JP2012001505A - Hair-treating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair-treating agent composition which has an excellent moisture-retaining property and an excellent conditioning effect and gives natural finishes.SOLUTION: The hair-treating agent composition is characterized by comprising (1) poly-γ-L-glutamic acid and/or a salt thereof, (2) an oxidizing agent comprising a salt, and (3) at least one cationic surfactant.

Description

The present invention relates to a hair treatment composition, more specifically, a hair treatment comprising poly-γ-L-glutamic acid and / or a salt thereof and a cationic surfactant added to an oxidizing agent comprising a salt. The agent composition.

Human skin is covered by the stratum corneum, and life activity can be maintained without losing moisture even in a dry atmosphere because the stratum corneum is in contact with the outside world. well known. The stratum corneum is thin and flexible and maintains moisture in the body and is adjusted to maintain a healthy skin state.

However, we often cause some damage to the epidermis due to environmental factors (eg temperature change, humidity change, light, contact with water, use of detergents, etc.). Damaged skin is hard, loses elasticity, and becomes rough and rough. Such rough skin has recently been pointed out to be associated with atopic dermatitis, which is rapidly increasing, and may cause serious skin troubles.

Rough skin may be due to exfoliation of keratinocytes, or may be caused by dryness and deterioration of skin health leading to hardening or damage of the epidermis. The former rough skin is elution of keratinocyte lipids such as cholesterol, ceramide, fatty acid, and the formation of stratum corneum permeation barrier due to degeneration of keratinocytes caused by UV rays, detergents, etc. Caused by. For the purpose of preventing or healing this rough skin, studies have been made on supplying a keratinocyte lipid component or a synthetic keratinocyte lipid similar thereto. This stratum corneum intercellular lipid is a lamellar granule that is biosynthesized by cells in the spinous layer and the granule layer, and is released between the cells just below the stratum corneum and extends, taking a lamellar (lamellar) structure. It has spread to. The lamellar granule is composed of glucosylceramide, cholesterol, ceramide, phospholipid, etc., but the horny layer intercellular lipid hardly contains glucosylceramide. That is, glucosylceramide in lamellar granules is hydrolyzed by β-glucocerebrosidase and converted to ceramide. As a result of this ceramide having a lamellar structure, formation of a stratum corneum permeation barrier is improved as a stratum corneum intercellular lipid. Therefore, it is considered to have a barrier function for preventing rough skin. It has been reported that ceramide supplementation is effective for rough skin caused by a cleaning agent, and shows a high effect in improving rough skin (Non-patent Document 1).

On the other hand, for the latter rough skin, in addition to maintaining the skin's homeostasis, the hair treatment composition prevents water from evaporating from the skin, and keeps the skin in the epidermis and stratum corneum to retain moisture, A moisturizer is blended for the purpose of maintaining softness and keeping fresh skin. Conventionally used moisturizers include glycerin, 1, 3 as hydrophilic moisturizers in addition to lipophilic moisturizers typified by vegetable oils such as olive oil and animal-derived lipids such as lanolin. -Water-soluble polyhydric alcohols such as butylene glycol, propylene glycol, sorbitol, polysaccharides such as hyaluronic acid and xanthan gum, water-soluble polymers such as polyethylene glycol, low molecular weight natural moisturizing typified by pyrrolidone carboxylates and amino acids Factors, plant extracts and the like are known.

There are various types of hydrophilic and lipophilic moisturizers as described above. However, due to the trend of emphasizing safety, animal-derived products and chemical synthetic products tend to be avoided recently, preferably natural. Biodegradable materials that are fermented products by products and microorganisms and that have less burden on the environment as well as the living body are expected and attracting attention.

On the other hand, biopolymers produced by microorganisms are promising. Among biopolymers, various functions have been found in a group of biopolymers called polyamino acids constituted by condensation polymerization of amino acids, and attention has been focused on their potential. Conventionally, three types of polyamino acids have been identified: poly-γ-glutamic acid (hereinafter sometimes referred to as “PGA”), poly-ε-lysine and cyanophysin.

PGA is a polyamino acid in which an α-amino group and a γ-carboxyl group of glutamic acid are amide-bonded. PGA is a water-absorbing polyamino acid known as the main material of stringing of natto, which has been familiar to Japanese people for a long time, but as a background of this familiarity, it is due to its attractive functionality. large. As an attractive function of PGA, it is known that it has both biodegradability and high water absorption. Utilizing these functions, it is expected to be used in various fields and applications such as the above-described hair treatment composition, medical products, foods and the like.

