TWI457371B - Shaped hollow fine particles, a production method, comprising a hollow shaped cosmetic material and fine particles of a resin composition - Google Patents

Description

Hollow shaped microparticles, method for producing the same, cosmetic material containing hollow shaped microparticles, and resin composition

The present invention relates to hollow shaped microparticles, a method of producing the same, and uses thereof. Microparticles of various materials have been practically supplied for various purposes. The shape is mostly amorphous, and it is also useful directly in the shape, and plays an important role in the industrial material type. However, in recent years, as the characteristics required for various applications have increased, it has been desired to control the shape of fine particles. As an example of the increase in the demand, the optical characteristics in the fields of display parts and light diffusing sheets, the miniaturization in the field of electronic parts, and the improvement in usability in cosmetics are exemplified. The present invention relates to hollow shaped microparticles suitable for such desired heightening, methods for their manufacture, and uses thereof.

Conventionally, as fine particles for controlling the shape, many proposals have been made for materials made of inorganic materials and substances made of organic materials. Among the materials made of organic materials, polystyrene-based fine particles (see, for example, Patent Documents 1 and 2), polyurethane-based fine particles (for example, refer to Patent Document 3), and polyimide-based fine particles (for example, reference) Patent Document 4), organic polyfluorinated fine particles (see, for example, Patent Document 5). However, since the microparticles of the prior art have a spherical shape or a substantially spherical shape, they have a problem that cannot be increased in response to the above-mentioned requirements in recent years. On the other hand, as fine particles having a controlled shape, fine particles having a hollow shape and having irregularities (for example, refer to Patent Document 6), and substantially spherical fine particles having many small pits on the surface (for example, refer to Patent Document 7), resembling a rugby-like shape. There have been many proposals for non-spherical fine particles such as fine particles (see, for example, Patent Document 8) and hemispherical fine particles (for example, see Patent Document 9). However, although the fine particles of the prior art have their own characteristics, they have a problem that cannot be sufficiently adapted to the above-mentioned requirements in recent years.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-103804

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-292907

(Patent Document 3) Japanese Patent Laid-Open No. Hei 11-116649

[Patent Document 4] Japanese Patent Laid-Open No. Hei 11-140181

[Patent Document 5] Japanese Patent Laid-Open No. 61-159427

[Patent Document 6] Japanese Patent Laid-Open No. Hei 7-157672

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2000-191788

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2003-171465

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2003-128788

The problem to be solved by the present invention is to provide an increase in the optical properties such as total light transmittance and light diffusibility in a resin molded body, and a feeling of use in cosmetics, soft focus, which is sufficient in response to recent demands. Hollow shaped microparticles with improved properties such as sex, concealability and persistence, methods for their manufacture, and uses thereof.

In order to solve the above problems, the inventors of the present invention have found that a plurality of concave portions having a predetermined size on the surface and one hollow portion connected to the surface are provided, and the hollow shaped irregular particles having a predetermined size of the entire shape of the spindle are just suitable.

That is, the present invention relates to a surface (11) having a plurality of recesses (21), the interior (31) having a hollow portion (41), a surface (11) of the hollow portion (41) through along the long diameter (L ₁₎ One of the cracks (51) in the direction is a hollow-shaped fine particle of a spindle shape, and the average value of the long diameter (L ₁ ) is 0.1 to 30 μm, and the average value of the short diameter (L ₂ )/long diameter (L ₁ ) The mean value = 0.3 to 0.8 is a hollow shaped microparticle characterized by it. Further, the present invention relates to a method for producing such hollow shaped microparticles, and a cosmetic and a resin composition using the hollow dissimilar microparticles.

First, the hollow shaped microparticles of the present invention will be described. The hollow shaped microparticle surface (11) of the present invention has a plurality of concave portions (21), and the inner portion (31) has one hollow portion (41), and the surface (11) and the hollow portion (41) are transmitted along the long diameter (L ₁ In the direction of one crack (51), the entire connection is a hollow shaped microparticle of a spindle shape. Among them, the hollow shaped microparticles of the present invention are preferably used in the use of a polyoxyalkylene crosslinked structure, which is more useful in terms of use. This polyoxyalkylene crosslinked structure system forms a structure of a three-dimensional mesh structure in units of a siloxane unit. The type and ratio of the oxirane unit constituting the polyoxyalkylene cross-linked structure are not particularly limited, and the oxime unit shown by the following formula 1 is represented by the oxime unit shown in the following formula 1. Preferably, the oxyalkylene unit and the oxane unit shown in Formula 3 are formed.

[Chemical 1]

SiO ₂

[Chemical 2]

R ¹ SiO _1.5

[Chemical 3]

R ² R ³ SiO

In Chemical Formula 2 and Chemical Formula 3, R ¹ , R ² , and R ³ : an organic group having a carbon atom directly bonded to a ruthenium atom.

