JPH0238562B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a pre-shampoo type hair treatment composition,
More specifically, the present invention relates to a shampoo type hair treatment composition containing a cationized keratin derivative as a peptide. Hair is extremely easily soiled by dirt from the outside world, decomposed products of sebum secreted from the scalp, oxides, etc., and shampoo compositions are used to wash the hair in order to remove this dirt. Shampoo compositions used when washing hair contain surfactants such as anionic surfactants and amphoteric surfactants as main ingredients, and they are used to remove dirt and give a moisturized feel to the hair during washing. It also removes necessary sebum. Hair from which sebum has been washed away has drawbacks such as being unpleasant to the touch, difficult to handle because it is difficult to brush or comb through, and easily damaging the hair and causing split ends and hair cut. In order to prevent such deterioration of hair due to hair washing, additives such as fats or polymer compounds are incorporated into shampoo compositions to improve the finish of the hair after washing. On the other hand, recently, a press shampoo-type hair treatment agent containing oils such as liquid lanolin has been developed and marketed as an innovative product for protecting hair, and has been well received. In other words, by applying a pre-shampoo type hair treatment agent to the hair before washing and washing the hair normally, hair damage that occurs during hair finishing such as washing, rinsing, and drying with a hair dryer can be prevented, and a conditioning effect can be achieved on the hair. It is intended to give However, when hair is protected with the hair treatment agent containing oils and fats such as lanolin as the main effect ingredient, it has disadvantages such as a heavy finish and sometimes stickiness, and further improvement research is required. was. The present inventors relate to a pre-shampoo type hair treatment agent (hereinafter referred to as a "pre-shampoo treatment agent"),
As a result of extensive research, it was discovered that by incorporating a cationized keratin derivative, a pre-shampoo treatment agent having an excellent hair conditioning effect that overcomes the above-mentioned drawbacks can be obtained, and the present invention was completed. That is, the present invention provides a shampoo treatment agent containing a cationized keratin derivative. The cationized keratin compound derivative used in the present invention is a reductive decomposition product of a keratin substance.

【formula】

It is a product to which a quaternary ammonium salt type cationizing agent having a group represented by the formula: [Formula] or CH ₂ ═CH 2 — and a quaternary nitrogen is added, and is produced as follows. Keratin substances include animal hair, hair, feathers,
Examples include nails, horns, hooves, scales, etc., with wool, feathers, and hair being particularly preferred. Although these keratin substances can be subjected to the reduction treatment as they are, it is also possible to use a keratin substance that has been subjected to a hydrolysis treatment prior to the treatment. If necessary, keratin materials are pretreated by crushing or cutting them into appropriate sizes, washing and degreasing them, and furthermore by heating them at high temperatures and then rapidly releasing them into the atmosphere to cause them to swell. Good too. Hydrolysis treatment can be performed using any of acids, alkalis, and enzymes. The conditions for hydrolysis treatment are not particularly limited, but if the molecular weight of the hydrolyzate is 500~
10,000, particularly preferably 1,000 to 5,000. Even if the molecular weight is less than 500, the effect is only inferior, and although it is sufficient to use a large amount, there is a drawback that it is difficult to use.
Among the above hydrolysis methods, the method using enzymes is particularly preferred because the molecular weight distribution of the decomposed product is narrow and uniform, and free amino acids are less produced. The reduction treatment of keratin materials (including their hydrolysates) is carried out, for example, by treatment with a reducing agent in water or a mixed solvent of water and a hydrophilic organic solvent. ―
S—S—) is cleaved into a sulfhydryl group (—SH). Reducing agents include any reducing agent capable of cleaving disulfide bonds in keratin materials to sulfhydryl groups. Such reducing agents include thiol derivatives of alcohols or carboxylic acids such as 2-mercabutoethanol and thioglycolic acid, phosphorus compounds such as tri-n-butylphosphine and triphenylphosphine, and organic reducing agents such as ascorbic acid. agent and sodium hydrogen sulfate,
Inorganic reducing agents such as sodium sulfite may be used. Examples of hydrophilic organic solvents include methanol,
Examples include ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, dimethyl formamide, dimethyl sulfoxide, hexamethyl phosphoric triamide and the like. There is no strict limit to the amount of the reaction solvent, as long as it is sufficient to uniformly carry out the reduction reaction, and the amount used is usually 10 to 100 times the weight of the keratin material. The amount of reducing agent used is generally 2 to 10 equivalents to the disulfide bonds in the keratin material as the raw material. In addition, the pH of the reaction system is usually 2~
12, particularly preferably in the range of 6 to 11. Furthermore, regarding the reaction temperature, room temperature is usually sufficient, but if necessary, heating can be applied to shorten the reduction time. As for the reaction time, it is necessary to sufficiently complete the reduction reaction, and it usually takes 2 to 3 hours or more, depending on the reaction temperature. Note that the reduction reaction is preferably carried out in an inert gas atmosphere such as nitrogen. This is because the sulfhydryl group produced by the reduction reaction is extremely easily oxidized and is also unstable to oxygen in the air. The reductive decomposition product of the keratin material thus obtained is treated with a quaternary ammonium salt type cationizing agent as described above to remove the sulfhydryl group or sulfhydryl group and other functional groups present in the molecule, such as By adding a cationizing agent to a hydroxyl group, amino group, carboxyl group, etc., for example, in the case of a sulfhydryl group,

