JP6172507B2 - Acyl carboxymethyl cellulose and cosmetics containing acyl carboxymethyl cellulose - Google Patents

Description

  The present invention relates to acylcarboxymethylcellulose (hereinafter sometimes referred to as “ACMC”) and cosmetics containing ACMC, and more specifically, high moisturizing property, excellent smoothness in skin, and excellent conformability in skin. ACMC having a high solubility in water, and a cosmetic that exhibits high moisture retention, excellent smoothness in skin, and excellent conformability in skin by containing ACMC. About.

  Conventionally, cellulose derivatives obtained by introducing various functional groups into the hydroxyl group of cellulose are widely known. Depending on the number and nature of functional groups introduced into cellulose, cellulose derivatives having various properties can be obtained. Therefore, the cellulose derivative can be used for various applications depending on its properties.

  For example, a cellulose derivative that is easily soluble in water can be obtained by introducing a hydrophilic functional group into cellulose. Many types of compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxyethyl cellulose are known as cellulose derivatives that are easily soluble in water. These cellulose derivatives that are easily soluble in water have a grinding property peculiar to polymers, so that they are conventionally mainly used as thickeners. In addition, since these cellulose derivatives that are easily soluble in water generally have low moisture retention performance and are not soft to the touch, they are rarely used as cosmetics applied to human skin.

  In addition, by introducing a hydrophobic functional group into cellulose, a cellulose derivative that is hardly soluble in water can be obtained. Acetylcellulose is known as a cellulose derivative that is hardly soluble in water. Acetylcellulose is difficult to dissolve in water and cannot be used as an aqueous solution. Conventionally, acetylcellulose is often used as a powdery or fibrous solid.

  Patent document 1 is mentioned as invention using a cellulose derivative. Patent Document 1 has an object of “providing a substance that is excellent in water retention and hygroscopicity and can be produced by an inexpensive and simple process” (see paragraph No. 0003 in Patent Document 1). "Fatty acid-bonded carboxymethyl cellulose obtained by addition" is disclosed (see claim 5 of Patent Document 1).

  However, according to the study by the present inventors, the number of carboxymethyl groups introduced per molecule of glucose is small, so that the carboxymethyl cellulose disclosed in Patent Document 1 is hardly soluble in water. Therefore, it is necessary to use the carboxymethyl cellulose disclosed in Patent Document 1 as a solid, and there is a problem that it cannot be used as an aqueous solution such as a skin lotion or an emulsion.

  Moreover, patent document 2 is mentioned as another invention using a cellulose derivative. Patent Document 2 has an issue of “providing a moisturizing agent having excellent moisture retention, low skin irritation and no stickiness” (see paragraph No. 0003 in Patent Document 2), A humectant characterized by containing, as essential components, a cellulose derivative (A) having 0.2 or more amide groups (a) and 0.2 or more carboxyl groups (b) per glucose unit ” It is disclosed (see claim 1 of Patent Document 2).

  However, an acyl group which is a hydrophobic group is not introduced into the cellulose derivative disclosed in Patent Document 2. Therefore, when the cellulose derivative disclosed in Patent Document 2 is used, for example, as a cosmetic, there is a problem that the conformability on the hydrophobic skin surface is poor. Further, in the cellulose derivative disclosed in Patent Document 2, since the carboxyl group introduced into cellulose is further amidated, there is a problem that the carboxyl group cannot be ionized and is hardly soluble in water.

  Furthermore, patent document 3 is mentioned as another invention using a cellulose derivative. Patent Document 3 has a problem of “providing cosmetics having a function of giving a protective and restorative effect to the skin, being easily kneaded with an oil component, and further leading to a whitening effect of inhibiting melanin production”. (See paragraph No. 0009 of Patent Document 3), “A cellulose derivative or salt thereof containing an O-acylation site in which at least a part of hydroxyl groups contained in cellulose is modified with an acyl group derived from monocarboxylic acid” ( (See claim 1 of Patent Document 3), “Cellulose derivative or salt thereof according to claim 1, comprising an O-sulfation site in which at least a part of the remaining hydroxyl group contained in cellulose is modified with a sulfate group” ( Patent Document 3 (see claim 2)) is disclosed.

  However, a carboxymethyl group which is a hydrophilic group is not introduced into the cellulose derivative disclosed in Patent Document 3. Therefore, the cellulose derivative disclosed in Patent Document 3 has a problem that it is difficult to dissolve in water and cannot be used as an aqueous solution such as a skin lotion or an emulsion.

JP 2006-117849 A JP2009-143892A JP2012-21119 Mitsuo Hirata, Faculty of Engineering, Nihon University, “Recent Water-soluble Polymers”, Coloring Materials, 49 (1976), 355-363

  The present invention solves such problems and provides ACMC having high solubility in water, and by containing such ACMC, it has high moisture retention, excellent smoothness in skin, and excellent conformability in skin. It is an object to provide a cosmetic material that demonstrates the above.

Means for solving the previous term issues are:
(1) The acylation degree is 1.0 to 2.0,
The degree of carboxymethylation is 0.7 to 1.3,
The weight average molecular weight is 5000-20000,
An acyl carboxymethyl cellulose having a structural unit represented by the general formula (1).