As in the of the 2 R ^1, in 3 of the R ² and R ^3, include alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, etc. The organic group having a carbon number 1 to 12, wherein The alkyl group having 1 to 4 carbon atoms or a phenyl group such as a methyl group, an ethyl group, a propyl group or a butyl group is preferred, and a methyl group is more preferred. When the sum of the 2 R ^1, in 3 of the R ² and R ³ is an organic group such as for 2 and 3 of the siloxane units in the silicon preferred silicon siloxane units include methyl silicon An oxane unit, an ethyl siloxane unit, a propyl siloxane unit, a butyl siloxane unit, a phenyl oxane unit, or the like.

When the polyoxoxane crosslinked structure is composed of the above-mentioned units of oxoxane, the proportion of each unit of the oxoxane is not particularly limited, but the unit of oxoxane represented by the formula 1 is 20 to 45 mol%. The unit ratio of the unit of oxane shown in the formula 2 is 50 to 75 mol%, and the unit of the oxoxane shown in the formula 3 is 5 to 27 mol% (total 100 mol%).

The hollow shaped microparticles of the present invention are as described above, the surface (11) has a plurality of concave portions (21), and the inner portion (31) has one hollow portion (41), and the surface (11) and the hollow portion (41) are transmitted along The whole of the cracks (51) in the long-diameter (L ₁ ) direction is a hollow-shaped fine particle having a spindle shape, and the average value of the long diameter (L ₁ ) is 0.1 to 30 μm, and the average value of the short diameter (L ₂ ) is The average value of the long diameter (L ₁ ) = hollow shaped microparticles in the range of 0.3 to 0.8 is preferably a hollow shaped microparticle having an average value of the long diameter (L ₁ ) of 0.5 to 20 μm.

The hollow shaped microparticles of the present invention have one crack (51) along the long diameter (L ₁ ) direction. This crack (51) is substantially sealed, is clearly opened, and is mixed in both cases, and is useful in any case. Such a crack (51) is connected to a hollow portion (41). The size of the hollow portion (41) is not particularly limited, but its presence is important in exerting the desired effects of the present invention.

The hollow shaped microparticles of the present invention have a plurality of recesses (21) on their surface (11). The size of the concave portion (21) is not particularly limited, and it is preferable that the average value of the maximum diameter (m ₁ ) of the concave portion (21)/the average value of the long diameter (L ₁ ) = 0.01 to 0.30, and the existence of such a concave portion It is important to exert the desired effects of the present invention.

In the hollow shaped microparticles of the present invention, the average value of the major axis (L ₁ ), the average value of the minor axis (L ₂ ), and the average value of the maximum diameter (m ₁ ) of the recess (21) are all for the present invention. The scanning electron microscope images of the hollow shaped microparticles were randomly selected and measured, and the average value thereof was determined.

As an index showing the characteristics of the hollow shaped microparticles of the present invention, it is the height of the oil absorption amount. The oil absorption amount is not particularly limited, but it is preferably in the range of 50 to 150 ml/100 g.

Next, a method of producing the hollow shaped microparticles of the present invention will be described. The hollow shaped microparticles of the present invention are formed by using the sterol-based fluorene compound 20 to 45 mol% shown in the following 4, and the sterol-based hydrazine compound 50 to 75 mol% and 6 as shown in the formula 5. The ratio of the sterol-based hydrazine compound shown in the range of 5 to 27 mol% (total 100 mol%) is first formed by the formation of a sterol-based hydrazine compound represented by the formula 4, which is in the presence of a basic catalyst. Hydrolyzed in contact with water to form a sterol compound, and secondly, the sterol compound is formed into a sterol-based hydrazine compound as shown in Formula 5, and a sterol-based hydrazine compound is formed in Chemical Group 6, and is used in an alkaline catalyst. A condensation reaction can be obtained under aqueous conditions in the presence of a cationic surfactant.

[Chemical 4]

SiX ₄

[Chemical 5]

R ⁴ SiY ₃

[Chemical 6]

R ⁵ R ⁶ SiZ ₂

In the formula 4, 5 and 6, R ⁴ , R ⁵ , R ⁶ : an organic group having a carbon atom directly bonded to a ruthenium atom; X, Y, Z: an alkoxy group having 1 to 4 carbon atoms, having carbon An alkoxyethoxy group having 1 to 4 alkoxy groups, a decyloxy group having 2 to 4 carbon atoms, an N,N-dialkylamino group having an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom or hydrogen atom.

As of the 5 R ^4, 6 of the R ⁵ and R ^6, include alkyl, phenyl, alkoxyalkyl and the like of the non-reactive organic group; an epoxy group, vinyl group, (meth) A reactive organic group such as an acrylalkyl group or a thiol group.

