obtained when used as a raw material for cosmetics. In the present invention, the average particle diameter of the fine particles means a 50% median diameter measured by a laser diffraction / scattering method.

  The polycaproamide resin composite fine particles of the present invention have an oil absorption in the range of 70 to 200 mL / 100 g, preferably 70 to 180 mL / 100 g, and more preferably 75 to 170 mL / 100 g. . When the amount of oil absorption of the composite fine particles is within this range, when used as a cosmetic raw material, the oily component contained in the cosmetic product, and in some cases, the aqueous component can be absorbed appropriately. Can be obtained.

In the present invention, the oil absorption amount of the fine particles refers to linseed oil obtained by accurately weighing about 1 g of fine particles in an environment of a temperature of 23 ° C. and a relative humidity of 50% in accordance with JIS K5101-13-1. The value calculated based on the following formula (2), with the end point being the state where the last drop can be spirally wound from the putty-like lump after dropping and kneading little by little Say that.
O ₁ = 100 V / m (2)
Here, O ₁ represents the oil absorption (mL / 100 g), V represents the capacity (mL) of the dropped linseed oil, and m represents the mass (g) of the sample.

The features of the polycaproamide resin composite particles of the present invention vary widely depending on the characteristics of the other fine particles covering the surface of the fine particles of the polycaproamide resin. Other particulates, oxidation, titanium oxide, zirconium oxide, zinc oxide, aluminum oxide, magnesium oxide, iron oxide, copper oxide, silicon oxide (silica), to fine particles of a metal oxide such as tin oxide. Surface properties of the resulting composite particles, functional, In consideration of easiness of compounding, other fine particles in the metal oxide. Of the metal oxides, titanium oxide and zinc oxide are preferable, and titanium oxide is particularly preferable.

  Titanium oxide particles are so fine that even if they are incorporated into cosmetics, the contact sensation with the skin of the cosmetics cannot be improved. The contact sensation may be reduced. However, by coating the surface of the fine particles of polycaproamide resin with titanium oxide, the resulting polycaproamide resin composite fine particles have a smooth surface, and the contact sensation with the skin that could not be expressed with conventional titanium oxide Can be expressed. Further, by covering the surface of the fine particles of the polycaproamide resin with the fine particles of titanium oxide, it is possible to impart an ultraviolet cut performance.

  Specific examples of titanium oxide include STR-100C from Sakai Chemical Industry Co., Ltd., MT-01, MT-05, MT-100TV, MT-100Z, MT-100ZR, MT150W, MT- 100AQ, MT-100SA, MT-500H, MT-500T, MT-500B, MT-500SA, MT-02, MT-03, MT-04, MT-100SAS, MT-100SAK, SMT-100SAS, SMT-100SAM, MT-500SAS, MT-500SAK, SMT-500SAS, SMT-500SAM, MTY-02, MPY-100M, JR-800S, Ishihara Sangyo Co., Ltd. TTO-55 (A), TTO-55 (B), TTO- 55 (C), TTO-55 (D), TTO-55 (S), TTO-55 (N), TO-51 (A), TTO-51 (C), TTO-S-1, TTO-S-2, TTO-S-3, TTO-S-4, TTO-S-6, TTO-V-3, Examples include TTO-V-4, TTO-D-1, TTO-D-2, TTO-F-1, TTO-F-2, TTO-F-6, TTO-F-11, and the like.

  In the present invention, the size of the other fine particles is not particularly limited, but is preferably smaller in view of covering the porous surface of the fine particles of the polycaproamide resin. The size of the other fine particles depends on the size of the fine particles of the polycaproamide resin to be coated, but usually the average particle size is 3 μm or less, preferably 1 μm or less, more preferably 0.01 to 0.5 μm. It is good to be.

  The shape of the other fine particles is not particularly limited, and can be selected according to characteristics expected of the obtained composite particles, such as a spherical shape, a quadrangular pyramid shape, a rectangular parallelepiped shape, a scale shape, and a star shape. In particular, when the smoothness of the surface of the composite particles is required, the shape of the other fine particles is preferably spherical or scaly.

  In the present invention, the amount of other fine particles used is not particularly limited. If the surface coverage of the polycaproamide resin fine particles is to be increased, use a large amount, and if it is desired to reduce the surface coverage, use a small amount. That's fine. In general, the surface of the fine particles of polycaproamide resin may be coated uniformly with other fine particles, so that it is preferably 3 to 80 parts by weight, more preferably 5 to 60 parts by weight with respect to 100 parts by weight of the fine particles of polycaproamide resin. Parts, more preferably 10 to 50 parts by weight.

  Moreover, when providing the performance of UV-cutting by coating other fine particles, the other fine particles are preferably 5 to 120 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the fine particles of the polycaproamide resin. It is better to use parts by weight.

  The polycaproamide resin fine particles used as the base of the polycaproamide resin composite fine particles of the present invention are preferably fine particles having a true spherical shape, a uniform particle diameter, and a porous particle surface.

The relative viscosity of the fine particles of polycaproamide resin used in the present invention, 1. 70 to 2.35 Der is, good Mashiku may If it is from 1.80 to 2.30. When the relative viscosity is lower than 1.70 and higher than 2.35, the porosity, sphericity, and uniformity of particle size of the polycaproamide resin fine particles are impaired, and composites are formed using these fine particles. When fine particles are produced, composite fine particles having a uniform shape and particle size may not be obtained. The relative viscosity of the fine particles of polycaproamide resin refers to a value measured with an Ubbelohde viscometer at 25 ° C. using a solution of 1 g of fine particles of polycaproamide resin in 100 mL of 98% sulfuric acid.