Recently, it has been found that structural characteristics of polyamino acids (optical activity and type of constituent amino acids, molecular size, binding mode, etc.) are strongly reflected in their functionality. A well-known point is that it has both biodegradability and high water absorption. Utilizing these functions, it is expected to have various applications in many fields such as foods, cosmetics, and medical products. However, currently commercially available PGA is a chemically heterogeneous DL-PGA. Specifically, PGA is produced from Bacillus natto and its related bacteria, and D-glutamic acid and L-glutamic acid are irregularly bound, and the content ratio and sequence vary depending on the culture of the producing bacteria. In general, the structural characteristics of polyamino acids (optical activity and type of constituent amino acids, molecular size, binding mode, etc.) strongly influence their functions. Since the DL-PGA has a different structure for each molecule, its property also differs for each molecule. This makes it difficult to stably produce DL-PGA having a desired quality.

Bacteria that produce homopoly-γ-glutamic acid have also been reported. For example, Bacillus anthracis has been reported to produce poly-γ-D-glutamic acid (hereinafter sometimes referred to as D-PGA) consisting only of D-glutamic acid (Non-patent Document 2). However, since this bacterium is a bacterium having a strong pathogenicity, it is inappropriate as an industrial PGA-producing bacterium, and the molecular weight of D-PGA produced is small. In addition, it has been reported that the alkalophilic bacterium Bacillus halodurans produces poly-γ-L-glutamic acid and / or a salt thereof (hereinafter sometimes referred to as L-PGA) consisting only of L-glutamic acid (non-native). Patent Document 3). However, L-PGA produced by this bacterium has an extremely small molecular weight, and is insufficient to obtain practical performance.

On the other hand, it has been reported that the halophilic archaeon Natrialba aegyptiaca produces L-PGA having a molecular weight of about 100,000 to 1,000,000 as a high-molecular-weight homopoly-γ-glutamic acid-producing bacterium. However, since this bacterium has a molecular weight as small as about 100,000 under liquid culture conditions and hardly produces poly-γ-L-glutamic acid and / or a salt thereof, there is a problem as an industrially producing bacterium (non-patent) Document 4, Patent Document 1).

In addition to the above, examples of organisms that produce L-PGA include hydra and the like, but hydra also has a problem that its molecular weight is extremely small (Non-patent Document 3).

On the other hand, the present inventors made it possible to prepare a large amount of poly-γ-L-glutamic acid and / or a salt thereof with uniform optical purity and high molecular weight by liquid culture or the like. More specifically, poly-γ-L-glutamic acid and / or a salt thereof having a number average molecular weight of 1.3 million or more and uniform optical purity are obtained with a high productivity of 4.99 g or more per liter of culture solution. (Patent Document 2).

Moreover, the crosslinking method of poly-γ-L-glutamic acid and a crosslinked product (Patent Document 3), and at least one of poly-γ-L-glutamic acid and poly-γ-L-glutamic acid crosslinked product are included. There is a report of a hair treatment composition (Patent Document 4).

Conventionally, as a method of waving hair, for example, a cystine bond of hair keratin is cleaved by a first agent mainly composed of a reducing agent such as thioglycolate or cysteine, and oxidation of bromate or hydrogen peroxide is performed. Means such as rebinding cystine bonds with a second agent mainly composed of an agent are used. However, according to this method, the hair is treated under the adverse conditions of oxidation and reduction, so that the strength of the hair is deteriorated and the touch is deteriorated. Causes hair and hair breakage.

In the first agent treatment stage, the alkaline agent swells the hair, so protein degradation in the hair, outflow of amino acids, etc. occur, and in the second agent treatment stage, the hair damaged by the first agent In addition, it is damaged by oxidation. For this reason, various research and development have been conducted in the past as attempts to provide a continuous conditioning effect in the permanent wave processing process. For example, a permanent wave second agent blended with a specific cationic polymer compound and an anionic surfactant or an amphoteric surfactant (Patent Documents 5 to 8), a blend of a specific cationic polymer compound (Patent Documents 9 and 10), those blended with a specific silicone polymer (Patent Documents 11 and 12), and the like have been proposed. However, according to this method, the hair is treated under the adverse conditions of oxidation and reduction, so that the strength of the hair is deteriorated and the touch is deteriorated. Causes hair and hair breakage. However, although all of the above techniques can improve the touch after treatment, there is a point that the hair may remain stiff, especially with the cationic polymer compound, it gives the hair a firmness and results. It was a result that gave a sense of inconvenience.