In the case of forming a sterol-based fluorene compound, the R ⁴ , R ⁵ and R ⁶ are each an alkyl group having 1 to 4 carbon atoms or a phenyl group, and the ease of production and stability of production are obtained. The ease of use is preferable.

The sterol-based hydrazine compound shown in Formula 4 is obtained as a compound of the oxoxane unit shown in Formula 1. X in the formula 4 is 1) an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group; 2) an alkyl group having a carbon number of 1 to 4 such as a methoxyethoxy group or a butoxyethoxy group. An alkoxyethoxy group of an oxy group; 3) an alkoxy group having a carbon number of 2 to 4 such as an ethoxycarbonyl group or a propenyloxy group; 4) a carbon number of 1 or a dimethylamino group or a diethylamino group; An alkyl group of N,N-dialkylamine; 5) a hydroxyl group; 6) a halogen atom such as a chlorine atom or a bromine atom; or 7) a hydrogen atom.

Examples of the sterol-based hydrazine compound represented by the formula 4 include tetramethoxy decane, tetraethoxy decane, tetrabutoxy decane, trimethoxyethoxy decane, tributyloxyethoxy decane, and tetra. Ethoxy decane, tetrapropoxy decane, tetrakis(dimethylamino) decane, tetrakis(diethylamino) decane, decanetetraol, chlorodecanetriol, dichlorodidecyl alcohol, tetrachloro The base decane, the chlorotrihydro decane, etc., of which tetramethoxy decane, tetraethoxy decane, and tetrabutoxy decane are preferred.

The sterol-based hydrazine compound represented by the formula 5 is obtained as a compound of the oxoxane unit represented by the formula 2. Y in the chemical formula 5 is the same as X in the above chemical formula 4, and R ⁴ in the chemical formula 5 is the same as R ¹ in the above chemical formula 2.

Examples of the sterol-based hydrazine compound represented by the formula 5 include methyltrimethoxydecane, ethyltriethoxydecane, propyltributyloxydecane, butyltributyloxydecane, and phenyltrimethyl. Oxyethoxy decane, methyl tributoxy ethoxy decane, methyl triethoxy decane, methyl tripropoxy decane, methyl decane triol, methyl chloro decyl alcohol, methyl Trichlorodecane, methyltrihydrononane, etc., wherein R ¹ in the formula ² , as described above, results in the formation of a methyloxane unit, an ethyloxane unit, a propyloxane unit, The formation of a sterol-based fluorene compound of a butyloxane unit or a phenyloxane unit is preferred, and a sterol-based hydrazine compound forming a methyl siloxane unit is more preferable.

The sterol-based hydrazine compound shown in Chemical Formula 6 is obtained as a compound of the oxoxane unit shown in Formula 3. Z in Chemical Formula 6 is the same as X in the above Chemical Formula 4, and R ⁵ and R ^{6 in} Chemical Formula 6 are the same as R ² and R ^{3 in} Chemical Formula ³ .

Examples of the sterol-based compound represented by Formula 6 include dimethyldimethoxydecane, diethyldiethoxydecane, dipropyldibutoxydecane, and dibutyldimethoxydecane. , Methyl phenyl methoxyethoxy decane, dimethyl butoxyethoxy decane, dimethyl diethoxy decane, dimethyl dipropoxy decane, dimethyl bis (dimethylamine Base) decane, dimethyl bis(diethylamino) decane, dimethyl decane diol, dimethyl chloro decyl alcohol, dimethyl dichloro decane, dimethyl dihydro decane, etc. R ² , R ^{3 in 3} , as described above, as a result, formation of dimethyloxane units, diethyl siloxane units, dipropyl decane units, dibutyl siloxane units or The thiol-based hydrazine compound is preferably formed of a phenyl fluorene oxide unit, and more preferably a sterol-based compound which forms a dimethyloxane unit.

When the organic polyfluorene fine particles of the present invention are produced, the sterol-based fluorene compound represented by the above-described formula 4, the sterol-based compound represented by the chemical formula 5, and the sterol-based structure shown in the formula 6 are formed. The compound is formed by using a sterol-based hydrazine compound of 20 to 45 mol% as shown in Chemical Formula 4, and a sterol-based compound having a sterol-based compound of 50 to 75 mol% and a sterol-based structure. The ratio of the compound 5 to 27 mol% (total 100 mol%) is first formed by the formation of a sterol-based hydrazine compound represented by the formula 4, which is hydrolyzed by contact with water in the presence of a basic catalyst to form a sterol. Compound. As the alkaline catalyst for hydrolysis, a previously known substance can be used. Examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, and ammonia; trimethylamine, triethylamine, tetraethylammonium hydroxide, and dodecyl hydroxide; An organic base such as methyl hydroxyethyl ammonium or sodium methoxide. The amount of the catalyst to be used in the hydrolysis is preferably 0.001 to 0.5% by mass based on the amount of the sterol-based hydrazine compound represented by the chemical compound 4.