[式中、
Ｒ^１、Ｒ^２、及びＲ^３は、水素、アセチル基、プロピオニル基、カルボキシメチル基、又はカルボキシメチル基の塩のいずれかであり、アシル化度とカルボキシメチル化度との和が３．０以下である。]
（２）上記（１）に記載のアシルカルボキシメチルセルロースを含有することを特徴とする化粧料であり、
（３）保湿剤を含有することを特徴とする上記（２）に記載の化粧料であり、
（４）前記保湿剤がヒドロキシ酸であることを特徴とする上記（３）に記載の化粧料であり、
（５）前記ヒドロキシ酸が乳酸であることを特徴とする上記（４）に記載の化粧料である。

[Where
R ¹ , R ² , and R ³ are any one of hydrogen, an acetyl group, a propionyl group, a carboxymethyl group, or a salt of a carboxymethyl group, and the sum of the acylation degree and the carboxymethylation degree is 3.0. It is as follows. ]
(2) A cosmetic comprising the acylcarboxymethylcellulose according to (1) above,
(3) The cosmetic according to (2) above, which contains a humectant,
(4) The cosmetic according to (3), wherein the humectant is a hydroxy acid,
(5) The cosmetic according to (4), wherein the hydroxy acid is lactic acid.

  According to the present invention, the degree of carboxymethylation indicating the content of carboxymethyl groups in ACMC (hereinafter sometimes referred to as “CM degree”) is relatively large, 0.7 to 1.3, and the molecular weight is Since the ACMC is relatively small as 5000 to 20000, the ACMC has a high solubility in water. Specifically, ACMC in the present invention can be dissolved up to about 40% by mass (ACMC 40 g with respect to 60 g of water) with respect to water. Therefore, the ACMC in the present invention can be used as an aqueous cosmetic.

  According to this invention, since the degree of acylation, the degree of CM, and the weight average molecular weight in ACMC are in the above ranges, the cosmetic containing the ACMC has high moisture retention. Therefore, the cosmetics which have the outstanding moisturizing function can be provided by using ACMC in this invention.

  According to the present invention, since the acylation degree, the CMation degree, and the weight average molecular weight in ACMC are in the above ranges, the cosmetic containing the ACMC can impart excellent smoothness to the skin. In other words, when the cosmetic containing ACMC in the present invention is applied to the skin, the irregularities of the stratum corneum on the skin surface can be suppressed, and the skin surface becomes smooth. Therefore, after applying the cosmetic containing ACMC in the present invention, the frictional force on the skin surface is reduced, and the user can obtain a smooth feeling.

  According to this invention, since the degree of acylation, the degree of CM, and the weight average molecular weight in ACMC are in the above range, the cosmetic containing the ACMC is excellent in skin conformability. In other words, when the cosmetic material containing ACMC in the present invention is applied to the skin, the cosmetic material tends to spread on the skin surface. Therefore, the user of the cosmetic containing ACMC in the present invention can easily spread the cosmetic on the skin surface.

  According to this invention, the moisturizing function of the cosmetic can be further enhanced by simultaneously containing ACMC and a humectant represented by lactic acid. Therefore, it is possible to provide a cosmetic that exhibits even higher moisture retention by using the ACMC and the humectant in the present invention.

  Hereinafter, physical properties, characteristics, manufacturing methods, uses, etc. of ACMC and cosmetics containing ACMC in the present invention will be described in detail.

  ACMC has a structural unit represented by the general formula (1). The structural unit is formed by replacing part or all of hydroxyl groups located at the 2-position, 3-position, and 6-position of glucose constituting cellulose with an acyl group, a carboxymethyl group, or a salt of a carboxymethyl group. . As an example of a more preferable structural unit of ACMC, as shown by the following formula (2), the hydroxyl groups located at the 2-position and 3-position of glucose constituting cellulose are substituted with acyl groups, and glucose constituting cellulose And a compound in which the hydroxyl group located at the 6-position is substituted with a salt of a carboxymethyl group. In the following formula (2), an acetyl group is used as the acyl group. In addition, ACMC in this invention is formed when many structural units couple | bond together repeatedly in the hydroxyl group located in 1-position, and the hydroxyl group located in 4-position, and are connected in a chain form.

  Since the acyl group is a hydrophobic functional group, the greater the number of acyl groups introduced into ACMC, the stronger the hydrophobicity of ACMC. ACMC having strong hydrophobicity is easily adsorbed to a hydrophobic substance such as a stratum corneum on a human skin surface. Therefore, a cosmetic containing ACMC having a large number of introduced acyl groups spreads smoothly on the skin surface and has a high compatibility with the skin.

  The degree of acylation is the number of acyl groups introduced per glucose molecule constituting cellulose. For example, the acylation degree of ACMC represented by the above formula (2) is 2.0. The acylation degree of ACMC in the present invention is 1.0 to 2.0, preferably 1.5 to 2.0. When the degree of acylation is less than 1.0, the strength of hydrophobicity in ACMC is not sufficient, and in particular, cosmetics containing such ACMC are unfavorable because they are poorly compatible with the skin. Moreover, when the acylation degree is larger than 2.0, the hydrophobicity of ACMC becomes strong and it becomes difficult to dissolve in water, which is not preferable. Further, when the acylation degree is larger than 2.0, the hydrolysis of ACMC easily proceeds, so that the storage stability of ACMC is lowered.

  The acyl group that can be used in the present invention is an acetyl group or a propionyl group. If an acyl group having more carbon atoms than a propionyl group is introduced into cellulose, the contribution of hydrophobicity due to the acyl group is increased, and ACMC is difficult to dissolve in water. In addition, both acetyl group and propionyl group may be introduced into one molecule of ACMC, or only one of them may be introduced.

