JP2000319117A - Moisture retaining composition containing cellulose fine particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new composition, especially a cosmetic containing a cellulose dispersion having excellent affinity for the skin and feeling in use and slight irritation to the skin as a moisture retaining component. SOLUTION: This composition comprises a cellulose being a humectant and a dispersion medium as essential components. The cellulose has <=100 average degree of polymerization(DP), <=0.1 fraction of cellulose I type crystal component, <=0.4 fraction of cellulose II type crystal component and <=5 μm average particle diameter and contains 0.1-10 wt.% of the cellulose.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a moisturizing composition and a moisturizing cosmetic using the moisturizing composition.

[0002]

2. Description of the Related Art The skin causes dryness and rough skin due to slight external irritation or internal factors, and impairs the appearance and beauty. In order to prevent these and keep the skin beautiful, skin care including maintenance of the moisturizing function of the skin is important. The key to keeping your skin clean is to keep your skin water content at a certain level.
Cosmetics often contain a "humectant".

Glycerin, 1,3-butylene glycol,
Polyhydric alcohols such as sorbitol have been widely used as humectants for cosmetics since ancient times. Also, amino acids, urea,
Organic acids and salts thereof are also widely used. In addition, hyaluronic acid and water-soluble collagen are sometimes used,
Since these humectants are special, there has been a demand for a versatile humectant having a high moisture retention function under low humidity.

[0004] On the other hand, cellulose, which is a natural polymer and has a high hydroxyl group density, is considered to be used as a humectant because of its relatively high hygroscopicity. However, it is hardly practical for the following reasons.

[0005] Existing microcrystalline cellulose (MCC) particles are not sufficiently hygroscopic. High crystallinity and particle size 2
This is because the shape is distorted at 0 μm or more, and the aqueous suspension of MCC is opaque and has a rough feeling, so that the feeling of use is not preferable.

[0006] Regenerated cellulose particles are more hygroscopic than MCC, but their aqueous suspensions have the same problems as those of the above-mentioned MCC, and thus have little practical use as humectants for cosmetics.

[0007] As described above, there is no composition using a hydrophilic and lipophilic cellulosic material as a humectant, especially a cosmetic.

There is also a need for a humectant which can eliminate the problems of existing polyhydric alcohol humectants such as solubility in water upon absorption of moisture and stickiness.

The present inventors have already proposed PCT / JP98 /
No. 05462 discloses a highly transparent cellulose dispersion having a low degree of polymerization which is insoluble in water and having a high degree of dispersion of low crystalline cellulose in a dispersion medium.

[0010]

DISCLOSURE OF THE INVENTION The present invention can solve the above-mentioned problems of the polyhydric alcohol-based humectant, and is excellent in affinity and use feeling to the skin and less irritating to the skin. It has been made to provide compositions, especially cosmetics, containing the ingredients.
Specifically, it is to provide a novel composition containing a cellulose dispersion as a moisturizing component.

[0011]

Means for Solving the Problems The present inventors have reported that the above-mentioned cellulose dispersion is insoluble in water, has excellent film-forming properties, has hydrophilicity and lipophilicity, and has a cellulose content in this dispersion. Have high hygroscopicity, and have completed the present invention.

That is, the present invention provides: A composition comprising cellulose as a humectant and a dispersion medium as essential components. The cellulose has an average degree of polymerization (DP) of 100 or less and a cellulose I type crystal fraction of 0.1 or less. 1. A composition having a fraction of type II crystal component of 0.4 or less, an average particle size of 5 μm or less, and containing 0.1 to 10% by weight of the cellulose. 2. The composition according to the above 1, wherein the dispersion medium is water or a water-soluble alcohol, or a mixture thereof. And a cosmetic comprising the composition of (1) or (2).

The composition of the present invention is a composition comprising, as essential components, low-crystalline cellulose having a low degree of polymerization and a specific crystal structure and a dispersion medium thereof. In addition, the physical property value prescribed | regulated by this invention employ | adopted the value obtained by the measuring method specified in Japanese patent application JP98-05462.