Special Table 2002-517204 JP 2007-314434 A JP 2008-120910 A JP 2008-120725 A JP 56-92810 A JP 57-31605 A JP 57-212111 A JP 61-183214 A Japanese Examined Patent Publication No. 63-28884 Japanese Patent Publication No. 64-3843 JP-A-1-110611 JP-A-2-255608

Journal of Bioscience and Bioengineering, 94,187 (2002) Handy, W. E., and H.N.Rydon, Biochem J., 40, 297-309 (1946) Biology and Chemistry Vol.40, No.4, p212-214 (2002) Hezayen, F. F., B. H. A. Rehm, B. J. Tindall and A. Steinbuchel, Int. J. Syst. E., 51, 1133-1142 (2001)

An object of the present invention is to provide a hair treatment composition that is excellent in the feel of the hair after treatment, eliminates the feeling of stiffness, improves combability, and reduces hair damage.

Under such circumstances, the present inventors have conducted intensive research. As a result, in the second agent for permanent wave containing bromate and the like, poly-γ-L-glutamic acid and / or salt thereof, cationic surfactant 1 It has been found that when a seed or two or more kinds are contained, the composition can be blended transparently or uniformly. Further, when the hair is treated with water and washed with water, the hair treatment composition containing the oxidant comprising this salt is diluted. As a result, poly-γ-L-glutamic acid and / or a salt thereof and a cationic surfactant are combined. Has been found to be formed on the hair, have excellent moisture retention and conditioning effects on the hair, and can give a natural finish.

That is, the present invention has the following configuration.
(1) Hair treatment characterized by comprising (1) poly-γ-L-glutamic acid and / or a salt thereof, (2) an oxidizing agent comprising a salt, and (3) at least one cationic surfactant. Agent composition.
(2) Poly-γ-L-glutamic acid is a cross-linked poly-γ-L-glutamic acid characterized by having a cross-linked structure between poly-γ-L-glutamic acid molecules (1) Hair treatment composition.
(3) The hair treatment composition according to (1) or (2), wherein the average molecular weight of poly-γ-L-glutamic acid is 1,000,000 or more.
(4) The hair treatment composition according to any one of (1) to (3), wherein the average molecular weight of poly-γ-L-glutamic acid is 2 million or more.
(5) The hair treatment composition according to any one of (1) to (4), wherein the average molecular weight of poly-γ-L-glutamic acid is 3.5 million or more.
(6) The hair treatment composition according to any one of (1) to (5), wherein the water absorption ratio of poly-γ-L-glutamic acid is 10 to 5000 times.
(7) The hair treatment composition according to any one of (1) to (6), wherein the oxidizing agent comprising a salt is bromate.
(8) Cationic surfactant is alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, cationized product of lanolin, γ-gluconamidopropyldimethylhydroxyethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride and hydrolyzed polypeptide The hair treatment composition according to any one of (1) to (7), wherein the hair treatment composition is one or more selected from the group consisting of cationized products.

The hair treatment composition of the present invention has good squeakiness at the time of rinsing, fingering, no wrinkle after drying, and moist feeling, and little damage to the hair after treatment.

The “poly-γ-L-glutamic acid” of the present invention is a homopolymer consisting only of L-glutamic acid. Its structure is the structure represented by formula (I). The hydrogen of α-COOH may be hydrogen or another metal counter ion. For example, there is no need to limit the general materials such as sodium, potassium, magnesium, manganese, calcium, zinc and iron. Of these, sodium is preferred.

The “molecular weight” of the present invention refers to the number average molecular weight (Mn) calculated in terms of the molecular weight of the pullulan standard substance.

The poly-γ-L-glutamic acid of the present invention can be obtained by an existing method. For example, poly-γ-L-glutamic acid can be obtained by the method described in Patent Document 2 (Japanese Patent Application Laid-Open No. 2007-314434). Hereinafter, as an example, a method for producing poly-γ-L-glutamic acid with reference to Patent Document 2 will be described, but the present invention is not limited thereto.

