JP3410592B2 - Cosmetic containing siloxane-grafted cellulose derivative and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cosmetic containing a siloxane-grafted cellulose derivative as a film forming agent.

[0002]

2. Description of the Related Art Polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer and the like have been used as compounds conventionally used as film forming agents for cosmetics for hair and skin. However, since the film formed by such a film-forming agent has a strong hygroscopic property, it absorbs moisture in the air under high humidity conditions,
The tackiness increases, and, for example, in the case of a hair styling agent such as hair foam, the hair becomes sticky and combing is poor, and the hair styling agent becomes difficult to wash off when washing the hair. Organopolysiloxane is also used as a film-forming agent because it is excellent in water repellency, lubricity, and gloss-imparting property, but if the compounding amount is large, stickiness occurs. To solve this problem for organopolysiloxanes, macromonomers containing organopolysiloxanes have been added:
It has also been proposed to use as a polymer by radical polymerization with a vinyl compound such as vinylpyrrolidone, acrylate, or methacrylate. However, since all of these materials are mainly composed of synthetic polymers, biodegradability cannot be expected, adverse effects on the environment are considered, and there is concern about the safety of skin, mucous membranes, and hair.

[0003]

DISCLOSURE OF THE INVENTION The present invention has various problems of cosmetics caused by the above-mentioned conventional film-forming agents, that is, it has a high hygroscopicity, so that it absorbs moisture in the air under high humidity conditions and has no tackiness. In the case of hair foams, etc., the hair was sticky, the combing was poor, and the hair styling agent was difficult to wash off during washing. Water repellency and lubricity of polysiloxane,
The present invention has been completed by discovering that the cellulose derivative has properties such as film-forming property, biodegradability, and safety, which are provided with glossiness.

[0004]

The present invention uses the following general formula (Chemical Formula 3) as a film forming agent.

[Chemical 3] [Here, Cell- represents a glucose residue of cellulose or a cellulose derivative, R ¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represents the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ⁸ , R ⁹ and R ¹⁰ respectively represent the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms. Or
-OSiR ¹¹ R ^{12 The} siloxy group represented by R ¹³ is (R
¹¹ , R ¹² and R ¹³ are monovalent hydrocarbon groups having 1 to 10 carbon atoms), m is an integer of 0 to 5, n is a number of 3 to 200, x and y are siloxanes relative to cellulose or a cellulose derivative. 1 to 30% by weight is contained], which is a cosmetic containing a siloxane-grafted cellulose derivative
This siloxane-grafted cellulose derivative has the following general formula (formula 4)

[Chemical 4] [Here, R ¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different from each other. Is a monovalent hydrocarbon group, and R ⁸ , R ⁹ and R ¹⁰ are the same or different from each other, respectively, a monovalent hydrocarbon group having 1 to 10 carbon atoms or -OSiR ¹¹
The siloxy group represented by R ¹² R ¹³ (R ¹¹ , R ¹² , R
¹³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms), m is 0
An integer of 5 and n is a number of 3 to 200]. The method for producing a cosmetic is characterized by being obtained by reacting with an isocyanate group-containing organopolysiloxane.

The present invention will be described in detail below. The siloxane-grafted cellulose derivative in the present invention is
It is obtained by reacting A) a thermoplastic cellulose derivative having a hydroxyl group with B) an isocyanate group-containing organopolysiloxane represented by the general formula (Formula 2) (hereinafter abbreviated as organopolysiloxane). As the cellulose derivative that can be used for, ethyl ether, cellulose ether derivative such as hydroxypropylmethyl cellulose, hydroxypropyl cellulose,
Cellulose ester derivatives such as cellulose acetate and cellulose acetate butyrate are exemplified.
In these cellulose derivatives, the average number of hydroxyl groups per glucose unit is preferably 0.3 or more.
If it is less than 0.3, the reaction between this and the organopolysiloxane is delayed, and it is difficult to sufficiently obtain the target product having the characteristics of the organopolysiloxane. The degree of polymerization may be in the range that a normal cellulose derivative has, but considering the viscosity of the solution at the time of reaction and the solubility when the obtained siloxane-grafted cellulose derivative is dissolved in an organic solvent, the viscosity of the solution is 50- 4,000 is preferred.