Next, the sterol compound produced as described above and the sterol-based hydrazine compound represented by Formula 5 and the sterol-based hydrazine compound represented by Formula 6 are formed in the presence of a basic catalyst and a cationic surfactant. Condensation reaction under aqueous conditions. As the basic catalyst for the condensation reaction, a conventionally known substance can be used similarly to the above-mentioned alkaline catalyst for hydrolysis. The basic catalyst for the condensation reaction is preferably present in a concentration of from 0.001 to 0.5% by mass based on the total amount of the sterol-based hydrazine compound used as the raw material.

As the cationic surfactant added to the reaction system together with the basic catalyst, a previously known substance can be used. Examples of such a cationic surfactant include lauryl trimethyl ammonium sulfate, tributyl methyl ammonium, tetrabutyl ammonium, trimethyl octyl ammonium, trimethyl lauryl ammonium, and trimethyl oil. a cationic surfactant such as a quaternary ammonium salt such as ammonium or a 2-heptadecenyl-hydroxyethyl imidazoline. The cationic surfactant is preferably present in a concentration of from 0.001 to 0.55% by mass based on the total amount of the sterol-based hydrazine compound used as a raw material.

The total amount of water/formation of the sterol-based hydrazine compound is usually 10/90 to 70/30 (mass ratio). The amount of the catalyst used varies depending on the kind and the type of the sterol-based hydrazine compound, and is preferably 1% by mass based on the total amount of the sterol-based hydrazine compound. Further, the reaction temperature is usually 0 to 40 ° C, but in order to avoid the immediate condensation reaction of the sterol compound formed by hydrolysis, it is preferably 30 ° C or lower.

The reaction liquid containing the sterol compound produced as described above is then supplied to a condensation reaction to form organic polyoxynene fine particles having a hollow spindle shape as a whole. In the production method of the present invention, since the catalyst in hydrolysis can be used as a catalyst for the condensation reaction, the reaction liquid containing the sterol compound formed by hydrolysis is directly or additionally added with a catalyst, and is added at 30 to 80 ° C. When the reaction is continued at a temperature, the condensation reaction can be carried out and the organopolyoxygen fine particles can be obtained in the form of an aqueous suspension. In the production method of the present invention, the pH of the aqueous suspension is preferably adjusted to a range of from 8 to 10 with a base such as ammonia, sodium hydroxide or potassium hydroxide. The solid concentration of the organic polyoxynene fine particles in the aqueous suspension is preferably in the range of 2 to 20% by mass, and more preferably in the range of 5 to 15% by mass, based on the amount of water to be used.

The hollow shaped microparticles of the present invention are separated from the above aqueous suspension, and are used, for example, by metal mesh extraction, and are adjusted to a solid content of 30 to 70% by mass by centrifugation, pressure filtration, or the like, and may be used. Dried product. The dried product is obtained by extracting the aqueous suspension through a metal mesh, dehydrating it by centrifugation, pressure filtration, etc., and heating and drying the dehydrated product at 100 to 250 ° C, and further, passing the aqueous suspension through a spray. The dryer can also be obtained by directly heating and drying at 100 to 250 °C. Such a dried product is preferably pulverized, for example, using a jet mill pulverizer.

The hollow shaped microparticle system of the present invention thus obtained has a plurality of concave portions (21) on the surface thereof, and the inner portion (31) has one hollow portion (41), and the surface (11) and the hollow portion (41) are transmitted along the long diameter (L). ₁ ) The whole crack (51) in the direction is a hollow shaped microparticle with a spindle shape, and the average value of the long diameter (L ₁ ) is 0.1 to 30 μm, and the average value/long diameter of the short diameter (L ₂ ) (L _{1 )} The average value of the range = 0.3 to 0.8.

Finally, the cosmetic raw materials and resin compositions of the present invention will be described. The cosmetic raw material of the present invention is a cosmetic raw material containing the hollow shaped microparticles of the present invention.

The cosmetic raw material of the present invention, when used as a base cosmetic or makeup cosmetic component in the form of a liquid, a cream or a squeeze, has excellent unevenness of the concave and convex feeling and less brilliance through its excellent optical characteristics and high oil absorption. The concealing effect of the coke effect, the skin spots, and the like, and the adhesion to the skin and the feeling of adhesion are excellent, and it is useful for makeup peeling caused by sebum. The amount of the cosmetic raw material to be used in the present invention can be appropriately selected depending on the form of use of the applied cosmetic, for example, in a squeeze-like makeup cosmetic, preferably 0.5 to 50% by mass, and in liquid cosmetic cosmetics, 0.1 to 30% by mass is preferred.