Further, the oil absorption of the fine particles of polycaproamide resin used in the present invention is in the range of 1 00~200mL / 100g, good Mashiku is may be in the range of 120~180mL / 100g. If the amount of oil absorption of the fine particles of polycaproamide resin deviates from this range, the surface coverage with other fine particles deteriorates when compounded, and the feel when used as a cosmetic raw material is reduced and it can be used as a product. There may not be. The oil absorption herein is a value obtained by the above-described method using polycaproamide resin fine particles as a sample.

The average particle size of the fine particles of the polycaproamide resin used in the present invention is in the range of 5~20μm in terms of sense of touch with the skin when used as a cosmetic material is complexed with other particulate. It decreases the feel of when used as a cosmetic raw material out of this range. A more preferable average particle diameter is 5 to 17 μm, and further preferably 5 to 15 μm.

In the present invention, the polycaproamide resin used as the raw material for the fine particles of the polycaproamide resin is a polyamide resin obtained by heating ε-coupler lactam in the presence of water or polycondensation of aminocaproic acid, that is, nylon 6 Resin. The structural unit is represented by the following chemical formula (I).
_{- (CH 2) 5 CONH- (} I)

  The polycaproamide resin used as a raw material for the fine particles of the polycaproamide resin may contain a polyamide unit other than the chemical formula (I) as long as the mol% in the total structural units is 5 mol% or less. Specific examples include polyamide units obtained from lactams other than ε-caprolactam such as undecaractam, dodecaractam, 2-aminoacetic acid, 3-aminopropionic acid, 4-aminobutanoic acid, 5-aminopentanoic acid, 7-aminoheptane. Polyamide units obtained from amino acids such as acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, tetramethylenediamine, pentamethylenediamine, 2-methyl- 1,5-diminopentane, 3-methyl-1,5-diminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamidecamethylenediamine, undecamethylenediamine, dodecamethylenediamine, o-xylylene Diamines such as amine, m-xylylenediamine, p-xylylenediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane and succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, 1,7-heptanedicarboxylic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,2 -Polyamide units obtained from dicarboxylic acids such as cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, or any combination of these polyamide units.

In the present invention, the terminal group concentration of the polycaproamide resin used as a raw material for the fine particles of the polycaproamide resin is not particularly limited, but the terminal amino group concentration [NH ₂ ] (mol / g) and the terminal carboxyl group are not limited. The relationship with the concentration [COOH] (mol / g) preferably satisfies the following formula (1).
[NH ₂ ] + 2.0 × 10 ⁻⁵ <[COOH] (1)

When the end group concentration relationship deviates from the range of the above formula (1), the particle size of the polycaproamide resin particles tends to be non-uniform and the oil absorption tends to decrease. It shows a tendency to decrease when touched. Further, the relationship of the terminal group concentration of the polycaproamide resin is more preferably satisfied with the following formula (3).
[NH ₂ ] + 2.5 × 10 ⁻⁵ <[COOH] (3)

In the present invention, the terminal amino group concentration [NH ₂ ] (mol / g) means that about 1 g of a sample of polycaproamide resin is precisely weighed and dissolved in 50 mL of a phenol / ethanol mixed solvent (phenol concentration 83.5 wt%). The value obtained by adding thymol blue as an indicator to the solution and titrating with 0.02 N hydrochloric acid.

  The terminal carboxyl group concentration [COOH] (mol / g) means that about 0.5 g of a polycaproamide resin sample is precisely weighed and dissolved in 20 mL of benzyl alcohol at 190 ° C., and phenolphthalein is used as an indicator in the solution. And titrating with a methanol solution of 0.02 N potassium hydroxide.

  The relative viscosity of the polycaproamide resin used as a raw material for the fine particles of the polycaproamide resin is not particularly limited, but if the relative viscosity of the obtained fine particles of the polycaproamide resin is taken into consideration, the relative viscosity of 2.1 to 3.4 is preferable, more preferably 2.2 to 3.1, and still more preferably 2.35 to 2.70. When the relative viscosity of the polycaproamide resin is outside such a range, the porosity, sphericity, and uniformity of particle size of the resulting fine particles may be impaired. The relative viscosity of the polycaproamide resin refers to a value measured with an Ubbelohde viscometer at 25 ° C. using a solution of 1 g of polycaproamide resin in 100 mL of 98% sulfuric acid.

  The method for producing fine particles of the polycaproamide resin used in the present invention is not particularly limited, but the polycaproamide resin is heated and dissolved in a polyhydric alcohol or a mixed solution of polyhydric alcohol and water, and then cooled. Thus, it is preferable to produce fine particles of polycaproamide resin.

  Specifically, the polycaproamide resin is immersed in a polyhydric alcohol or a mixture of polyhydric alcohol and water, and the polycaproamide resin is dissolved while heating and stirring at about 80 to 300 ° C. The melting temperature is preferably 100 to 280 ° C, more preferably 120 to 250 ° C. If the temperature is too low, the polycaproamide resin will not dissolve sufficiently, or even if dissolved, the particle size will be non-uniform at the time of precipitation, or particles with a form in which the particles are fused will tend to be generated. Show. On the other hand, when the temperature is too high, the polycaproamide resin is decomposed and colored yellow, the particle size becomes uneven, or the shape tends to be distorted. At this time, it is preferable to carry out in an atmosphere of an inert gas such as nitrogen, argon, carbon dioxide gas or the like so that the polycaproamide resin is not oxidized and deteriorated.

  The concentration of the polycaproamide resin when dissolved in a polyhydric alcohol or a mixture of polyhydric alcohol and water is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, still more preferably. It may be 10 to 30% by weight. If the concentration of the polycaproamide resin is too low, the particles become too fine and the resulting fine particles tend to agglomerate secondary. On the other hand, when the concentration is too high, the particle size tends to be too large, or the particles tend to show a shape in which the particles are fused during precipitation.

