JPH0816046B2 - Raw material for cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to raw material substances used in cosmetics.

[Conventional technology]

Various water-soluble polymers are used in cosmetics by utilizing functions such as an emulsion stabilizing effect, a thickening effect, a moisturizing effect, a suspension stabilizing effect, and a fluidity improving effect.

Such water-soluble polymers are represented by, for example, methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose. Among them, commercially available water-soluble cellulose ethers used in cosmetics are produced by a so-called heterogeneous reaction system in which cellulose ether as a raw material is subjected to an etherification reaction in a state where it is not dissolved in a solvent to produce a cellulose ether. Specifically, there is a production method by a gas phase reaction in which chip-like or powdery cellulose is reacted with a gaseous etherifying agent in the presence of an alkaline substance (generally caustic soda) to produce cellulose ether. Also,
There is also a production method by a slurry reaction in which cellulose in the form of chips or powder is slurried in a solvent and reacted with an etherifying agent in the presence of an alkaline substance to produce a cellulose ether.

In any case, since water-soluble cellulose ether is a semi-synthetic polymer obtained by reacting cellulose widely distributed in nature with an etherifying agent, compared to natural water-soluble polymer, stable products of stable quality can be obtained. Can be supplied by
It has excellent antimicrobial properties. Furthermore, compared with synthetic water-soluble polymers such as polyvinyl alcohol (PVA) and polyacrylic acid soda, it has superior characteristics not found in other water-soluble polymers, such as higher physiological stability, making it suitable for cosmetics. Widely used as a raw material.

[Problems to be solved by the invention]

However, even the water-soluble cellulose ether having excellent characteristics as described above causes the inconvenience that the compatibility with certain surfactants mixed in cosmetics and the resistance to microorganisms are not sufficiently satisfied. ing.

The present invention has been made in order to solve the above-mentioned inconveniences, and provides a raw material substance for cosmetics, which has excellent compatibility with a surfactant in various cosmetic formulation compositions and is less susceptible to deterioration by microorganisms. With the goal.

[Means for solving problems]

In order to achieve the above-mentioned object, the present inventors have conducted research so as not to impair the advantages of water-soluble cellulose and to eliminate the above-mentioned inconvenience. As a result, the water-soluble cellulose ether produced in the homogeneous reaction system showed good results, and it was found that the cosmetics containing the same have an unprecedented excellent quality, and the present invention has been completed.

The present invention made based on the above findings is a raw material material for cosmetics comprising water-soluble cellulose ether etherified in a homogeneous reaction system in which cellulose or a cellulose derivative is dissolved in a solvent.

The structure of water-soluble cellulose ether is generally used by adding to cosmetics, for example, methyl cellulose,
Hydroxypropyl cellulose, hydroxypropylmethyl cellulose, and hydroxyethyl cellulose are preferable because they have excellent stability over time.

In order to obtain water-soluble cellulose ether, a method of carrying out an etherification reaction in a state where cellulose is dissolved in a solvent in which cellulose is soluble (MDNicholson, IPC Technical Pap
er Series36 (1976), JP-A-52-133394, USP40
24335 specification). As another example, a method of dissolving cellulose acetate in an organic solvent and then simultaneously performing an etherification reaction while saponifying with an alkaline substance (E. Husemann, Makromol Chem, 117 , 141 (1971),
JP-A-60-212401). As another example, after carrying out an etherification reaction in a state where cellulose acetate is dissolved in an organic solvent, deacetylation (E. Husema
nn, Makromol Chem, 176 , 3269 (1975)).

The water-soluble cellulose ether of the present invention is used in cosmetics and exerts its function. The objects to be used are, for example, cream, emulsion, foundation, makeup, lotion, eye shadow, eyeliner, shampoo, rinse, lipstick, lotion, pack and toothpaste.

[Action]

The raw material material for cosmetics of the present invention is a water-soluble cellulose ether produced by a homogeneous reaction system, and its superiority is clearly shown as compared with a water-soluble cellulose ether produced by a conventional heterogeneous reaction system. The reason for this is not clear, but it is presumed that the distribution of the substituents of the water-soluble cellulose ether becomes uniform by producing the water-soluble cellulose ether by a homogeneous reaction system. It is presumed that if the substituents of the water-soluble cellulose ether are evenly distributed, the compatibility with various surfactants will be good, and that it will function as a water-soluble polymer in a wide range of cosmetic formulation processes. . In addition, since the microorganism easily acts on the unsubstituted glucose ring, the more uniformly the substituents are distributed, the less the unsubstituted glucose ring is, and the less likely it is that the microorganism is affected. Therefore, when this is mixed with cosmetics, cosmetics of excellent quality can be provided, and the quality of the cosmetics immediately after production can be maintained for a long period of time.