For example, the National Institute of Advanced Industrial Science and Technology (AIST) Patent Biological Depositary Center has a Natrialba aegyptiaca 0830-82 strain (trusted organization: National Institute of Advanced Industrial Science and Technology Patent Biological Depositary Center), date of deposit: Heisei April 4, 2006, accession number: FERM BP-20872), Natrialba aegyptiaca 0830-243 strain (trusted institution: National Institute of Advanced Industrial Science and Technology, Patent Organism Depositary), accession date: 2006 April 4, 2000, accession number: FERM BP-20873), or Natrialba aegyptiaca 0831-264 strain (trusted institution name: National Institute of Advanced Industrial Science and Technology, Patent Biological Depositary Center), trust date: 2006 Deposited on April 4, 2000 as accession number: FERM BP-20874) To obtain poly-gamma-L-glutamic acid using a with that strain, it is possible to obtain poly-gamma-L-glutamic acid by liquid culture. Alternatively, a microorganism can be mutated by the method described in Patent Document 2 (Japanese Patent Application Laid-Open No. 2007-314434) to produce a microorganism capable of producing poly-γ-L-glutamic acid by liquid culture, and poly-γ-L- Glutamic acid can also be produced. Moreover, it is also possible to produce poly-γ-L-glutamic acid by solid-phase culture of Natrialba aegyptiaca by a conventional method.

In the case of liquid culture, it is desirable to perform under aerobic conditions such as shaking culture and aeration and agitation culture. The culture temperature at that time is 30 to 50 ° C, preferably 35 to 45 ° C. The pH of the medium can be adjusted with sodium hydroxide, potassium hydroxide, ammonia, hydrochloric acid, sulfuric acid, or an aqueous solution thereof, but is not limited as long as the pH can be adjusted. It is desirable to culture at a culture pH of 5.0 to 9.0, preferably at a pH of 6.0 to 8.5. In addition, the culture period is usually about 2 to 7 days. Further, it is desirable to culture at a NaCl concentration of 10 to 30%, preferably 15 to 25% during culture. Further, it is desirable to culture at a yeast extract concentration of 0.1 to 10%, preferably 0.5 to 5.0%. Also in the case of solid culture, the culture temperature is 30 to 50 ° C., preferably 35 to 45 ° C., and the pH during the culture is 5.0 to 9.0, preferably pH 6.0, in the case of liquid culture and application. -8.5, NaCl concentration during culture is 10-30%, preferably 15-25%, Yeast Extract concentration is 0.1-10%, preferably 0.5-5%. When cultured in this manner, poly-γ-L-glutamic acid is mainly accumulated outside the cells and contained in the culture described above. Although not specifically limited, PGA production liquid medium-1 (22.5% NaCl, 2% MgSO ₄ .7H ₂ O, 0.2% KCl, 3% Trisodium Citrate, 1% Yeast Extract, 0.75% Casamino acid ) May be used, and the amount of each additive may be appropriately adjusted according to the strain.

As a method for quantifying poly-γ-L-glutamic acid in a culture solution, precipitation is carried out from a sample containing poly-γ-L-glutamic acid using copper sulfate or ethanol, and the weight measurement of the precipitate and the Kijderder method (M. Bovarnick, J. Biol. Chem., 145, 415, 1942), a method for measuring the amount of glutamic acid after hydrochloric acid hydrolysis (RD Housewright, CB Thorne, J. Bacteriol., 60, 89, 1950) and a colorimetric method using quantitative binding with basic dyes (M. Bovarnick et al., J. Biol). Chem., 207, 593, 1954), preferably using quantitative binding with basic dyes. A color process.

Examples of basic dyes include crystal violet, aniline blue, safranino, methylene blue, methyl violet, toluine nebula, congo red, azocarmine, thionine, and hematoxylin, with safranino being preferred.

In order to separate and collect poly-γ-L-glutamic acid from this culture, the above-mentioned known methods such as precipitation using copper sulfate or ethanol may be used. As an example, for example, the culture solution is centrifuged to remove the cells. Subsequently, after adding and diluting 3 times the amount of water to the obtained supernatant, the pH is adjusted to 3.0. After pH adjustment, the mixture was stirred at room temperature for 5 hours. Thereafter, 3 times the amount of ethanol was added, and poly-γ-L-glutamic acid was recovered as a precipitate. The precipitate is dissolved in 0.1 mM Tris-HCl buffer (pH 8.0), and low-molecular substances are removed by dialysis. After dialysis, the resulting solution may be treated with DNase or RNase for nucleic acid removal, and then with proteinase treatment for protein removal. After the proteinase treatment, the low molecular weight substance may be removed by dialysis. After dialysis, dry poly-γ-L-glutamic acid may be obtained by freeze-drying or the like. Moreover, although refinement | purification using an anion exchange resin can be performed if necessary, it can refine | purify on general conditions.

