HK1186687A1 - Metal oxide conjugated highly-flat cellulose powder and cosmetic containing same - Google Patents

Abstract

The purpose of the present invention is to provide a powder for a cosmetic having, when compared to conventional powders for cosmetics, a better skin feel, and high functionality such as a UV blocking ability, and also to provide a cosmetic using the same. The cosmetic is a metal oxide conjugated highly-flat cellulose powder obtained by mechanically grinding a cellulosic material, a grinding aid, and a metal oxide, and combines the same.

Description

Metal oxide composite highly-flat cellulose powder and cosmetic containing same

Technical Field

The present invention relates to a highly flat cellulose powder composed of metal oxides and having a high degree of flatness and a powder cosmetic containing the same, and more particularly to a highly flat cellulose powder composed of metal oxides and having a shape having a high degree of flatness and a surface coated with metal oxides and a cosmetic containing the same.

Background

Powder cosmetics containing a powder component, an oil component, and the like are widely used in the field of cosmetics, and examples thereof include foundations, eye shadows, face powder, blushes, and the like.

The powder cosmetic is usually produced by filling a powder mixture of a powder component such as an extender pigment or a pigment and an oily component in a dish-shaped container and press-molding the powder mixture.

As the powder component used in the powder cosmetic, a sheet-like mica flake, sericite, talc or a surface-treated product thereof derived from a natural material is used as an extender pigment in order to improve spreadability and adhesion on the skin. In addition, spherical organic powder and the like are used together with the extender pigment in order to improve smoothness or touch on the skin. Further, as the pigment, a white pigment such as titanium dioxide, a colored pigment such as iron oxide red, and a luster pigment such as mica titanium are used.

Further, powders in which a powder component is coated with a metal oxide are also known (patent documents 1 to 3). For example, in both of the powders of patent documents 1 and 2, a fine polymer powder or spherical resin powder is coated with a fine metal oxide, and the powder of patent document 3 is treated with hydroxyapatite and zinc oxide on a substrate that can be used for a cosmetic powder.

However, although powder components have various shapes, flake-shaped inorganic powders such as mica flakes, sericite, talc and the like are commonly used, they are all aluminosilicate minerals and have slightly different properties depending on the production place, and thus, for example, there is a problem that oil absorption is low and target physical properties cannot be obtained. On the other hand, there is almost no report on a flat organic powder, and for example, only a flat cellulose particle obtained by mixing a cellulose-based material with a fatty acid and mechanically pulverizing the mixture is known (patent document 4).

However, although patent document 4 discloses flattened cellulose particles, it does not disclose a specific use form thereof, and it is only a very simple disclosure about application to cosmetics.

In addition, a technique of treating the surface of crystalline cellulose with hydrogenated lecithin is also known (patent document 5). However, the ratio (L/D) of the major axis to the minor axis of the crystalline cellulose is 3 or less, and it cannot be said that the crystalline cellulose is flat; it is actually disclosed that, although there is a difference in the good property of makeup retention when compared with an untreated material, there is no difference in the feeling of use — the "pick-up property", "spreadability", "accomplishment property (shiwa り)".

The present inventors have previously developed and applied for a patent a flat cellulose powder having an extremely high flatness (aspect ratio) of 20 to 200 (hereinafter referred to as "highly flat cellulose powder") and a method for producing the same (patent document 6). The highly flat cellulose powder is obtained by subjecting cellulose powder derived from refined wood pulp to reduced pressure drying to sufficiently remove adsorbed moisture, and then pulverizing the cellulose powder together with a pulverization aid and, if necessary, a hydrophobizing agent by means of a planetary ball mill.

Since the raw material of the obtained highly flat cellulose powder is cellulose and has a high flatness, when it is blended as a component of a powder cosmetic, it has the following characteristics: even if the amount of the oily component is large, the powder does not agglomerate, the properties such as the dry feeling of the powder itself can be maintained, and the agglomeration is hardly caused even when the powder is pressed.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 3-200721

Patent document 2: japanese laid-open patent publication No. 8-59433

Patent document 3: japanese laid-open patent publication No. 2002-20218

Patent document 4: japanese patent laid-open publication No. 2004-230719

Patent document 5: japanese patent laid-open publication No. 2003-146829

Patent document 6: WO/2010/026925

Disclosure of Invention

Problems to be solved by the invention

Although various cosmetic powders have been provided, consumer demand for cosmetics with better feeling in use and high usability is a natural trend; the present invention addresses the problem of providing a cosmetic powder that can provide such a cosmetic, and a cosmetic using the cosmetic powder.

Means for solving the problems

The present inventors have further studied a high-flatness cellulose powder obtained from a cellulose-based material, and as a result, have found that: the present inventors have found that a metal oxide-composited high-aspect cellulose powder having properties which cannot be obtained at all by conventional cosmetic powders can be obtained by adding a pulverization aid and a metal oxide to a cellulose-based material by a specific method and compositing them, and that the marketability of a cosmetic such as a powder cosmetic can be greatly improved by compositing a high-aspect cellulose powder with the metal oxide, and have completed the present invention.

That is, the present invention relates to a metal oxide-composited highly-flattened cellulose powder obtained by subjecting a cellulose-based material, a grinding aid, and a metal oxide to mechanical grinding treatment.

The present invention also relates to a cosmetic preparation containing the metal oxide-composited high-flattening cellulose powder.

The present invention also relates to a method for producing a metal oxide-composited highly flat cellulose powder, characterized by adding a pulverization aid and a metal oxide to a cellulose-based material to prepare a mixture, and mechanically pulverizing the mixture.

Effects of the invention

The metal oxide-composited high-flatness cellulose powder of the present invention has a novel effect in addition to the effect of the conventional high-flatness cellulose powder, by compositing a metal oxide on the surface thereof. Specifically, when the metal oxide after composite formation is in the range of 10nm to 100nm on the powder, an extremely excellent UV shielding effect and a smooth feeling in use can be obtained. Further, when the metal oxide after composite formation exceeds 100nm and is 1000nm or less on the powder, natural concealing properties, excellent color developing properties, and a smooth feeling in use can be obtained.

The cosmetic composition containing the metal oxide composite highly-flat cellulose powder has excellent uniformity of a cosmetic film, smooth feeling in use, excellent UV shielding effect, natural concealing property, coloring effect, and sustained effect of makeup such as prevention of color from being lowered.

Therefore, the cosmetic using the metal oxide composite highly-flat cellulose powder of the present invention can be suitably used as a foundation, an eye shadow, face powder, a blush, and the like.

Drawings

Fig. 1 is a photograph of the surface of the product 6 obtained in example 6 observed with a scanning microscope (10,000 times).

Fig. 2 is a photograph of the surface of the same article as in fig. 1, observed with a scanning microscope (50,000 times).

Fig. 3 is a photograph of the surface of the same article as in fig. 1, observed with a scanning microscope (200,000 times).

Detailed Description

The metal oxide-composited high-tabular cellulose powder of the present invention is a powder in which fine metal oxide powder is firmly adhered to and composited with the surface of the high-tabular cellulose powder.

The metal oxide-composited high-aspect cellulose powder is produced by adding a pulverization auxiliary and a metal oxide to a cellulose-based material to prepare a mixture, and mechanically pulverizing the mixture.

The cellulose-based substance used as a starting material for the metal oxide-composited high-aspect ratio cellulose powder is not particularly limited, but for example, a woody material such as fibrous or powdery wood flour or wood pulp derived from wood, a cotton-based material such as fibrous or powdery cotton or cotton linter fibers derived from cotton, or a fibrous or powdery cellulose-based substance obtained by purifying a woody material or a cotton-based material, or a purified cellulose-based substance obtained by acid hydrolysis may be used. The cellulose-based material derived from cotton may be one derived from cotton which has been subjected to organic authentication.

The cellulose-based material as the raw material is easy to adsorb or absorb moisture, and has adsorbed moisture of about 3 to 10 mass% (hereinafter simply referred to as "%") in a normal state. In order to efficiently obtain a flat cellulose powder from the cellulose-based material, it is preferable to remove adsorbed moisture by drying in advance by hot air drying, vacuum drying, reduced pressure drying, or the like before the pulverization treatment.

On the other hand, the grinding aid used for producing the metal oxide composite highly flat cellulose powder of the present invention is used for highly flattening the cellulose-based substance, and examples thereof include an amphiphatic agent, an amino acid, a fatty acid, and the like. One kind of these may be blended, and two or more kinds may be blended.

Among them, examples of the amphiphiles include phospholipids, ceramides, cholesterol or a derivative thereof, phytosterols or a derivative thereof, and the like. These are lipids in the living body, or substances having a common property such as a long-chain alkyl structure and a hydrophilic group having a structure close to that of the lipid.

Among the above amphiphiles, phospholipids are a generic term for lipids having a phosphate moiety in their structure. Specific examples of the phospholipid include natural products obtained by hydrogenating natural lecithins such as egg yolk lecithin and soybean lecithin; and substances obtained by hydrogenating lysolecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingomyelin, and the like. Among these phospholipids, hydrogenated lecithin, phosphatidylcholine, phosphatidylethanolamine, and hydrogenated phosphatidylglycerol are preferable.

The ceramide is a generic term for nonionic amphiphiles having 1 or more long-chain linear and/or branched alkyl groups or alkenyl groups, at least 2 hydroxyl groups, and 1 or more amide groups (and/or amino groups) in the molecule. Specific examples of ceramides include natural ceramides such as ceramide 1, ceramide 2, ceramide 3B, ceramide 4, ceramide 5, ceramide 6I, and ceramide 6II, which are long-chain fatty amides of sphingosine and phytosphingosine. Among these ceramides, ceramide 2 and ceramide 3 are preferable. These ceramides may be natural or synthetic.

Further, cholesterol is higher alcohol component obtained by saponifying animal fat or white or yellowish solid obtained by extracting, crystallizing and drying fraction obtained from fish oil, and has molecular formula C₂₇H₄₆And O. The cholesterol derivative is an ester derivative of the cholesterol with a saturated or unsaturated fatty acid such as oleic acid, palmitoleic acid, palmitic acid, stearic acid, 2-ethylhexanoic acid, capric acid, and lauric acid; hydrolyzing natural vegetable oil such as olive oil, avocado oil, sesame oil, rice germ oil, macadamia nut oil, etc., and animal oil such as fish oil, butter, etcEsterified derivatives of the resulting fatty acid mixtures, and the like. Specific examples of preferable cholesterol derivatives include cholesteryl hydroxystearate, polyoxyethylene cholesteryl ether, and the like. Among these cholesterol or derivatives thereof, cholesterol is preferable.

Further, phytosterols are a generic term for sterol compounds obtained from plants. Specific examples of the phytosterol include sitosterol, stigmasterol, fucosterol, spinasterol, brassicasterol, and the like. The phytosterol derivative is an ester derivative of the phytosterol with saturated or unsaturated fatty acids such as oleic acid, palmitoleic acid, palmitic acid, stearic acid, 2-ethylhexanoic acid, capric acid, and lauric acid; and esterified derivatives of fatty acid mixtures obtained by hydrolyzing natural vegetable oils and fats such as olive oil, avocado oil, sesame oil, rice germ oil, and macadamia nut oil. Specific examples of preferred phytosterol derivatives include phytosterol hydroxystearate, polyoxyethylene phytosterol, polyoxyethylene phytostanol, and the like. Among these phytosterols or derivatives thereof, phytosterols are preferred.