  Since the carboxymethyl group or carboxymethyl group salt is a hydrophilic functional group, the more carboxymethyl group or carboxymethyl group salt introduced into ACMC, the stronger the hydrophilicity of ACMC. ACMC having strong hydrophilicity is easily dissolved in water. Moreover, the cosmetics containing ACMC with strong hydrophilic property are excellent in moisture retention. A salt of a carboxymethyl group can be formed by ionizing a carboxymethyl group in an aqueous solution to generate a carboxylate. The cation component forming this carboxylate is preferably an alkali metal such as Na or K, or an alkanolamine such as triethanolamine, a basic amino acid such as lysine, arginine, ornithine, or histidine.

  The degree of CM conversion is the number of carboxymethyl groups and carboxymethyl group salts introduced per molecule of glucose constituting cellulose. For example, the degree of CM conversion of ACMC represented by the above formula (2) is 1.0. The degree of commercialization of ACMC in the present invention is 0.7 to 1.3. When the degree of CM conversion in ACMC is less than 0.7, ACMC is not easily dissolved in water, and the moisture retaining property of cosmetics containing ACMC is not preferable. On the other hand, if the degree of CM conversion is greater than 1.3, the cosmetic properties of ACMC-containing cosmetics are insufficiently compatible with the skin, and the skin surface after use of the cosmetics becomes sticky and feels poor. Therefore, it is not preferable. In Non-Patent Document 1, in carboxymethyl cellulose (CMC), the degree of CM conversion (expressed as “DS” in the text of Non-Patent Document 1) is “0.2 to 0.3 and alkali-soluble. , 0.4, becomes water-soluble, and becomes transparent at 0.6 or more ”(see Non-Patent Document 1, page 358, right column, lines 13-17).

  In this invention, acyl groups, carboxymethyl groups, or salts of carboxymethyl groups can be introduced into only three of the hydroxyl groups located at the 2nd, 3rd, and 6th positions per glucose molecule. Therefore, the sum of the acylation degree and the CMation degree is always 3.0 or less.

  The weight average molecular weight of ACMC is 5000-20000. When the weight average molecular weight of ACMC is more than 20000, it is difficult to dissolve in water. On the other hand, when the weight average molecular weight is more than 20000, it is not preferable because the cosmetic composition is remarkably thickened when the ACMC of the present invention is contained in the cosmetic composition, and a large amount of ACMC cannot be contained in the cosmetic composition. Moreover, when the weight average molecular weight of ACMC is smaller than 5000, it is not preferable because it does not have sufficient moisture retention. In addition, the number of repetitions of the structural unit represented by the general formula (1) is determined so that the weight average molecular weight of ACMC is 5000 to 20000.

  Although the manufacturing method of ACMC in this invention is not specifically limited, For example, the method of obtaining ACMC by introduce | transducing a fatty acid into carboxymethylcellulose can be used. Introduction of a fatty acid into carboxymethylcellulose can be easily performed using methods known to those skilled in the art. For example, a solution in which carboxymethyl cellulose, carboxylic acid or carboxylic anhydride, and an acid catalyst are mixed is refluxed to cause an ester reaction, and the solution after the reaction is alkali-neutralized to obtain a neutralized solution of ACMC. be able to. By passing this neutralized solution through a membrane such as a UF membrane, inorganic salts can be removed and the purity of ACMC can be increased. The neutralized solution can be used as it is, or can be used as ACMC powder by freeze-drying the neutralized solution. The carboxymethyl cellulose may be a commercially available product, or may be synthesized from cellulose using methods known to those skilled in the art. As an example of a method for synthesizing carboxymethyl cellulose from cellulose, there is a method of reacting cellulose with monochloromethylcarboxylic acid or sodium monochloromethylcarboxylate under alkaline conditions. Thus, ACMC can be produced using cellulose contained in a large amount in plants as a raw material. Therefore, compared with hyaluronic acid which has been widely used as a moisturizing cosmetic and is obtained from fungi or chicken crown extract, ACMC in the present invention can be produced in large quantities at a low cost.

In the present invention, the degree of CM conversion of ACMC can be determined by measuring the degree of anionization. For example, the anionization degree and the degree of cationization can be measured by using the method described in “Colloidal titration method Shinichi Sente Minami-Edo”. Further, the acylation degree of ACMC in the present invention can be determined by measuring the saponification value. For example, the degree of acylation of ACMC is determined by the method for measuring the saponification value described in “General Test Method for Quasi-drug Material 2006” be able to. As a method for determining the degree of acylation of ACMC in the present invention, ¹ H-NMR and IR can also be employed. Furthermore, the weight average molecular weight of ACMC in this invention can be calculated | required by a conventionally well-known method, for example, a gel permeation chromatography can be used.

  The cosmetic in this invention contains ACMC in this invention. A cosmetic is a composition for treating the human body for the purpose of beautification, cleanliness, protection, or deodorization. Cosmetics include, for example, lotions, packs, milky lotions, various creams, body shampoos, bath preparations, foundations, funnier, body powder, stick lipstick, blusher, eyeliner, eyeshadow, mascara, nail polish, cleansing gel, nail remover , PA, insect repellent, deodorant, shampoo, hair treatment, hair spray, hair mousse, pomade, permanent wave lotion, hair color, hair bleach, hair growth promotion, hair growth inhibitor, shaving cream, toothpaste, mouthwash, perfume And an eau de colon. A particularly preferred embodiment is an example in which ACMC according to the present invention is used for a lotion that is a cosmetic comprising an aqueous solution.

  The state of the cosmetic in the present invention is arbitrary, and any state such as a fine powder form, a fine crystal form, a liquid form, or a pellet form may be used. When manufacturing cosmetics, ACMC can be used as a solid or an aqueous solution. In order to prepare an ACMC aqueous solution, for example, a method in which ACMC powder is dissolved in water together with a pH adjusting solution typified by an acid solution and an alkaline solution can be employed.