〔Example〕

Examples 1 to 12 for producing the water-soluble cellulose ether of the present invention in a homogeneous reaction system are shown below.

Example 1 30 g of cellulose powder was added to 950 ml of dimethylsulfoxide, heated to 120 ° C. with stirring, and then 60 g of paraformaldehyde was added and stirred for 15 minutes to dissolve cellulose. After cooling this cellulose solution to room temperature, 40 g of sodium hydride was added and stirred for 2 hours, and 140 g of methyl iodide was added and reacted for 24 hours. The reaction solution was poured into an excess of formic acid-toluene mixed solution to precipitate a product. The product was washed with isopropanol / water = 90/10 (volume ratio) and dried to obtain methylcellulose (MC) having an average number of substituted methoxyl groups per unit glucose ring (hereinafter abbreviated as DS) of 1.8.

Example 2 The reaction and post-treatment are carried out in the same manner as in Example 1 except that 140 g of methyl iodide and 12 g of propylene oxide are used instead of methyl iodide. Hydroxypipropylmethylcellulose (HPMC) having a methoxyl group DS of 1.8 and an average number of substituted hydroxypropoxyl groups per anhydrous glucose ring (hereinafter abbreviated as MS) of 0.21 was obtained.

Example 3 Substituting 40 g of ethylene oxide for methyl iodide,
After carrying out the reaction in the same manner as in Example 1 except that the reaction time was 3 hours, the product was precipitated by pouring into an excess formic acid-isopropanol mixed solution. The product is isopropanol /
Wash with water = 85/15 (volume ratio) and dry. Hydroxyethyl cellulose (HEC) having a hydroxyethoxyl group MS of 2.6 was obtained.

Example 4 The reaction was performed in the same manner as in Example 3 except that 84 g of propylene oxide was used instead of ethylene oxide, and the product was precipitated by pouring into excess formic acid-toluene. The product is washed with an acetone-toluene mixed solution and then dried. MS is 3.
8 hydroxypropyl cellulose (HPC) was obtained.

Example 5 30 g of cellulose diacetate (average degree of substitution of acetyl groups per anhydrous glucose ring: 2.4) was added to 600 ml of acetone, and the temperature was raised with stirring to dissolve the cellulose diacetate at a temperature of 55 ° C. While stirring, 600 g of dimethylsulfate and 480 ml of a 30% aqueous sodium hydroxide solution were added, and the mixture was reacted at 55 ° C. for 3 hours. Next, the reaction solution was poured into toluene to precipitate a product. The product is washed with isopropanol / water = 90/10 (volume ratio) and then dried. Methylcellulose having a methoxyl DS of 1.9 was obtained.

Example 6 The reaction and post-treatment are carried out in the same manner as in Example 5 except that 600 g of dimethyl sulfate and 7 g of propylene oxide are used instead of dimethyl sulfate. Hydroxypropylmethylcellulose having a methoxyl group DS of 1.8 and a hydroxypropoxyl group MS of 0.19 was obtained.

Example 7 The reaction and post-treatment are carried out in the same manner as in Example 5 except that 250 g of ethylene oxide is used instead of dimethyl sulfate.
Hydroxyethyl cellulose having a hydroxyethoxyl group MS of 2.5 was obtained.

Example 8 After carrying out the reaction in the same manner as in Example 5 except that 47 g of propylene oxide was used instead of dimethyl sulfate, the reaction solution was poured into excess toluene to precipitate the product. The product is washed with a mixed solution of acetone / toluene = 5/5 (volume ratio) and then dried. Hydroxypropyl cellulose having a DS of 3.6 was obtained.

Example 9 To a solution of 10 g of cellulose triacetate in 100 ml of methylene chloride was added 100 ml of acetic acid, and then methylene chloride was removed from this solution by vacuum distillation to prepare an acetic acid solution of cellulose triacetate. After adding 100 ml of a mixed solution of acetic acid / water = 4/1 to this acetic acid solution, 0.8 ml of sulfuric acid was added, and the mixture was allowed to stand at 40 ° C. for 7 days (during this reaction, water was added to the reaction solution at appropriate times to react. Was adjusted so that a uniform solution was obtained). Add the reaction to excess isopropyl alcohol,
Precipitate the product. The precipitate was washed with methanol and then dried to obtain acetyl cellulose having an acetyl group substitution degree of 0.8.