The organopolysiloxane used in the present invention is represented by the general formula (Formula 2). This R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R
Examples of the monovalent or divalent hydrocarbon group having 1 to 10 carbon atoms represented by ¹⁰ , R ¹¹ , R ¹² , and R ¹³ include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; a cyclopentyl group, Cycloalkyl group such as cyclohexyl group; aryl group such as phenyl group; aralkyl group such as benzyl group; alkenyl group such as vinyl group, allyl group; substituted carbonization such as chloromethyl group, 3,3,3-trifluoropropyl group Examples of hydrogen groups, R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ may be the same or different from each other. Further, R ⁸ , R ⁹ and R ¹⁰ may be a siloxy group represented by -OSiR ¹¹ R ¹² R ¹³ , and as the siloxy group, a trimethylsiloxy group, an ethyldimethylsiloxy group, a phenyldimethylsiloxy group, vinyl Examples thereof include a dimethylsiloxy group, a chloromethyldimethylsiloxy group, and a 3,3,3-trifluoropropyldimethylsiloxy group.

The organopolysiloxane used in the present invention is represented by the above general formula (Formula 2), and n is preferably 3 to 200. This is because when n is less than 3, there is no property as an organopolysiloxane, and when n
If it exceeds 200, the grafting reaction rate becomes slow and it is not practical. Further, one example of the method for producing this organopolysiloxane is one in which a silicone compound having an isocyanate group and a vinyl group in a molecule and a SiH group are included in a molecule.
An organopolysiloxane having one isocyanate group in one molecule can be produced by hydrosilylating a linear organohydrogenpolysiloxane having one unit in the presence of a hydrosilylation catalyst such as a platinum-based catalyst. . The organopolysiloxane used in the present invention is preferably contained in an amount of 1 to 30% by weight based on the thermoplastic cellulose derivative having a hydroxyl group. If it is less than 1% by weight, the oil resistance and water resistance of the film formed by the siloxane-grafted cellulose derivative are insufficient, and if it exceeds 30% by weight, the film removal property becomes poor when washing the hair, and it is not suitable for soap and shampoo. It will not dissolve.

A second invention of the present invention is a siloxane-grafted cellulose derivative obtained by reacting a thermoplastic cellulose derivative having a hydroxyl group with an organopolysiloxane represented by the general formula (Formula 2) under melting conditions as described above. This is a method for producing a cosmetic composition containing a film-forming agent. The conventional method for producing a siloxane-grafted cellulose derivative is to react a cellulose derivative with a normal organopolysiloxane in a solvent, and a complicated post-treatment such as a step of washing and removing unreacted substances and a catalyst, a step of recovering a solvent, a step of drying, etc. Since the process is required, the manufacturing cost is remarkably high, and it is industrially extremely disadvantageous. Therefore, the siloxane-grafted cellulose derivative is currently used only for a special purpose.

[0009] The inventors previously filed an application for a novel siloxane-grafted cellulose derivative not listed in the literature and a method for producing the same by Japanese Patent Application No. 7-85490. It was a reaction with an organopolysiloxane. The method for producing a siloxane-grafted cellulose derivative according to the second aspect of the present invention is carried out under the melting condition of the thermoplastic cellulose derivative having a hydroxyl group, and the reaction temperature varies depending on the kind of the cellulose derivative and is usually 130 to 20.
0 ° C. is preferred. The reaction method is a method in which an organopolysiloxane represented by the general formula (Formula 2) is added little by little while kneading a cellulose derivative in a molten state and mixed and reacted, and both are mixed at a low temperature in advance and melted. There is a method of raising the temperature to the reaction, but this method may be used. The reaction is preferably carried out in the presence of an inert gas such as nitrogen in order to prevent the oxidation reaction. The reaction product can be obtained as a molded product such as a pellet.

The novel method for producing the siloxane-grafted cellulose derivative in the present invention is carried out under the melting condition of the thermoplastic cellulose derivative having a hydroxyl group. The important point is that the isocyanate equivalent of the organopolysiloxane of the general formula (Formula 2) is cellulose. It is necessary to mix and react with the addition amount of the organopolysiloxane which is slightly lower than the equivalent amount of the hydroxyl group contained in the derivative. This is to minimize the unreacted substances of the relatively expensive organopolysiloxane (formula 2). For the reasons described above, it is preferable to add the organopolysiloxane so that it is usually grafted to the cellulose derivative in an amount of 1 to 30% by weight.

As an example of the production of the organopolysiloxane represented by the formula (2), for example, a one-end hydrogenene polysiloxane produced by a known method and a vinylisocyanatopropyltetramethylsiloxane represented by the following formula (formula 5) are subjected to an addition reaction. To manufacture.