  Once the polycaproamide resin is dissolved, cool it naturally at room temperature, cool the entire container in a place controlled at a constant temperature, or apply water, air, or inert gas around the container. To do. By cooling in 1 to 60 minutes, the dissolved polycaproamide resin is precipitated as true spherical particles. When cooled slowly, particles having a large particle diameter can be obtained, but care must be taken because particles having a shape in which the particles are fused together may be produced. On the other hand, when cooled rapidly, particles having a small particle diameter can be obtained, but care must be taken because particles having a shape in which the particles are fused with each other may be produced.

  Since the cooling method of the polycaproamide resin solution varies depending on the particle size of the target fine particles, the container to be used, the concentration of the polycaproamide resin solution, and the like, adjustment is necessary as appropriate. For example, in the case of producing polycaproamide resin fine particles having an average particle diameter exceeding 20 μm, the polycaproamide resin solution concentration is preferably 5% by weight or less, and the cooling rate is preferably 0.1 ° C./min or less. It is good to cool under conditions. When producing fine particles of polycaproamide resin having an average particle size of less than 5 μm, the polycaproamide resin solution concentration is preferably 5 to 10% by weight, and the cooling rate is preferably 100 ° C./min or more. Good.

  Moreover, when precipitating on the conditions of 5-20 micrometers which is the preferable average particle diameter of the fine particle of the polycaproamide resin used for this invention, the polycaproamide resin solution density | concentration shall preferably be 5-30 weight%, and the cooling rate should be set. It is good to cool on the conditions of 0.1 degree-C / min-100 degree-C / min. The fine particles of polycaproamide resin precipitated by cooling are separated as a cake by centrifugation, and the resulting cake is vacuum-dried to obtain pure polycaproamide resin fine particles.

  The polyhydric alcohol used here is a compound having two or more hydroxy groups in one molecule. For example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Diols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-di (hydroxymethyl) cyclohexane, 1,3-di (hydroxymethyl) cyclohexane, Alicyclic diols such as 1,4-di (hydroxymethyl) cyclohexane, 1,2-di (hydroxymethyl) benzene, 1,3-di (hydroxymethyl) benzene, 1,4-di (hydroxymethyl) benzene, etc. Aromatic diol, Pentaeri Alkane polyols such as itolitol and glycerin, sugars such as sucrose, sugar derivatives such as saccharides such as sorbitol and mannitol, polyglycerin such as pentaglycerin, hexaglycerin and decaglycerin, and poly such as dipentaerythritol and tripentaerythritol Alkane polyol etc. are mentioned, These are used as a 1 type, or 2 or more types of mixture. Among these, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-di (hydroxymethyl) benzene, 1,3-di (hydroxymethyl) benzene, 1,4-di (hydroxymethyl) benzene is preferably used.

  When the polycaproamide resin is dissolved in a polyhydric alcohol or a mixture of polyhydric alcohol and water, a small amount of an alkali compound may be added to promote dissolution. Specific examples include alkali metal, alkaline earth metal hydroxides, carbonates, hydrogen carbonates, and organic acid salts. More specifically, sodium hydroxide, calcium hydroxide, magnesium hydroxide, water, and the like. Potassium oxide, lithium hydroxide, sodium carbonate, calcium carbonate, magnesium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, calcium bicarbonate, magnesium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium acetate, calcium acetate, magnesium acetate , Potassium acetate, lithium acetate and the like. Particularly preferred is calcium carbonate. The amount of the alkali compound used is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, still more preferably 0.1 to 2% by weight, based on the dissolved polycaproamide resin. Good.

  Further, when an alkali compound as described above is used, it is preferable to neutralize before separating the fine particles of the polycaproamide resin, and it can be neutralized by adding an acidic compound. Specific examples of acidic compounds include mineral acids and organic acids. More specifically, hydrochloric acid, sulfuric acid, nitric acid, sulfurous acid, nitrous acid, hypochlorous acid, hypobromous acid, phosphoric acid, polyphosphoric acid, sulfurous acid, and the like. Examples thereof include phosphoric acid, hypophosphorous acid, formic acid, acetic acid, propionic acid, butyric acid, and caproic acid. Particularly preferred is sulfuric acid. The amount used is an amount necessary to neutralize the alkali compound used previously.

  The method for producing the polycaproamide resin composite fine particles of the present invention includes polycaproamide resin fine particles having a relative viscosity of 1.70 to 2.35, an average particle size of 5 to 20 μm, and an oil absorption of 100 to 200 mL / 100 g. The fine particles of polycaproamide resin are coated on the surface of the fine particles of polycaproamide resin with other fine particles, the average particle size of the resulting polycaproamide resin composite fine particles is 5 to 20 μm, and the oil absorption is 70 to 200 mL / 100 g.

  The method of coating the surface of the fine particles of polycaproamide resin with other fine particles is to mix the fine particles of polycaproamide resin and other fine particles and mix them in a pulverizer. May be used. There are no particular restrictions on the type of stirrer or pulverizer, but a hammer type fine pulverizer or sample mill is preferred from the standpoints of good coating efficiency and decomposability. Specifically, a cantilever type atomizer manufactured by Fuji Paudal Co., Ltd. is suitable, and examples thereof include KIIWG-1 type, KIIWG-1F type, and KIIG-1S type. A suitable amount of fine particles of polycaproamide resin and other fine particles are charged into these fine pulverizers, and stirred for 10 seconds to 1 hour, preferably 15 seconds to 30 minutes, more preferably 20 seconds to 15 minutes.

  The polycaproamide resin composite fine particles of the present invention are useful as a base material for cosmetics because of their uniform shape and particle size and a large oil absorption. At the same time, since the surface of the fine particles of polycaproamide resin is coated with other fine particles, it has excellent properties for cutting ultraviolet rays (especially UV-A, UV-B), and is a raw material for cosmetics that requires an ultraviolet ray prevention function. It is also useful.