Among the grinding aids, examples of the amino acids include N-acylamino acids such as N-lauroyl-L-lysine and amino acids such as theanine.

Examples of the fatty acids include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid, and salts thereof, and unsaturated fatty acids such as oleic acid, and salts thereof.

On the other hand, the metal oxide used for producing the metal oxide composite highly-flat cellulose powder of the present invention can be used without any particular limitation as long as it is blended as a powder component such as an extender pigment or a coloring pigment in a general cosmetic. Examples of the metal oxide include iron oxide, titanium dioxide, zinc oxide, and cerium oxide. One or two or more kinds of the metal oxides can be used.

The particle size of the metal oxide is preferably 10nm to 10000nm, but the difference in the average particle size of the obtained metal oxide composite highly flat cellulose powder partially causes the difference in the effects obtained as described later, and it is desirable to select the particle size of the raw material metal oxide in consideration of this point.

In the production of the metal oxide composite highly flat cellulose powder of the present invention, the amount of the grinding aid added to the entire components is 0.5 to 5%, preferably 1 to 3%. The amount of the metal oxide in the whole is 5 to 50%, preferably 20 to 40%.

The timing of adding these grinding aid or metal oxide to the cellulose-based material may be any timing before the grinding treatment, or the grinding aid and metal oxide may be added simultaneously or separately. In addition, as a method of adding the pulverization aid, it may be added to the cellulose-based material after dissolving it in an appropriate solvent. Examples of the solvent used for dissolving the pulverization aid herein include paraffin such as hexane, alcohol such as ethanol, ketone such as acetone, ether such as tetrahydrofuran, and aromatic hydrocarbon such as toluene.

In the treatment of mechanically pulverizing the mixture of the cellulose-based material, the pulverization aid and the metal oxide, the pressure or the shearing force by the pulverization needs to be continuously applied for a certain period of time. Therefore, in the pulverization treatment, a pulverization device such as a vibration ball mill, a rotary ball mill, a planetary ball mill, a roll mill, a media mill, a disc mill, a high-speed mixer using a high-speed rotating blade, a homomixer, or the like is preferably used, and a planetary ball mill is particularly preferable. The pulverization treatment method is preferably a dry pulverization treatment without using a solvent. It is preferable that the grinding energy applied when the grinding treatment is performed (the acceleration of gravity applied to the planetary ball mill in the case of the planetary ball mill) is 3G to 20G, preferably 5G to 15G.

In addition, in the metal oxide composite highly flat cellulose powder, the particle size, thickness, and flatness (aspect ratio) are important, and further, depending on the application, the particle size of the metal oxide powder to which the metal oxide composite powder is firmly attached and combined is also important, and therefore, the above-mentioned pulverization time needs to be determined in consideration of these factors. This relationship also relates to the target flat cellulose itself, the particle size of the metal oxide as a raw material, and the like, and therefore it is desirable to experimentally determine the pulverization conditions, the pulverization time, and the like in advance.

Next, a preferred embodiment for obtaining the metal oxide composite high-aspect cellulose powder of the present invention will be described. First, cellulose powder derived from refined wood pulp is dried under reduced pressure at 30 to 50 ℃ to sufficiently remove adsorbed moisture to 0.1% or less. The cellulose powder and alumina or zirconia milling balls are put into a sealable alumina or zirconia milling container, and a milling aid and metal oxide powder are further added to the cellulose powder in the above amounts. Thereafter, the above-mentioned grinding vessel was set in a planetary ball mill and ground at a rotation speed of 100rpm to 250 rpm. For the pulverization treatment, the pulverization treatment can be continuously and repeatedly carried out for about 2-72 cycles by taking 1 cycle of pulverization for 5-15 minutes and suspension for 5-15 minutes; the pulverization treatment may be continuously carried out for about 5 to 120 minutes without suspension.

After the pulverization treatment, the moisture and the like adhering to the metal oxide composite highly flat cellulose powder may be further removed by a known drying means such as air drying, hot air drying, vacuum drying, or reduced pressure drying.

The metal oxide composite highly flat cellulose powder obtained as described above is, for example, a flake having an average particle diameter of 1 to 50 μm, preferably 5 to 40 μm, and an average thickness of 0.1 to 10 μm, preferably 0.2 to 2 μm, and has a flatness of 4 to 200, preferably 10 to 100. Here, the average particle diameter refers to an average value (a particle diameter value with a cumulative volume of 50%) of widths and lengths of the flat cellulose particles measured in a dispersed state in ethanol by using a particle size distribution measuring device such as a laser diffraction/scattering particle size distribution measuring device. The average thickness is an average value obtained by selecting a plurality of particles having the same size as the average particle diameter obtained above by an electron microscope such as a scanning electron microscope, measuring the thicknesses thereof, and averaging the thicknesses thereof. Further, the flatness is the average particle diameter/average thickness determined as described above. The particle size of the metal oxide after the composite treatment can also be measured by a scanning electron microscope.

The metal oxide-composited highly flat cellulose powder obtained in this way has slightly different properties and different applications when the particle size of the metal oxide firmly adhered and composited as described above exceeds 100nm and is 1000nm or less (pigment-grade size) and when the particle size is 10nm to 100nm (fine particle-grade size). That is, when the composite metal oxide is in the fine particle level, extremely excellent UV shielding effect and uniformity of a cosmetic film can be obtained. In addition, when the composite metal oxide is of pigment grade, excellent color developability can be obtained. Since the particle size of the metal oxide hardly changes before and after the composite formation, the particle size of the metal oxide added before the composite formation is substantially the same as the particle size of the metal oxide after the composite formation.

In addition, the metal oxide-composited high-oblate cellulose powder has smooth use feeling originally possessed by the high-oblate cellulose powder, so that a cosmetic material containing the metal oxide-composited high-oblate cellulose powder has excellent uniformity and smooth use feeling of a cosmetic film, and also has excellent UV shielding effect and color development effect, and furthermore, has excellent lasting effect of making up such as no color sinking

The obtained metal oxide composite highly-flat cellulose powder is thin and flaky compared with talc or sericite, which are conventional extender pigments, and has excellent properties in terms of transparency, softness, spreadability, natural gloss, etc., and also has excellent affinity with an oil agent used, and has excellent UV shielding effect and color developing effect, and thus, specifically, as a cosmetic material that can utilize the metal oxide composite highly-flat cellulose powder, many cosmetic materials using powder, for example, various cosmetic materials such as foundation (skin care) cosmetic materials, sunscreen cream cosmetic materials, hair cosmetic materials, and the like can be cited. In particular, it is preferably used in powder cosmetics such as foundation, foundation solution, eye shadow, blush, face powder, etc., and cosmetics requiring a UV-shielding effect such as sunscreen cream, makeup cream (under makeup), etc.

The cosmetic containing the metal oxide composite highly flat cellulose powder of the present invention is prepared by combining the powder with an appropriate cosmetic base and formulating the composition. For example, when the cosmetic is a powder cosmetic, the metal oxide-composited highly flat cellulose powder of the present invention may be used in place of a part or all of the conventional powder components in a production method similar to that of a conventional powder cosmetic. The amount of the metal oxide composite high-flattening cellulose powder to be mixed in the cosmetic is 1% to 90%, preferably 5% to 90%, and particularly preferably 5% to 70%.

In the cosmetic, it is preferable to blend an oily component as a base for the cosmetic. The oily component to be blended in the cosmetic is not particularly limited, and examples thereof include hydrocarbons such as paraffin wax, microcrystalline wax (セレシンワックス), ceresin, microcrystalline wax, montan wax, fischer-tropsch wax, polyethylene wax, liquid paraffin, squalane, vaseline, polyisobutylene, and polybutene; natural waxes such as carnauba wax, beeswax, lanolin wax, and candelilla wax; esters such as glyceryl tribehenate, pentaerythritol abietate, jojoba oil (jojoba oil), cetyl isooctanoate, isopropyl myristate, glyceryl tricaprylate, diglyceryl triisostearate, and dipentaerythritol fatty acid ester; fatty acids such as stearic acid, behenic acid and 12-hydroxystearic acid; higher alcohols such as cetyl alcohol, stearyl alcohol, and behenyl alcohol; oils and fats such as olive oil, castor oil, mink oil, and wood wax; lanolin derivatives such as isopropyl lanolate fatty acid ester and lanolin alcohol; amino acid derivatives such as N-lauroyl-L-glutamic acid di (cholesteryl ester behenyl ester octyldodecyl ester); fluorine-containing oils such as perfluoropolyether, perfluorodecane and perfluorooctane. These oily components can be used in 1 or 2 or more. The amount of the oily component to be blended in the cosmetic of the present invention is not particularly limited, but is preferably 0.1% to 25%.

In addition, the cosmetic may contain conventional powder components, for example, inorganic powder such as talc or organic powder such as nylon. In this case, the metal oxide composite high-flat cellulose powder of the present invention may be produced by adding an inorganic powder or an organic powder together with the metal oxide composite high-flat cellulose powder, dispersing the inorganic powder or the organic powder, and adding an oil component if necessary.

In addition, in the cosmetic composition, components used in general cosmetic compositions, for example, a surfactant, an oil gelling agent, a water-soluble component such as a polyhydric alcohol or a humectant, an ultraviolet absorber, a preservative, a cosmetic component, a perfume, and the like can be appropriately blended as necessary within a range not to impair the effects of the present invention.

The properties and formulation of the cosmetic are not particularly limited, and can be selected according to the purpose. The cosmetic of the present invention may be in any form of liquid, powder, solid, emulsion, cream, gel, etc., or may be in any form of aqueous, oily, soluble, water-in-oil, oil-in-water, etc.

The reason why the metal oxide composite high-aspect cellulose powder of the present invention described above has particularly excellent performance as compared with conventional metal oxide composite particles is presumably because the metal oxide is formed into a composite with the high-aspect cellulose powder in the form of extremely fine primary particles. That is, fig. 1 to 3 are views of the surface of the product 6 obtained in example 6 observed with a scanning electron microscope, and in fig. 1 in which the magnification is about 10,000 times, fine zinc oxide particles are not observed at all. However, when the magnification was increased to 50,000 times, fine zinc oxide particles having a white color began to be observed on the surface, and when the magnification was increased to 200,000 times, fine zinc oxide particles having a size of about 20nm were observed in the mother powder. Further, since the particle size of the fine zinc oxide particles is originally about 20nm, the following can be understood as follows: the fine zinc oxide particles are relatively combined in the form of primary particles without being aggregated on the surface of the metal oxide composite highly flat cellulose powder of the present invention. Namely, the reason is considered as follows: in the metal oxide composite highly flat cellulose powder, the metal oxide is present in the form of primary particles that can exert its effect to the maximum extent, and particularly excellent performance can be exerted.

As described above, the reason why the metal oxide is combined in the state of primary particles in the metal oxide-combined highly flat cellulose powder of the present invention is not clear, but may be understood as follows: since fine metal oxide powder is present when highly flat cellulose particles are produced from a cellulose-based material and stirred with high shear, the metal oxide powder preferentially adheres to the surface of the cellulose that has just been produced, and has strong bonding.