[Chemical 5] The compound of (Chemical Formula 5) is a compound of vinylaminopropyltetramethylsiloxane obtained by disproportionating divinyltetramethylsiloxane and diaminopropyltetramethylsiloxane as shown in the chemical formula (Chemical Formula 6), using phosgene or chloroformate. Is obtained by a known method.

[Chemical 6]

As an example of the method for producing the siloxane-grafted cellulose derivative in the present invention, for example, as an example of (Chemical formula 2), R ¹ =-(CH ₂ ) _3- , R ^{2 to} R ⁹ = C
H _3, and the _{^{R 10 = C 4 H 9,}} m = 1, n = 30, in addition 5% by weight of an organopolysiloxane with respect hydroxypropyl cellulose, is reacted according to the method of the present invention, the water - ethanol What is obtained is one which is soluble in the mixed solution and has the properties of organopolysiloxane, such as water repellency, lubricity, gloss imparting property, and good film-forming property of the cellulose derivative, which are the same as those of the present invention. It is extremely useful as a film-forming agent as a raw material for cosmetics.

Further, as an example of (Chemical Formula 2) in ethyl cellulose, in (Chemical Formula 2), R ¹ =-(CH ₂ ) _3- , R ^{2 to} R ⁹ = CH _3, R ¹⁰
= C ₄ H ₉ , m = 1, n = 30, when the organopolysiloxane is reacted at 10% by weight with respect to ethyl cellulose by the method of the present invention, water repellency which is a characteristic of the organopolysiloxane,
A siloxane-grafted cellulose derivative having both the lubricity and the film-forming property of the cellulose derivative is obtained, which is extremely useful as a film-forming agent as a raw material of the cosmetic of the present invention.

As described above, since the siloxane-grafted cellulose derivative produced by the method of the present invention is a material having both the properties of organopolysiloxane and cellulose, it has other uses as a film-forming agent of the above cosmetics. It is also useful as a gas separation membrane, adhesive, paint, medical material and the like. The method for producing the siloxane-grafted cellulose derivative in the present invention is characterized by no solvent and no catalyst, but a small amount of a catalyst such as triethylamine or the like in order to increase the reaction rate under the melting condition of the thermoplastic cellulose derivative having a hydroxyl group. A solvent such as dimethylformamide may be added for the reaction. Further, for the purpose of imparting another function to the siloxane-grafted cellulose derivative in the second aspect of the present invention, other organic isocyanates such as isocyanate propyltriethoxysilane represented by the following formula may be simultaneously reacted. (H ₅ C ₂ O) ₃ Si (CH ₂ ) ₃ NCO

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to Examples.

【Example】

(Manufacturing example 1 of siloxane-grafted cellulose derivative) Laboplast mill [manufactured by Toyo Seiki Seisaku-sho, Ltd.] and hydroxypropyl cellulose [Shin-Etsu Chemical Co., Ltd. HPC, LE-G]
Type] 100 parts by weight and the average composition formula is the following formula (Formula 7) (A)
5 parts by weight of the organopolysiloxane represented by (4) were thoroughly mixed and charged, and the mixture was melted and mixed for 10 minutes at 140 to 150 ° C. in a nitrogen atmosphere and reacted. This was cooled and taken out, and it was confirmed by infrared absorption spectrum that the absorption wave number (2,350 cm ^-1 ) of the NCO group had disappeared, and the reaction was confirmed to be complete. 105 parts by weight of siloxane-grafted hydroxypropylcellulose were obtained.

Example 1 It was confirmed that the product was dissolved in a mixed solution of ethyl alcohol and water (weight ratio 1: 1), ethyl alcohol and isopropyl alcohol. Then, a 5% by weight ethanol solution of this siloxane-grafted hydroxypropyl cellulose was applied to the surface of the polyester film, and the coefficient of kinetic friction was measured after drying and found to be 0.21. The coefficient of kinetic friction of hydroxypropyl cellulose was similarly measured and found to be 0.39. From this result, it was confirmed that the lubricity of the organopolysiloxane was imparted to the siloxane-grafted hydroxypropyl cellulose. [The dynamic friction coefficient is
It is a value obtained by using a device manufactured by Kyowa Interface Science Co., Ltd., with a load of 50 g of SUS ball and at a speed of 20 cm / min. ]

(Production Example 2 of siloxane-grafted cellulose derivative) Ethyl cellulose [trade name N-7-G manufactured by Shin-Etsu Chemical Co., Ltd., ethyl group per glucose unit = 2.3, hydroxyl group =
0.7 content] 100 parts by weight and the average composition formula is the following formula (Formula 7).
10 parts by weight of the organopolysiloxane represented by (B) was mixed well, and the same procedure as in Production Example 1 was performed with a Labo Plastomill.
The mixture was melted and mixed at 205 ° C for 20 minutes and reacted. Then, this was cooled and taken out, and it was confirmed by the infrared absorption spectrum that the absorption wave number of the NCO group was gone, and it was confirmed that the reaction was completed. 110 parts by weight of siloxane-grafted ethyl cellulose were obtained.