As other raw materials which can be used together with the cosmetic raw material of the present invention, an extender pigment, a white pigment, a pearl pigment, a coloring pigment (dye), a binder, a water, a surfactant, a tackifier, a preservative, and an antioxidant can be cited. , spices, etc. The desired cosmetic preparation can be prepared by a known method in which the cosmetic raw material of the present invention is simultaneously dispersed uniformly with other related raw materials.

Further, the resin composition of the present invention contains the resin composition of the hollow shaped microparticles of the present invention described above, and can be used for improving the properties of various resin molded bodies obtained therefrom. For example, in the case of a resin molded body which requires a high degree of optical characteristics such as a lighting fixture or a display part, it is desirable that the light transmittance and the fog value are high and the light diffusibility is good due to the efficient use of light and the improvement of the function. The resin composition of the present invention can be used to obtain a resin molded body satisfying such characteristics. In the case of producing the resin molded body of the resin composition of the present invention, the amount of the hollow shaped microparticles of the present invention is preferably 0.1 to 5% by mass in the resin composition, but the resin composition of the present invention is coated. When the surface of the resin molded body to be separately produced is applied, the resin composition may be contained in an amount of about 30% by mass as long as the strength of the coating film is acceptable.

According to the present invention described above, it is possible to sufficiently increase the height of the resin, and the optical characteristics such as the total light transmittance and the light diffusibility in the resin molded body, and the feeling of use in cosmetics, soft focus. Sexuality, concealment and persistence are more effective.

[Examples]

Hereinafter, in order to more specifically exemplify the constitution and effects of the present invention, examples and the like are given, but the present invention is not limited to the embodiments. Further, in the following examples and comparative examples, the parts mean parts by mass, and % means mass%.

The present invention, FIGS. 1 to 3 are slightly shown the in empty shaped particles, which based surface 11 having a recessed portion a plurality of 21, the interior 31 having a hollow portion 41, the surface 11 and the interior 31 through along the major axis _direction L of a The entire connection of the cracks 51 has a spindle shape, and the average value of the long diameter L ₁ is 0.5 to 20 μm, the average value of the short diameter L ₂ / the average value of the long diameter L ₁ = 0.3 to 0.8, and the average of the maximum diameter m ₁ of the concave portion 21 The average value of the value/long diameter L ₁ = hollow shaped microparticles in the range of 0.01 to 0.30. Such a profiled hollow fine particles was in fact presents a scanning electron micrograph of Figure 4 illustrated the shape and configuration presented in FIG. 5 of a scanning electron microscope photograph illustrating the longitudinal section thereof along the direction of the minor axis L _2.

Test distinction 1 (synthesis of hollow shaped microparticles, etc.) ‧Example 1 {Synthesis of hollow shaped microparticles (P-1)}

2000 g of ion-exchanged water was taken in a reaction vessel, and 0.11 g of 30% sodium hydroxide was added thereto and dissolved. Further, 199.7 g (0.96 mol) of tetraethoxysilane was added and hydrolyzed at 15 ° C for 60 minutes with stirring. In a separate reaction vessel, an aqueous solution of 0.7 g of lauryl trimethylammonium ethane sulfate and 2.68 g of 30% sodium hydroxide dissolved in 350 g of ion-exchanged water was prepared, cooled to 10 ° C, and stirred under stirring. The above hydrolyzate solution adjusted to the same temperature was slowly dropped. Further, 93.6 g (0.78 mol) of dimethyldimethoxydecane and 267.9 g (1.97 mol) of methyldimethoxydecane were added, and the whole was kept at 13 to 15 ° C, and allowed to stand for 1 hour. After maintaining at the same temperature for 4 hours, the mixture was heated to 60 ° C and reacted at the same temperature for 5 hours to obtain a white suspension. After the obtained suspension was allowed to stand overnight, the liquid phase was removed by decantation, and the obtained white solid phase was washed with water and dried to obtain hollow shaped microparticles (P-1). Regarding the hollow shaped microparticles (P-1), observation and measurement of the surface of the microparticles by the following scanning electron microscope, observation of the cross section, elemental analysis, ICP emission spectroscopic analysis, FT-IR spectral analysis, NMR spectral analysis, and the hollow profile The microparticle (P-1)-based surface (11) has a plurality of concave portions (21), and the inner portion (31) has one hollow portion (41), and the surface (11) and the hollow portion (41) are transmitted through the long-diameter direction. The entire crack (51) is a hollow-shaped fine particle of a spindle shape, and the average value of the long diameter (L ₁ ) is 7.6 μm, and the average value of the short diameter (L ₂ )/the average value of the long diameter (L ₁ ) is 0.55. As a constituent unit, there are 26 mole % of the oxirane unit shown by Formula 1, 53 mole % of the oxoxane unit shown by the 2, and 21 mole % of the oxoxane shown by the 3 (total) 100 mole %) of organic polyoxynene microparticles.