Examples

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1

Production of lauroyl lysine-treated fine particle titanium dioxide composite high-aspect cellulose powder (1):

(1) cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed to 0.1% or less by drying under reduced pressure at 40 ℃ and the obtained cellulose powder (55.3g) was charged into a sealable alumina grinding vessel (volume 500mL) together with alumina grinding balls, and further, 14g of lauroyl lysine (manufactured by Amihope LL Soxhlet Co., Ltd.) and fine particles of titanium dioxide (manufactured by TTO-S-4 Shigaku Kogyo Co., Ltd.) (minor axis of particle diameter: 10 to 20nm, major axis: 50 to 100nm) were added. Thereafter, the resultant was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a lauroyl lysine-treated fine particulate titanium dioxide composite high-platy cellulose powder (product 1).

(2) The average particle diameter, thickness and flatness of the product 1 were measured as follows. That is, the average particle diameter (average value on the device of width and length) of the obtained powder in a state of being dispersed in ethanol was determined by using a laser diffraction/scattering particle size distribution measuring device (horiba, LA-920) using a flow cell. The average particle diameter herein is a value of 50% cumulative volume of the particle diameter. In the particle size distribution measurement, 50mg of the obtained powder was dispersed in 10mL of ethanol, and the obtained suspension was dropped into a sample circulation tank of a particle size distribution measuring apparatus using ethanol as a medium to obtain an appropriate concentration, and then the concentration was measured. As a result, the average particle diameter of the powder was 16 μm.

The average thickness of the obtained granules was determined by directly observing the granules with a scanning electron microscope (S-2150, manufactured by Hitachi Ltd.), selecting a plurality of granules having the same size as the average particle diameter determined above, measuring the thickness, and averaging the thicknesses. In the observation by the scanning electron microscope, a very small amount of the obtained powder was placed on a sample stage of the scanning electron microscope, dried under reduced pressure, and then platinum was vapor-deposited to prepare a microscopic sample. The microscopic sample was observed at an acceleration voltage of 10kV to 25kV at a magnification of 500 times to 10,000 times, and the thickness of particles having a size equivalent to the average particle diameter measured above was measured from the obtained image, and the average thickness was determined from these. As a result, the average thickness was 1.7. mu.m.

As a result, it was found that the product 1 was flat cellulose particles (lauroyl lysine-treated fine titanium dioxide composite high-flat cellulose powder) having an average particle diameter of 16 μm, an average thickness of 1.7 μm, and a flatness (average particle diameter/average thickness) of 9.4. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 2

Production of lauroyl lysine-treated fine particle titanium dioxide composite high-aspect cellulose powder (2):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (41.3g) was charged into a sealable alumina grinding vessel (500 mL capacity) together with alumina grinding balls, and 0.7g of lauroyl lysine (manufactured by Amihope LL Sokoku Co., Ltd.) and 28g of fine titanium dioxide (manufactured by TTO-S-4 Stone Ltd.) were further added. Thereafter, the resultant was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a lauroyl lysine-treated fine particulate titanium dioxide composite high-platy cellulose powder (product 2).

The obtained product 2 was measured for average particle diameter, thickness and flatness in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 15 μm, an average thickness of 1.0 μm and a flatness (average particle diameter/average thickness) of 15. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 3

Production of hydrogenated lecithin-treated particulate titanium dioxide composite highly flat cellulose powder (3):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (55.3g) was charged into a sealable alumina grinding vessel (capacity 500mL) together with alumina grinding balls, and further 0.7g of hydrogenated lecithin (manufactured by Lecinol S-10Nikko Chemicals) and 14g of fine particulate titanium dioxide (manufactured by TTO-S-4 Stone Ltd.) were added. Thereafter, the resultant was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho industoryco., Ltd.) to obtain a hydrogenated lecithin-treated fine particulate titanium dioxide composite high-aspect cellulose powder (product 3).

The average particle diameter, thickness and flatness of the obtained product 3 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 16 μm, an average thickness of 1.9 μm and a flatness (average particle diameter/average thickness) of 8.4. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 4

Production of hydrogenated lecithin-treated particulate titanium dioxide composite highly flat cellulose powder (4):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (41.3g) was charged into a sealable alumina grinding vessel (capacity 500mL) together with alumina grinding balls, and further 0.7g of hydrogenated lecithin (manufactured by Lecinol S-10Nikko Chemicals) and 28g of fine particulate titanium dioxide (manufactured by TTO-S-4 Stone Ltd.) were added. Thereafter, the resultant was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho industoryco., Ltd.) to obtain a hydrogenated lecithin-treated fine particulate titanium dioxide composite high-aspect cellulose powder (product 4).

The average particle diameter, thickness and flatness of the obtained product 4 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 15 μm, an average thickness of 1.2 μm and a flatness (average particle diameter/average thickness) of 12.5. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 5

Production of ceramide-treated particulate titanium dioxide composite highly flat cellulose powder (5):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed to 0.1% or less by drying under reduced pressure at 40 ℃ and the obtained cellulose powder (41.3g) was charged into a sealable alumina grinding vessel (volume 500mL) together with alumina grinding balls, and 0.7g of Ceramide (Ceramid II, manufactured by Wako pure chemical industries, Ltd.) and 28g of fine titanium dioxide (manufactured by TTO-S-4 stone industries, Ltd.) were further added. Thereafter, the resultant was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a ceramide-treated fine-particle titanium dioxide composite high-aspect cellulose powder (product 5).

The average particle diameter, thickness and flatness of the obtained product 5 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 16 μm, an average thickness of 1.2 μm and a flatness (average particle diameter/average thickness) of 13.3. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 6

Production of fine particulate zinc oxide composite high-platy cellulose powder treated with lauroyl lysine (6):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (55.3g) was charged into a sealable alumina grinding vessel (volume 500mL) together with alumina grinding balls, and 0.7g of lauroyl lysine (manufactured by Amihope LL, Inc.) and 14g of fine zinc oxide (manufactured by ZnO-610 Sumitomo Osaka Cement Co., Ltd.) (average particle diameter 20nm) were further added. Thereafter, the fine zinc oxide composite high flat cellulose powder treated with lauroyl lysine (product 6) was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes using a planetary ball mill (Sansho Industry co., Ltd.).

The average particle diameter, thickness and flatness of the obtained product 6 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 16 μm, an average thickness of 1.7 μm and a flatness (average particle diameter/average thickness) of 9.4. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 7

Production of lauroyl lysine-treated fine particle zinc oxide composite high-platy cellulose powder (7):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (41.3g) was charged into a sealable alumina grinding vessel (volume 500mL) together with alumina grinding balls, and 0.7g of lauroyl lysine (manufactured by Amihope LL, Inc.) and 28g of fine particle zinc oxide (manufactured by ZnO-610 Sumitomo Osaka Cement Co., Ltd.) were further added. Thereafter, the fine zinc oxide composite high flat cellulose powder treated with lauroyl lysine (product 7) was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes using a planetary ball mill (Sansho Industry co., Ltd.).

The average particle diameter, thickness and flatness of the obtained product 7 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 15 μm, an average thickness of 1.0 μm and a flatness (average particle diameter/average thickness) of 15. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 8

Production of hydrogenated lecithin-treated fine-particulate zinc oxide composite high-oblate cellulose powder (8):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (41.3g) was charged into a sealable alumina grinding vessel (capacity 500mL) together with alumina grinding balls, and further 0.7g of hydrogenated lecithin (manufactured by Lecinol S-10Nikko Chemicals) and 28g of fine zinc oxide (manufactured by ZnO-610 Sumitomo Osaka Cement Co., Ltd.) were added. Thereafter, the resultant was pulverized at a rotation speed of 200rpm (a pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho industoryco., Ltd.) to obtain a hydrogenated lecithin-treated fine particulate zinc oxide composite high-platy cellulose powder (product 8).

The average particle diameter, thickness and flatness of the obtained product 8 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 15 μm, an average thickness of 1.2 μm and a flatness (average particle diameter/average thickness) of 12.5. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 9

Production of ceramide-treated fine-particle zinc oxide composite highly flat cellulose powder (9):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (41.3g) was charged into a sealable alumina grinding vessel (volume 500mL) together with alumina grinding balls, and 0.7g of Ceramide (Ceramide II, manufactured by Wako pure chemical industries) and 28g of fine zinc oxide (ZnO-610 manufactured by Sumitomo Osaka Cement Co., Ltd.) were further added. Thereafter, the powder was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a ceramide-treated fine-particulate zinc oxide composite high-platy cellulose powder (product 9).

The average particle diameter, thickness and flatness of the obtained product 9 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 15 μm, an average thickness of 1.2 μm and a flatness (average particle diameter/average thickness) of 12.5. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 10

Production of hydrogenated lecithin-treated titanium dioxide composite high-aspect cellulose powder (10):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (55.3g) was charged into a sealable alumina grinding vessel (volume: 500mL) together with alumina grinding balls, and further 0.7g of hydrogenated lecithin (manufactured by Lecinol S-10Nikko Chemicals) and 14g of titanium dioxide (manufactured by TIPAQUE CR-50 Shikuyao Co., Ltd.) (average particle size: 250nm) were added thereto. Thereafter, the resultant was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a hydrogenated lecithin-treated titanium dioxide composite highly flat cellulose powder (product 10).

The obtained product 10 was measured for average particle diameter, thickness and flatness in the same manner as in example 1(2), and as a result, was a flat powder having an average particle diameter of 18 μm, an average thickness of 2.2 μm and a flatness (average particle diameter/average thickness) of 8.2. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 11

Production of hydrogenated lecithin-treated titanium dioxide composite highly flat cellulose powder (11):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (41.3g) was charged into a sealable alumina grinding vessel (capacity 500mL) together with alumina grinding balls, and further 0.7g of hydrogenated lecithin (manufactured by Lecinol S-10Nikko Chemicals) and 28g of titanium dioxide (manufactured by TIPAQUE CR-50 Shikuyao Co., Ltd.) were added thereto. Thereafter, the resultant was pulverized at a rotation speed of 200rpm (a pulverization energy of about 10G (gravitational acceleration)) for 40 minutes using a planetary ball mill (Sansho industoryco., Ltd.) to obtain a hydrogenated lecithin-treated titanium dioxide composite high-aspect cellulose powder (product 11).

The average particle diameter, thickness and flatness of the obtained product 11 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 17 μm, an average thickness of 1.5 μm and a flatness (average particle diameter/average thickness) of 11.3. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 12

Production of ceramide-treated titanium dioxide composite high-oblate cellulose powder (12):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (55.3g) was charged into a sealable alumina grinding vessel (volume 500mL) together with alumina grinding balls, and further 0.7g of Ceramide (Ceramid II, manufactured by Wako pure chemical industries, Ltd.) and 14g of titanium dioxide (manufactured by TIPAQUE CR-50 stone Seiko Co., Ltd.) were added thereto. Thereafter, the mixture was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a ceramide-treated titanium dioxide composite highly flat cellulose powder (product 12).