Cosmetics containing polycaproamide resin composite fine particles include, for example, foundations, cheeks, eye shadows, cleansing agents, facial cleansing creams, sunscreen creams, antiperspirants, pre-shave lotions, after-shave lotions, fun, lotions, packs, massages. Cream, milky lotion, moisture cream, essence, lipstick, eyeliner, nail enamel, soap, bath salt, shampoo, rinse, hair treatment, sun oil, depigmenting / hair removal cream, insect repellent lotion, insect repellent, hair liquid, pomade, hair color agents, eau de cologne, shampoo, rinse, hair styling agents, Chichishiroeki, but white UV lotion is preferably cited, et al., among others foundation, blusher, eye shadow, cleansing agents, cleansing cream, sunscreen Cream, antiperspirants, pre-shave lotion, Chichishiroeki, the White UV lotion preferable.

  In addition, since the polycaproamide resin composite fine particles of the present invention retain the surface characteristics of the fine particles of the polycaproamide resin used as a base to some extent, the oil absorption is high, the surface area is large, and the dispersibility in water is high. It has a feature such as high. Therefore, when the composite microparticles of the present invention are used in cosmetics such as foundations, it has a refreshing feel while maintaining a moist feeling, an excellent refreshing feel, a smooth feeling, a smooth feeling, and a fit feeling (familiarity). There is an advantage of giving a touch. In addition, the water absorption and high oil absorption of the composite fine particles of the present invention prevent the makeup from collapsing, make the makeup last a long lasting effect, achieve a uniform finish based on slipperiness and good dispersibility, and soft focus (皺) And natural finishes. Furthermore, it has the advantage of being excellent in dispersibility when dispersed in oils, and has the potential to create cosmetics with a new touch that has never been seen before.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

  Characteristic evaluation of the polycaproamide resin, the polycaproamide resin fine particles, and the polycaproamide resin composite fine particles obtained in the following Reference Examples, Examples, and Comparative Examples was performed as follows.

  Relative viscosity: Measured with an Ubbelohde viscometer at 25 ° C. using a solution of 1 g of polycaproamide resin or polycaproamide resin fine particles in 100 mL of 98% sulfuric acid.

  Morphological observation with a scanning electron microscope: Observation was performed using JSM-6360LV manufactured by JEOL Datum.

  Average particle diameter: Measured using 9.0 L (MT3000) manufactured by Microtrac Corporation using ethanol as a dispersion medium, and the 50% median diameter (cumulative median diameter) was defined as the average particle diameter (unit: μm). .

  Oil absorption amount: The oil absorption amount (unit: mL / 100 g) was measured by the method described above in accordance with JIS K5101-13-1.

  Dispersibility in aqueous solvent: 1 g of polycaproamide resin fine particles or polycaproamide resin composite fine particles was added to a mixed solvent of 90 mL of distilled water and 10 mL of ethylene glycol, and stirred well using a stir bar. The state in which the particles are uniformly mixed in the solvent by stirring is indicated as ◯, the state where the particles are separated from the solvent, floats, settles, or solidifies into a lump, and the intermediate state is indicated as △. did.

  Friction coefficient (slipping property evaluation): Using a KES-SE-STP friction tester manufactured by Kato Tech Co., Ltd., the friction coefficient (unit: dimensionless) of polycaproamide resin fine particles or polycaproamide resin composite particles was measured. . As measurement conditions, polycaproamide resin fine particles or polycaproamide resin composite particles were smoothly applied to an area of 2 cm × 10 cm on the sample stage, and the moving speed of the sample stage was set to 1 mm / sec for evaluation. . The smaller the coefficient of friction, the better the slipperiness.

  UV resistance evaluation: After adding 0.4 g of polycaproamide resin fine particles or polycaproamide resin composite particles to 0.6 g of petroleum jelly, a sample obtained by thoroughly stirring with a mortar and pestle was used as a sample. UV-1000S manufactured by Labsphere Was used to evaluate the resistance of UV-A and UV-B. The UV-B resistance evaluation measures the Sun Protection Factor (SPF, unit: dimensionless), and the higher this value, the better the UV-B resistance and the higher the sunburn prevention effect.

  In the UV-A resistance evaluation, SPF and UVA ratio were measured, and the PA class (Protection Grade of UV-A) was obtained from these measurement results. The UVA ratio (unit: dimensionless) indicates the ratio of the absorbance of UV-A and UV-B, and the higher the value, the better the resistance of UV-A. The PA class is an index that cuts UV-A among ultraviolet rays, and is classified into three stages: PA + (effective), PA ++ (highly effective), and PA ++ (highly effective). .

[Production of polycaproamide resin]
[Reference Example 1] Production of polycaproamide resin (A-1) A 30-liter stainless steel autoclave was charged with 10 kg of ε-caprolactam, 43 g of benzoic acid, and 200 g of ion-exchanged water. A polycaproamide resin was prepared by heating and stirring for 10 hours. The obtained polycaproamide resin was drawn into a strand from the lower part of the autoclave and cut into pellets. The pellets were extracted in boiling water for 15 hours and then vacuum dried at 80 ° C. for 24 hours. The relative viscosity ηr of the obtained polycaproamide resin (A-1) was 2.31, the terminal amino group concentration [NH ₂ ] was 4.8 × 10 ⁻⁵ mol / g, and the terminal carboxyl group concentration [COOH] was 7 It was 2 × 10 ⁻⁵ mol / g.

[Reference Example 2] Production of polycaproamide resin (A-2) A polycaproamide resin was produced in the same manner as in Reference Example 1 except that 21 g of acetic acid was used instead of benzoic acid. The relative viscosity ηr of the obtained polycaproamide resin (A-2) was 2.35, the terminal amino group concentration [NH ₂ ] was 4.9 × 10 ⁻⁵ mol / g, and the terminal carboxyl group concentration [COOH] was 7 It was 4 × 10 ⁻⁵ mol / g.

