JPH02174709A - Cellulose particle-containing cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic having excellent spreading ability and uniformly covering property in using, hardly crumbling of make-up, keeping initial finished state for a long time after using and having high safety by containing natural cellulose particles having specific shape, structure and particle size. CONSTITUTION:Cellulose particles having I-type crystal form, <=3, preferably <=2 ratio of long axis to short axis of particle, having a porous structure of >=0.01mum diameter and >=0.2cm<3>/g pore volume and having 2-60mum averaged particle diameter are mixed in the aimed cosmetic. The above-mentioned cellu lose particle is obtained by pulverizing and drying fine particle-like natural cellulose dispersed in organic solvent with spray-drying method. As said cellulose particle is exceedingly porous and natural cellulose particle having excellent water absorption properties and oil absorption properties, the aimed cosmetic contains sufficient amount of sebaceous matter or sweat, further having suffi cient moisture retention to prevent stickiness for moisture absorption, so clean and wet state is able to be kept for a long time.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to cosmetics containing cellulose particles, and more specifically, to cosmetics containing natural cellulose particles having a specific shape, structure, and particle size. The present invention relates to cosmetics containing the following.

(Conventional technology and its problems) Cosmetics generally have the original purpose of making one's body beautiful, beautifying, increasing attractiveness, changing appearance, and keeping skin or hair healthy. In addition to the purpose of cosmetics, sensory functions such as ease of use, feel, finish, and makeup durability, or workability functions are required at the same time.To improve these functions, cosmetics It is known that it is effective to incorporate spherical and/or specific particle size and/or porous particles therein.

JP-A-60-255710 discloses that cosmetics containing inorganic and organic powders with a uniform particle size distribution and an average particle size of 2.5 to 5 μm can be used in a mild range and have a natural finish. It is stated that it has. Unexamined Japanese Patent Publication 1986-
Publication No. 126813 describes particles in which a porous, spherical core material such as silicic acid, titanium oxide, or thermoplastic resin is impregnated with a fragrance, and is further coated with fine powder such as iron oxide or mica, which improves color, luster, transparency, and texture. It is described as having excellent functions as a cosmetic, such as smoothness, spreadability, and good adhesion. JP-A-59-193901 discloses a method for producing hollow synthetic resin spherical particles that are excellent in soft feel when applied to cosmetics and transparent finish. Japanese Unexamined Patent Publication No. 61-83109 discloses a material with an average particle size of 0.1 to 70 μm that has good slippage when applied to cosmetics and has a unique sliminess.
There is a description of a cosmetic containing epoxy-based spherical particles of m. However, in either case, the substances used are inorganic substances such as heavy metals or synthetic resins, and the nature of cosmetics that come into direct contact with the skin raises concerns about their safety.

In addition to the above-mentioned functions, it is essential for cosmetics to be safe. Conventionally, cosmetics that have the above-mentioned high functions and are made from safe natural cosmetic ingredients have been manufactured. There was no charge. Natural cellulose has been used as an edible plant fiber since ancient times, and is now widely used as a dispersion stabilizer for liquid foods and as an excipient for pharmaceuticals. It can be said that it is an extremely suitable material.

Of course, there are examples of natural cellulose being used as a cosmetic material; for example, Japanese Patent Publication No. 40-6118 describes the application of microcrystalline cellulose particles to cosmetics;
Publication No. 21201 describes the application of microcrystalline cellulose particles having a relatively oval particle shape and an average particle size of 3 to 30 μm. However, in either case, there is no clear description of the porosity of the particles, and considering the manufacturing method, it is unlikely that they have a porous structure. Therefore, they have a light spreadability when used as cosmetics, and a function that suppresses sweat and sebum. is insufficient. In addition, as a cellulose material, porous spherical cellulose particles have been applied to powder cosmetics to improve spreadability and powder floating (Japanese Patent Application Laid-Open No. 61-1989-1).
No. 100514), applied to emulsified cosmetics to improve spreadability, blendability, moist feeling, lightness, and skin irritation (
However, since the cellulose particles used in this technology are prepared by melting and regenerating cellulose or cellulose derivatives, their crystalline form is cellulose type. Ta. True natural cellulose means one having a cellulose type crystal structure. In addition, the description regarding porosity is only qualitative, and as in the previous cases, it cannot be considered that the pores have a large pore diameter and sufficient pore volume considering the manufacturing method. In terms of functionality, it seems that it cannot fully exhibit its effects such as hygroscopicity.

(Means for Solving the Problems) The present invention addresses these current circumstances, and has excellent spreadability and uniform applicability during use, prevents makeup from coming off after use, maintains the initial finished state for a long time, and is safe. The present invention was developed as a result of intensive studies aimed at obtaining cosmetics with high levels of oxidation.