The molecular weight of poly-γ-L-glutamic acid used in the present invention is not particularly limited, but is preferably 500,000 or more, more preferably 800,000 or more, still more preferably 1,000,000 or more, and particularly preferably 1.3 million or more.

The upper limit value of the molecular weight of L-PGA is not particularly limited, but according to the above-described L-PGA production method, for example, L-PGA having 6 million or 15 million at the maximum can be obtained.

Since this poly-γ-L-glutamic acid and / or salt thereof is produced by archaea, the specific odor is reduced compared to poly-γ-L-glutamic acid and / or its salt produced by Bacillus natto. Thus, the quality is not impaired even when used for cosmetics, quasi-drugs, medical supplies, hygiene products, or pharmaceutical applications.

The oxidizing agent used in the present invention is an oxidizing agent comprising a salt. For example, bromate (eg, potassium bromate, sodium bromate, etc.), persulfate, perborate (eg, sodium perborate, etc.) Percarbonate, periodate and the like. In addition, as a metal in the said salt, an alkali metal (Na or K etc.) or an alkaline earth metal (Mg or Ca etc.) is mentioned, Preferably it is an alkali metal. The blending amount of the oxidizing agent is generally preferably 0.5 to 20% by weight in the hair treatment composition.

The compounding amount of the anionic polymer compound is generally 0.01 to 50% by weight, preferably 0.01 to 20% by weight, and most preferably 0.01 to 5% by weight in the hair treatment composition. is there. If the blending amount is less than 0.01% by weight, the improvement of the conditioning effect is not preferable, and if the blending amount exceeds 50% by weight, the hair may become sticky from excessive residue, which is preferable. Absent.

Examples of the cationic surfactant used in the present invention include alkyltrimethylammonium chlorides such as lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride; dilauryldimethylammonium chloride, dicetyldimethylammonium chloride, distearyl chloride. Dialkyldimethylammonium chloride such as dimethylammonium; cationized lanolin such as ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium chloride; γ-gluconamidopropyldimethylhydroxyethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride, N- (3 Cationization of hydrolyzed polypeptides such as -trimethylammonium-2-hydroxypropyl) -polypeptide Although the like, they may be bromide or Metasurufon acid salts is not limited to chloride.

These cationic surfactants can be used alone or in combination of two or more. The blending amount of the cationic surfactant is generally 0.1 to 50% by weight, preferably 0.1 to 20% by weight in the hair treatment composition from the balance between the obtained texture and the effect. More preferably, it is 0.1 to 5% by weight. If the blending amount is less than 0.1% by weight, the conditioning effect cannot be improved, which is not preferable. If the blending amount exceeds 50% by weight, the squeaky feeling when rinsing the hair and the moist feeling after treatment are improved. Although there is an improvement, it is not preferable from the viewpoint of stability because precipitation may occur.

Further, the hair treatment composition of the present invention includes pH adjusters such as carbonates, phosphates and citrates, sequestering agents such as EDTA, wetness such as glycerin and 1,3-butanediol. Agents, nonionic surfactants, amphoteric surfactants, penetrating aids such as anionic surfactants, fragrances, various vitamins, plant extracts, protein and protein hydrolysates, oils, UV absorbers, Preservatives, water, alcohol, thickeners, colorants, and the like can be blended within a range that does not impair the present invention.

The dosage form of the hair treatment composition of the present invention is not particularly limited, and can be any dosage form such as liquid, emulsion, foam, paste, gel, cream and the like. The hair treatment composition usually contains water as the main solvent, but the hair treatment composition of the present invention is preferably in a liquid form using water as the main solvent.

The hair treatment composition of the present invention usually contains water or an aqueous medium mainly composed of water with an oxidizing agent comprising a salt, at least one anionic polymer compound, and at least one cationic surfactant. It can be prepared by adding and mixing other optional components as necessary. Alternatively, it may be prepared by adding at least one anionic polymer compound and at least one cationic surfactant to a hair treatment composition that has already been prepared to contain an oxidizing agent.