‧ The shape of the hollow shaped microparticles (P-1), the average value of the long diameter (L ₁ ), the average value of the minor axis (L ₂ ), and the average value of the maximum diameter (m ₁ ) of the concave portion (21): Scanning type is used. An electron microscope (SEMEDX Type N manufactured by Hitachi, Ltd.) was used to obtain an SEM image at 2000 to 5000 times. Observing any 20 hollow shaped microparticles (P-1) of the SEM image, and measuring the maximum diameter (m ₁ ) of the long diameter (L ₁ ), the short diameter (L ₂ ), and the concave portion (21) of the surface (11), and Find the average value.

‧ Confirmation of the hollow portion of the hollow shaped microparticles (P-1): The cross section of the obtained hollow shaped microparticles was exposed using FIB (FB-2100-shaped bundle ion beam processing observation apparatus). The obtained hollow-shaped particle segment was obtained by scanning electron microscopy (S-4800, manufactured by Hitachi, Ltd.) and observed at 8000 to 15000 times. From this SEM image, it was confirmed whether or not the hollow shaped microparticles had a hollow portion.

‧ Measurement of oil absorption of hollow shaped microparticles (P-1): Measured according to JIS-K 5101-13-1 (2004).

‧ Analysis of the combination of hollow heterogeneous microparticles (P-1) in the unit of helium oxide: 5 grams of hollow shaped microparticles (P-1), and added to a 0.05N aqueous solution of sodium hydroxide in 250 ml, the hollow shaped microparticles The entire hydrolyzable group is extracted and treated in an aqueous solution. The hollow shaped microparticles were separated from the extraction treatment liquid by ultracentrifugation, and the separated hollow shaped microparticles were washed with water, dried at 200 ° C for 5 hours, and the obtained product was subjected to elemental analysis, ICP emission spectrometry, FT-IR spectroscopy. Analysis, determination of the total carbon content and strontium content, while confirming the 矽-carbon bond, 矽-oxy-矽 bond. The analysis value of the above, the integrated value of the NMR spectrum of the CP/MAS of the solid ²⁹ Si, the carbon number of R ⁴ which forms the sterol oxime compound shown by the chemical 5 of the raw material, and the formation of ruthenium 6 The carbon number of R ⁵ and R ⁶ of the alcoholic hydrazine compound is calculated as the ratio of the unit of the oxoxane shown in the formula 1, the ratio of the unit of the oxoxane shown in the formula 2, and the ratio of the unit of the oxoxane shown in the formula 3. .

‧Examples 2~7{Synthesis of hollow shaped microparticles (P-2)~(P-7)}

In the same manner as in Example 1, the hollow shaped microparticles (P-2) to (P-7) were synthesized, and the same observation, measurement, and analysis as in Example 1 were carried out.

‧Comparative Example 1 {Synthesis of Microparticles (R-1)}

To the reaction vessel were placed 2000 g of ion-exchanged water, 0.11 g of acetic acid, and 6.8 g of a 10% aqueous solution of sodium dodecylbenzenesulfonate to prepare a uniform aqueous solution. 207.7 g (1.30 mol) of tetraethoxy decane, 277.7 g (2.04 mol) of methyltrimethoxydecane and 80.4 g (0.67 mol) of dimethyldimethoxydecane were added to the aqueous solution. Hydrolysis was carried out at 30 ° C for 30 minutes. Next, 700 g of ion-exchanged water and 1.77 g of a 30% aqueous sodium hydroxide solution were added to other reaction vessels to prepare a uniform aqueous solution. This aqueous solution was gradually added to the above hydrolyzate while stirring, and the reaction was carried out at 15 ° C for 5 hours and at 80 ° C for 5 hours to obtain a suspension. After the suspension was allowed to stand overnight, the liquid phase was removed by decantation, and the obtained white solid phase was washed with water and dried to obtain fine particles (R-1). The same observation, measurement, and analysis as in Example 1 were carried out for the fine particles (R-1). The contents of the hollow shaped microparticles and the like in the respective examples of the above synthesis are shown in Tables 1 to 3.