A group such as [Formula] (R, R', R'' represents lower alkyl, allyl, etc.) is formed. Quaternary ammonium salt type cationizing agents include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, allyltrimethylammonium chloride and corresponding bromides and iodides, with glycidyltrimethylammonium chloride being the most common. Reductive decomposition products of keratin materials and the cations concerned. The addition reaction with the cationizing agent is carried out by adding the cationizing agent to the reaction mixture that has been reduced as described above. However, when the cationizing agent is added in an amount equivalent to or more than the sulfhydryl group, other functional groups other than the sulfhydryl group, such as hydroxyl group, amino group,
Addition reactions also occur to carboxyl groups. The amount of the cationizing agent added is 0.1 to 0.1 to sulfhydryl groups present in the reductive decomposition product of the keratin material.
6 times equivalent is appropriate, more preferably 0.5~
This is twice the equivalent. If it is less than 0.1 times equivalent,
A substance having sufficient solubility in water and a mixed solvent of water and a hydrophilic organic solvent cannot be obtained, and if the amount is more than 6 times equivalent, the original properties of the keratin substance are impaired, which is not preferable. Any temperature from room temperature to 90°C is selected as the reaction temperature, but the higher the temperature, the more the addition reaction of the cationizing agent is accelerated. Further, regarding the pH of the system during the addition reaction, there is no need to particularly adjust the pH after the reduction reaction is completed. That is, it is carried out in the range of PH2 to 12, usually in the range of PH6 to 11. As the addition reaction of the quaternary ammonium salt type cationizing agent to the reductive decomposition product of keratin progresses, the reductive decomposition product dissolves in the reaction medium, and ultimately the insoluble matter is less than 30% of the reductive decomposition product of keratin. becomes. Therefore, by removing this insoluble matter by filtration, centrifugation, etc., and distilling off the solvent, a cationized keratin compound derivative can be obtained. In the shampoo treatment composition of the present invention, the amount of the cationized keratin derivative blended is not particularly limited, but it is preferably 0.01 to 5% by weight (hereinafter simply expressed as %) of the total composition for convenience of use. If the blending amount is less than 0.01%, the effect cannot be fully exhibited, and if it exceeds 5%, the cationic keratin derivative adsorbed to the hair becomes sticky under high humidity conditions. The press shampoo treatment composition of the present invention is produced by dissolving or dispersing a cationized keratin derivative and any known optional ingredients in a solvent such as water. Optional ingredients include oils and fats such as higher alcohols and fatty acid esters; nonionic surfactants such as polyoxyalkylene alkyl ethers that act as emulsifiers and solubilizers; humectants such as glycerin, pyrrolidone carboxylic acid, and propylene glycol. For example, by combining these,
The addition of ingredients such as fatty acid esters, liquid nonionic surfactants, and polypropylene glycol makes the hair even more moisturized, and the addition of ingredients such as solid higher alcohols, wax, and silicone oil makes the hair even more moisturized. By adding moisturizing ingredients such as glycerin and pyrrolidone carboxylic acid, which give the hair a smooth finish, it is possible to appropriately adjust the finish of the hair, such as making the hair even more moisturized. If hair is treated with the pre-shampoo treatment composition thus obtained and then shampooed, the hair will be less damaged, have a good moisturizing effect, and have a moist finish. The present invention will be further explained below with reference to synthesis examples and examples, but the present invention is not limited by these synthesis examples or examples. Synthesis Example 1 10.0 g of wool fiber was immersed in 600 g of an aqueous solution containing 0.02 M Tris buffer, and 6.0 ml of 2 was added as a reducing agent.
- After adding mercaptoethanol, the pH was adjusted to 8.5 with 1N hydrochloric acid, and the reduction reaction was carried out at room temperature for 24 hours under a nitrogen stream. Next, 2.0g of glycidyltrimethylammonium chloride was added to the reaction system, and the mixture was heated to 50℃ for 6 hours.
After stirring for a period of time, approximately 80% of the wool fibers were dissolved in the reaction solution. Insoluble parts are removed by filtration, and low-molecular impurities such as reducing agents are removed from the resulting aqueous solution of the cationized keratin derivative by ultrafiltration, and the aqueous solution of the cationized keratin compound is concentrated to about 1/5. did. By freeze-drying this, 7.5 g of a cationized keratin derivative was obtained. The average molecular weight of this product was determined by gel filtration method and was found to be 41,000. Synthesis Example 2 In Synthesis Example 1, a 50% n-propanol aqueous solution was used as the reaction solvent, and tris-n was used as the reducing agent.
-Synthesis Example 1 except for using 4 ml of butylphosphine