The hair treatment composition of the present invention may be used as the second agent for straight perm, or may be used as the second agent for imparting waves. In addition, the hair treatment composition of the present invention is a cold two-bath type, a heated two-bath type, a heated exothermic two-bath type, and a cold or heated two-bath type curly hair as the second agent for permanent wave. It is useful in any orthodontic treatment.

Hereinafter, the present invention will be described in more detail based on examples. The present invention is not particularly limited to the examples. Moreover, all the academic literatures and patent literatures described in this specification are incorporated herein by reference. In the following examples, “%” is “% by weight”.

[Production Example 1; Production of poly-γ-L-glutamic acid]
To an L dry ampoule of Natrialba aegyptica (Accession Number: FERM BP-10749), 0.4 ml of PGA production liquid medium (22.5% NaCl, 2% MgSO ₄ .7H ₂ O, 0.2% KCl, 3% (Trisodium Citrate, 1% Yeast Extract, 0.75% Casamino acid) was added to obtain a suspension. 0.2 ml of the suspension was added to PGA agar medium (10% NaCl, 2% MgSO ₄ .7H ₂ O, 0.2% KCl, 3% Trisodium Citrate, 1% Yeast Extract, 0.75% Casamino acid, 2% Agar) and cultured at 37 ° C. for 3 days to obtain a single colony.

Next, in each of five 18 ml test tubes, 3 ml of PGA production liquid medium (22.5% NaCl, 2% MgSO ₄ .7H ₂ O, 0.2% KCl, 3% Trisodium Citrate, 1% Yeast Extract, 0.75% Casamino acid, pH 7.2) was added, and the single colony was scraped and inoculated with one platinum ear with a platinum ear. The test tube after inoculation was cultured at 37 ° C. and 300 rpm for 3 days, and 0.5 ml of the obtained culture solution was inoculated into 10 500 ml Sakaguchi flasks each containing 50 ml PGA production liquid medium. And cultured at 37 ° C. for 5 days. After culturing, the obtained culture solution was centrifuged, the cells were removed, and the supernatant was collected.

Next, 3 times the amount of water was added to the collected supernatant for dilution, and then the pH was adjusted to 3.0 with 1N sulfuric acid. After adjusting the pH, the mixture was stirred at room temperature for 5 hours. Thereafter, 3 times the amount of ethanol was added and centrifuged, and the precipitate was collected. This precipitate is L-PGA.

The collected L-PGA was dissolved in 0.1 mM Tris-HCl buffer (pH 8.0), and dialyzed to remove impurities such as low molecular weight substances. Next, in order to remove nucleic acid contained in the liquid after dialysis, MgCl ₂ is 1 mM, DNase I (manufactured by TAKARA) is 10 U / ml, and RNase I (manufactured by Nippon Gene) is 20 μg / ml. In addition, it was incubated at 37 ° C. for 2 hours. Next, in order to remove the protein, Proteinase K (manufactured by Takara Bio Inc.) was added to the liquid after removing the nucleic acid so as to be 3 U / ml, and incubated at 37 ° C. for 5 hours to carry out Proteinase K treatment.

After Proteinase K treatment, dialyzed with ultrapure water to remove low molecular weight substances. Next, L-PGA was adsorbed on an anion exchange resin (Q Sepharose Fast Flow, manufactured by GE Healthcare Bioscience), washed with 0.5 M NaCl aqueous solution, and then eluted with 1 M NaCl aqueous solution. The obtained solution was further dialyzed with ultrapure water, and the solution after dialysis was freeze-dried to obtain a sodium salt of L-PGA (hereinafter referred to as “L-PGA / Na salt”). In addition, the ultrapure water was produced with MilliQ (pure water production apparatus manufactured by Millipore).

[Production Example 2; Molecular weight analysis of poly-γ-L-glutamic acid-1]
The average molecular weight of the L-PGA · Na salt obtained in Production Example 1 was measured by GPC analysis. As a result, it was confirmed that Mw = 7,522,000, Mn = 3,704,000, and Mw / Mn = 2.031 (in pullulan conversion).