Separately, add 3.5 parts of sodium hydride in a nitrogen atmosphere to
Add 5 parts of dimethylsulfoxide and stir at 60 ° C. for 2 hours to prepare a solution of methylsulfinylmethylcarbanion in dimethylsulfoxide.

After adding 5 g of the cellulose acetate with the degree of acetyl group substitution of 0.8 obtained above to 100 ml of dimethyl sulfoxide, in a nitrogen atmosphere, add 65 g of the previously prepared dimethyl sulfoxide solution of methylsulfinylmethyl carbanion 2
The mixture was stirred at 0 g for 3 hours. Then add 17 g of methyl iodide and add 30 g.
The mixture was stirred at ° C for 5 hours. The reaction solution was poured into an excess of water to precipitate and then dried. 95% of this product 5g
After dissolving in water-containing acetone, 0.5 g of concentrated sulfuric acid was added, and the mixture was reacted at 50 ° C. for 6 hours. The precipitated product is washed with a mixed solution of methanol / water (weight ratio 90/10) and then dried. DS is 1.8
Was obtained.

Example 10 A DS of 1. was obtained in the same manner as in Example 9 except that 17 g of methyl iodide and 1 g of propylene oxide were used instead of methyl iodide.
7 Hydroxypropylmethylcellulose with an MS of 0.25 was obtained.

Example 11 A reaction liquid containing hydroxyethylacetyl cellulose was obtained in the same manner as in Example 9 except that 8.4 g of ethylene oxide was used instead of methyl iodide. The reaction solution was poured into excess toluene to cause precipitation and then dried. This hydroxyethyl acetyl cellulose was deacetylated in the same manner as in Example 9 to obtain hydroxy ethyl cellulose having MS of 2.4.

Example 12 Hydroxypropyl cellulose having an MS of 3.7 was obtained in the same manner as in Example 9 except that 19 g of propylene oxide was used instead of methyl iodide.

Average substitution degree and viscosity for each sample of the water-soluble cellulose ethers produced in the above-mentioned Examples 1 to 12 and commercially available methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose 1 sample each as a comparative example, a total of 16 samples , Viscosity stability over time, compatibility with surfactants are tested.

Table 1 shows the average degree of substitution and the viscosity of a 2% aqueous solution at 20 ° C.

Table 2 shows the viscosity stability over time. The measuring method is to leave a 2% aqueous solution of various cellulose ethers in an atmosphere at a temperature of 20 ° C. and a humidity of 70% RH, and measure the viscosity at 20 ° C. over time. From that value, the change in viscosity retention with time is calculated by the following formula.

Table 3 shows the compatibility with surfactants. The test method mixes 10 parts of a 1% aqueous solution of various cellulose ethers with 90 parts of a 30% aqueous solution of various surfactants and examines the compatibility at 10 ° C.

Use examples 1 to 12 in which the water-soluble cellulose ethers of the above examples 1 to 12 are used in cosmetics will be described below.

Use Example 1 Using the I-MC obtained in Example 1, a cleansing cream having the following composition was prepared.

Liquid paraffin 30.0 parts by weight Vaseline 20.0 parts by weight Water 32.0 parts by weight Stearic acid monoglyceride 10.0 parts by weight Polyoxyethylene sorbitan monolaurate 3.0 parts by weight Glycerin 3.0 parts by weight I-MC 2.0 parts by weight Fragrance and preservative Appropriate amount This cleansing cream is stable over time. It had excellent properties, good elongation during use, no sticky feeling, and a moist feel.

Use Example 2 Using the I-HPMC obtained in Example 2, a lotion having the following composition was prepared.

Ethanol 10.0 parts by weight Propylene glycol 5.0 parts by weight Sodium lauryl sulphate 1.5 parts by weight I-HPMC 1.0 parts by weight Water 82.5 parts by weight Fragrances and preservatives Appropriate amount This lotion had an excellent feeling of use and gave a moist feel.

Use Example 3 Using I-HEC obtained in Example 3, an emulsion having the following composition was prepared.

Liquid paraffin 50.0 parts by weight Beeswax 10.0 parts by weight Water 35.0 parts by weight Cetyl alcohol 3.0 parts by weight I-HEC 2.0 parts by weight Fragrances and preservatives Appropriate amount This emulsion has excellent stability over time, good elongation during use,
There was no stickiness and a moist feel was provided.

Use Example 4 Using I-HPC obtained in Example 4, a pack agent having the following composition was prepared.

Polyvinyl alcohol 20.0 parts by weight Glycerin 4.0 parts by weight Ethyl alcohol 6.0 parts by weight I-HPC 5.0 parts by weight Water 65.0 parts by weight Fragrances and preservatives Appropriate amount This pack is excellent in stability over time and has good stretchability during use, Was excellent.