In Table 1,

Amount used: 100% by mole of mol% based on the total amount of sterol-based hydrazine compound used as a raw material

Concentration of hydrolysis catalyst: Catalyst concentration (% by mass) relative to the formation of sterol-based hydrazine compound represented by Formula 4

Concentration of condensation catalyst: concentration (mass%) of catalyst relative to the total amount of sterol-based hydrazine compound used as a raw material

Concentration of surfactant: relative to the total surfactant concentration (% by mass) of the sterol-based hydrazine compound used as a raw material

SM-1: tetraethoxy decane

SM-2: tetramethoxy decane

SM-3: methyltrimethoxydecane

SM-4: propyl tributoxy decane

SM-5: Phenyltrimethoxydecane

SM-6: dimethyldimethoxydecane

SM-7: methyl phenyl methoxyethoxy decane

CA-1: sodium hydroxide

CA-2: Ammonia

CA-3: Acetic acid

C-1: lauryl trimethyl ammonium sulfate

C-2: tributylmethylammonium diethyl diphosphate

A-1: sodium dodecylbenzene sulfonate

In Table 2,

S-1: phthalic anhydride unit

S-2: methyl oxirane unit

S-3: propyl decane unit

S-4: phenyl siloxane unit

S-5: dimethyloxane unit

S-6: methylphenyl siloxane unit

Proportion: Moll%

1*: the entire surface of the recess having a plurality of recesses and one slit along the long diameter direction is a spindle shape

2*: The whole surface of the crack with a crack along the long axis is similar to a football

3*: The surface of the microparticles has a plurality of recesses.

4*: The surface of the microparticles is a smooth surface.

5*: The inside of the fine particles has one hollow portion.

6*: There is no hollow part inside the microparticles.

In Table 3,

The average value of the long diameter (L ₁ ), the average value of the minor axis (L ₂ ), and the average value of the maximum diameter (m ₁ ) of the recess: the unit is μm

Oil absorption: the unit is ml/100g

Test distinction 2

In order to investigate the usefulness of the hollow shaped microparticles and the like of the present invention as a cosmetic, the following cosmetics were prepared and evaluated.

‧ Cosmetic modulation

The composition of the mass ratio described in Table 4 was prepared. In the preparation, the pigments of Nos. 1 to 7 were mixed in a mixer to form a mass ratio as shown in Table 4, and the components of Nos. 8 to 12 were added in advance to obtain the mass ratio of Table 4, and were heated to The mixture at 40 ° C was mixed again. After the mixture was placed and cooled, it was pulverized and molded to prepare a sample.

‧Evaluation

For the above-mentioned samples, 20 of the female panelists were evaluated for their usability (extended expansion during use) and feeling of use (stickiness, unevenness, and persistence) on the evaluation criteria shown in Table 5. The results are shown in Table 6 with the average point rounded off.

In Table 6,

R-2: globular polyfluorene fine particles (trade name TAK-100 made by Takeshi Oil)

R-3: spherical vinyl-based fine particles (trade name Gantsu Pearl GSM1261 manufactured by Gantsu Chemical Co., Ltd.)

R-4: talc

Test distinction 3

In order to investigate the usefulness of the hollow shaped microparticles and the like of the present invention as a resin composition, a polycarbonate resin having more intense optical properties and heat resistance was used, and preparation of the following resin composition and production of a molded body were carried out and evaluated.

‧Preparation of resin composition and production of formed body

0.7 parts of the hollow shaped microparticles of the present invention were added to 100 parts of a polycarbonate resin (trade name Panlite K1285 manufactured by Teijin Chemical Co., Ltd.), and after mixing, a twin-screw extruder with a diameter of 40 mm and a vent hole was used to adjust the resin temperature. The mixture was melt-kneaded at 280 ° C and extruded to obtain a granular resin composition. Next, this granular resin composition was molded at a cylinder temperature of 230 ° C and a mold temperature of 60 ° C through an injection molding machine, and a test piece having a thickness of 3 mm was produced at 200 × 500 mm.

‧Evaluation

With respect to the above test piece, optical characteristics (total light transmittance, haze value) and heat-resistant coloring property were measured as follows. The results are shown in Table 7.

‧ Total light transmittance and haze value: Measured according to JIS-K7105 (1981) using the trade name NDH-2000 manufactured by Nippon Denshoku Co., Ltd.

‧ Heat-resistant coloring property: The above test piece was cut out into a sample film of 200 × 200 mm. The cut sample film was placed in a hot air circulating oven at a temperature of 80 ° C and held for 180 minutes. Thereafter, the degree of heat coloration of the sample film was measured by b value using a color difference meter (trade name CR-300, manufactured by Minolta Co., Ltd.). According to JIS-Z8729 (2004), Δb was calculated from the following number 1, and the results are shown in Table 7.

[Number 1]

△b=b ₂ -b ₁

b ₁ : b value of the sample film before heat treatment

b ₂ : b value of the sample film after heat treatment

In Table 7,

R-5: calcium carbonate

Total light penetration: %

Heat resistant coloring: Δb value

As described in the results of Tables 6 and 7, the hollow shaped microparticles of the present invention can sufficiently satisfy the high requirements as a cosmetic raw material or as a resin composition.