That is, the present invention provides porous particles whose crystal form is type II, the ratio of the long sleeve to the short axis of the particle is 3 or less, and the pore volume of the pores with a diameter of 0.01 μm or more is 0.2 cd/g or more. This is a cosmetic containing cellulose particles having a structure and an average particle size of 2 to 60 μm.

In the present invention, the amount of cellulose particles blended depends on the type (or form) of the cosmetic and cannot be specified in a specific manner. Approximately 5 to 45% by weight, 1 to 30% by weight for creams and emulsions,
In the case of lipsticks, a content of about 1 to 40% by weight, and in the case of antiperspirant stains, a content of about 10 to 70% by weight is effective in improving the functionality of cosmetics.

The present invention will be explained below.

The cellulose particles used in the present invention have type I crystals and are natural materials having the same crystal structure as natural cellulose such as ramie, cotton linters, and wood pulp. There are many cellulosic substances in the world, such as viscose rayon, cupra, cellulose acetate, and carboxymethyl cellulose, but the only one that can truly be called a natural material is cellulose! Only those with a type crystal structure.

Furthermore, the cellulose particles used in the present invention have a ratio of long sleeve to short axis of 3 or less, preferably 2 or less. Since human skin is extremely sensitive, if the ratio of the long axis to the short axis of the particles contained in a cosmetic product exceeds 3, the cosmetic product may have a disadvantage in spreadability when applied.

In this specification, "spherical particles with a ratio of major axis to minor axis of 3 or less" means particles with a shape close to a true sphere, or particles with a relatively oval shape without sharp corners. are doing.

Furthermore, the cellulose particles used in the present invention need to have a specific average particle size of 2 μm to 60 μm. The average particle size of cellulose particles is a factor that affects the performance of cosmetics even more than the particle shape.
If the particle size is larger than 0 μm, the cosmetic will spread well, but the particles will feel rough, and will not adhere well and will be thick.

Furthermore, if the average particle size is smaller than 2 μm, the adhesion to the skin will be improved, but the slippage will be poor and the finish will be powdery and unnatural. By the way, the particle size frequency distribution curve generally has a single peak where the average particle size and the top of the peak coincide, and the curve is often not symmetrical (and the largest particle is approximately 100 μm or less). be.

The cellulose particles used in the present invention have pores with a diameter of 0.01 μm or more with a volume of 0.2 cn! It has an extremely large pore structure of more than /g. Porous particles generally have a high liquid absorption ability, but porous particles made of natural cellulose have extremely excellent water and oil absorption properties in combination with the essential properties of the material. absorbs sebum and sweat quickly and well, making it difficult for makeup to come off.

Moreover, unlike many moisturizers, it does not absorb water and turn into a paste, or dissolve and become sticky, so it can maintain a light and moist state for a long time. In order to develop the above properties, the more porous the particles are, the more advantageous it is, and the pore volume of pores with a diameter of 0.01 μm or more is 0.2 μm.
Cal/g must be greater than or equal to 0. In both conditions, a larger value can provide a more favorable effect, but the upper limit is naturally determined due to constraints on the strength of the particles, and the value is determined by the average pore diameter. The particle size is about 1/1O, and the pore volume is about 1.2 ci/g.

The cellulose particles used in the present invention can be produced, for example, by the following methods, but are not limited to these methods.

The cellulose particles used in the present invention can be obtained by granulating and drying particulate natural cellulose dispersed in an organic solvent using a spray drying method. Although cellulose particles can be prepared using water without using an organic solvent, the pore volume of pores with a diameter of 0.01 μm or more is extremely low or zero, and the present invention This method is inappropriate as a method for producing cellulose particles.

An organic solvent slurry of cellulose microparticles can be prepared in various ways. For example, natural cellulose raw materials can be treated chemically (such as acid hydrolysis) and/or mechanically (
It is possible to prepare a slurry for spray drying by converting the cellulose into fine particles by pulverizing, grinding, etc.), replacing the water serving as a dispersion medium with an organic solvent, and further adjusting the solid content concentration. can. In this case, the size of the dispersed fine particles dispersed in the organic solvent is 10 μm or less,
Preferably, the particle size is 1 μm or less, which is suitable as an intermediate raw material for the cellulose particles used in the present invention. As natural cellulose raw materials, ramie, cotton linters, wood pulp, crystalline cellulose, etc., which have cellulose type I crystal forms, are used, and as organic solvents, acetone, methanol, ethanol, isopropyl alcohol, n-
One or more of hexane, n-pentane, cyclohexane, benzene, etc. may be used. Since the dispersion medium of the slurry is an organic solvent, spray drying must be carried out using a closed system with explosion protection in mind, such as a nitrogen gas circulation type spray dryer.