The cellulose of the present invention has an average degree of polymerization (D
P) is 100 or less, preferably 50 or less. DP is preferably 20 or more. Those having a degree of polymerization of 7 to 10 or less,
It is not preferred because it exhibits water solubility.

[0015] The cellulose of the present invention are cellulose I type crystal component amount (chi _I) is 0.1 or less, preferably 0.
06 or less, and low crystallinity with a cellulose II type crystal component amount (χ _II ) of 0.4 or less, preferably 0.3 or less. Fraction of the crystalline component of the cellulose of the present invention (chi _I and chi _II
Can be almost zero. The cellulose type I crystal described in the present invention has a crystal structure of a natural cellulose material. Cellulose type II crystal has a crystal structure generally found in a solid obtained by dissolving natural cellulose in a solvent and coagulating it.

The cellulose of the present invention has an average particle size of 5 μm.
m or less, preferably 3.5 μm or less, more preferably 2 μm or less.
μm or less. Japanese Patent Application JP98-0546
As described in detail in No. 2, the cellulose of the present invention has a network structure in which fine fibrous materials having a width of several tens of nanometers (nm) are innumerably entangled in a dispersion medium. The average particle diameter as referred to in the present invention refers to the "spreading (cell size)" of cellulose when a microgel of cellulose isotropically associated in a dispersion medium is dispersed as much as possible by means such as ultrasonic waves. Diameter) ”. This is to distinguish existing cellulose, such as MCC, from the existing form in the dispersion medium because it is clearly different.

The cellulose of the present invention having the above structure is highly dispersible in a dispersion medium and has high hygroscopicity due to low crystallinity. Therefore, the composition of the present invention can be a composition having high transparency and high hygroscopicity due to the above-mentioned network structure.

The hygroscopicity of the cellulose of the present invention is specified in Example 1, but is about three times that of the existing MCC. Therefore, high moisturizing properties can be imparted to cosmetics and the like by using a small amount of addition.

The concentration of cellulose in the composition of the present invention depends on the required moisturizing performance, but is in the range of 0.1 to 10% by weight, more preferably 0.1 to 6% by weight. . In particular, when the cellulose concentration is more than 0.5% by weight, a viscous composition having a moisturizing property can be obtained. Therefore, when a composition in the form of an emulsion, cream or gel is desired, It is convenient. If the content is less than 0.1% by weight, sufficient moisture retention cannot be secured. On the other hand, when the cellulose concentration exceeds 10% by weight, the moisturizing property is improved, but the composition becomes extremely viscous and the usability is deteriorated.

As the dispersion medium of the present invention, many media such as water, water-soluble alcohols such as methanol, ethanol and propanol, acetone, acetonitrile, dimethylacetamide and the like can be used. ,
Water and ethanol are preferred.

In addition, the cellulose of the present invention is hydrophilic because of its high hydroxyl group density, and is also excellent in affinity for oily substances. Therefore, the composition of the present invention has a high ability to absorb sweat and sebum secreted from sweat glands and sebaceous glands, lipids derived from epidermis, and the like.

The cellulose of the present invention is dispersed in a dispersing medium in a very fine state, so that it hardly has a rough feeling and does not dissolve in water or lipids, so it has no sticky feeling and is excellent in so-called feeling of use. To give a composition.

Furthermore, because of its excellent spreadability and film forming property,
A composition having high adhesion to skin can be obtained.

As described above, the composition containing the cellulose of the present invention as a humectant not only has high moisturizing performance, but also is excellent in terms of transparency, feeling of use, and adhesion to skin. Compositions, especially cosmetics.

The precursor of the composition of the present invention can be obtained by any of the following methods.

That is, a cellulose solution obtained by dissolving cellulose in an inorganic acid aqueous solution is reprecipitated in water or a coagulant containing 50% by weight or more of water to prepare a cellulose suspension.
Subsequently, the cellulose in the suspension is subjected to an acid hydrolysis treatment and then obtained by a method of removing the acid from the suspension (method I). Alternatively, a cellulose solution obtained by dissolving cellulose in an aqueous solution of an inorganic acid is reprecipitated in water or a coagulant containing 50% by weight or more of water to prepare a cellulose suspension. After the cake is prepared, the dehydrated cake is poured into water at 50 ° C. or higher to subject the cellulose to an acid hydrolysis treatment, and then the acid is removed from the suspension (method II).