The average particle diameter, thickness and flatness of the obtained product 12 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 18 μm, an average thickness of 2.2 μm and a flatness (average particle diameter/average thickness) of 8.2. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 13

Production of ceramide-treated titanium dioxide composite highly flat cellulose powder (13):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (41.3g) was charged into a sealable alumina grinding vessel (volume 500mL) together with alumina grinding balls, and 0.7g of Ceramide (Ceramid II, manufactured by Wako pure chemical industries, Ltd.) and 28g of titanium dioxide (manufactured by TIPAQUE CR-50 Shikuyao Co., Ltd.) were further added. Thereafter, the mixture was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a ceramide-treated titanium dioxide composite highly flat cellulose powder (product 13).

The average particle diameter, thickness and flatness of the obtained product 13 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 17 μm, an average thickness of 1.5 μm and a flatness (average particle diameter/average thickness) of 11.3. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 14

Ceramide-treated titanium dioxide:

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, 41.3g (59%) of the obtained cellulose powder was charged into a sealable alumina pulverization vessel (volume: 500mL) together with alumina pulverization balls by sufficiently removing adsorbed water by drying under reduced pressure at 40 ℃ to 0.1% or less, and 0.7g (1%) of Ceramide (manufactured by Ceramid II and Wako pure chemical industries, Ltd.), 21g (30% of titanium dioxide (manufactured by TITANIX JR-800 TAYCA) (average particle diameter: 270 nm)), 0.875g (1.25% of red iron oxide (manufactured by TAROXR-516P Titan Kogyo) (average particle diameter short axis: 80nm, long axis: 800nm), and 6.125g (8.75%) of yellow iron oxide (manufactured by TAROX synthetic iron oxide YP1200P Titan Kogyo) (average short axis: 90nm, long axis: 900nm) were further added thereto. Thereafter, the mixture was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a ceramide-treated titanium dioxide/iron oxide composite high-aspect cellulose powder (product 14).

The average particle diameter, thickness and flatness of the obtained product 14 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 17 μm, an average thickness of 1.5 μm and a flatness (average particle diameter/average thickness) of 11.3. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 15

Production of ceramide-treated titanium dioxide/iron oxide composite highly flat cellulose powder (15):

a Ceramide-treated titanium dioxide-iron oxide composite highly flattened cellulose powder (product 15) was obtained in the same manner as in example 14, except for using 59% of a cellulose powder derived from refined wood pulp (W-400G), 1% of Ceramide (Ceramide II), 38.2% of titanium dioxide (TITANIX JR-800), 0.45% of iron oxide red (TAROXR-516P) and 1.35% of iron oxide yellow (TAROX synthetic iron oxide YP 1200P).

The average particle diameter, thickness and flatness of the obtained product 15 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 17 μm, an average thickness of 1.5 μm and a flatness (average particle diameter/average thickness) of 11.3. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 16

Production of stearic acid-treated titanium dioxide/iron oxide composite highly-flat cellulose powder (16):

in the same manner as in example 14, 57% of refined wood pulp-derived cellulose powder (W-400G), 3% of stearic acid instead of ceramide, 38.2% of titanium dioxide (TITANIX JR-800), 0.45% of red iron oxide (TAROXR-516P) and 1.35% of yellow iron oxide (TAROX synthetic iron oxide YP1200P) were used to obtain stearic acid-treated titanium dioxide-iron oxide composite highly flat cellulose powder (product 16).

The obtained product 16 was measured for average particle diameter, thickness and flatness in the same manner as in example 1(2), and found to be a flat powder having an average particle diameter of 17 μm, an average thickness of 1.1 μm and a flatness (average particle diameter/average thickness) of 15.5. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 17

Production of ceramide-treated titanium dioxide/iron oxide composite highly flat cellulose powder (17):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed to 0.1% or less by drying under reduced pressure at 40 ℃ and the obtained cellulose powder (41.3g) was charged into a sealable alumina grinding vessel (volume 500mL) together with alumina grinding balls, and further, 0.7g of Ceramide (Ceramid II, manufactured by Wako pure chemical industries, Ltd.), 25.9g of titanium dioxide (manufactured by TITANIX JR-800TAYCA Co., Ltd.), 0.525g of red iron oxide (manufactured by TAROX R-516P Titan Kogyo Co., Ltd.), and 1.575g of yellow iron oxide (manufactured by TAROX synthetic iron oxide YP1200P Titan Kogyo Co., Ltd.) were added. Thereafter, the mixture was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a ceramide-treated titanium dioxide/iron oxide composite high-aspect cellulose powder (product 17).

The average particle diameter, thickness and flatness of the obtained product 17 were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 17 μm, an average thickness of 1.5 μm and a flatness (average particle diameter/average thickness) of 11.3. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Comparative example 1

Ceramide-treated high-platy cellulose powder/titanium dioxide:

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (63.3g) was charged into a sealable alumina grinding vessel (volume 500mL) together with alumina grinding balls, and 0.7g of Ceramide (Ceramid II and Wako pure chemical industries, Ltd.) was further added. Thereafter, the resulting mixture was pulverized at a rotation speed of 200rpm (a pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a ceramide-treated flat cellulose powder. Then, the obtained ceramide-treated high-flaked cellulose powder (60g), titanium dioxide (TiTANIX JR-800 TAYCA), iron oxide red (TAROX R-516P Titan Kogyo Co., Ltd.) 1.25g, and iron oxide yellow (TAROX synthetic iron oxide YP1200P Titan Kogyo Co., Ltd.) 8.75g were mixed by a Henschel mixer (comparative product 1) for 10 minutes to obtain a ceramide-treated high-flaked cellulose powder/titanium dioxide-iron oxide mixture.

The average particle diameter, thickness and flatness of the comparative product 1 thus obtained were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 19 μm, an average thickness of 1.4 μm and a flatness (average particle diameter/average thickness) of 13.6.

Comparative example 2

Production of ceramide-treated highly flat cellulose powder/titanium dioxide/iron oxide mixture (2):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (63.3g) was charged into a sealable alumina grinding vessel (volume 500mL) together with alumina grinding balls, and 0.7g of Ceramide (Ceramid II and Wako pure chemical industries, Ltd.) was further added. Thereafter, the resulting mixture was pulverized at a rotation speed of 200rpm (a pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a ceramide-treated flat cellulose powder. Then, the obtained ceramide-treated flat cellulose powder (60g), titanium dioxide (TITANIXJR-800 TAYCA), iron oxide red (TAROX R-516P Titan Kogyo Co., Ltd.) 0.75g, and iron oxide yellow (TAROX synthetic iron oxide YP1200P Titan Kogyo Co., Ltd.) 2.25g were mixed for 10 minutes by a Henschel mixer to obtain a ceramide-treated high flat cellulose powder/titanium dioxide-iron oxide mixture (comparative product 2).

The average particle diameter, thickness and flatness of the comparative product 2 thus obtained were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 19 μm, an average thickness of 1.4 μm and a flatness (average particle diameter/average thickness) of 13.6.

Comparative example 3

Production of lauroyl lysine-treated high-platy cellulose powder/particulate titanium dioxide mixture (3):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (63.3g) was charged into a sealable alumina grinding vessel (500 mL in volume) together with alumina grinding balls, and 0.7g of lauroyl lysine (manufactured by Amihope LL K.K.) was further added. Thereafter, the resulting mixture was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a lauroyl lysine-treated high-platy cellulose powder. Subsequently, the obtained lauroyl lysine-treated flat cellulose powder (60g) and fine titanium dioxide (12g) produced by TTO-S-4 Shigaku Kogyo Co., Ltd.) were mixed in a Henschel mixer (manufactured by Mitsui Kaisha) for 10 minutes to obtain a lauroyl lysine-treated high flat cellulose powder/fine titanium dioxide mixture (comparative product 3).

The average particle diameter, thickness and flatness of the comparative product 3 thus obtained were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 19 μm, an average thickness of 1.4 μm and a flatness (average particle diameter/average thickness) of 13.6.

Comparative example 4

Production of lauroyl lysine-treated high-platy cellulose powder/fine particle zinc oxide mixture (4):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (63.3g) was charged into a sealable alumina grinding vessel (500 mL in volume) together with alumina grinding balls, and 0.7g of lauroyl lysine (manufactured by Amihope LL K.K.) was further added. Thereafter, the resulting mixture was pulverized at a rotation speed of 200rpm (pulverization energy of about 10G (gravitational acceleration)) for 40 minutes by using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a lauroyl lysine-treated high-platy cellulose powder. Subsequently, the obtained lauroyl lysine-treated flat cellulose powder (60g) and fine zinc oxide (ZnO-610, manufactured by saka cement corporation) (12g) were mixed by a henschel mixer for 10 minutes to obtain a mixture of the lauroyl lysine-treated high flat cellulose powder and the fine zinc oxide (comparative product 4).

The average particle diameter, thickness and flatness of the comparative product 4 thus obtained were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 19 μm, an average thickness of 1.4 μm and a flatness (average particle diameter/average thickness) of 13.6.

Comparative example 5

Production of hydrogenated lecithin-treated high-aspect cellulose (5):

cellulose powder derived from refined wood pulp (Nippon Paper Chemicals, W-400G) was used as a raw material. First, the adsorbed water was sufficiently removed by drying under reduced pressure at 40 ℃ to 0.1% or less, and the obtained cellulose powder (63.3g) was charged into a sealable alumina grinding vessel (capacity 500mL) together with alumina grinding balls, and 0.7g of hydrogenated lecithin (manufactured by Lecinol S-10Nikko Chemicals) was further added. Thereafter, the resultant was pulverized at a rotation speed of 200rpm (a pulverization energy of about 10G (gravitational acceleration)) for 40 minutes using a planetary ball mill (Sansho Industry co., Ltd.) to obtain a hydrogenated lecithin-treated high-tabular cellulose powder (comparative product 5).

The average particle diameter, thickness and flatness of the comparative product 5 thus obtained were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 19 μm, an average thickness of 1.4 μm and a flatness (average particle diameter/average thickness) of 13.6.

Comparative example 6

Titanium dioxide/iron oxide composite cellulose powder (6):

60 mass% of cellulose powder (W-400G) derived from refined wood pulp was taken into a planetary ball mill (Sansho industry Co., Ltd.), 38.2% of titanium dioxide (TITANIX JR-800), 0.45% of red iron oxide (TAROXR-516P) and 1.35% of yellow iron oxide (TAROX synthetic iron oxide YP1200P) were added thereto, and the mixture was pulverized at a rotation speed of 200rpm (a pulverization energy of about 10G (gravitational acceleration)) for 40 minutes to obtain a titanium dioxide-iron oxide composite cellulose powder (comparative product 6).

The average particle diameter, thickness and flatness of the comparative product 6 thus obtained were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 18 μm, an average thickness of 2.0 μm and a flatness (average particle diameter/average thickness) of 9.0. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Comparative example 7

Polysiloxane-treated titanium dioxide/iron oxide composite sericite (7):

60 mass% of dimethylpolysiloxane 3% treated Sericite (SA series FSE, manufactured by sanko chemical industries, Ltd.) was put into a planetary ball mill (Sansho Industry co., Ltd.), 38.2% of titanium dioxide (TITANIXJR-800), 0.45% of red iron oxide (TAROX R-516P) and 1.35% of yellow iron oxide (TAROX synthetic iron oxide YP1200P) were added thereto, and the mixture was pulverized at a rotation speed of 200rpm (about 10G of pulverization energy) for 40 minutes to obtain polysiloxane-treated titanium dioxide-iron oxide composite Sericite (comparative product 7).