(Effects of the Invention) The cellulose particle-containing cosmetic of the present invention contains spherical natural cellulose particles with a long-to-short axis ratio of 3 or less and an average particle size of 2 to 60 μm, so it spreads easily when used. ,
It glides on well, does not cause irritation to the skin like roughness, and has good adhesion to the skin, so it can be applied evenly and evenly, creating what is known as a state where makeup adheres well.
And your makeup will last longer.

In addition, since the cellulose particles are natural cellulose particles that are extremely porous and have good water and oil absorption properties, they retain sebum and sweat well, and also have moisturizing properties that do not make them sticky even when they absorb moisture. Therefore, it can maintain a light and moist state for a long time.

Prior to Examples, a method for evaluating the physical properties of cellulose particles will be described.

<Average particle size (μm)> Measurement was carried out by a dry method using an SK laser micron sizer manufactured by Seishin Enterprise ■.

Ratio of long axis to short axis> Disperse an appropriate amount of the powder sample in a mixed solution of equal weights of water, ethanol, and glycerin, take a photograph of it using an optical microscope, and examine the individual particles shown in the photograph. (L)
and the short axis (D) were measured, and the average value of the quotient (L/D) was defined as the "ratio of the long axis to the short axis." By the way, the short axis (D) is the distance between two parallel lines that sandwich one particle so that the distance between them is the shortest, and the long axis (L) is the two parallel lines that are perpendicular to the two parallel lines. It is the distance when sandwiched,
The number of specimens was 100.

Pore diameter (μm) and pore volume (c111/g) >
The pore distribution was determined by mercury porosimetry using Shimadzu Pore Sizer 9300, and the pore volume was expressed as the volume of particulate mercury infiltration.

<Crystal form> X-ray diffraction was performed by X-ray diffractometry, and the determination was made from the diffractogram.

Note that the cellulose particle samples used in the Examples and Comparative Examples were prepared by the following method.

Sample A: A commercially available DP valve was placed in a 2.4 N hydrochloric acid aqueous solution.
Hydrolysis was carried out at 98° C. for 230 minutes at a bath ratio of 100 times, and the resulting acid-insoluble residue was neutralized, filtered and washed to obtain a wet cake with a water content of 50% by weight.

This wet cake was mixed with isopropyl alcohol (hereinafter referred to as IPA).
), repeat filtration, dehydration, and redispersion three times.
Further, at a solid content concentration of 1001%, a processing pressure of 400 k was used using a Gorlin homogenizer 15M manufactured by Nippon Seiki Seisakusho.
After performing dispersion treatment once at g/cffl, spray drying was performed using a nitrogen circulation type spray dryer.

The coarse particles of 180 μm or more of the powder thus obtained are
It was cut using an S standard sieve (JIS Z8801 180 μm), and the through-line fraction was designated as sample A. The basic physical properties of Sample A are shown in Table 1.

Sample B: The wet cake was replaced with IPA once, the solid content concentration of the IPA slurry was reduced to 13.0% by weight, and then sample A
Sample B was a powder prepared in the same manner as in the case of .

The basic physical properties of Sample B are shown in Table 1.

Sample C: Commercially available crystalline cellulose “Avicel PH-IOI
J (manufactured by Asahi Kasei Corporation) with a solid content concentration of 4.8% by weight.
After dispersing in IPA so that The obtained powder was classified using a micron separator manufactured by Hoiyo Iron Works ■ to obtain Sample C. The basic physical properties of Sample C are shown in Table 1.

Sample D: A commercially available DP bulb was placed in a 2.4 N hydrochloric acid aqueous solution.
Hydrolysis was carried out at 100 times the bath ratio for 140 minutes at 105°C, and the resulting acid-insoluble residue was neutralized, filtered, and washed to obtain a wet cake with a water content of 50% by weight. Disperse this wet cake in acetone, repeat filtration, dehydration, and redispersion three times.
After the solid content concentration was reduced to 3.5% by weight, dispersion treatment was performed three times using the homogenizer described above at a processing pressure of 400 kg/ctll, and the resultant was spray-dried using a nitrogen circulating spray dryer. The obtained powder was classified using the aforementioned micron separator to obtain a sample. Table 1 shows the basic physical properties of the sample.

Sample E, the solid content concentration of IPA slurry was 3.0% by weight,
The homogenizer treatment was carried out three times, and the remaining powder was prepared in the same manner as in the case of sample A. The resulting powder was crushed using an ACM valveizer manufactured by Hoiyo Ironworks, and then classified using the micron separator mentioned above to obtain sample E. I got it.

The basic physical properties of Sample E are shown in Table 1.