The composition of the present invention is obtained by kneading or coarsely pulverizing the precursor obtained by the method I or II with a kneading device such as a kneading machine or a homogenizer, and further performing a bead mill treatment or a high pressure / ultra high pressure It can be obtained by highly pulverizing treatment with a homogenizer or the like. When the highly pulverizing treatment is performed, the composition of the present invention having higher transparency can be obtained.

When a dispersion medium other than water is mixed or replaced with a medium other than water, it may be carried out in any step after hydrolysis.

The composition of the present invention is particularly useful as a cosmetic.

The cosmetic composition of the present invention is effective for skin cosmetics, hair and scalp cosmetics and the like which preferably contain a moisturizing component, but in particular, basic cosmetics, makeup cosmetics, body cosmetics. And the like.

In the cosmetic of the present invention, in addition to the cellulose of the present invention, which is an essential component, and a dispersion medium, an oily raw material, a surfactant, a thickener, an ultraviolet absorber, an antioxidant, a preservative, and a sequestering metal ion. Agents, coloring agents, fragrances, etc., as well as whitening agents, anti-inflammatory agents,
Various agents such as skin roughness inhibitors, antiperspirants, vitamins, hormones and the like can be appropriately compounded depending on the use.

The oily raw materials of the present invention include olive oil,
Fats and oils such as camellia oil, macadamia nut oil and castor oil; waxes such as carnauba wax, candelilla wax, jojoba oil, beeswax and lanolin; hydrocarbons such as liquid paraffin, paraffin, vaseline, ceresin, microcrystalline wax, squalane; Fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid and isostearic acid; higher alcohols such as cetyl alcohol, stearyl alcohol, isostearyl alcohol and 2-octyldodecanol, isopropyl myristate;
Esters such as 2-octyldodecyl myristate, cetyl 2-ethylhexanoate, and diisostearyl malate; silicone oils and the like, but are not limited thereto.

Examples of the surfactant include anionic salts such as higher fatty acid soaps, alkyl sulfates, polyoxyethylene alkyl ether sulfates, acyl N-methyltaurine salts, alkyl ether phosphates, and N-acyl amino acid salts. Surfactants; cationic surfactants such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and benzalkonium chloride; alkyldimethylaminoacetic acid betaine, alkylamidodimethylaminoacetic acid betaine, 2-alkyl-N-carboxy-
Amphoteric surfactants such as N-hydroxyimidazolinium betaine; nonionic surfactants such as polyoxyethylene type, polyhydric alcohol ester type and ethylene oxide / propylene oxide block copolymer, but are not limited thereto is not.

For example, powder components such as talc, mica, and titanium dioxide; para-aminobenzoic acid and its derivatives, butylmethoxybenzoylmethane, paramethoxycinnamic acid derivatives, salicylic acid derivatives, benzophenone derivatives, imidazoline derivatives, liquid lanolin acetate, and koganebana root UV absorbers such as extracted extracts and triazine derivatives; whitening ingredients such as ascorbic acid and its derivatives, licorice extract, tea extract, tocophenol and its derivatives, tranexamic acid and its salts, azulene, γ-hydroxybutyric acid;
Thickeners such as carboxycellulose, ethylcellulose, soluble starch, polyvinyl alcohol, xanthan gum, carrageenan, gelatin, polyacrylate copolymers; sequestering agents such as phosphoric acid, ascorbic acid, and succinic acid; ethanol, propylene glycol, etc. Organic solvents; antioxidants such as butylhydroxytoluene, tocophenol, phytin; benzoic acid and salts thereof;
Salicylic acid and its salts, dehydroacetic acid and its salts,
Antibacterial and preservatives such as hexachlorophen, boric acid, resorcin, zinc pyrithione, hinokitiol; citric acid,
Organic acids such as lactic acid, adipic acid, glutamic acid and maleic acid; nutrients such as vitamin A and its derivatives, vitamins B, vitamin E, vitamin D, vitamin H, pantothenic acid and various vitamins and amino acids; nicotinic acid Amides, glycyrrhetinic acid and its derivatives, saponins,
Blood circulation promoters such as tranexamic acid, cephalandin, and assembly extract; local stimulants such as pepper tincture, cantharistin tincture and benzyl nicotinate; anti-inflammatory agents such as glycyrrhizinate derivatives, azulene, aminocaproic acid, and hydrocortisone; zinc oxide and sulfuric acid Astringents such as zinc, aluminum chloride and tannic acid; cooling agents such as menthol and camphor; antihistamines, tocophenols, B
Various drugs such as HA, BHT, gallic acid, and NDGA; animals and plants such as yeasts, filamentous fungi, bacteria, garlic, loofah, rose, dokudami, mallow, assembly, spruce, cedar, horse chestnut, malonier, mugwort, aloe, adlay, etc.
A natural extract obtained by extracting or hydrolyzing a microorganism and a part thereof with an organic solvent, alcohol, water, or the like; a pigment; a fragrance;