[Reference Example 3] Production of polycaproamide resin (A-3) A polycaproamide resin was produced in the same manner as in Reference Example 1 except that the polymerization time was 12 hours. The relative viscosity ηr of the obtained polycaproamide resin (A-3) was 2.48, the terminal amino group concentration [NH ₂ ] was 3.8 × 10 ⁻⁵ mol / g, and the terminal carboxyl group concentration [COOH] was 6 It was 2 × 10 ⁻⁵ mol / g.

[Reference Example 4] Production of polycaproamide resin (A-4) A polycaproamide resin was produced in the same manner as in Reference Example 1 except that the polymerization time was 8.5 hours. The relative viscosity ηr of the obtained polycaproamide resin (A-4) was 2.15, the terminal amino group concentration [NH ₂ ] was 5.2 × 10 ⁻⁵ mol / g, and the terminal carboxyl group concentration [COOH] was 8 It was 1 × 10 ⁻⁵ mol / g.

[Reference Example 5] Production of polycaproamide resin (A-5) A polycaproamide resin was produced in the same manner as in Reference Example 1 except that benzoic acid was not used and the polymerization time was 8 hours. The relative viscosity ηr of the obtained polycaproamide resin (A-5) was 2.35, the terminal amino group concentration [NH ₂ ] was 7.10 × 10 ⁻⁵ mol / g, and the terminal carboxyl group concentration [COOH] was 7 It was 30 × 10 ⁻⁵ mol / g.

[Reference Example 6] Production of polycaproamide resin (A-6) A polycaproamide resin was produced in the same manner as in Reference Example 1 except that 41 g of hexamethylenediamine was used instead of benzoic acid. The relative viscosity ηr of the obtained polycaproamide resin (A-6) was 2.33, the terminal amino group concentration [NH ₂ ] was 7.1 × 10 ⁻⁵ mol / g, and the terminal carboxyl group concentration [COOH] was 4 It was 7 × 10 ⁻⁵ mol / g.

[Reference Example 7] Production of polycaproamide resin (A-7) A polycaproamide resin was produced in the same manner as in Reference Example 1 except that 21 g of benzoic acid was used and the polymerization time was 15 hours. The resulting polycaproamide resin (A-7) had a relative viscosity ηr of 2.70, a terminal amino group concentration [NH ₂ ] of 3.9 × 10 ⁻⁵ mol / g, and a terminal carboxyl group concentration [COOH] of 5 It was 4 × 10 ⁻⁵ mol / g.

[Reference Example 8] Production of polycaproamide resin (A-8) A polycaproamide resin was produced in the same manner as in Reference Example 1 except that the polymerization time was 8 hours. The relative viscosity ηr of the obtained polycaproamide resin (A-8) was 2.07, the terminal amino group concentration [NH ₂ ] was 6.5 × 10 ⁻⁵ mol / g, and the terminal carboxyl group concentration [COOH] was 8 It was 7 × 10 ⁻⁵ mol / g.

[Reference Example 9] Production of polylauramide resin fine particles (A-9) 190 g of anhydrous laurolactam, 1200 mL of liquid paraffin, and 3.8 g of potassium stearate were placed in a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. After replacing the inside of the flask with dry nitrogen, the flask was heated to 160 ° C., and laurolactam was dissolved in liquid paraffin. While maintaining the solution at 160 ° C., 7.6 g of caprolactam potassium salt and 1.12 g of phosphorus trichloride were added and stirred for 2 hours. After cooling the solution to room temperature, the solution was filtered, and the resulting polylauramide resin microparticles were isolated. The particles were washed with n-butanol, further washed with water, and dried in a vacuum dryer overnight to obtain 150 g of polylauramide resin (N12) fine particles. The resulting polylauramide resin fine particles (A-9) had a relative viscosity of 2.91, an average particle size of 15.1 μm, and an oil absorption of 75.2 mL / 100 g.

[Production of fine particles of polycaproamide resin]
[Reference Example 10] Production of polycaproamide resin fine particles (B-1) To 100 g of the polycaproamide resin (A-1) produced in Reference Example 1, 525 g of ethylene glycol was added, and 180 ° C was added under a nitrogen atmosphere. Stir at ° C. Since the polycaproamide resin dissolved after stirring for 30 minutes, the solution was poured into a stainless steel vat kept at 166 ° C. and left at that temperature for 30 minutes. Since the fine particles of polycaproamide resin were precipitated, the precipitate was centrifuged to remove ethylene glycol, and a cake of fine particles of polycaproamide resin was obtained. The cake was taken out, spread on a bat and dried in a vacuum dryer at 80 ° C. for 24 hours.

  Scanning electron micrographs of the resulting polycaproamide resin fine particles (B-1) are shown in FIGS. It can be seen that the fine particles are spherical and have a porous surface.