The average particle diameter, thickness and flatness of the comparative product 7 thus obtained were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 7.0 μm, an average thickness of 1.0 μm and a flatness (average particle diameter/average thickness) of 7.0. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Comparative example 8

Polysiloxane-treated titanium dioxide-iron oxide composite talc (8):

60 mass% of dimethylpolysiloxane 2% treated Talc (SA Talc JA-68R; manufactured by Sansho Industry Co., Ltd.) was taken out into a planetary ball mill (Sansho Industry Co., Ltd.), 38.2% of titanium dioxide (TITANIXJR-800), 0.45% of red iron oxide (TAROX R-516P) and 1.35% of yellow iron oxide (TAROX synthetic iron oxide YP1200P) were added thereto, and the mixture was pulverized at a rotation speed of 200rpm (about 10G (gravitational acceleration) as pulverization energy) for 40 minutes to obtain a silicone-treated titanium dioxide-iron oxide composite Talc (comparative product 8).

The average particle diameter, thickness and flatness of the comparative product 8 thus obtained were measured in the same manner as in example 1(2), and as a result, it was a flat powder having an average particle diameter of 7.0 μm, an average thickness of 0.7 μm and a flatness (average particle diameter/average thickness) of 10.0. The particle diameter of the metal oxide after the composite formation is substantially the same as the particle diameter before the composite formation.

Example 18

UV screening test (1):

the UV shielding ability of the fine-particle titanium dioxide composite high-aspect cellulose powders (product 1 and product 2) produced in examples 1 and 2 was examined. In the experiment, 0.04g of each powder was measured at 1mg/cm²Uniformly applied to a Transpore tape (5 cm. times.8 cm), and the UV-shielding ability in the 300nm-450nm region was measured using an SPF analyzer (manufactured by Sanyo trade Co., Ltd.). For comparison, comparative product 3 was used. The results are shown in Table 1.

TABLE 1

Test specimen	SPF	UVA transmittance (%)	UVB transmittance (%)
				Article 1	19.41	21.55	4.07
Article 2	33.29	13.07	2.43
				Comparative product 3	4.31	66.7	74.3

As shown in table 1, the SPF values of the products 1 and 2 of the present invention are about 5 times or more higher than that of the highly flat cellulose powder (comparative product 3) containing fine titanium dioxide, and the powder is excellent in UV shielding ability.

Example 19

UV screening test (2):

the UV shielding ability of the fine-particle zinc oxide-composited high flat cellulose powders (products 6 to 9) produced in examples 6 to 9 was examined in the same manner as in example 18. For comparison, comparative product 4 was used. The results are shown in Table 2.

TABLE 2

Test specimen	SPF	UVA transmittance (%)	UVB transmittance (%)
				Article 6	6.17	23.45	15.87
Article 7	10.96	16.24	8.86
				Article 8	13.59	13.79	7.08
Article 9	12.76	13.84	7.68
				Comparative product 4	3.41	43.61	29.22

As shown in table 2, the SPF value of the product 6 of the present invention was about 2 times or more higher than that of the highly flat cellulose powder (comparative product 4) containing fine zinc oxide particles, and the SPF values of the products 7 to 9 were about 3 times or more higher than that of the product.

Example 20

Color variability test:

with respect to the powders prepared in examples 15 and 16 and comparative examples 6 to 8, the color variability thereof was tested.

First, each powder was thoroughly mixed with the same weight of oil (glycerol tris (2-ethylhexanoate)) with a spatula to prepare a test sample. The sample to be measured and the powder itself thus produced were filled in a glass dish, and then the color values (a value: red/b value: yellow) were measured by a spectrocolorimeter SE-2000 (manufactured by Nippon Denshoku industries Co., Ltd.).

Among these color values, differences (Δ a and Δ b) between the a value (a1) and the b value (b1) of the pigment itself and the a value (a2) and the b value (b2) of the oil-blended pigment were obtained, and the overall color variability was obtained from these values by the following equation. Based on this color variability, the color variability was evaluated according to the following criteria. The results are shown in Table 3.

Color variability = √ (Δ a)²+(Δb)²)

Wherein Δ a is the difference between a1 and a2, and Δ b is the difference between b1 and b 2.

(evaluation criteria)

Color variability: evaluation of

0 or more and 1.5 or less: very good

More than 1.5 and 2.0 or less: o-

More than 2.0 and 2.5 or less: delta

More than 2.5 to: is prepared from

TABLE 3

As shown in table 3, the products 15 and 16 of the present invention are excellent because they show little change in color even when mixed with oil. In contrast, comparative product 6 in which no grinding aid was used, comparative product 7 in which dimethylpolysiloxane-treated sericite was a mother powder, and comparative product 8 in which dimethylpolysiloxane-treated talc was a mother powder were inferior to those in that the color changed greatly when they were mixed with oil even when the amounts of titanium dioxide and iron oxide were the same.

Example 21

Foundation (1):

foundations of the cosmetic compositions 1 to 5 of the present invention were prepared by using the fine particle titanium dioxide composite high-flattening cellulose powders (products 1 to 5) produced in examples 1 to 5, according to the formulation shown in table 4 and the following method. The foundation was examined for UV-screening ability, SPF value, uniformity of cosmetic film, natural makeup (no powder white), makeup retention, stability (presence or absence of aggregates), and feeling of use (smooth feeling upon application) by the following methods. For comparison, a powder (comparative cosmetic 1) using mica (mica 58.5%, titanium dioxide 40%, iron oxide 1.5%) coated with fine-particle titanium dioxide (manufactured by SPS-LTF TAYCA corporation) and a powder (comparative cosmetic 2) using a mixture (comparative product 3) of high-aspect cellulose powder and fine-particle titanium dioxide were used. The results are also shown in Table 4.

TABLE 4

(production method)

The components 1 to 18 were mixed for 10 minutes in a Henschel mixer, and then the components 19 to 23 were added and stirred for 5 minutes. Thereafter, the mixture was pulverized by a nebulizer (1HP mesh diameter: 1.5 mm. phi.) and filled in a resin pan to obtain a foundation.

(test method)

UV shielding ability and SPF value:

the UV-screening ability of the foundations made with the cosmetic compositions 1 to 5 of the present invention and the comparative cosmetic compositions 1 and 2 was examined. In the experiment, 0.04g of each powder was uniformly applied to a Transpore band (5 cm. times.8 cm) at 1mg/cm2, and the UV-shielding ability in the 300nm-450nm region was measured using an SPF analyzer (manufactured by Sanyo trade Co.). The evaluation was performed by the following judgment.

Evaluating content

Very good: the SPF is 25 or more.

O: the SPF is 20 or more and less than 25.

And (delta): the SPF is 15 or more and less than 20.

X: the SPF is less than 15.

"uniformity of cosmetic film", "natural makeup (powder-free white)", "makeup retention (adhesion and no color change)" and "feeling of use":

with 20 cosmetic evaluation panelists who used foundations of the cosmetic compositions 1 to 5 of the present invention and the comparative cosmetic compositions 1 and 2, 7 grades of evaluation were performed for "uniformity of cosmetic film", "natural makeup (no powder white)", "cosmetic retention (adhesion and no color change)" and "feeling of use" on the basis of the following evaluation criteria, and each sample was scored. Next, each product was judged by the average score of the total staff score according to the following judgment criteria. The "feel in use" was evaluated as the smoothness during application.

Evaluating a standard;

(evaluation): (Contents)

6: is very good

5: good taste

4: slightly better

3: general purpose

2: a little bit worse

1: difference (D)

0: very poor

Judging a reference;

(average score of scores): (judgment)

5.0 or more: very good (very good)

3.5 or more and less than 5.0: good (good)

1.5 or more and less than 3.5: delta (slightly poor)

Less than 1.5: x (bad)

Stability (presence or absence of aggregates):

the stability was evaluated for the presence of aggregates. The surface condition of the makeup bases of the present invention cosmetics 1 to 5 and comparative cosmetics 1 and 2 molded on the resin plate was visually observed 20 times with a cosmetic sponge. The evaluation was performed by the following judgment.

Evaluating content

Very good: no agglomerates were observed.

O: aggregates were observed, but the amount was small.

And (delta): aggregates were observed in large amounts.

X: large aggregates were observed, and the amount thereof was large.

As shown in table 4, the foundations of the cosmetic compositions 1 to 5 of the present invention have high SPF values and excellent UV shielding ability, and are excellent in all items of cosmetic film uniformity, natural makeup (no powder white), cosmetic retainability (adhesion and no color change), stability (presence or absence of aggregates), and feeling of use (smooth feeling upon application).

On the other hand, the foundation of comparative cosmetic 1 in which product 1 of cosmetic 1 of the present invention was replaced with conventional fine particle titanium dioxide composite mica was observed to be aggregated, and the cosmetic film had poor uniformity, natural makeup, and the like. Moreover, the product 1 of the cosmetic composition 1 of the present invention was replaced with the comparative product 2 of the comparative product 3, and all items such as the low SPF value, the poor UV-shielding ability, and the feeling of use (smooth feeling upon application) were poor.

Example 22

Foundation (2):

foundations of the cosmetic materials 6 to 9 of the present invention were prepared using the fine-particle zinc oxide-composited high-flattening cellulose powder produced in examples 6 to 9, according to the formulation shown in table 5 and the following method. The UV-shielding ability, SPF value, uniformity of cosmetic film, natural makeup (no powder white), makeup retentivity, feeling of use, and stability of this foundation were examined in the same manner as in example 21. For comparison, a powder (comparative cosmetic material 3) using a mica/barium sulfate composite (mica 40%, zinc oxide 50%, barium sulfate 10%) coated with fine zinc oxide particles (manufactured by rohannair SHADELEAF A merck) and a powder (comparative cosmetic material 4) using a mixture (comparative product 4) of high-flattening cellulose powder and fine zinc oxide particles were used. The results are also shown in Table 5.

TABLE 5

(production method)

The components 1 to 17 were mixed for 10 minutes in a Henschel mixer, and then the components 18 to 22 were added and stirred for 5 minutes. Thereafter, the mixture was pulverized by a nebulizer (1HP mesh diameter: 1.5 mm. phi.) and filled in a resin pan to obtain a foundation.

As shown in table 5, the foundations of the cosmetic compositions 6 to 9 of the present invention have high SPF values and excellent UV shielding ability, and are excellent in all items of uniformity of cosmetic film, natural makeup (no powdery white), makeup retainability, stability (presence or absence of aggregates), and feeling of use (smooth feeling upon application).

On the other hand, foundation of comparative cosmetic 3 in which product 6 of cosmetic 6 of the present invention was replaced with mica/barium sulfate composite powder coated with fine zinc oxide particles, was observed to be aggregated, and had poor cosmetic film uniformity, natural makeup appearance, and the like. Further, the product 6 of the cosmetic preparation 6 of the present invention was replaced with the comparative product 4 of the comparative product 4, and the foundation had a low SPF value, poor UV-screening ability, and poor feeling in use (smooth feeling upon application).