11. . . surface

twenty one. . . Concave

31. . . internal

41. . . Hollow part

51. . . crack

L ₁ . . . Long Trail

L ₂ . . . Short diameter

m ₁ . . . Maximum diameter of the recess

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an enlarged front elevational view showing a hollow shaped microparticle of the present invention.

Fig. 2 is an enlarged plan view showing the same hollow shaped microparticles as in Fig. 1.

Figure 3 is a cross-sectional view taken along line A-A of Figure 2.

Fig. 4 is a scanning electron micrograph showing 4000 times of the hollow shaped microparticles of the present invention.

Fig. 5 is a scanning electron micrograph showing 10000 times of the hollow shaped microparticles of the present invention in a cross section along the minor axis direction.

11. . . surface

51. . . crack

Claims (9)

A hollow shaped microparticle having a plurality of concave portions (21) on a surface (11), a hollow portion (41) in the inner portion (31), and a long diameter (L ₁ ) through the surface (11) and the hollow portion (41) A crack (51) in the direction and the whole of the connection is a spindle shape, wherein the average value of the long diameter (L ₁ ) is 0.1 to 30 μm, and the average value/long diameter (L ₁ ) of the short diameter (L ₂ ) The mean value is 0.3 to 0.8; and the hollow shaped microparticles are composed of organic polyoxo fine particles, which are represented by the unit of oxime shown in the following formula 1, and the oxane shown by the formula 2. The unit is composed of a unit of oxoxane shown in the formula 3, and has a unit of oxoxane of 20 to 45 mol% shown by the formula 1, and a unit of oxoxane of 50 to 75 mol% represented by the formula 2. a polyoxoxane crosslinked structure having a ratio of 5 to 27 mol% (total 100 mol%) of a naphthoxane unit; [Chemical 1] SiO ₂ [Chemical 2] R ¹ SiO _1.5 3] R ² R ³ SiO (in R ² and R ³ , R ¹ , R ² , R ³ : an organic group having a carbon atom directly bonded to a ruthenium atom). The hollow shaped microparticles of the first aspect of the patent application, wherein the average value of the long diameter (L ₁ ) is in the range of 0.5 to 20 μm. The hollow shaped microparticles of claim 1 or 2, wherein the average value of the maximum diameter (m ₁ ) of the concave portion (21) / the average value of the long diameter (L ₁ ) = 0.01 to 0.30. For example, the hollow shaped microparticles in the third application of the patent scope, wherein the oil absorption is 50-150 ml/100 g. The scope of the patent in item 1 empty shaped particles, wherein the sum of the 2 R ^1, in 3 of the R ² and R ³ is ^an alkyl group having 1 to 4 carbon atoms or the phenyl group. A method for producing a hollow shaped microparticle, which is a method for producing a hollow shaped microparticle according to the first aspect of the invention, which comprises a sterol-based bismuth compound 20 to 45 mol% and 5 The ratio of the sterol-based hydrazine compound 50 to 75% and the sterol-based hydrazine compound 5 to 27 mol% (total 100 mol%) is shown, which is first formed by the formation of 4 a sterol-based hydrazine compound which is hydrolyzed by contact with water in the presence of a basic catalyst to form a sterol compound, and secondly, a sterol-based hydrazine compound and a sterol-based hydrazine compound are formed. The sterol-based hydrazine compound represented by 6 is subjected to a condensation reaction under the aqueous conditions in which a basic catalyst and a cationic surfactant are present; [Chemical 4] SiX ₄ [Chemical 5] R ⁴ SiY ₃ [Chemical 6] R ⁵ R ⁶ SiZ ₂ (in R ⁴ , R ⁵ , and R ⁶ : R ⁴ , R ⁵ , R ⁶ : an organic group having a carbon atom directly bonded to a ruthenium atom; X, Y, Z: carbon number 1 to 4 Alkoxy group, alkoxyethoxy group having alkoxy group having 1 to 4 carbon atoms, decyloxy group having 2 to 4 carbon atoms, N,N-dialkylamino group having an alkyl group having 1 to 4 carbon atoms Hydroxyl, halogen Promoter or a hydrogen atom). The scope of the patent application in Item 6. The method for manufacturing fine particles of shaped blank, wherein 5 of the R ^4, R & lt oriented in the ⁵ and 6 carbon atoms R ⁶ is an alkyl group of 1 to 4 or a phenyl group. A cosmetic raw material containing the hollow shaped microparticles of any one of claims 1 to 5. A resin composition containing the hollow shaped microparticles of any one of claims 1 to 5.