The composition of the present invention can also be used as ointments and patches.

[0036]

The present invention will be described below in detail with reference to examples. The physical properties (average degree of polymerization (DP), average particle diameter, fraction of cellulose I-type crystal component, fraction of cellulose II-type crystal component) of the dispersion shown in this example were evaluated by the following methods. did.

In the present invention, the average particle size of the dispersion is determined by a laser diffraction type particle size distribution analyzer (Horiba Seisakusho Co., Ltd., laser diffraction / scattering type particle size distribution analyzer LA-920); ). In order to measure the particle diameter in a state where the association between the particles in the dispersion medium was cut as much as possible, a sample was prepared in the following step. After diluting the water of the dispersion with water so that the cellulose concentration becomes about 0.5%, the mixture is mixed for 10 minutes by a blender having a rotation speed of 15,000 rpm or more to form a uniform suspension. Next, an aqueous dispersion sample obtained by subjecting this suspension to ultrasonic treatment for 30 minutes was supplied to a cell of a particle size distribution measuring device, and subjected to ultrasonic treatment again (3 minutes), and then the particle size distribution was measured. . The average particle diameter of the present invention corresponds to the weight average particle diameter obtained from the volume conversion particle size distribution calculated from the Mie scattering theory.

The average particle size of the cellulose fine particles can be determined by observation with a scanning electron microscope (S-800A, manufactured by Hitachi, Ltd.).
(Type), the value measured by the following method was adopted.

A fine powder sample is placed on a sample table for a microscope, and a metal such as gold or platinum is vapor-deposited by an ion sputtering device or the like to obtain a sample for a microscope. The average particle diameter was obtained by measuring the particle diameter of 50 particles randomly extracted from an image obtained by observing the microscopic sample at an accelerating voltage of 5 KV at a magnification of 3000 times, and calculating the weight average particle diameter.

In the present invention, cellulose I and cellulose
The fraction of the type II crystal component (χ _I and χ _II ) was determined by a wide-angle X-ray diffraction method (Rotaflex RU-30 manufactured by Rigaku Corporation).
0 using the following procedure.

Fraction of cellulose type I crystal component (χ _I )
Is to pulverize the dried cellulose sample into powder and form into tablets,
In the wide-angle X-ray diffraction diagram obtained by the reflection method with the source CuKα,
From the absolute peak intensity h _{0 at} 2θ = 15.0 ° attributed to the (110) plane peak of the cellulose type I crystal and the peak intensity h ₁ from the baseline at this plane interval, it is determined by the following equation (1). Values were used.

Similarly, the fraction (χ _II ) of the cellulose type II crystal component can be calculated from the wide-angle X-ray diffraction pattern obtained by pulverizing a dried cellulose sample into a powder and forming it into a tablet, and using a source CuKα to obtain a reflection method. Absolute peak intensity h _{0 at} 2θ = 12.6 ° attributed to the (110) plane peak of cellulose II crystal
From * and the peak intensity h ₁ * from the baseline at this plane interval, a value obtained by the following equation (2) was used.

Χ _I = h ₁ / h ₀ (1) χ _II = h ₁ * / h ₀ * (2) FIG. 1 is a schematic diagram for determining χ _I and χ _II .