Example 2 This was dissolved in a mixed solvent of toluene-butyl cellosolve (weight ratio 9: 1) in an amount of 5% by weight, and the dynamic friction coefficient was measured in the same manner as in Example 1.
It was confirmed to be 0.14, and it was confirmed that the lubricity of the organopolysiloxane was well imparted to the siloxane-grafted ethyl cellulose. On the other hand, the coefficient of dynamic friction of ethyl cellulose is 0.32
Met.

[Chemical 7]

[Examples 3 to 4] (Preparation of hair foam agent) Using the siloxane-grafted cellulose derivative obtained in Examples 1 and 2, hair foam agents having the following compositions were prepared.
The present invention product of No. 4 was used. (Hair foam composition) Siloxane-grafted cellulose derivative (Examples 1 and 2) 5.0% by weight Liquid paraffin 5.0〃 Polyoxyethylene hydrogenated castor oil 1.0〃 Fragrance 〃 Deionized water Adequate quantity〃 Ethanol 15.0〃 Liquefied petroleum gas 8.0〃 Total 100.0 weight%

Comparative Example 1 A hair foam was prepared with the same composition as in Examples 3 to 4, except that hydroxypropyl cellulose was blended in place of the siloxane-grafted cellulose derivative used in Examples 3 to 4 as a comparative example. And Table 1
For each item, the preparations of Examples and Comparative Examples were compared and evaluated according to the following criteria, and the results are shown in Table 1. (Evaluation Criteria) Good: The product of the present invention is superior to the product of the comparative example. Δ: The product of the present invention is equivalent to the product of the comparative example. X: The product of the comparative example is superior to the product of the present invention.

[0021]

[Table 1]

From the results of the above examples, it is found that the cosmetics of the present invention using the siloxane-grafted cellulose derivative having excellent lubricity as a film forming agent are extremely superior to the products of Comparative Examples. confirmed.

[0023]

The cosmetics of the present invention using the siloxane-grafted cellulose derivative as a film-forming agent are superior in lubricity and the like to conventional products and competitive products, and have the same film removability. The method for producing a siloxane-grafted cellulose derivative as a film-forming agent according to the second aspect of the present invention not only does not require a washing step and a solvent recovery step, but also has a high reaction yield and therefore a small loss and is almost quantitative. Since it has the advantage that the target substance can be obtained in a short time and is an extremely industrially advantageous method, the cosmetics produced using this are excellent in terms of lubricity and are inexpensive. It's safe.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Makoto Kamei, 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) Reference JP-A-7-70204 ( JP, A) Patent 3016543 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K ⁷ /00-7/50 C08B 15/00-15/10 C08L 1/00-1 / 32 CA (STN)

Claims (2)

(57) [Claims] 1. A film forming agent represented by the following general formula (Chemical Formula 1): [Here, Cell- represents a glucose residue of cellulose or a cellulose derivative, R ¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represents the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ⁸ , R ⁹ and R ¹⁰ respectively represent the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms. Or
-OSiR ¹¹ R ^{12 The} siloxy group represented by R ¹³ is (R
¹¹ , R ¹² and R ¹³ are monovalent hydrocarbon groups having 1 to 10 carbon atoms), m is an integer of 0 to 5, n is a number of 3 to 200, x and y are siloxanes relative to cellulose or a cellulose derivative. 1-30% by weight] A cosmetic containing a siloxane-grafted cellulose derivative. 2. A thermoplastic cellulose derivative in which the siloxane-grafted cellulose derivative has a hydroxyl group is melted under the following general formula (Chemical Formula 2): [Here, R ¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different from each other. Is a monovalent hydrocarbon group, and R ⁸ , R ⁹ and R ¹⁰ are the same or different from each other, respectively, a monovalent hydrocarbon group having 1 to 10 carbon atoms or -OSiR ¹¹
The siloxy group represented by R ¹² R ¹³ (R ¹¹ , R ¹² , R
¹³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms), m is 0
An integer of 5 and n is a number of 3 to 200], and is obtained by reacting with an isocyanate group-containing organopolysiloxane.