  The ACMC contained in the cosmetic of the present invention is usually contained in a proportion of 0.0001 to 40.0 mass%, preferably 0.001 to 10.0 mass%. When the content of ACMC in the cosmetic is less than the lower limit, the moisturizing effect is insufficient, and when the content exceeds the upper limit, the sticky cosmetic is not preferred.

  In the cosmetic of the present invention, various surfactants and auxiliaries commonly used in the following cosmetics can be used as necessary.

  An example of the surfactant is an anionic surfactant. Examples of the anionic surfactant include alkylbenzene sulfonate, α-olefin sulfonate, sodium lauryl sulfate, lauryl sulfate such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, POE (3) sodium lauryl ether sulfate, POE (3) POE lauryl ether sulfates such as lauryl ether sulfate triethanolamine, higher alcohol phosphates, acylmethyl taurine salts such as cocoyl methyl taurine sodium, lauroyl methyl taurine sodium, disodium lauryl sulfosuccinate, POE (1-4) sulfosuccinate Sulfosuccinic acid type interfaces such as disodium lauryl acid, POE sulfosuccinic acid POE (5) disodium lauroyl ethanolamide, disodium oleic acid amidosulfosuccinate Sex agent, alkyl ether carboxylate, acylated isethionate, fatty acid amide ether sulfate, monoalkyl phosphate ester salt, polyoxyethylene fatty acid ethanolamide phosphate ester salt, coconut oil fatty acid sodium, sodium laurate, sodium myristate, beef tallow Higher fatty acid salts such as fatty acid sodium, coconut oil fatty acid triethanolamine, lauric acid triethanolamine, myristic acid triethanolamine, beef tallow fatty acid triethanolamine, coconut oil fatty acid potassium, lauric acid potassium, myristic acid potassium, beef tallow fatty acid potassium, Cocoyl Sarcosine Sodium, Lauroyl Sarcosine Sodium, Myristoyl Sarcosine Sodium, Lauroyl Sarcosine Potassium, Lauroyl Sarcosine Triethanol Acyl sarcosine salts such as amines, cocoylmethyl-β-alanine sodium, lauroylmethyl-β-alanine sodium, myristoylmethyl-β-alanine sodium, palmitoylmethyl-β-alanine sodium, stearoylmethyl-β-alanine sodium, lauroylmethyl- β-alanine potassium, acylmethyl-β-alanine salts such as lauroylmethyl-β-alanine triethanolamine, acyl-β-alanine salts such as lauroyl-β-alanine triethanolamine, N-2-hydroxyethyl-N-2 -Lauric acid amidoethylglycine, N-2-hydroxyethyl-N-2-coconut fatty acid amidoethylglycine, N-2-hydroxyethyl-N-2-lauric acid amidoethyl-β-alanine, N-2-hydroxyethyl -N 2-coconut oil fatty acid amidoethyl-β-alanine, N- (carboxymethyl) -N- {2- [N- (2-hydroxyethyl) lauric acid amide] ethyl} glycine, N- (carboxymethyl) -N- Amide amino acid salts such as {2- [N- (2-hydroxyethyl) coconut oil fatty acid amide] ethyl} glycine, coconut oil fatty acid acyl hydrolyzed silk peptide, lauroyl hydrolyzed silk peptide, palm kernel oil fatty acid acyl hydrolyzed silk peptide , Palm oil fatty acyl hydrolyzed collagen peptide, lauroyl hydrolyzed collagen peptide, palm kernel fatty acid acyl hydrolyzed collagen peptide, palm oil fatty acyl hydrolyzed casein peptide, lauroyl hydrolyzed casein peptide, palm kernel fatty acid acyl hydrolyzed casein peptide Thailand Coconut oil fatty acid hydrolyzed keratin peptide, lauroyl hydrolyzed keratin peptide, palm hydrolyzed fatty acid acyl hydrolyzed keratin peptide and other protein hydrolysates, N-cocoyl-L-glutamate sodium, N-lauroyl-L There are acyl glutamates such as, but not limited to, sodium glutamate, N-cocoyl-L-glutamate triethanolamine.

  An example of the surfactant is an amphoteric surfactant. Examples of amphoteric surfactants include alkyls such as 2-coconut oil alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and 2-palm kernel oil alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine. -N-carboxyethyl-N-hydroxyethyl imidazolinium betaine, 2-coconut oil alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, 2-palm kernel oil alkyl-N-carboxymethyl-N-hydroxy Amide pros such as alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine such as ethylimidazolinium betaine, coconut oil fatty acid amidopropyl betaine, lauric acid amidopropyl betaine, palm kernel oil fatty acid amidopropyl betaine Rubetain, alkyl betaines such as lauryl betaine, lauric acid amide sulfobetaine, sulfobetaine, such as lauric acid amide sulfobetaine, there is alkyldiaminoethylglycine hydrochloride.

  An example of the surfactant is a cationic surfactant. Examples of the cationic surfactant include lauryltrimethylammonium chloride and distearyldimethylcyammonium chloride.

  An example of the surfactant is a nonionic surfactant. Nonionic surfactants include fatty acid diethanolamide, fatty acid monoethanolamide, POE fatty acid monoethanolamide, amine oxide, POE higher alcohol ether, POE alkylphenyl ether, and the like.