The resulting polycaproamide resin fine particles (B-1) had a relative viscosity of 1.96, an average particle size of 12.8 μm, and an oil absorption of 139.8 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

[Reference Example 11] Production of fine particles of polycaproamide resin (B-2) A polycaproamide resin was produced in the same manner as in Reference Example 10 except that the polycaproamide resin (A-2) produced in Reference Example 2 was used. Fine particles were produced. The resulting polycaproamide resin fine particles (B-2) had a relative viscosity of 1.99, an average particle size of 13.1 μm, and an oil absorption of 139.4 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

[Reference Example 12] Production of fine particles of polycaproamide resin (B-3) Polycaproamide resin was prepared in the same manner as in Reference Example 10 except that the polycaproamide resin (A-3) produced in Reference Example 3 was used. Fine particles were produced. The resulting polycaproamide resin fine particles (B-3) had a relative viscosity of 2.20, an average particle size of 14.3 μm, and an oil absorption of 130.6 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

Reference Example 13 Production of polycaproamide resin fine particles (B-4) Polycaproamide resin was prepared in the same manner as in Reference Example 10 except that the polycaproamide resin (A-4) produced in Reference Example 4 was used. Fine particles were produced. The resulting polycaproamide resin fine particles (B-4) had a relative viscosity of 1.76, an average particle size of 14.4 μm, and an oil absorption of 128.9 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

Reference Example 14 Production of polycaproamide resin fine particles (B-5) Polycaproamide resin was prepared in the same manner as in Reference Example 10 except that the polycaproamide resin (A-5) produced in Reference Example 5 was used. Fine particles were produced. The obtained polycaproamide resin fine particles (B-5) had a relative viscosity of 2.00, an average particle size of 14.1 μm, and an oil absorption of 128.5 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

Reference Example 15 Production of polycaproamide resin fine particles (B-6) Polycaproamide resin was prepared in the same manner as in Reference Example 10 except that the polycaproamide resin (A-6) produced in Reference Example 6 was used. Fine particles were produced. The resulting polycaproamide resin fine particles (B-6) had a relative viscosity of 1.97, an average particle size of 14.3 μm, and an oil absorption of 128.7 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

Reference Example 16 Production of polycaproamide resin fine particles (B-7) Polycaproamide resin was prepared in the same manner as in Reference Example 10 except that the polycaproamide resin (A-7) produced in Reference Example 7 was used. Fine particles were produced. The resulting polycaproamide resin fine particles (B-7) had a relative viscosity of 2.40, an average particle size of 15.5 μm, and an oil absorption of 110.2 mL / 100 g. Further, the dispersibility in an aqueous solvent was Δ.

Reference Example 17 Production of polycaproamide resin fine particles (B-8) Polycaproamide resin was prepared in the same manner as in Reference Example 10 except that the polycaproamide resin (A-8) produced in Reference Example 8 was used. Fine particles were produced. The resulting polycaproamide resin fine particles (B-8) had a relative viscosity of 1.68, an average particle size of 15.6 μm, and an oil absorption of 108.9 mL / 100 g. Further, the dispersibility in an aqueous solvent was Δ.

[Production of polycaproamide resin composite fine particles]
<Example 1> Production of polycaproamide resin composite fine particles (C-1) Fine oxidation of Sakai Chemical Industry Co., Ltd. with respect to 100 parts by weight of polycaproamide resin fine particles (B-1) produced in Reference Example 10 30 g of a mixture obtained by adding 15 parts by weight of titanium STR-100C was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Co., Ltd.

Scanning electron micrographs of the obtained polycaproamide resin composite fine particles (C-1) are shown in FIGS. It can be seen that the composite fine particles (C-1) have a smooth surface as the porous surface of the fine particles of the polycaproamide resin is coated with titanium oxide. The polycaproamide resin composite fine particles (C-1) had an average particle size of 11.0 μm and an oil absorption of 85.6 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○. The average particle size of the composite fine particles (C-1) is smaller than that of the original polycaproamide resin fine particles (B-1), but the titanium oxide fine particles probably cover the surfaces of the polycaproamide resin fine particles. It is presumed that the size of the fine particles was reduced due to the pressure applied.

Example 2 Production of Polycaproamide Resin Composite Fine Particles (C-2) Fine Titanium Oxide from Teica Co., Ltd. with respect to 100 parts by weight of the fine particles of polycaproamide resin (B-2) produced in Reference Example 11 -05 30 g of a mixture obtained by adding 15 parts by weight was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Corporation.

The resulting polycaproamide resin composite particles (C-2) had an average particle size of 11.3 μm and an oil absorption of 85.3 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

Example 3 Production of Polycaproamide Resin Composite Fine Particles (C-3) Fine Titanium Oxide from Teica Co., Ltd. with respect to 100 parts by weight of the fine particles of polycaproamide resin (B-3) produced in Reference Example 12 30 g of a mixture obtained by adding 15 parts by weight of -500 SA was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Corporation.

The resulting polycaproamide resin composite particles (C-3) had an average particle size of 12.5 μm and an oil absorption of 79.5 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

Example 4 Production of Polycaproamide Resin Composite Fine Particles (C-4) Fine Titanium Oxide of Teika Co., Ltd. with respect to 100 parts by weight of the fine particles of polycaproamide resin (B-4) produced in Reference Example 13 30 g of a mixture obtained by adding 15 parts by weight of −100 TV was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Co., Ltd.

The resulting polycaproamide resin composite particles (C-4) had an average particle size of 12.6 μm and an oil absorption of 78.1 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

<Example 5> Production of polycaproamide resin composite fine particles (C-5) Fine titanium oxide particles produced by Ishihara Sangyo Co., Ltd. with respect to 100 parts by weight of polycaproamide resin fine particles (B-5) produced in Reference Example 14. 30 g of a mixture obtained by adding 15 parts by weight of TTO-55- (A) was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Corporation.

The resulting polycaproamide resin composite particles (C-5) had an average particle size of 12.3 μm and an oil absorption of 77.9 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○ .

<Example 6> Production of polycaproamide resin composite fine particles (C-6) Fine oxidation of Sakai Chemical Industry Co., Ltd. with respect to 100 parts by weight of polycaproamide resin fine particles (B-6) produced in Reference Example 15 30 g of a mixture obtained by adding 15 parts by weight of titanium STR-100C was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Co., Ltd.

The resulting polycaproamide resin composite particles (C-6) had an average particle size of 12.5 μm and an oil absorption of 78.0 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○ .

