JPS6123764B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel hair rinse composition for making hair supple and easy to comb. Generally, anionic surfactants are mainly used as detergents for removing dirt from hair. However, when such detergents are used, the oil that protects the hair surface is removed at the same time, and a small amount of anionic surfactant is inevitably adsorbed and remains on the hair surface after washing. As a result, the hair loses its flexibility, resulting in hair that is dull, difficult to comb, and easily damaged.
Split ends and hair breakage are more likely to occur. Therefore, in the past, hair rinses have been used to improve this undesirable condition of the hair. By the way, this hair rinse agent is known to contain a cationic surfactant as its main ingredient, with oily substances, nonionic surfactants, bactericides, etc., and is highly effective in restoring flexibility. ing. However, in recent years, along with technological advances related to detergents, the performance required for hair rinses has gradually escalated. There has been an increasing demand for hair rinses that provide natural shine. A technique that has recently attracted attention is a technique that combines an anionic compound and a cationic compound to create a stable system that exhibits the performance of both. For example, a detergent that can soften at the same time as cleaning is a combination of a cationic surfactant and an anionic surfactant (JP-A-53-6437), and a cationic surfactant and anionic surfactant are used as a fabric softener. A method using a polymer compound in combination (U.S. Pat. No. 3,360,470) has been proposed. The present inventors have conducted extensive research in order to develop a hair rinse that exhibits superior softening effects and has good storage stability compared to conventional hair rinses. The inventors have discovered that the object can be achieved by using a quaternary ammonium salt and carboxymethylated hydroxyethylcellulose in combination, and based on this knowledge, the present invention has been completed. That is, the present invention (R in the formula is an alkyl group with 10 to 22 carbon atoms or an aliphatic hydrocarbon group with a total of 10 to 24 carbon atoms having an ether bond or amide bond in the main chain, R ₁ is a lower alkyl group or benzyl group, R ₂ and R ₃ are a lower alkyl group, a lower hydroxyalkyl group, or a hydroxypolyoxy lower alkylene group, and X is a monovalent anion). In a range of quantities, (b) general formula [A in the formula is a hydrogen atom or -CH ₂ COOM (M is an alkali metal or 1/2 alkaline earth metal)
, p, q, and r are each an integer of 0 or 1 or more. Carboxymethylated hydroxyethyl cellulose which is 0.5-4.0
The present invention provides a hair rinse composition comprising an aqueous solution containing component (a) in an amount within the range of 0.1 to 5% by weight and in an amount not greater than component (a). Examples of the mono-long chain alkyl quaternary ammonium salt used as component (a) of the composition of the present invention include diethyl-dodecyl-benzylammonium chloride, trimethyl-dodecylammonium bromide, triethyl-dodecyloxymethylammonium chloride, and dimethyl-dodecyl-benzylammonium chloride. Tridecyl-benzylammonium chloride, diethyl-pentadecyl-benzylammonium bromide, cetyl-
Trimethylammonium chloride, cetyl-trimethylammonium bromide, stearyl-trimethylammonium chloride, methyl-diethyl-oleylamide ethylammonium iodide,
Examples include octadecyl-dimethyl-benzylammonium chloride, trimethyl-octadecyloxymethylammonium chloride, dimethyl-(2-hydroxyethyl)-dodecylammonium chloride, and dimethyl-(2-hydroxyethoxyethyl)-dodecylammonium chloride. These may be used alone or in the form of a mixture derived from two or more types of alkyl groups having different carbon numbers. Examples of such include _C16 - _C18 alkyltrimethylammonium chloride, _C16 - _C18 alkyl-bis(2-hydroxyethyl)methylammonium chloride, and the like. This component (a) needs to be a mono-long chain alkyl type quaternary ammonium salt, and if a di-long chain alkyl type quaternary ammonium salt is used, a sufficient softening effect cannot be obtained. Component (a) is blended in an amount of 1 to 10% by weight based on the total amount of the hair rinse composition. If the amount is less than this, the effect will be insufficient, and if the amount is more than this, there will be no particular difference in the effect, so it will be economically disadvantageous. In the composition of the present invention, the desired effect cannot be obtained by using component (a) alone, and component (b), that is, carboxymethylated hydroxyethyl cellulose having a structural unit represented by the general formula () above, is used in combination. is necessary. This carboxymethylated hydroxyethylcellulose preferably has a degree of polymerization of about 50 or more. In addition, the average number of moles of ethylene oxide added (MS) of this product is 0.5 to 4.0, preferably 1.0.
~3.0. If this value is less than 0.5, the affinity with component (a) will decrease, dispersion stability will deteriorate, and precipitation and turbidity will occur. It causes a sticky feeling. Next, (b)
The average degree of substitution (DS) of carboxymethyl groups per constituent unit of the component must be selected within the range of 0.05 to 2.0; if it is smaller than this, it will be difficult to form a complex with component (a). Therefore, a sufficient stabilizing effect cannot be obtained, and if it is larger than this, compatibility with component (a) is lost and dispersion stability is reduced. This component (b) is produced, for example, by reacting hydroxyethyl cellulose and monochloroacetic acid in the presence of sodium hydroxide, and then neutralizing the excess alkali with an acid. It is necessary to use component (b) in an amount of 0.1 to 5% by weight based on the total amount of the hair rinse composition, and in an amount not greater than component (a).