The average degree of polymerization (DP) specified in the present invention is:
The specific viscosity of a dilute cellulose solution obtained by dissolving the above dried cellulose sample in cadoxene was measured with an Ubbelohde viscometer (25 ° C.), and the intrinsic viscosity number [η] was used to determine the following viscosity equation (3).
And the value calculated by the conversion formula (4) was adopted.

[0045] [η] = 3.85 × 10 ~ 2 × M W 0.76 (3) DP = M W / 162 (4)

[0046]

Examples 1 and 2 Preparation of Precursor Sulfite pulp sheet (average degree of polymerization: 760) cut into chips of 5 mm × 5 mm was prepared at 65 ° C. in 65% by weight sulfuric acid aqueous solution at −5 ° C. so that the cellulose concentration was 5% by weight. To obtain a cellulose dope. The cellulose dope was poured into 2.5 times by weight of water (5 ° C.) while stirring, and the cellulose was flocculated to obtain a suspension. This suspension was hydrolyzed at 85 ° C. for 60 minutes, and then washed thoroughly with water and dewatered under reduced pressure until the pH became 4 or more, further washed once with diluted ammonia water, and washed with ion-exchanged water. Specifically, a white and transparent gel-like substance having a pH of 6 or more and a cellulose concentration of 6.2% by weight was obtained. This gel sample was mixed and homogenized for 3 minutes with a household food processor (knife cutter, rotation speed of 15000 rpm or more) to prepare an aqueous gel (H0 sample).

Next, the H0 sample was diluted with ion-exchanged water to a cellulose concentration of 5% by weight, and 10,000 r.
Mix for 5 minutes at a rotation speed of pm. Then, the diluted sample was subjected to an ultra-high pressure homogenizer (Microflui).
dizer M-110EH type, manufactured by Mizuho Industry Co., Ltd.
The treatment was performed four times at an operating pressure of 1750 kg / cm ² ) to obtain a transparent H1 sample (Example 1).

Further, the H0 sample was washed / dehydrated three times with ion-exchanged water / ethanol = 50/50 (weight ratio), diluted to a cellulose concentration of 5% by weight, and blended with a blender at 100%.
Mix for 5 minutes at a rotation speed of 00 rpm. This sample is
Treat with the ultra-high pressure homogenizer described above four times to obtain clear H
Two samples (Example 2) were obtained. Table 1 shows Examples 1 and 2
Shows the properties of the sample.

[0049]

[Table 1]

[0050]

Example 3 Measurement of Moisture Retention The moisture content after drying of Examples 1 and 2 (ie, H1 and H2 samples) was measured by the following method.

Examples 1 and 2 were applied to a glass plate at about 200 μm.
m. These two samples were heated at 120 ° C and 1m
It dried for 2 hours using the reduced pressure dryer under the environment of mHg.
Thereafter, it was taken out of the dryer and weighed as quickly as possible (W0).

Immediately after the measurement of the weight, the film was immediately transferred to an environment of 25 ° C. and 50% RH, and the hygroscopicity of the coating film was evaluated as a moisture content from the weight increase (ΔW) after 200 hours. Here, the moisture content is calculated from the weight immediately after drying (W0) and the weight increment (△ W) from immediately after drying to reaching the moisture absorption equilibrium, as follows: moisture content = (△
W / (W0 + △ W)) × 100 (%).

As a reference example, a commercially available MCC particle (Avicel PH-101, registered trademark of Asahi Kasei Kogyo Co., Ltd.) was also evaluated for moisture absorption under the above conditions. Table 2 shows the obtained results.

[0054]

[Table 2]

[0055]

Examples 4 and 5 Cream (Preparation of Cream) A cream having the composition shown in Table 3 was prepared using H1 described above.

[0056]

[Table 3]

The preparation of the cream was performed as follows.

An alkali and an emulsifier were added to purified water, and in Example 5, titanium dioxide was added and premixed.
The temperature was adjusted to ° C. The oily raw material is heated and dissolved, and a preservative, an antioxidant, a fragrance and, in Example 5, oxybenzozone and octyl paramethoxycinnamate are further added thereto.
Then, the mixture was added to the aqueous phase to perform preliminary emulsification.
Thereafter, sample H1 was added, and after premixing, the emulsified particles were homogenized with a homogenizer, followed by degassing, filtration and cooling to obtain a cream.