  Examples of the adjuvant include polyhydric alcohols such as glycerin, propylene glycol, 1,3-butylene glycol, and sorbitol, higher alcohols such as cetyl alcohol and myristic acid, higher fatty acids, hyaluronic acid, carboxymethyl chitin, and elastin. , Chondroitin sulfate, dermatanic acid, fibronectin, ceramides, collagen and other water-soluble polymer substances, aloe extract, mucin, placenta extract and other cell binding agents, ogon extract, tea extract, milk extract, etc. Production inhibitor, allantoin, anti-inflammatory agent such as glycyrrhizinate, edetate, chelate such as citric acid, malic acid, gluconic acid, benzoate, salicylate, sorbate, dehydroacetate, paraoxybenzoate 2,4,4′-trichloro-2′-hydroxy Antiseptics such as diphenyl ether, 3,4,4'-trichlorocarbanito, benzalkonium chloride, hinokitiol, resorcin, antifungal agents such as zinc pyrithione, piroctone olamine, dibutylhydroxytoluene, butylhydroxyanisole, gallic Antioxidants such as propyl acid and ascorbic acid, ultraviolet absorbers such as oxybenzone, 4-tert-butyl-4′-methoxybenzoylmethane, 2-ethylhexylparadimethylaminobenzoate, silicon such as amino-modified silicon and polyether-modified silicon Compounds, kojic acid, arbutin, whitening agents such as vitamin C, fragrances, pigments and the like can be used.

  A moisturizing agent is preferably used as the auxiliary agent. Cosmetics containing ACMC and a humectant are synergistically enhanced in moisturizing properties compared to cosmetics that do not contain a humectant as an adjuvant. As the humectant, hydroxy acid is preferably used, and lactic acid is more preferably used.

  The content of these surfactants and adjuvants in the cosmetic of the present invention is appropriately selected according to the use and purpose, and is not particularly limited. The content of various surfactants and adjuvants is usually preferably in the range of 0.0001 to 50% by mass with respect to the total weight of the cosmetic, for example.

The product containing the ACMC of the present invention is not limited to cosmetics, and various products containing the ACMC of the present invention can be manufactured and used. For example, as products containing ACMC of the present invention, paper additives, plastic materials such as pharmaceutical capsules, surface treatment agents, cleaning agents, foam increasing agents, surfactants, emulsion stabilizers, dispersion stabilizers, and fire extinguishing agents Examples include drugs.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

Example 1
(Manufacturing ACMC)
Carboxymethylcellulose (Nippon Paper Chemicals F350HC-4, CM conversion 0.9 mol / C6, weight average molecular weight several hundred thousand) 20 g and glacial acetic acid 133 g are placed in a 300 ml four-necked flask and stirred at 70 ° C. for 30 minutes. Activated. Further, 67 g of acetic anhydride and 9 g of concentrated sulfuric acid were added and reacted at 70 ° C. for 40 minutes for acylation. Further, 500 g of distilled water and 270 g of 48% NaOH were added for neutralization. The obtained neutralization solution is treated with Millipore UF membrane (ultrafiltration membrane, product name: Pericon XL, type PXC005C50, molecular weight cut-off 5,000) to remove sodium acetate and sodium sulfate in the neutralization solution. Removal gave an ACMC aqueous solution. This ACMC aqueous solution was freeze-dried to obtain 10 g of ACMC powder.
(Measurement of acylation degree)
The concentration of the ACMC aqueous solution was calculated using a digital saccharimeter (HI 96801 / HANNA), diluted, added with a predetermined amount of 0.2M aqueous sodium hydroxide solution, and stirred at room temperature for 3 hours. Further, 0.2 M hydrochloric acid was added, and titration was performed with a 0.2 M aqueous sodium hydroxide solution using an automatic potentiometric titrator (EBU-610-20B / KEM). From the saponification value obtained by titration, the amount of acid produced by hydrolysis was determined, and the amount of acyl group added to CMC was calculated. Other methods and operations were performed in accordance with the saponification value measuring method described in the quasi-drug raw material specifications. The degree of acylation of ACMC in Example 1 was 1.8.
(Measurement of weight average molecular weight)
The weight average molecular weight of ACMC was determined using gel permeation chromatography (hereinafter sometimes abbreviated as “GPC”). Specifically, using a column (Shodex OHpak SB-800M HQ) and an RI detector (RI-2031 plus / JASCO), an eluent (0.1 M NaCl aqueous solution), a flow rate of 1.0 ml / min, 40 ° C. Under these conditions, the detected intensity of RI was measured. Pullulan was used as a standard sample. The weight average molecular weight of ACMC was determined based on the area area in the GPC elution curve and the calibration curve. The weight average molecular weight of ACMC in Example 1 was 10,000.