If used in an amount greater than component (a), it will give an oily, sticky feeling after use. In addition to the components (a) and (b) described above, the composition of the present invention may optionally contain additives commonly used in hair rinses, such as other cationic surfactants, oily substances, solubilizers, Emulsifiers, disinfectants, fragrances, pigments, etc. can be added. The composition of the present invention can be easily prepared by dissolving predetermined amounts of the above-mentioned components (a) and (b) in water, and adding other additives as desired. The hair rinse composition obtained in this way is
At least a portion of component (b), ie, carboxymethylated hydroxyethyl cellulose, forms a complex with component (a), ie, quaternary ammonium salt, and maintains a uniform and transparent state. This complex is characterized in that when a hair rinse is diluted and hair is treated with it, this complex precipitates on the hair surface and adheres in the form of a film, so that a large amount remains after rinsing. Therefore, the hair rinse composition of the present invention has the advantage that it has a high softening effect because the amount of the quaternary ammonium salt deposited is large, and that it has a small coefficient of static friction, so it is smooth and easy to comb. Furthermore, carboxymethylated hydroxyethylcellulose assists in film formation, which improves the elasticity and suppleness of the hair.
Both components have good lubricity, and the use of oily substances to reinforce lubricity can be omitted, making it possible to suppress the occurrence of stickiness and shiny luster. Next, the present invention will be explained in more detail with reference to Examples. In addition, the performance evaluation of the hair rinse shown in each example was performed as follows. (1) Amount of adhesion (amount remaining on hair) Dilute the hair rinse agent 50 times (concentration 2%),
Prepare the rinse solution. Next, add 5 g of hair cut into approximately 1 cm pieces to 100 ml of pre-prepared rinse solution.
After shaking at 40°C for 24 hours, the rinse agent components adhering to the hair were extracted with ethanol, and the amount of hair adhesion was measured. (2) Coefficient of Static Friction The coefficient of static friction was measured using hair strands immersed in a 50-fold diluted hair rinse for 3 minutes, rinsed with warm water, and dried overnight at 25°C and 65% RH. (3) Flexibility, suppleness, and stickiness After treating hair with 500ml of a 50-fold dilution of hair rinse, rinsing twice with warm water and air-drying the product was compared with a standard hair rinse using a panel of 10 people. Products that are especially superior to standard products are ◎.
Good quality was rated as ○, equivalent as △, and inferior to standard product as ×. (4) Storage stability The hair rinse agent was stored at 0°C for one month and the state of phase separation was examined. The evaluation is 〇 for no separation, △ for slight separation.
Those where separation was observed were marked as ×. Further, the quantitative determination of the carboxymethyl group in the carboxymethylated hydroxyethyl cellulose and the calculation of the degree of substitution (DS) of the carboxymethyl group were performed as follows. (b) Quantification of carboxymethyl group Accurately weigh 1 g of sample and dissolve in 250 ml of ion-exchanged water. After dissolving, transfer to volumetric flask 1 and bring up to the marked line to use as a sample solution. 5
Collect the sample solution with a ml whole pipette and add it to
After adding 45 ml of ion-exchanged water and 1/200 N glycol chitosan solution with a 5 ml pipette, use toluidine blue as an indicator and add 1/200 N glycol chitosan solution.
Titrate with 400N polyvinyl potassium sulfate solution. The end point is the point where the color changes from blue to reddish-purple. In addition, a blank was prepared by adding 50 ml of ion-exchanged water to 5 ml of 1/200N glycol chitosan solution. The content of carboxyl groups is calculated from the following formula. COO (wt%) = (B-A) x f x 44.01/5 x S
×400×100 However, A: Titration number of 1/400N polyvinyl potassium sulfate solution of sample solution (ml) B: Titration number of blank 1/400N polyvinyl potassium sulfate solution (ml) f: 1/400N polyvinyl Potency of potassium sulfate solution S: Weight of collected sample (g) (b) Degree of substitution of carboxymethyl group (DS) The degree of substitution used here refers to the degree of substitution of carboxymethyl groups to three hydroxyl groups in the glucose unit of hydroxyethylcellulose. The degree of substitution (DS) is 3 at the highest value. DS = (molecular weight of glucose unit of hydroxyethyl cellulose) × COO (wt%) / 4401-80.02 × C
OO (wt%) Reference example Weigh out 180 g of isopropanol and 16.9 g of 50% by weight sodium hydroxide (1.7 mol of hydroxyethyl cellulose) into a 500 ml reactor, and while stirring, add hydroxyethyl cellulose (manufactured by Fuji Chemical Co., Ltd., MS1. 7) 38g was introduced. Next, 7.0 g of monochloroacetic acid (0.6 mol of hydroxyethyl cellulose) was dissolved in 36.6 g of water and added dropwise.
The mixture was heated in a hot water bath and reacted at 65°C for 2 to 3 hours. After the reaction was completed, 6.3 g of hydrochloric acid (36%) necessary for neutralizing excess sodium hydroxide was diluted with 120 g of an 80% by weight aqueous isopropanol solution and used for neutralization. After neutralizing for 1 hour at room temperature, the mixture was thoroughly washed with 300 g of an 80% by weight aqueous isopropanol solution, dried under reduced pressure, and the degree of substitution (DS) of the carboxymethyl group was 0.5.
A reaction product was obtained. By reacting hydroxyethylcellulose and monochloroacetic acid under similar reaction conditions, sodium salts of carboxymethylhydroxyethylcellulose with degrees of substitution of 0.1, 0.2, 0.3, and 1.0, respectively, were obtained. (The molar ratio of sodium hydroxide and monochloroacetic acid is
1.7/0.6=2.83. ) Example 1 A hair rinse composition was prepared according to the formulation shown in Table 1. Table 1 shows the results of a performance test conducted on the four types of samples thus obtained and a commercially available hair rinse agent.