The same operation as above was performed to obtain 7.8 g of a cationized keratin derivative having an average molecular weight of 40,000. Synthesis Example 3 Feathers were heated in a high-pressure container with 6 kg/cm ² of superheated steam at 240°C for 6 minutes, and then rapidly released into the atmosphere. 10.0 g of the porous puffed product was then buffered with 0.02 M Tris buffer. 30% ethanol aqueous solution
Soak in 700g and add 4ml of tri-nn- as reducing agent.
After adding butylphosphine, PH8.0 with 1N hydrochloric acid
The reduction reaction was carried out at room temperature under a nitrogen stream for 24 hours. Next, 2.5 g of allyltrimethylammonium chloride was added to the reaction system, and the reaction was carried out at 70°C for 5 hours, so that about 90% of the puffed feathers were dissolved in the reaction solution. Insoluble portions were removed by filtration, and the resulting solution was subjected to ultrafiltration to remove low-molecular impurities such as reducing agents and concentrated to about 150 ml. By freeze-drying this, 8.5 g of a cationized keratin derivative having an average molecular weight of 38,000 was obtained. Synthesis example 4 10g of wool fiber in 1% sodium sulfite aqueous solution
Soak in 300g and PH with 5N sodium hydroxide aqueous solution
After adjusting to 6.7, add 0.2g of papain and incubate at 60℃.
After 15 hours of hydrolysis, approximately 80% of the wool fibers were removed.
was solubilized. Insoluble materials are removed by filtration, and sulfites in the resulting solution are removed by ultrafiltration using a membrane with a molecular weight cutoff of 500.The aqueous hydrolyzate solution is concentrated and freeze-dried to reduce the molecular weight. 7.7 g of 2000 hydrolyzate was obtained. This is an aqueous solution containing 0.02M Tris buffer.
After dissolving in 450 g of the solution and adding 4.5 ml of 2-mercaptoethanol for reduction, the pH was adjusted to 8.5 with 1N hydrochloric acid, and the reduction reaction was carried out at room temperature under a nitrogen stream for 18 hours. Next, 16 g of glycidyltrimethylammonium chloride was added to the reaction system, and the mixture was stirred at 50°C for 6 hours. Low-molecular impurities such as reducing agents were removed from the resulting reaction solution by ultrafiltration, and the aqueous solution was reduced to about 1/5.
Concentrated into By freeze-drying this,
6.2g of cationized keratin derivative was obtained. Synthesis Example 5 Wool was heated in a high-pressure container with saturated steam at 4 kg/cm ³ for 8 minutes, and then rapidly released into the atmosphere to obtain a porous puffed product. 10 g of this expanded product was immersed in 300 g of a 75% phosphoric acid aqueous solution and stirred at 120 to 130° C. for 5 hours to perform a hydrolysis reaction. After cooling this and removing the insoluble portion by filtration, 4 to 5 times the amount of water was added, and the insoluble portion was further removed by centrifugation. Next, calcium carbonate was added to adjust the pH to 6.7, and the precipitate was collected and dried to obtain 8.5 g of a hydrolyzate with a molecular weight of 2000. This is an aqueous solution containing 0.02M Tris buffer.
Disperse in 500g and add 4ml of tri-n as reducing agent.
-After adding butylphosphine, PH with 1N hydrochloric acid
8.0, and the reduction reaction was carried out for 24 hours under a nitrogen stream. Next, 2.0 g of glycidyltrimethylammonium chloride was added to the reaction system, and the mixture was stirred at 50°C for 6 hours. Low-molecular impurities such as reducing agents are removed from the resulting reaction solution by ultrafiltration, the aqueous solution is concentrated,
By freeze-drying, 6.7 g of cationized keratin derivative was obtained. Synthesis Example 6 In Synthesis Example 4, cations were obtained by reacting in the same manner as in Synthesis Example 4, using 10g of puffed feather instead of wool fiber and 20g of 2-chloro-2-hydroxypropyltrimethylammonium chloride instead of glycidyltrimethylammonium chloride. A chemically modified keratin derivative was obtained. Example 1 A shampoo composition having the following composition was prepared, containing the cationized keratin derivative obtained in the synthesis example and other peptides, and its performance was evaluated. The results are shown in Table 1. Composition: Cationized keratin derivative (or other peptides) 3.0% Polyoxyethylene (10) cetyl ether 2.0 Hydroxyethyl cellulose 1.0 Propylene glycol 5.0 Water Remaining evaluation method: (1) Feel of hair during hair washing Made with hair of Japanese women Ivy length 20cm, weight
Apply 2g of the pre-shampoo treatment composition to 20g of hair, leave it for 5 minutes, and apply a commercially available plain shampoo containing an anionic surfactant.
Sensory evaluation was conducted on the feel of the hair when 2 g was lathered for 1 minute in the usual manner. For the sensory evaluation, the following evaluation points were assigned based on paired comparisons using hair tresses treated with a commercially available shampoo treatment agent containing lanolin as the main effect ingredient. (The table shows the average scores of the 20 expert panelists.) Evaluation Point Evaluation +2 Feels better than the standard hair +1 Feels slightly better than the standard hair bundle 0 Feels the same as the standard hair bundle -1 Standard hair Slightly poor feel compared to the standard hair bundle -2 Result with poor feel compared to the standard hair bundle:

[Table] Example 2 A shampoo composition having the following composition was manufactured and the effect of varying the amount of the cationized keratin derivative blended was investigated. The results are shown in Table 2. Note that the evaluation criteria were in accordance with Example 1. Composition: Cationized keratin derivative (Table 2) Polyoxyethylene (10) cetyl ether 2.0% Hydroxyethyl cellulose 1.0 Propylene glycol 5.0 Water Result:

[Table] Example 3 A pre-shampoo treatment composition having the following composition using the cationized keratin derivative of the present invention was produced,
This was compared with a conventional press shampoo treatment agent containing liquid lanolin emulsified in an o/w type. The evaluation was carried out by a panel of women between the ages of 18 and 35 who rated the usability on a five-point scale using the paired comparison method. The results are shown in Table 3. Composition: (Product of the present invention) Cationized keratin derivative (synthesis example 1)
2.0% Polyoxyethylene (10) lauryl ether 2.0 Hydroxyethyl cellulose 0.5 Propylene glycol 5.0 Water Balance (comparative product) Liquid lanolin 20.0 Polyoxyethylene (5) lanolin alcohol ester 7.0 Stearic acid triethanolamine salt 3.0 Water Balance results:

[Table] * Regarding oiliness, items that were not oily were rated as good.
** Regarding stickiness, non-sticky products were rated as good.
Example 4 Ten female monitors with experience in perm treatments evaluated the combability,
The feel of the hair was compared with the same pre-shampoo treatment composition applied to hair after shampooing and rinsing. The results are shown in Table 4. Composition: Cationized keratin derivative (synthesis example 1)
3.0% Polyoxyethylene (10) Cetyl Ether 2.0 Hydroxyethyl Cellulose 1.0 Propylene Glycol 5.0 Water Residual Result: Example 4 Ten female monitors with experience in perm treatments performed shampoo after using the pre-shampoo treatment composition with the following composition. The combability and feel of the hair during shampooing were compared with those obtained when the same pre-shampoo treatment composition was applied to hair after shampooing and rinsed. The results are shown in Table 4. Composition: Cationized keratin derivative (synthesis example 1)
3.0% Polyoxyethylene(10) Cetyl Ether 2.0 Hydroxyethyl Cellulose 1.0 Propylene Glycol 5.0 Water Residual Results:

[Table] From the above results, it is clear that with the composition of the present invention, pre-shampoo treatment is more effective than after-shampoo treatment on hair damaged by perms.

Claims (1)

[Claims] 1. A quaternary compound having a group represented by [Formula] [Formula] or CH ₂ =CH- and a quaternary nitrogen in the molecule of a keratin material or a reductive decomposition product of its hydrolyzate. A press shampoo type hair treatment composition characterized in that it contains a cationized keratin derivative to which an ammonium salt type cationizing agent has been added. 2. The pre-shampoo type hair treatment composition according to claim 1, wherein the amount of the cationized keratin derivative is 0.01 to 5% by weight of the total composition.