In Example 4, the cream was white and glossy, had a good touch, and was smooth and refreshing.

In Example 5, a cream having a low glossiness but a good touch was obtained as compared with Example 4. Table 6 shows the evaluation of moisture retention.

[0061]

Example 6, Comparative Example 1 Emulsion Emulsion (emollient lotion) having the composition shown in Table 4 was prepared.

[0062]

[Table 4]

After adding a coloring agent and an emulsifier to the purified water and premixing, the aqueous phase mixture treated with a high-pressure
The temperature was adjusted to ° C. A preservative was added to the oily raw material, and after heating and mixing, the preservative was added to the previously prepared aqueous phase, followed by preliminary stirring. Ethanol and sample H2 were added thereto, and after premixing, emulsified particles were homogenized with a high-pressure homogenizer, followed by degassing, filtration and cooling to obtain an emollient lotion.

Example 6 is a slightly viscous emulsion,
The feel was good and smooth and refreshing. In contrast, Comparative Example 1 was an emulsion having a lower viscosity. Table 6 shows the evaluation of moisture retention.

[0065]

Example 7 and Comparative Example 2 Foundation A foundation (liquid type) having the composition shown in Table 5 was prepared.

[0066]

[Table 5]

An alkali, an emulsifier and sample H2 were added to purified water.
(In Comparative Example 2, a commercially available MCC was used instead of H2.)
The particles “Avicel PH-101, a registered trademark of Asahi Kasei Kogyo Co., Ltd.” are used. ), And a mixing process was performed at 70 ° C. using a blender. A sufficiently mixed powder mixture was added thereto with stirring, and subjected to a homomixer treatment at 70 ° C. Further, the oily raw material dissolved at 80 ° C. and mixed with a preservative was gradually added, and homomixer treatment was performed at 70 ° C. The mixture was cooled under stirring, and when the temperature reached 45 ° C., a fragrance was added, and the mixture was cooled to room temperature to obtain a foundation.

The foundation of Example 7 had a relatively low viscosity, was excellent in texture, had a refreshing feel and a fresh feeling, and exhibited extremely good moisture retention. However, the foundation of Comparative Example 2
It had a rough touch and lacked moisturizing properties. Table 6 shows the evaluation of moisture retention.

(Evaluation of Moisturizing Property) The creams of Examples 4 to 7 and Comparative Examples 1 and 2 were applied to the back of the hand in winter and kept for 24 hours. Table 6 shows the results.

[0070]

[Table 6]

[0071]

Industrial Applicability The present invention can provide a novel composition, particularly a novel cosmetic, containing a specific cellulose as a humectant.

According to the present invention, it is possible to provide a moisturizing composition which is excellent in affinity for skin and in use, has no stickiness, and gives a moist feeling.

Further, since cellulose as a starting material is used as a starting material, there is no problem in safety.

[Brief description of the drawings]

FIG. 1 Wide-angle X-ray diffraction pattern of a dried sample of cellulose fine particles

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yuji Matsue 6-4100 Asahicho, Nobeoka-shi, Miyazaki F-term in Asahi Kasei Kogyo Co., Ltd. 4C083 AA082 AB051 AB052 AB232 AB242 AB432 AC012 AC022 AC062 AC072 AC101 AC102 AC182 AC232 AC242 AC422 AC442 AC542 AD152 AD261 AD262 AD512 CC01 CC04 CC05 CC12 DD31 EE06 EE10 EE17

Claims (3)

[Claims] 1. A composition comprising, as essential components, cellulose as a humectant and a dispersion medium, wherein said cellulose has an average degree of polymerization (DP) of 100 or less and a fraction of cellulose I type crystal component of 0. 0.1 or less, a composition having a fraction of cellulose type II crystal component of 0.4 or less, an average particle size of 5 μm or less, and containing 0.1 to 10% by weight of the cellulose. 2. The composition according to claim 1, wherein the dispersion medium is water or a water-soluble alcohol, or a mixture thereof. 3. A cosmetic comprising the composition according to claim 1.