Sample F, solid content concentration of IPA slurry 12.0% by weight
Sample F was obtained by performing homogenizer treatment once and adjusting the other conditions in the same manner as in Sample A. The basic physical properties of Sample F are shown in Table 1.

J&R G, H; - Commercially available crystalline cellulose “Avicel PH
-MO6J and Avicel PH-101J (manufactured by Asahi Kasei Corporation) were used as Sample G and Sample H.

The basic physical properties of Sample G and Sample H are shown in Table 1.

Table 1 (blank below) (Example) Example 1 The powder raw materials in the basic recipe below were mixed in a high-speed blender, processed in a pulverizer, further sieved, and then compression molded. , I got a cake-type foundation. In addition,
The aforementioned samples A to D were used as cellulose particle samples.

Basic prescription> ■Cellulose particles 23.0% by weight■
Titanium oxide 7.0 //■ Colloidal kaolin 20.0 〃■ Talc
40.88〃■Red iron 0.8 ■I■Yellow iron oxide 2.5〃■Black iron oxide
0.1〃■Magnesium stearate 5
．． O〃■Ethyl paraoxybenzoate 0.2〃[phase]
Butylhydroxyanisole 0.02〃■Fragrance
In order to evaluate the usability of the cake-type foundation prepared at 0.5 No. I, 15 professional female panelists conducted a one-month trial test. The evaluation results are shown in Table 2. The symbols in the table represent the following contents.

◎・・・ 11 to 15 people judged it to be good ○・・・・ 6
~10 people judged it to be good Δ... θ~ 5 people judged it to be good Comparative Example 1 A cake-type foundation was made in the same manner as in Example 1 except that the cellulose particles in Example 1 were replaced with Samples E to H. were prepared and evaluated. The evaluation results are shown in Table 2.

(Left below) Table (Left below) Example 2 <Basic formulation> ■Stearic acid ■Propylene glycol monost7phosphate ■Cetostearyl alcohol ■Liquid lanolin ■Liquid paraffin ■Isopropyl myristate ■Propyl paraoxybenzoate ■Cellulose particles ■Purified water () Sodium carneximethylceltos■Bontonite @ propylene glycol @ triethanolamine 0% Methyl oxybenzoate ■Titanium oxide [phase] Talc ■Colored pigment [phase] Fragrance 2.4 Weight% 2.0 〃 0. 2 2.0 2.5 8.0 0.0 8.0 57.24 0.2 0.5 3.5 1.1 0.01 8, O 4, O〃 0.2 〃 0.1 4 Table 3 (margins below) Add 0 to ■ heated to 75°C, and add @ to it in advance.
Add the [phase] that has been dispersed into the solution, and then add @ and ■ to dissolve. Mixed and pulverized ① to O are added to this aqueous phase component, and the mixture is passed through a colloid mill. Add this to ■～■ heated, melted and mixed at 80"C with stirring, then cool,
An emulsified foundation was prepared by adding ■ at 45°C, stirring and cooling to room temperature. Samples A to D were used for cellulose particles (2). Usability evaluation of the prepared emulsified foundation was carried out in the same manner as in Example 1. The evaluation results are shown in the third page.

Comparative Example 2 An emulsified foundation was prepared and evaluated in the same manner as in Example 2, except that the cellulose particles (1) in Example 2 were used as Samples E to H. The evaluation results are shown in Table 3.

(Left below) Example 3 Basic recipe> ■1 malt particle (sample C) 4.0% by weight■
■Stearic acid 2. O〃■Stearyl alcohol 7.0 ft% by weight■Reduced lanolin
2.0〃■Squalane 5.
0〃■Octyldodecanol 6.0〃■Polyoxyethylene cetyl ether 3. O
〃■Glyceryl monostearate 2.0〃■Fragrance 0.3〃qΦDiptylph Fa-
t Citoluene 0.02
〃■Butyl paraoxybenzoate 0.2〃@Propylene glycol 5.0〃■Purified water
63.48 First, propylene glycol @ was added to purified water 0 and heated to 70°C to adjust the aqueous phase.

On the other hand, other components (1) to (2) were mixed, heated (70°C), and melted to prepare an oil phase. The aqueous phase was added to the oil phase, and after preliminary emulsification, the mixture was homogenized using a homomixer, and then cooled to room temperature to prepare a neutral cream. Although this neutral cream had excellent skin moisturizing properties, it was a cosmetic with little stickiness and excellent spreadability and texture upon application.

Claims (1)

[Claims] The crystal form is type I, the ratio of the long axis to the short axis of the particle is 3 or less, and the pore volume of pores with a diameter of 0.01 μm or more is 0.2
A cellulose particle-containing cosmetic containing cellulose particles having a porous structure of cm^3/g or more and an average particle size of 2 to 60 μm.