Use Example 5 Using II-MC obtained in Example 5, a lipstick having the following composition was prepared.

Beeswax 30.0 parts by weight Castor oil 45.0 parts by weight Lanolin 5.0 parts by weight Hardened oil 3.0 parts by weight Lake 7.0 parts by weight Liquid paraffin 5.0 parts by weight Pigment 2.0 parts by weight II-MC 3.0 parts by weight Fragrance and preservatives Appropriate amount This lipstick has excellent stability over time. It had good elongation during use, excellent moisturizing properties, and gave a moist feel.

Use Example 6 Using II-HPMC obtained in Example 6, a rinse having the following composition was adjusted.

Glyceryl monostearate 3.0 parts by weight Alkyldimethylbenzylammonium chloride 4.0
Part by weight II-HPMC 1.0 part by weight Water 92.0 parts by weight Fragrance and dye Appropriate amount This rinse was excellent in stability over time and gave good gloss and moist feel to hair.

Use Example 7 Using II-HEC obtained in Example 7, a set lotion having the following composition was prepared.

Ethanol 14.0 parts by weight Glycerin 2.0 parts by weight Polyoxyethylene sorbitan monolaurate 1.0 parts by weight II-HEC 0.5 parts by weight Water 82.5 parts by weight Fragrances and dyes Appropriate amount This set lotion has excellent stability over time and gives good moisturizing properties during use. It gave a feeling that

Use Example 8 Using II-HPC obtained in Example 8, shampoo was adjusted according to the following formulation.

Lauryl sulfate triethanolamine 10.0 parts by weight Fatty acid monoethanolamide 5.0 parts by weight II-HPC 1.0 part by weight Water 84.0 parts by weight Fragrance and dye Appropriate amount This shampoo was excellent in stability over time and had good transparency.

Use Example 9 A set lotion was prepared in the same composition as in Use Example 7 except that III-MC obtained in Example 9 was used instead of II-HEC. It was excellent in elongation and gave a moist feel.

Use Example 10 An emulsion was prepared in the same manner as in Use Example 3 except that III-HPMC obtained in Example 10 was used in place of I-HEC, and this emulsion was excellent in stability over time and had good elongation during use. It gave a good and moist feel without stickiness.

Use Example 11 A cleansing cream was prepared in the same formulation as in Use Example 1 except that III-HEC obtained in Example 11 was used in place of I-MC. The cleansing cream was excellent in stability over time. It had good elongation when used and gave a moist feel.

Use Example 12 A lotion was formulated in the same manner as in Use Example 2 except that III-HPC obtained in Example 12 was used in place of I-HPMC. The lotion had an excellent feeling of use and was moisturized. It gave a feeling that

〔The invention's effect〕

As described in detail above, the raw material material for cosmetics of the present invention has excellent compatibility with various surfactants as compared with conventional water-soluble cellulose ethers. When used in various cosmetics, the emulsion stabilizing effect as a water-soluble polymer,
It exerts functions such as thickening effect, moisturizing effect, suspension stabilizing effect, and fluidity improving effect. Therefore, the cosmetic product containing the raw material material for cosmetics of the present invention has excellent spreadability, is not sticky, and has an excellent quality of moist finish.

Furthermore, it is possible to suppress the chemical change with time of the cosmetics and to be less susceptible to deterioration by microorganisms, so that the initial quality immediately after production can be maintained for a long period of time.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-57-176906 (JP, A) JP-A-60-212401 (JP, A) JP-A-59-207901 (JP, A) JP-A-50- 38782 (JP, A) JPK 45-9398 (JP, B1) Kokichi Kameme Soto 6 "Handbook-Cosmetics / Pharmaceutical Raw Materials-Revised Edition" (1972) P. 137-141 Nikko Chemicals Co., Ltd. 1 Issue

Claims (3)

[Claims] 1. At least one water-soluble cellulose ether selected from methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose etherified in a homogeneous reaction system in which cellulose or a cellulose derivative is dissolved in an organic solvent. Raw material substance for cosmetics consisting of. 2. The water-soluble cellulose ether, wherein the cellulose derivative is cellulose acetate, which is etherified while being saponified with an alkaline substance by a homogeneous reaction system in which the cellulose acetate is dissolved in an organic solvent. The raw material substance for cosmetics according to claim 1. 3. The cellulose derivative is cellulose acetate, and the acetyl cellulose etherified by a homogeneous reaction system in which the cellulose acetate is dissolved in an organic solvent is the deacetylated water-soluble cellulose ether. The raw material substance for cosmetics according to claim 1.