[Table] As is clear from this table, the hair rinse composition of the present invention is superior to comparative examples and commercially available products in terms of combability, flexibility, suppleness, and non-stickiness. Stability is also good. Example 2 A hair rinse composition was prepared according to the formulation shown in Table 2. Table 2 shows the results of performance tests conducted on each of these hair rinse compositions.

[Table] As is clear from this table, even when using various different carboxymethyl hydroxyethyl celluloses, good results can be obtained if the average degree of carboxymethyl group substitution is in the range of 0.05 to 2.0. . In this example, as the quaternary ammonium salt,
Exactly the same results were obtained when using _C16-18 alkyl-dimethyl-(2-hydroxyethyl) ammonium chloride or _C16-18 alkyl-dimethyl-pentaethoxylated ammonium chloride. Example 3 A hair rinse composition was prepared according to the formulation shown in Table 3. Table 3 shows the results of performance tests conducted on each of these hair rinse compositions.

[Table] As is clear from this table, the hair rinse composition of the present invention exhibits superior performance compared to those containing less than 1% by weight of quaternary ammonium salt (comparative example). Example 4 A hair rinse composition was prepared according to the formulation shown in Table 4. Table 4 shows the results of a performance test conducted on this product.

【table】

[Table] As is clear from this table, all hair rinse compositions having the above compositions exhibit excellent performance.

Claims (1)

[Claims] 1 (a) General formula (R in the formula is an alkyl group with 10 to 22 carbon atoms or an aliphatic hydrocarbon group with a total of 10 to 24 carbon atoms having an ether bond or amide bond in the main chain, R ₁ is a lower alkyl group or benzyl group, R ₂ and R ₃ are a lower alkyl group, a lower hydroxyalkyl group, or a hydroxypolyoxy lower alkylene group, and X is a monovalent anion). In a range of quantities, (b) general formula [A in the formula is a hydrogen atom or -CH ₂ COOM (M is an alkali metal or 1/2 alkaline earth metal)
, p, q, and r are each an integer of 0 or 1 or more. Carboxymethylated hydroxyethyl cellulose which is 0.5-4.0
A hair rinse composition comprising an aqueous solution containing component (a) in an amount within the range of 0.1 to 5% by weight and in an amount not greater than that of component (a).