Example 23

Foundation (3):

foundations of the cosmetics 10 to 13 of the present invention were prepared by using the titanium dioxide composite high-flattening cellulose powders (products 10 to 13) produced in examples 10 to 13, according to the formulation shown in table 6 and the following method. The concealing properties of this foundation were examined by the following methods, and the uniformity, makeup retentivity and feeling of use of the makeup film were examined in the same manner as in example 21. For comparison, powders prepared by separately blending a highly flat cellulose powder and titanium dioxide (comparative cosmetics 5 and 6) were used. The results are also shown in Table 6.

TABLE 6

(production method)

After mixing components 1 to 16 for 10 minutes in a Henschel mixer, components 17 to 19 were added and stirred for 2 minutes. Thereafter, the mixture was pulverized by a nebulizer (1HP mesh diameter: 1.5 mm. phi.) and filled in a resin pan to obtain a foundation.

(test method)

Concealment:

to evaluate the "hiding properties" of 20 cosmetic evaluation panelists using foundations of the cosmetic materials 10 to 13 of the present invention and the comparative cosmetic materials 5 and 6, 7 grades of evaluation were performed on each sample according to the following evaluation criteria. Next, each product was judged by the average score of the total staff score according to the following judgment criteria.

Evaluating a standard;

(evaluation): (Contents)

6: is very good

5: good taste

4: slightly better

3: general purpose

2: a little bit worse

1: difference (D)

0: very poor

Judging a reference;

(average score of scores): (judgment)

5.0 or more: very good (very good)

3.5 or more and less than 5.0: good (good)

1.5 or more and less than 3.5: delta (slightly poor)

Less than 1.5: x (bad)

As shown in table 6, the foundations of the cosmetic compositions 10 to 13 of the present invention are excellent in all items of uniformity, concealing properties, makeup retention properties, and feeling of use (smooth feeling at the time of application).

On the other hand, comparative cosmetic preparation 5 in which titanium dioxide having substantially the same mass as that of cosmetic preparation 10 of the present invention was blended with other components without treatment exhibited poor dispersion of titanium dioxide, poor cosmetic retainability, and poor concealing and use feeling (smooth feeling upon application). In addition, comparative cosmetic material 6 containing titanium dioxide in an amount twice the amount exhibited hiding properties, but had poor feeling in use (smooth feeling upon application), uniformity of cosmetic film, and cosmetic retention properties.

Example 24

Foundation (4):

using the titanium dioxide. Color development of this foundation was examined by the following method, and uniformity, makeup retentivity, and feeling of use of the makeup film were examined in the same manner as in example 21.

TABLE 7

(production method)

The components 1 to 13 were mixed for 10 minutes in a Henschel mixer, and then the components 14 to 16 were added and stirred for 3 minutes. Thereafter, the mixture was pulverized by a nebulizer (1HP mesh diameter: 1.5 mm. phi.) and filled in a resin pan to obtain a foundation.

(test method)

Color rendering property:

to 20 cosmetic evaluation panelists were asked to rate the "color development" of each of the cosmetics 14 to 15 of the present invention and the foundations of the comparative cosmetics 7 and 8 on a 7-grade basis according to the following evaluation criteria, and each sample was scored. Next, each product was judged by the average score of the total staff score according to the following judgment criteria.

Evaluating a standard;

(evaluation): (Contents)

6: is very good

5: good taste

4: slightly better

3: general purpose

2: a little bit worse

1: difference (D)

0: very poor

Judging a reference;

(average score of scores): (judgment)

5.0 or more: very good (very good)

3.5 or more and less than 5.0: good (good)

1.5 or more and less than 3.5: delta (slightly poor)

Less than 1.5: x (bad)

As shown in table 7, the foundations of the cosmetic materials 14 and 15 of the present invention are excellent in all items of uniformity of cosmetic film, concealing property, makeup retainability, and feeling of use (smooth feeling at the time of application).

In contrast, comparative cosmetics 7 and 8, which contained a mixture obtained by mixing titanium dioxide, iron oxide and cellulose powder, were particularly inferior in color developability and cosmetic retainability.

Example 25

Foundation (5):

using the fine-particulate zinc oxide-compounded high-flattening cellulose powder (product 7) produced in example 7, a foundation of cosmetic material 16 of the present invention was prepared using the recipe of table 8 and the method described below. The SPF value of this foundation was examined by the following method, and the UV-shielding ability, the uniformity of the cosmetic film, the natural makeup (no powdery white), the cosmetic retentivity, the stability (presence or absence of aggregates), and the feeling of use (smooth feeling upon application) were examined in the same manner as in example 21. As a comparison, a cosmetic material (comparative cosmetic material 9) using a mixture of the flat cellulose powder of comparative example 4 and fine zinc oxide particles was used. The results are shown in Table 8.

(production method)

A: the components 1 to 12 were mixed for 10 minutes by a Henschel mixer.

B: the components 13 to 18 were added to A and mixed for 4 minutes.

C: b was pulverized by a nebulizer (1HP mesh diameter 1.5 mm. phi.).

D: 60 parts of light liquid paraffin and 100 parts of C were mixed, filled in a resin pan, and then dried at 70 ℃.

(actual SPF value)

Evaluation was performed by the following method based on "SPF measurement standards (revised 2007)" stipulated by the japan cosmetic industry association.

First, 10 subjects were selected from healthy men and women aged 18 to 60 years old inclusive who were fit in Fitzpatrick skin types I, II, and III (with the exception of a person who was asked for a diagnosis of photosensitivity and a person who took drugs (anti-inflammatory agents, hypotensive agents, etc.) related to photosensitivity of the skin). The part to be measured is selected to be a part of the back of the subject having a substantially uniform skin color, such as a non-pigmented part or a birthmark. A test sample was applied to 50cm2 of the test site. The coating weight was 2.00mg/cm²±2.5%/cm²。

The test sample application part of the subject was irradiated with ultraviolet LIGHT using a xenon arc SOLAR simulator (manufactured by SOLAR LIGHT Co., Ltd.) as a LIGHT source. The xenon arc simulator has continuous spectrums similar to sunlight in UV-B and UV-A areas with the wavelength of 290-400 nm. In addition, ultraviolet rays having a wavelength of 290nm or less are removed as much as possible by using an optical filter.

After 16 to 24 hours after the irradiation with ultraviolet light, the occurrence of erythema at the ultraviolet-irradiated site was examined in a sufficiently bright room. The minimum ultraviolet irradiation dose at which a sharp and slight erythema is first induced at a site above 2/3 of the irradiated site was defined as the Minimum Erythema Dose (MED). The measured SPF values of the subjects were obtained by the following equation using the MED of the sample-to-be-tested coated portion and the non-coated portion, respectively, and the results were arithmetically averaged to obtain the actual SPF value.

SPF value = MED (sample coated portion)/MED (sample uncoated portion)

TABLE 8

Note 3: SPS-LTF (manufactured by TAYCA)

Note that a RONAFLAIR BLANCSEALER (manufactured by Merck)

Note b KSG-16 (manufactured by shin-Etsu chemical Co., Ltd.)

Note A that a mixture of 47% titanium dioxide and 47% mica was surface-treated with 6% zinc laurate.

Note B KSP-101 (manufactured by shin-Yue chemical industries Co., Ltd.)

Note C3% treatment with perfluorohexylethyltriethoxysilane (manufactured by Dadonghua chemical Co., Ltd.)

As shown in table 8, the foundation of cosmetic 16 of the present invention has a higher SPF measured value than comparative cosmetic 9, has excellent UV shielding ability, and is excellent in all items of cosmetic film uniformity, natural makeup (no powdery white), makeup retention (adhesion and no color change), stability (presence or absence of aggregates), and feeling of use (smooth feeling upon application).

On the other hand, comparative cosmetic preparation 9 obtained by replacing product 7 of cosmetic preparation 16 of the present invention with a lauroyl lysine-treated high-platy cellulose powder/fine-particle zinc oxide mixture had a slightly low SPF measured value and UV shielding ability, and was inferior in all items such as feeling of use (smooth feeling at the time of application).

Example 26

Foundation make-up (6)

Using the pigments of the product 14 prepared in example 14 and the product 15 prepared in example 15, a foundation (formulations 1 to 3) was produced by the following method according to the composition described in table 9 below. For comparison, a powder using iron oxide without special treatment (comparative formula) was used. In the total amount of iron oxide in each formulation in this example, composition 1 was the same as the amount of the comparative formulation (100%), and compositions 2 and 3 were 80% of the comparative formulation.

TABLE 9

Note that aRONAFLAIR BLANCSEALER (manufactured by Merck)

Note bKSG-16 (manufactured by shin & Yue chemical industries Co., Ltd.)

Note A is a mixture of 47% titanium dioxide and 47% mica which was surface-treated with 6% zinc laurate.

3% treatment with perfluorohexylethyltriethoxysilane (manufactured by Dadong chemical industry Co., Ltd.)

Note 3SPS-LTF (manufactured by TAYCA)

< production method >

A: the components 1 to 13 were mixed for 10 minutes by a Henschel mixer.

B: adding 14-20 parts of the component A to the component A, and mixing for 5 minutes.

C: b was pulverized by a nebulizer (1HP mesh diameter 1.5 mm. phi.).

D: 60 parts of light liquid paraffin and 100 parts of C were mixed, filled in a resin pan, and then dried at 70 ℃.

The obtained compositions were examined for "color developability", "makeup retention (no color sinking)", and "makeup retention (adhesion)". The makeup retention property (adhesion property) was examined in the same manner as in example 21. Further, regarding "color developability", each foundation in a state molded by the above-described manufacturing method was used, and regarding "cosmetic retainability (no color sink)", each foundation was applied to the inner side of the upper arm, and for each appearance color, a and b or L, a and b were measured by using a spectrocolorimeter SE-2000 (manufactured by japan electrical appliances industries, inc.) and evaluated by the following calculation. The results are shown in Table 10.

Color rendering property:

for each recipe, the measured values of a and b are compared with the values of a and b (as and bs) of the comparative recipe, and the difference (Δ a and Δ b) is determined. The squares of Δ a and Δ b are added, and the value is squared, and this value is used as the evaluation value of "color rendering". The evaluation values were evaluated as "x" in 1 or more, 0.5 or more and less than 1, 0.25 or more and less than 0.5, and 0.25 or less than 0.5.

Cosmetic hold (no color dip):

the values of L, a and b were determined for the appearance of the inventive and comparative formulations immediately after coating and 2 hours after coating. The difference (. DELTA.L) between the measured values of each formulation immediately after coating and 2 hours after coating was taken_0-2、Δa_0-2And Δ b_0-2) After adding them, the square is squared. This value was used as an evaluation value of "makeup retention (no color dip)". Regarding the evaluation value, 0 or moreAnd 1 or less was evaluated as ∈, more than 1 and 1.5 or less was evaluated as ≈ o, more than 1.5 and 2 or less was evaluated as Δ, and more than 2 was evaluated as ×.