<Example 7> Production of polycaproamide resin composite particles (C-7) Fine titanium oxide MTY produced by Teika Co., Ltd. with respect to 100 parts by weight of fine particles (B-1) of polycaproamide resin produced in Reference Example 10. -02 30 g of a mixture obtained by adding 67 parts by weight was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Corporation.

The resulting polycaproamide resin composite fine particles (C-7) had an average particle size of 11.5 μm and an absorption of 83.4 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

Example 8 Production of Polycaproamide Resin Composite Particles (C-8) Fine Titanium Oxide MTY from Teika Co., Ltd. with respect to 100 parts by weight of fine particles (B-1) of polycaproamide resin produced in Reference Example 10 -02 30 g of a mixture obtained by adding 100 parts by weight was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Corporation.

The resulting polycaproamide resin composite fine particles (C-8) had an average particle size of 12.1 μm and an absorption of 79.7 mL / 100 g. Further, the dispersibility in an aqueous solvent was ○.

  Obtained in polycaproamide resin composite fine particles (C-2), (C-3), (C-7), (C-8) and Reference Example 10 obtained in Examples 2, 3, 7, and 8 above. The fine particles (B-1) of the obtained polycaproamide resin were evaluated for friction coefficient (sliding property) and ultraviolet resistance. The results are summarized in Table 1.

<Comparative Example 1> Production of polycaproamide resin composite fine particles (C-9) Fine titanium oxide particles produced by Ishihara Sangyo Co., Ltd. with respect to 100 parts by weight of the fine particles of polycaproamide resin (B-7) produced in Reference Example 16. 30 g of a mixture obtained by adding 15 parts by weight of TTO-S-3 was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Corporation.

The obtained polycaproamide resin composite particles (C-9) had an average particle size of 14.0 μm and an oil absorption of 63.2 mL / 100 g. Further, the dispersibility in an aqueous solvent was Δ.

Comparative Example 2 Production of Polycaproamide Resin Composite Fine Particles (C-10) Fine Titanium Oxide of Ishihara Sangyo Co., Ltd. per 100 parts by weight of polycaproamide resin fine particles (B-8) produced in Reference Example 17 30 g of a mixture obtained by adding 15 parts by weight of TTO-S-3 was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Corporation.

The resulting polycaproamide resin composite particles (C-10) had an average particle size of 14.1 μm and an oil absorption of 60.9 mL / 100 g. Further, the dispersibility in an aqueous solvent was Δ.

<Comparative Example 3> Production of polylauramide resin composite fine particles (C-11) Ishihara Sangyo Co., Ltd. with respect to 100 parts by weight of the polylauramide resin (nylon 12) fine particles (A-9) produced in Reference Example 9 30 g of a mixture of 15 parts by weight of fine titanium oxide TTO-S-3 was stirred at 12,000 rpm for 40 seconds using a KIIW-1 type cantilever atomizer manufactured by Fuji Powder Co., Ltd.

The obtained polylauramide resin composite particles (C-11) had an average particle size of 7.0 μm and an oil absorption of 65.5 mL / 100 g. Further, the dispersibility in an aqueous solvent was x.

<Comparative Example 4> Production of polycaproamide resin composite fine particles (C-12) Fine oxidation of Sakai Chemical Industry Co., Ltd. with respect to 100 parts by weight of polycaproamide resin fine particles (B-1) produced in Reference Example 10 30 g of a mixture obtained by adding 15 parts by weight of titanium STR-100C was introduced into a hybridization system NHS-0 type (power: 2.2 kW) manufactured by Nara Machinery Co., Ltd. to produce composite fine particles. The system is a device composed of a rotor, a stator, and a circulation circuit that rotate at a high speed. Once the coating particles are adhered to the surface of the substrate particles by a frictional charging phenomenon by a mechanical mixing operation, the inside of the device starts from the center of the rotor. It is subjected to impact, compression, and shear due to collision between the rotor and particles, moves to the outer periphery together with the air current, and is transferred to the center of the rotor again through the circulation path. The particles are firmly compounded by the mechanochemical action by this repetition. In Comparative Example 4, composite fine particles were produced at a peripheral speed of 80 m / second and a processing time of 180 seconds.

  The resulting polycaproamide resin composite fine particles (C-12) had an average particle size of 13.0 μm and an oil absorption of 61.1 mL / 100 g. Further, the dispersibility in an aqueous solvent was x.

<Examples 9 to 14 and Comparative Examples 5 to 9>
Polycaproamide resin composite fine particles (C-1) to (C-6), (C-9), (C-10), (C-) obtained in Examples 1 to 6 and Comparative Examples 1, 2 and 4 12) The polylauramide resin composite fine particles (C-11) obtained in Comparative Example 3 and the polylauramide resin fine particles (A-9) obtained in Reference Example 9 were used for testing as follows. A milky white solution was produced.

  Appropriate amounts of the 11 types of milky white liquids (Examples 9 to 14 and Comparative Examples 5 to 9) obtained as described above are applied to the back of the hand, and in this case, while maintaining a moist feeling, it is excellent in a refreshing feeling and a refreshing feeling. Twenty monitors evaluated each feeling of touch, smoothness, smoothness, and fit (familiarity). Evaluation of each touch was good: 5 points, slightly good: 4 points, normal: 3 points, slightly bad: 2 points, bad: 1 point, and averaged the evaluation results of 20 people. The results are summarized in Table 1.