The ACMC obtained in Example 1 was used to evaluate moisture retention, smoothness, and conformability by the following methods. The measurement is performed in a constant temperature and humidity chamber (25 ° C., humidity 50%). The moisturizer aqueous solution is adjusted with citric acid and NaOH so that the ACMC concentration is 1% by mass and pH 6.0. The application amount was 10 μL per 1 cm ² of skin. The evaluation results are shown in Table 1.
(Measurement of moisture retention)
Skin conductance was measured using a skin stratum corneum moisture measuring device SKICON-200EX (made by IBS). The skin conductance when no distilled water was applied was K ₀ , the conductance after applying distilled water was K _w , and K _w / K ₀ was a reference value of 1.0. Further, the conductance after applying a humectant solution was K _S. The value of K _S / K ₀ relative to the reference value K _w / K ₀ was determined. The value of K _S / K ₀ was classified as follows, and the moisture retention was evaluated. It shows that a moisturizing effect is so high that a numerical value is high.
<Evaluation criteria for moisture retention>
○: 1.6 or more Δ: 1.3 or more and 1.5 or less ×: 1.0 or more and 1.2 or less (Measurement of skin smoothness)
Using a digital microscope VHX-1000 (manufactured by Keyence), a tape-stripped stratum corneum was photographed on the skin after application of the humectant aqueous solution. The light source was set at a position of 80 degrees with respect to the plane of the tape, and the ratio (%) of the area where the luminance range in the shooting screen was 200 or more was calculated. The calculated values were classified as follows, and the smoothness was evaluated. The portion where the stratum corneum has peeled off and the skin surface has become rough has higher brightness, so the smaller the value, the smoother the skin.
<Evaluation criteria for smoothness>
○: 9% or less △: 10% or more and 13% or less ×: 14% or more (Measurement of skin conformability)
Using a digital microscope, the diameter of 10 μL of water droplets of the moisturizer aqueous solution dropped on the skin surface was measured. The measured values were classified as follows, and the conformability was evaluated. A moisturizer aqueous solution that is easy to adjust to the skin spreads in a disk shape, so that a larger value indicates that it is easier to adjust to the skin.
<Familiarity evaluation criteria>
○: 600 μm or more Δ: 550 μm or more and 599 μm or less ×: less than 550 μm

(Example 2)
A neutralized solution was obtained in the same manner as in (Production of ACMC) in Example 1. To this neutralized solution, 2 L of saturated saline was added, salted out, filtered and dried to obtain 10 g of ACMC powder. ACMC had an acylation degree of 1.8, a CMation degree of 0.9, and a weight average molecular weight of 10,000. In addition, the obtained ACMC was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 3)
ACMC was produced in the same manner as in Example 1 except that F800HC manufactured by Nippon Paper Chemicals (degree of CM conversion 0.8 mol / C6, weight average molecular weight million) was used as carboxymethylcellulose. The degree of acylation of ACMC was 1.2, the degree of CMization was 0.8, and the weight average molecular weight was 20,000. In addition, the obtained ACMC was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4
ACMC was produced in the same manner as in Example 1, except that CMC Daicel 2450 (degree of CM conversion 1.2 mol / C6, weight average molecular weight several hundreds of thousands) manufactured by Daicel Finechem was used as carboxymethylcellulose. ACMC had an acylation degree of 1.6, a CMation degree of 1.2, and a weight average molecular weight of 10,000. In addition, the obtained ACMC was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 5)
Daicel Finechem's CMC Daicel 1260 (CM conversion rate 0.9 mol / C6, weight average molecular weight tens of thousands) was used as carboxymethylcellulose, and Millipore UF membrane (Product name Ultracell, type PLBC7610, fractional molecular weight 3,000) ACMC was produced in the same manner as in Example 1 except that the treatment was performed in the same manner as in Example 1. ACMC had an acylation degree of 1.8, a CMation degree of 0.9, and a weight average molecular weight of 6,000. In addition, the obtained ACMC was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 6)
ACMC was produced in the same manner as in Example 1 except that propionic anhydride was used instead of acetic anhydride. ACMC had an acylation degree of 1.2, a CMation degree of 0.9, and a weight average molecular weight of 10,000. In addition, the obtained ACMC was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 7)
The moisture retention was evaluated in the same manner as in Example 1 except that the concentration of the ACMC aqueous solution was 2% by mass. In addition, smoothness and familiarity were not evaluated. The evaluation results are shown in Table 1.

(Example 8)
For the aqueous solution (adjusted to pH 6.0 with NaOH) in which ACMC obtained in Example 1 was 1% by mass and lactic acid was 1% by mass, the moisture retention was carried out in the same manner as in Example 1. The smoothness and the conformability were evaluated. The evaluation results are shown in Table 1.