Watch 10

As shown in table 10, using the product 14 of example 14, the color development of formulation 1 in which iron oxide of the same quality as the comparative formulation was added to the entire formulation was improved, the color deposition after 2 hours of coating was small, and the adhesion was excellent, as compared to the comparative formulation. In addition, in the case of the formula 2 in which the amount of iron oxide mixed is reduced from the formula 1 and the amount of iron oxide mixed is 80% of the comparative formula, the amount of iron oxide mixed is smaller than that of the comparative formula, but the color developing property is excellent as compared with the comparative formula, and other items are also excellent. In formulation 3 in which the product 15 of example 15 was used and the amount of iron oxide mixed was 80% of the comparative formulation in the same manner as in formulation 2, the color developing property was also good, and the other items were also excellent.

Example 27

Two-layer toning lotion:

a two-layer type cosmetic lotion having the following composition was produced by the following method.

Note 1) Nikkol DDP-8 (manufactured by Nihon surfactant kogyo K.K Co., Ltd.)

Note 2) EMALEX RWIS-150(Nihon Emulsion Co., Ltd.)

(preparation method)

(1) Mixing the components 1-3.

(2) Adding 4-9 components into the mixture obtained in the step (1), and uniformly stirring to obtain the two-layer type toning lotion.

The obtained two-layer lotion is excellent in powder dispersibility, smooth feeling in use, and uniformity of cosmetic film.

Example 28

Emulsion:

an emulsion having the following composition was produced by the following method.

Note 3) KF-96(10CS) (manufactured by shin-Etsu chemical Co., Ltd.)

Note 4) CARBOPOL1342 (manufactured by LUBRIZOL ADVANCED MATERIALS Co., Ltd.)

(preparation method)

(1) The components 1-7 are mixed evenly at 80 ℃.

(2) Uniformly mixing the components 8-14 at 80 ℃.

(3) Adding (2) to (1) and emulsifying.

(4) The emulsion (3) was cooled while being stirred, and after adding component 15, the mixture was uniformly mixed to obtain an emulsion.

The obtained emulsion is excellent in emulsion stability, smooth feeling in use, uniformity of cosmetic film, and UV shielding ability.

Example 29

And (3) cream:

a cream having the following composition was produced by the following method.

(preparation method)

(1) The components 1-7 are mixed evenly at 80 ℃.

(2) Uniformly mixing the components 8-13 at 80 ℃.

(3) Adding (2) to (1) and emulsifying.

(4) Cooling the mixture of (3) while stirring to obtain cream.

The obtained cream has excellent emulsion stability, smooth feeling in use, uniformity of cosmetic film, and UV shielding ability.

Example 30

Cosmetic liquid:

a cosmetic liquid having the following composition was produced by the following method.

(preparation method)

(1) Mixing and dissolving the components 1-10 at normal temperature, and stirring to obtain the beauty solution.

The obtained cosmetic liquid has excellent stability, smooth feeling in use, uniformity of cosmetic film, and UV shielding ability.

Example 31

Face pack:

a facial mask having the following composition was produced by the following method.

(preparation method)

(1) The components 1-4 are mixed evenly at 80 ℃.

(2) The components 5-12 are mixed evenly at 80 ℃.

(3) Adding (2) to (1) and emulsifying.

(4) Cooling the mixture of (3) while stirring to obtain the facial mask.

The obtained face mask has excellent emulsion stability, smooth feeling in use, and excellent uniformity of the cosmetic film.

Example 32

Washing the face cream:

a face wash having the following composition was produced by the following method.

(preparation method)

(1) The components 1-7 are mixed evenly at 80 ℃.

(2) The components 8-11 are mixed evenly at 80 ℃.

(3) Adding (2) to (1) and neutralizing.

(4) Component (3) was added with component (12) and mixed homogeneously.

(5) And (4) cooling the mixture while stirring to obtain the face wash.

The obtained face wash is smooth and has excellent feeling in use.

Example 33

Cleaning cream:

a cleansing cream having the following composition was produced by the following method.

(preparation method)

(1) The components 1-8 are mixed evenly at 80 ℃.

(2) The components 9-14 are mixed evenly at 80 ℃.

(3) Adding (1) to (2) and emulsifying.

(4) And (4) cooling the mixture obtained in the step (3) while stirring the mixture to obtain the cleansing cream.

The obtained cleansing cream is excellent in emulsion stability and smooth feeling in use.

Example 34

Waxing:

hair wax having the following composition was produced by the following method.

Note 5) Nikkol MYS-40V (manufactured by Nihon surfactant kogyo K.K Co., Ltd.)

(preparation method)

(1) The components 1-3 are mixed evenly at 80 ℃.

(2) The components 4-8 are mixed evenly at 80 ℃.

(3) Adding (2) to (1) and emulsifying.

(4) Adding 9-16 of the components to (3), and cooling while stirring to obtain the hair wax.

The obtained hair wax is excellent in emulsion stability, hair styling property, smooth feeling in use, and UV shielding ability.

Example 35

Oily eyeliner:

an oil-based eyeliner having the following composition was produced by the following method.

Note 6) SA-BLACK BL-100(100%) (manufactured by Sanhao Kaisha)

Note 7) SA-Talc JA-13R (manufactured by Sanhao Kaisha)

(preparation method)

(1) Heating the components 1-4 to 100 ℃, and uniformly mixing.

(2) Heating the components 5-9 to 80 ℃, and uniformly mixing.

(3) Adding (2) to (1), and uniformly mixing.

(4) And (4) treating the (3) by using a roller to obtain the oily eyeliner.

The obtained oily eyeliner has smooth feeling, uniform cosmetic film, and excellent cosmetic lasting effect.

Example 36

An aqueous eyeliner:

an aqueous eyeliner having the following composition was produced by the following method.

Note 8) Nikkol DDP-6 (manufactured by Nihon surfactant kogyo K.K Co., Ltd.)

Note 9) Nikkol BC-20TX (manufactured by Nihon surfactant kogyo K.K Co., Ltd.)

Note 10) YODOSOL32A707(45% solid content) (manufactured by NSC corporation, Japan)

(preparation method)

(1) Uniformly dispersing the components 1 to 5 by using a roller.

(2) Uniformly mixing the components 6-10.

(3) Adding the mixture (1) into the mixture (2), and uniformly mixing to obtain the water-based eyeliner.

The obtained aqueous eyeliner is smooth in use feeling, uniform in cosmetic film, and excellent in cosmetic lasting effect.

Example 37

Eyebrow pencil:

the eyebrow pencil having the composition shown below was manufactured by the following method.

(preparation method)

(1) Uniformly mixing the components 1-4.

(2) The components 5 to 10 are treated by a roller.

(3) Adding the components (2), (11) and (12) into the mixture (1), and uniformly mixing to obtain the eyebrow pencil.

The obtained eyebrow pencil has smooth use feeling, uniform cosmetic film, and excellent cosmetic effect.

Example 38

O/W type mascara:

an O/W type mascara having the following composition was produced by the following method.

(preparation method)

(1) The components 1-8 are uniformly mixed at 80 ℃ and subjected to roller treatment.

(2) The components 9-14 are mixed evenly at 80 ℃.

(3) Adding (2) to (1) and emulsifying.

(4) And (4) cooling the (3) to obtain mascara (O/W).

The obtained O/W type mascara has excellent powder dispersibility, smooth feeling in use, uniform cosmetic film, and excellent makeup sustaining effect.

Example 39

Nonaqueous mascara:

a nonaqueous mascara having the following composition was produced by the following method.

Note 11) BENTONE38V BC (manufactured by Elementis Co., Ltd.)

(preparation method)

(1) Heating the components 1-5 to 110 ℃.

(2) Adding 6-9 of the components to (1) and mixing.

(3) Adding 10-13 of the components to (2) and mixing.

(4) And (4) treating the product (3) by using a roller to obtain the nonaqueous mascara.

The obtained nonaqueous mascara is smooth in use, and excellent in uniformity of a makeup film and makeup sustainability effect.

Example 40

Strip lipstick:

a strip lipstick having the composition shown below was produced by the following method.

Note 12) KF-96(10CS) (manufactured by shin-Etsu chemical Co., Ltd.)

(preparation method)

(1) The components 1-7 are dissolved and mixed evenly at 100 ℃.

(2) Adding 8-13 of the components into the mixture obtained in the step (1), and uniformly mixing.

(3) And (3) filling the mixture obtained in the step (2) into a container, and cooling to obtain the strip lipstick.

The obtained strip-shaped lipstick has smooth use feeling, uniform cosmetic film, and excellent cosmetic lasting effect.

EXAMPLE 41

Annatto milk (リキッドルージュ):

the following procedure was used to produce a rouge milk having the following composition.

(preparation method)

(1) The components 1-5 are uniformly dissolved and mixed at 100 ℃.

(2) Adding 6-12 of the components in the step (1) and uniformly mixing.

(3) And (3) filling the mixture obtained in the step (2) into a container, and cooling to obtain the annatto milk.

The obtained rouge was smooth in use, and had excellent uniformity of the cosmetic film and makeup-sustaining effect.

Example 42

O/W type foundation:

an O/W type foundation having the following composition was produced by the following method.

Note 13) SA-titanium CR-50 (manufactured by Sanhao Kaisha)

Note 14) SA-bengala cloisonne (SA- ベンガラ Qibao) (manufactured by Sanhao Kaisha)

Note 15) SA-yellow lemon (manufactured by Sanhao Kaisha)

(preparation method)

(1) Uniformly dispersing the components 1-8 by using a roller.

(2) Mixing the components 9-12 uniformly.

(3) Adding (1) to (2), and uniformly mixing.

(4) Mixing and dissolving the components 13-19 at 80 ℃.

(5) (4) was added to (3) at 80 ℃ to conduct emulsification.

(6) The powder of type O/W was obtained by cooling the product of (5) and adding the component 20.

The obtained O/W type foundation was excellent in powder dispersibility, smooth feeling in use, uniformity of cosmetic film, concealing property, UV-shielding ability, and makeup-sustaining effect.

Example 43

W/O type foundation:

a W/O type foundation having the following composition was produced by the following method.

Note 16) KF-6026 (manufactured by shin-Etsu chemical Co., Ltd.)

Note 17) KF-6015 (manufactured by shin-Etsu chemical Co., Ltd.)

(preparation method)

(1) Uniformly mixing the components 1-3.

(2) Uniformly dispersing the components 4-11 by using a roller.

(3) Adding (2) to (1), and uniformly mixing.

(4) And (3) adding 12-15 of the components to the mixture, and emulsifying to obtain the W/O foundation.

The obtained W/O foundation was excellent in powder dispersibility, smooth feeling in use, uniformity of cosmetic film, concealing property, UV-shielding ability, and makeup-sustaining effect.

Example 44

O/W type eye color:

an O/W type eye color having the following composition was produced by the following method.

Note 18) SA-Flamenco Gold (manufactured by Sanhao Kaisha)

(preparation method)

(1) The components 1-5 are mixed evenly at 80 ℃.

(2) Adding 6-8 of the component (1) and emulsifying.

(3) Uniformly dispersing the components 9-14 by using a roller.

(4) Adding the component (3) and the component (15) to the component (2) to obtain the O/W type eye color.

The obtained O/W type eye color has excellent powder dispersibility, smooth use feeling, uniformity of cosmetic film, color development property and cosmetic lasting effect.

Example 45

Oily solid foundation:

an oil-based solid foundation having the following composition was produced by the following method.