[Prescription]
Among the following raw materials, vegetable emulsified wax, jojoba oil, xanthan gum and silk powder were manufactured by Natural Laboratories. Other raw materials were purchased as reagents.
Vegetable emulsified wax (Arachides-20 and stearyl alcohol mixture): 20 g
Jojoba oil: 20g
Xanthan gum: 20g
Distilled water: 400mL
Example, Comparative Example, Reference Example Polycaproamide Resin Composite Fine Particles: 10 g
Silk powder: 10g

[Production method]
The jojoba oil and the emulsified wax are heated to 50 to 60 ° C. with stirring to completely dissolve (solution A). The polycaproamide resin composite fine particles, distilled water, and silk powder of Examples, Comparative Examples, and Reference Examples are heated to 50-60 ° C. with stirring and stirred for 2 minutes (Liquid B). Mix half of the B liquid with the A liquid at a temperature of 50-60 ° C. and stir well. To this mixture, xanthan gum is added little by little with stirring, and the remaining half of solution B is added with stirring. The mixture was stirred well and stirred uniformly so that no lumps were formed.

<Examples 15-20, Comparative Examples 10-14>
Polycaproamide resin composite fine particles (C-1) to (C-6), (C-9), (C-10), (C-) obtained in Examples 1 to 6 and Comparative Examples 1, 2 and 4 12) Using the polylauramide resin composite fine particles (C-11) obtained in Comparative Example 3 and the polylauramide resin fine particles (A-9) obtained in Reference Example 9, the test white was as follows. A UV lotion was produced.

  Appropriate amounts of the 11 types of white UV lotions (Examples 15 to 20 and Comparative Examples 10 to 14) obtained as described above were applied to the back of the hand, while maintaining a moist feeling and a refreshing feel and refreshing feeling. Twenty monitors evaluated each feeling of excellent feeling, smooth feeling, smoothness, and fit (familiarity). Evaluation of each touch was good: 5 points, slightly good: 4 points, normal: 3 points, slightly bad: 2 points, bad: 1 point, and averaged the evaluation results of 20 people. The results are summarized in Table 2.

[Prescription]
Of the following raw materials, plant placenta, fine titanium oxide, and talc were purchased from Natural Laboratories. Other raw materials were purchased as reagents.
Plant placenta (manufactured by Natural Laboratories): 14 drops Fine particle titanium oxide (average particle size 0.03 μm): 10 g
Example, Comparative Example, Reference Example Polycaproamide Resin Composite Fine Particles: 10 g
Talc: 2.5g
Glycerin: 10mL
Distilled water: 190 mL

[Production method]
Distilled water, placenta, and glycerin were added to a mixture of the polycaproamide resin composite fine particles, titanium oxide, and talc of Examples, Comparative Examples, and Reference Examples, and stirred well. Since it separated into two layers when allowed to stand, the container was vigorously shaken before use and used uniformly.

  From Examples 9 to 20 and Comparative Examples 5 to 14, it can be seen that cosmetics using the polycaproamide resin composite fine particles of the present invention are excellent in touch when in contact with the skin.

6 is a scanning electron micrograph of fine particles of polycaproamide resin obtained in Reference Example 10. FIG. It is the scanning electron microscope photograph figure which expanded a part of FIG. 2 is a scanning electron micrograph of polycaproamide resin composite fine particles obtained in Example 1. FIG. It is the scanning electron micrograph figure which expanded a part of FIG.

Claims (9)

Composite fine particles in which the surface of fine particles of polycaproamide resin having a relative viscosity of 1.70 to 2.35, an average particle size of 5 to 20 μm, and an oil absorption of 100 to 200 mL / 100 g are coated with metal oxide fine particles Polycaproamide resin composite fine particles having an average particle diameter of 5 to 20 μm and an oil absorption of 70 to 200 mL / 100 g. The polycaproamide resin fine particles have a polycaproamide in which the relationship between the terminal amino group concentration [NH ₂ ] (mol / g) and the terminal carboxyl group concentration [COOH] (mol / g) satisfies the following formula (1): The polycaproamide resin composite fine particles according to claim 1 , which are fine particles obtained by heating and dissolving a resin in a polyhydric alcohol or a mixed solution of polyhydric alcohol and water and then cooling.
[NH ₂ ] + 2.0 × 10 ⁻⁵ <[COOH] (1) The polyhydric alcohol is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-di (hydroxymethyl) benzene, 1,3-di (hydroxymethyl). The polycaproamide resin composite fine particles according to claim 2 , which is at least one selected from benzene and 1,4-di (hydroxymethyl) benzene. The polycaproamide resin composite fine particles according to any one of claims 1 to 3, wherein the metal oxide is titanium oxide. The polycaproamide resin fine particles and the metal oxide fine particles having a relative viscosity of 1.70 to 2.35, an average particle size of 5 to 20 μm, and an oil absorption of 100 to 200 mL / 100 g are stirred in a pulverizer. Polycaproamide resin composite fine particles in which the fine particles of the metal oxide are coated on the surface of the fine particles of the polycaproamide resin to produce composite fine particles having an average particle diameter of 5 to 20 μm and an oil absorption of 70 to 200 mL / 100 g. Manufacturing method. The polycaproamide resin fine particles have a polycaproamide in which the relationship between the terminal amino group concentration [NH ₂ ] (mol / g) and the terminal carboxyl group concentration [COOH] (mol / g) satisfies the following formula (1): The method for producing polycaproamide resin composite fine particles according to claim 5 , wherein the resin is fine particles obtained by heating and dissolving a resin in a polyhydric alcohol or a mixed solution of polyhydric alcohol and water and then cooling.
[NH ₂ ] + 2.0 × 10 ⁻⁵ <[COOH] (1) The polyhydric alcohol is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-di (hydroxymethyl) benzene, 1,3-di (hydroxymethyl). The method for producing polycaproamide resin composite fine particles according to claim 6 , which is at least one selected from benzene and 1,4-di (hydroxymethyl) benzene. Cosmetics containing the polycaproamide resin composite fine particles according to any one of claims 1 to 4 . The cosmetic according to claim 8 , which is a foundation, blusher, eye shadow, cleansing agent, facial cleansing cream, sunscreen cream, antiperspirant or pre-shave lotion.