(Comparative Example 1)
ACMC was produced in the same manner as in Example 1 except that Serogen BS (CM conversion 0.6 mol / C6, weight average molecular weight tens of thousands) manufactured by Daiichi Kogyo Seiyaku was used as carboxymethylcellulose. The degree of acylation of ACMC was 1.9, the degree of CMization was 0.6, and the weight average molecular weight was 8,000. In addition, the obtained ACMC was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 2)
As carboxymethylcellulose, CMC Daicel 1380 (CM conversion 1.4 mol / C6, weight average molecular weight several hundreds of thousands) manufactured by Daicel Finechem was used, and a UF membrane manufactured by Millipore (product name: Ultracell, type PLBC07610, fractional molecular weight 30, ACMC was produced in the same manner as in Example 1, except that it was treated in the same manner as in Example 1. The degree of acylation of ACMC was 1.9, the degree of CMization was 1.4, and the weight average molecular weight was 6,000. In addition, the obtained ACMC was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 3)
0.11 g (1.3 mmol) of 48% caustic soda was added to 100 g of a 5% aqueous solution of ACMC (acylation degree 1.8) obtained in Example 1 (amount of ACMC contained 1.6 mmol), The acyl group was hydrolyzed by stirring at room temperature for 3 hours. The hydrolyzed solution was purified with a UF membrane to remove sodium acetate. The degree of acylation of the obtained ACMC was 0.9, the degree of CMization was 0.9, and the weight average molecular weight was 9,000. In addition, the obtained ACMC was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 4)
A neutralized solution was obtained in the same manner as in (Production of ACMC) in Example 1. Sodium acetate and sodium sulfate were removed by treating this neutralized solution with a UF membrane manufactured by Millipore (product name: Ultracell, type PLAC07610, molecular weight cut off: 1,000). The degree of acylation of the obtained ACMC was 1.8, the degree of CMization was 0.9, and the weight average molecular weight was 4,000. In addition, the obtained ACMC was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 5)
ACMC was produced in the same manner as in Example 1, except that CMC Daicel 2280 (degree of acylation 0.8 mol / C6, weight average molecular weight several millions) manufactured by Daicel Finechem was used as carboxymethylcellulose. The degree of acylation of ACMC was 1.1, the degree of CMization was 0.8, and the weight average molecular weight was 40,000. In addition, the obtained ACMC was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 6)
The degree of CM conversion and the weight average molecular weight were measured in the same manner as in Example 1 except that carboxymethyl cellulose (manufactured by Nippon Paper Chemicals, trade name: F350HC-4) was used instead of the ACMC powder in Example 1. did. In addition, using this carboxymethylcellulose, the moisturizing property, smoothness, and conformability were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 7)
The weight average molecular weight was measured in the same manner as in Example 1 except that oligohyaluronic acid (trade name, Hyarooligo) manufactured by Kewpie was used instead of the ACMC powder in Example 1. Further, using this oligohyaluronic acid, evaluation of moisture retention, smoothness, and conformability was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 8)
The weight average molecular weight was measured in the same manner as in Example 1 except that hyaluronic acid (trade name Bio Sodium Hyalulonate HA12, manufactured by Shiseido Co., Ltd.) was used instead of the ACMC powder in Example 1. Further, using this hyaluronic acid, evaluation of moisture retention, smoothness, and conformability was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 9)
The degree of acylation and the weight average molecular weight were measured in the same manner as in Example 1 except that acetyl hyaluronic acid (trade name Sodium Acetyl Hyalulonate, manufactured by Shiseido) was used instead of the ACMC powder in Example 1. . In addition, the acetyl hyaluronic acid was used to evaluate moisture retention, smoothness, and conformability in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 10)
The acylation degree and the weight average molecular weight were measured in the same manner as in Example 1 except that acylcellulose (manufactured by Wako Pure Chemical Industries, cellulose triacetate) was used instead of the ACMC powder in Example 1. . Moreover, since this acyl cellulose has low solubility in water and cannot prepare a 1% by mass aqueous solution, it has not been possible to evaluate moisture retention, smoothness, and conformability. The results are shown in Table 1.

(Comparative Example 11)
In place of the 1% ACMC aqueous solution in Example 1, a 1% by mass aqueous solution of lactic acid (adjusted to pH 6.0 with NaOH) was used to evaluate the moisture retention by the same method as in Example 1. It was. The evaluation results are shown in Table 1.

  The measured values of the acylation degree, the degree of CMization, and the weight average molecular weight of the materials used in Examples and Comparative Examples, and the measurement values and evaluation results of moisture retention, smoothness, and conformability are shown in Table 1. Shown in In addition, the evaluation result of moisture retention, smoothness, and conformability is shown in the upper part of each column, and the measured value is shown in the lower part of each column.

In each of Examples 1 to 6 using ACMC in the present invention, moisture retention, smoothness in skin, and conformability in skin were good. In Example 7, where a 2% aqueous solution of ACMC in the present invention was prepared, the moisture retention was good. In Example 8 where an aqueous solution containing two components of ACMC and lactic acid according to the present invention was prepared, the moisture retention, smoothness in skin, and conformability in skin were good.
On the other hand, Comparative Example 1 with a low CM degree, Comparative Example 2 with a high CM degree, Comparative Example 3 with a low degree of acylation, Comparative Example 4 with a low weight average molecular weight, Comparative Example 5 with a high weight average molecular weight, and acylation The comparative example 6 using the carboxymethyl cell source which was not done was not good in moisture retention, smoothness in skin, and conformability in skin. In Comparative Examples 7 to 9 using hyaluronic acid generally used as a moisturizing agent, the moisturizing property, the smoothness of the skin, and the conformability to the skin were not good. Since the acylcellulose in Comparative Example 10 has a low solubility in water and an aqueous solution cannot be prepared, the moisture retention, smoothness, and conformability could not be evaluated. Moreover, in the comparative example 11 using the aqueous solution containing only lactic acid, moisture retention was not favorable.

Example 9
<Evaluation of solubility of ACMC>
4 g of the lyophilized powder of ACMC obtained in Example 1 was added to 6 g of distilled water and stirred to obtain an aqueous solution of 40% by mass of ACMC. The appearance was colorless and transparent, had no insoluble matter, and had fluidity. It was shown that ACMC in the present invention can be dissolved by 40% by mass with respect to water.

(Example 10)
When the hair brushing agent composition shown below was prepared and the performance was evaluated, this hair brushing agent composition showed high moisturizing property, and the user could feel an excellent moist feeling. The numbers in the composition indicate mass%.
(composition)
Cocoyl arginine ethyl ester / PCA salt 0.5
ACMC 0.3 obtained in Example 1
Ethanol 5.0
Methylparaben 0.1
Fragrance 0.1
Purified water balance (prepared so that the total is 100)

(Example 11)
When the hair treatment composition shown below was prepared and its performance was evaluated, the hair treatment composition showed high moisture retention, and the user could feel an excellent moist feeling.
(composition)
PPG-1 / PEG-1 stearamine 3.0
ACMC 0.15 obtained in Example 1
Cetostearyl alcohol 2.5
Liquid paraffin 1.5
POE (5) stearyl ether 1.0
Glycerin 5.0
Preservative 0.1
Purified water balance (prepared so that the total is 100)