Note 19) KF-6026 (manufactured by shin-Etsu chemical Co., Ltd.)

(preparation method)

(1) Heating and dissolving the components 7-13 at 90 ℃.

(2) Adding 1-6 of the components into the mixture (1), and uniformly dispersing by using a roller.

(3) Component 14 was added to (2), dissolved at 80 ℃ and then filled in a metal pan to obtain an oil-based solid foundation.

The obtained oil-based solid foundation was excellent in powder dispersibility, smooth feeling in use, uniformity of cosmetic film, UV-shielding ability, and makeup sustainability.

Example 46

Stick concealer:

a stick concealer having the composition shown below was produced by the following method.

(preparation method)

(1) Heating and dissolving the components 1-5 at 90 ℃.

(2) Adding 6-12 of the components into the mixture (1), and uniformly dispersing by using a roller.

(3) The component 13 was added to the mixture of (2), dissolved at 80 ℃ and filled in a container to obtain a stick-like concealer.

The obtained stick concealer is excellent in powder dispersibility, smooth use feeling, uniformity of a makeup film, concealer property, UV shielding ability, makeup lasting effect.

Example 47

Body milk:

body milk having the composition shown below was produced by the following method.

(preparation method)

(1) The components 1-7 are dissolved uniformly at 80 ℃.

(2) Uniformly dissolving the components 8-16 at 80 ℃.

(3) Adding (1) to (2) and emulsifying.

(4) Adding the component 17 into the mixture obtained in the step (3), uniformly mixing, stirring and cooling to obtain the body lotion.

The obtained body lotion is excellent in emulsion stability, smooth feeling in use, uniformity of cosmetic film, UV shielding ability, and cosmetic persistence effect.

Example 48

And (3) conditioner:

the hair conditioner having the composition shown below was produced by the following method.

Note 20) Arquad22-80 (manufactured by LION AKZO)

(preparation method)

(1) The components 1-5 are mixed evenly at 80 ℃.

(2) The components 6-9 are mixed evenly at 80 ℃.

(3) Adding (2) to (1) and emulsifying.

(4) Adding the component 10 into the mixture obtained in the step (3), uniformly mixing, stirring and cooling to obtain the hair conditioner.

The obtained hair conditioner has excellent emulsion stability and smooth feeling in use.

Example 49

And (3) film forming:

a hair mask having the following composition was produced by the following method.

Note 21) BY22-050A (manufactured BY Dow Corning Toray Co., Ltd.)

(preparation method)

(1) The components 1-6 are mixed evenly at 80 ℃.

(2) The components 7-9 are mixed evenly at 80 ℃.

(3) Adding (2) to (1) and emulsifying.

(4) The component 10 was added to the mixture of (3), and after uniform mixing, the mixture was stirred and cooled to obtain a hair film.

The obtained hair mask has excellent emulsion stability and a smooth feeling in use.

Example 50

W/O type sunscreen cream:

sunscreen cream having the composition shown below was produced by the following method.

Note 22) ABIL EM90 (manufactured by EVONIC GOLDSCHMIDT GMBH)

(preparation method)

(1) Uniformly dispersing the components 1 to 5 by using a roller.

(2) Adding 6-9 of the components into the mixture obtained in the step (1), and uniformly mixing.

(3) And (3) adding 10-14 of the components to the (2), and emulsifying to obtain the W/O type sunscreen cream.

The obtained W/O sunscreen cream has excellent powder dispersibility, smooth use feeling, cosmetic film uniformity, UV shielding ability, and cosmetic lasting effect.

Example 51

Nail polish:

nail polish having the composition shown below was produced by the following method.

(preparation method)

(1) And uniformly mixing the components 1-9 to obtain the nail polish.

The obtained nail polish has excellent powder dispersibility, smooth feeling in use, uniform cosmetic film, and excellent lasting effect.

Example 52

Makeup base (make-up):

a base cream having the following composition was produced by the following method.

Note 23) CARBOPOL940 (manufactured by LUBRIZOL ADVANCED MATERIALS Co., Ltd.)

(preparation method)

(1) The components 1-4 are dissolved uniformly at 80 ℃.

(2) The components 5-12 are dissolved uniformly at 80 ℃.

(3) Adding (1) to (2) and emulsifying.

(4) And (4) adding 13-14 of the mixed components in the step (3), and cooling to obtain the sun screen.

The obtained makeup base cream is excellent in emulsion stability, smooth feeling in use, uniformity of a makeup film, UV shielding ability, and makeup sustainability.

Example 53

White powder:

white powders having the following compositions were produced by the following methods.

(preparation method)

(1) Uniformly mixing 1-5 parts of the components and 8-10 parts of the components.

(2) The components 6 and 7 were added to (1) and mixed uniformly.

(3) And (3) crushing the (2) by using a crusher to obtain white powder.

The obtained white powder has excellent powder dispersibility, smooth feeling in use, uniformity of cosmetic film, UV-shielding ability, and cosmetic persistence effect.

Example 54

Solid powder foundation:

a solid powder foundation having the following composition was produced by the following method.

(preparation method)

(1) Uniformly mixing 1-7 parts of the components and 11-13 parts of the components.

(2) Adding 8-10 of the components into the mixture obtained in the step (1), and uniformly mixing.

(3) And (3) crushing the (2) by using a crusher.

(4) The metal plate was filled with (3) to obtain a solid powder foundation.

The obtained solid powder foundation was excellent in powder dispersibility, smooth feeling in use, uniformity of cosmetic film, UV shielding ability, and makeup sustainability.

Example 55

Solid powder type rouge:

a solid powder type rouge having the following composition was produced by the following method.

(preparation method)

(1) Uniformly mixing 1-4 of the components and 7-9 of the components.

(2) The components 5 and 6 were added to (1) and mixed uniformly.

(3) And (3) crushing the (2) by using a crusher.

(4) And (4) filling the powder in the metal plate to obtain the solid powder type rouge.

The obtained solid powder type rouge is excellent in powder dispersibility, smooth feeling in use, uniformity of cosmetic film, UV shielding ability, and cosmetic persistence effect.

Example 56

Solid powder type eye shadow:

a solid powder type eye shadow having the composition shown below was produced by the following method.

(preparation method)

(1) Uniformly mixing 1-6 parts of the components and 10-12 parts of the components.

(2) Adding 7-9 of the components into the mixture obtained in the step (1), and uniformly mixing.

(3) And (3) crushing the (2) by using a crusher.

(4) The metal plate was filled with (3) to obtain a solid powder foundation.

The obtained solid powder-type eye shadow is a foundation excellent in powder dispersibility, smooth feeling in use, uniformity of cosmetic film, color developability, and makeup sustainability.

Industrial applicability

In the metal oxide-composited highly-flattened cellulose powder of the present invention, the base cellulose itself is an organic substance, is flattened, and the surface thereof is composited with extremely fine metal oxide particles, so that the powder has high adhesion and an excellent feeling in use as compared with a powder obtained by compositing talc, a metal oxide for sericite, which are conventional flattened inorganic substances, and is excellent in UV shielding ability and color developing ability by the metal oxide.

Therefore, the metal oxide-composited high-flattening cellulose powder of the present invention can be used in various cosmetics, and as a cosmetic which particularly easily exhibits the effect thereof, there are given cosmetics containing a powder component and an oil component such as foundation, eye shadow, blush, face powder and the like. Among these cosmetic materials, those filled by compression are preferable, and foundation and eye shadow are particularly preferable. When the cosmetic of the present invention is used to make foundation and eye shadow, it has no powdery feeling, a moist feeling, and good adhesion to the skin, and as a result, it naturally blends with the skin, and has no unevenness, wrinkles, dullness in color, floating, and the like, and the makeup retainability is good.

Claims (20)

1. A metal oxide-composited highly-flattened cellulose powder obtained by mechanically pulverizing a cellulose-based material, a pulverization aid, and a metal oxide.

2. The metal oxide-composited high-platy cellulose powder according to claim 1, wherein the metal oxide-composited high-platy cellulose powder has an average particle diameter of 1 to 50 μm, an average thickness of 0.1 to 10 μm, and a flatness of 4 to 200.

3. The metal oxide-composited high flat cellulose powder according to claim 1 or 2, wherein the amount of the metal oxide in the whole is 5 to 50% by mass.

4. The metal oxide composite high flat cellulose powder according to any one of claims 1 to 3, wherein the amount of the grinding aid in the whole is 0.5 to 5% by mass.

5. The metal oxide-composited high-tabular cellulose powder according to any one of claims 1 to 4, wherein the mechanical pulverization treatment is performed by a planetary ball mill.

6. The metal oxide-composited high-aspect cellulose powder according to any one of claims 1 to 5, wherein the cellulose-based substance is a cellulose-based substance selected from the group consisting of fibrous or powdery wood flour or pulp derived from wood, fibrous or powdery cotton or cotton linter fibers derived from cotton, and fibrous or powdery substances obtained by refining the same.

7. The metal oxide composite high-flattening cellulose powder according to any one of claims 1 to 6, wherein the pulverization aid is a substance selected from the group consisting of an amphiphatic agent, an amino acid and a fatty acid.

8. The metal oxide-composited highly flat cellulose powder according to claim 7, wherein the amphiphatic agent is a substance selected from the group consisting of a phospholipid, a ceramide, cholesterol or a derivative thereof, and a phytosterol or a derivative thereof.

9. The metal oxide-composited high-platy cellulose powder according to claim 7, wherein the amino acid is selected from the group consisting of N-acylamino acids and theanine.

10. The metal oxide-composited high-flattening cellulose powder according to claim 7, wherein the fatty acid is selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and salts thereof.

11. The metal oxide composite high flat cellulose powder according to any one of claims 1 to 10, wherein the metal oxide is a compound selected from the group consisting of iron oxide, titanium dioxide and zinc oxide.

12. The metal oxide-composited high-tabular cellulose powder according to any one of claims 1 to 11, wherein the average particle diameter of the metal oxide after compositing is 10nm to 100 nm.

13. The metal oxide-composited high-platy cellulose powder according to any one of claims 1 to 11, wherein the average particle diameter of the metal oxide after compositing is more than 100nm and 1000nm or less.

14. A cosmetic material comprising the metal oxide-composited high-flattening cellulose powder according to any one of claims 1 to 13.

15. The cosmetic according to claim 14, wherein the cosmetic is a powder cosmetic.

16. The cosmetic formulation of claim 14 or 15, wherein the cosmetic formulation is a foundation, eye shadow, blush, face powder, sunscreen or makeup base.

17. A process for producing a metal oxide-composited highly-flattened cellulose powder, characterized by adding a pulverization aid and a metal oxide to a cellulose-based material to prepare a mixture and subjecting the mixture to mechanical pulverization treatment.

18. The method for producing a metal oxide-composited high-flaxen cellulose powder according to claim 17, wherein the amount of the metal oxide added is 5 to 50% by mass based on the whole.

19. The method for producing a metal oxide composite highly flat cellulose powder according to claim 17 or 18, wherein the amount of the grinding aid added is 0.5 to 5% by mass based on the whole.

20. The method for producing a metal oxide composite high-aspect ratio cellulose powder according to any one of claims 17 and 19, wherein the mechanical pulverization treatment is performed by a planetary ball mill.