(Example 12)
When the emulsion shown below was prepared and the performance was evaluated, this emulsion showed high moisturizing properties and the user could feel an excellent moist feeling.
(composition)
Liquid paraffin 10.0
Squalane 2.0
Vaseline 2.0
Sorbitan sesquioleate 0.9
Polyoxyethylene oleyl ether 1.2
Glycerin 3.0
Ethanol 3.0
Carboxyvinyl polymer 0.2
Potassium hydroxide 0.1
ACMC 0.08 obtained in Example 1
PCA soda 1.0
Loofah extract 1.0
Preservative 0.5
Purified water balance (prepared so that the total is 100)

(Example 13)
When the hair rinse composition shown below was prepared and the performance was evaluated, this hair rinse composition showed high moisturizing property, and the user was able to feel an excellent moist feeling.
(composition)
PPG-1 / PEG-1 stearamine 3.0
Cetanol 3.5
Jojoba oil 2.0
Lipophilic glyceryl monostearate 1.0
Polyethylene glycol (8EO) 0.3
1.3-Butylene glycol 5.0
ACMC 0.2 obtained in Example 1
Hyaluronic acid 0.2
Amino-modified silicone polymer 0.5
Preservative 0.3
Purified water balance (prepared so that the total is 100)

(Example 14)
When the hair shampoo composition shown below was prepared and the performance was evaluated, this hair shampoo composition showed high moisturizing property and the user could feel an excellent moist feeling.
(composition)
Polyoxyethylene (3) sodium lauryl ether sulfate (25%) 10.0
Lauroylmethyl-β-alanine sodium (30%) 15.0
Amidopropyl betaine laurate (30%) 15.0
N-cocoyl-L-glutamic acid monotriethanol amine salt (30%) 10.0
Lauric acid diethanolamide 3.0
ACMC 0.2 obtained in Example 1
Sodium edetate 0.2
Preservative 0.3
Purified water balance (prepared so that the total is 100)

(Example 15)
When the lotion composition shown below was prepared and the performance was evaluated, this lotion showed high moisturizing properties and the user could feel an excellent moist feeling.
(composition)
Ethanol 10.0
Glycerin 5.0
ACMC 2.0 obtained in Example 1
Methylparaben 0.1
Sodium edetate 0.1
Purified water balance (prepared so that the total is 100)

(Example 16)
When the hair essence composition shown below was prepared and the performance was evaluated, this hair essence showed high moisturizing property and the user was able to feel an excellent moist feeling.
(composition)
Ethanol 20.0
ACMC 0.1 obtained in Example 6 0.1
Methylparaben 0.1
Sodium edetate 0.1
Purified water balance (prepared so that the total is 100)

(Example 17)
When the lotion composition shown below was prepared and the performance was evaluated, this lotion showed high moisturizing properties and the user could feel an excellent moist feeling.
(composition)
ACMC 0.5 obtained in Example 1
Sorbit liquid 2.00
Polyoxyethylene sorbitan monooleate 0.50
Ethanol 5.00
Methyl paraoxybenzoate 0.20
Purified water balance (prepared so that the total is 100)

(Example 18)
When the following O / W type cream was prepared and its performance was evaluated, this O / W type cream showed high moisturizing properties and the user could feel an excellent moist feeling.
(composition)
Olive oil 9.00
Paraffin 3.00
Isopropyl myristate 2.50
Lanolin 3.50
Beeslow 2.00
Cetanol 5.50
Tetraoleic acid polyoxyethylene sorbit (40 mol) 2.00
Tetraoleic acid polyoxyethylene sorbit (60 mol) 2.00
Propyl paraoxybenzoate 0.10
Ethyl paraoxybenzoate 0.10
Propylene glycol 9.00
Fragrance 0.20
ACMC 0.5 obtained in Example 1
Purified water balance (prepared so that the total is 100)

(Example 19)
When the emulsion shown below was prepared and the performance was evaluated, this emulsion showed high moisturizing properties and the user could feel an excellent moist feeling.
(composition)
Isopropyl myristate 3.50
Lanolin 2.00
Olive oil 1.50
Cetanol 2.00
Squalane 0.50
Tetraoleic acid polyoxyethylene sorbit (40 mol) 2.00
Tetraoleic acid polyoxyethylene sorbit (60 mol) 2.00
Propyl paraoxybenzoate 0.10
Ethyl paraoxybenzoate 0.10
Propylene glycol 9.00
ACMC 0.6 obtained in Example 4
Purified water balance (prepared so that the total is 100)

(Example 20)
When the hair shampoo composition shown below was prepared and the performance was evaluated, this hair shampoo composition showed high moisturizing property and the user could feel an excellent moist feeling.
(composition)
ACMC 0.4 obtained in Example 5 0.4
Sodium lauryl ether (2EO) sulfate 6.0
Sodium lauryl sulfate 3.5
Palm oil fatty acid diethanolamide 4.5
Propylene glycol 2.0
Edetic acid 0.2
Purified water balance (prepared so that the total is 100)

Claims (5)

The acylation degree is 1.0-2.0,
The degree of carboxymethylation is 0.7 to 1.3,
The weight average molecular weight is 5000-20000,
An acyl carboxymethyl cellulose having a structural unit represented by the general formula (1).

[Where
R ¹ , R ² , and R ³ are any one of a salt of hydrogen, acetyl group, propionyl group, carboxymethyl group, or carboxymethyl group, and the sum of the acylation degree and the carboxymethylation degree is 3.0 or less. It is. ]   A cosmetic comprising the acylcarboxymethyl cellulose according to claim 1.   The cosmetic according to claim 2, comprising a moisturizing agent.   The cosmetic according to claim 3, wherein the humectant is a hydroxy acid.   The cosmetic according to claim 4, wherein the hydroxy acid is lactic acid.