The GPC analysis was performed under the following conditions.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel α-M (manufactured by Tosoh Corporation)
Flow rate: 0.6 ml / min
Eluent: 0.15M NaCl aqueous solution Column temperature: 40 ° C
Injection volume: 10 μl
Detector: Differential refractometer

[Production Example 3; Molecular weight analysis of poly-γ-L-glutamic acid-2]
In Production Example 1, after elution of a 1.0 M NaCl aqueous solution, L-PGA · obtained by performing the same operation as in Production Example 1 except that 1N HCl was used to adjust the pH to 2.0. The average molecular weight of the Na salt was measured by GPC analysis. As a result, it was confirmed that Mw = 2,888,000, Mn = 1,327,000, and Mw / Mn = 2.176 (in pullulan conversion). The GPC analysis in this production example was performed in the same manner as in Production Example 2.

[Production Example 4: Production of crosslinked poly-γ-L-glutamic acid]
A 5% aqueous solution of the L-PGA · Na salt obtained in Production Example 1 was prepared.

Next, the L-PGA / Na salt aqueous solution was bubbled with nitrogen for 3 minutes, and then 2 ml was taken into a 10 ml sample bottle with a lid and the lid was closed.

Next, the sample bottle was irradiated with γ-rays using a γ-ray irradiation device using cobalt 60 as a radiation source. Irradiation dose was 5 kGy. The product obtained after γ-ray irradiation was taken out of the sample bottle, excess water was drained with an 80-mesh wire mesh, and freeze-dried to obtain L-PGA crosslinked powder. The excess water contains uncrosslinked L-PGA, and the main purpose of draining is to remove uncrosslinked L-PGA.

Hereinafter, the compounding amount in the examples is% by weight. Hair treatment compositions (Examples 1 to 5 and Comparative Examples 1 to 3) whose formulations are shown in Tables 1 and 2 were prepared and evaluated according to the following evaluation items.

(1) Hair condition After leaving the hair treatment composition at room temperature for 7 days, it was evaluated by visual observation as follows.
○: Transparent and uniform △: Cloudy ×: Cloudy and separated

(2) Hair touch hair bundle (1.5 g, length 12 cm) that is not chemically treated, permanent wave rod with a diameter of 12 mm, thioglycolic acid-based and cysteine-based permanent wave first agents shown below Wave hair was obtained using each composition (permanent wave second agent) shown in the composition, Table 1 (treated with the first agent at 25 ° C. for 15 minutes, treated with the second agent at 25 ° C. for 15 minutes). At the time of washing with water after the treatment of the second agent, three professional panels evaluated the squeaky feeling during rinsing and the fingering during rinsing according to the following evaluation criteria. Then, after natural drying, the non-stickiness after drying and the moist feeling after drying were evaluated.
Evaluation standard ◎: Very good feeling ○: Good feeling △: Slightly bad feeling ×: Bad feeling

(3) Damage to hair A tensile strength test was performed on the hair bundles that were treated when the hair was touched. That is, 50 breaks from each treated hair bundle were measured for breakage weight using an autograph AGS-50A manufactured by Shimadzu Corporation, and the average value was obtained. The measurement conditions were a temperature of 25 ° C. and a humidity of 90% at a measurement site of 10 mm and a test speed of 20 mm / min. It is assessed that the hair is damaged as the breaking weight decreases.

Formulation of thioglycolic acid permanent wave first agent composition (compounding ingredients) (wt%)
Ammonium thioglycolate solution (50%) 14
Polyoxyethylene (20E.O.) oleyl ether 1
Ammonia water (28%) Adjusted to pH 9.0 Metal sequestering agent Appropriate amount of perfume Appropriate amount of purified water Adjusted to total amount of 100.0

Formulation of cysteine-based permanent wave first agent composition (formulation component) (wt%)
DL-cysteic acid 8
Polyoxyethylene (20E.O.) oleyl ether 1
Ammonia water (28%) Adjusted to pH 9.0 Metal sequestering agent Appropriate amount of perfume Appropriate amount of purified water Adjusted to total amount of 100.0

Table 1 shows the formulations and evaluation results of Examples and Comparative Examples in which the first agent treatment was performed with the thioglycolic permanent wave first agent composition, and the first agent treatment with the cysteine permanent wave first agent composition. Table 2 shows the formulations and evaluation results of the examples and comparative examples.

The present invention comprises poly-γ-L-glutamic acid and / or a salt thereof, an oxidizing agent comprising a salt, and (3) at least one cationic surfactant, thereby squeezing at the time of rinsing, It is possible to provide a hair treatment composition that does not feel stiff after drying, has a moist feeling, and has little hair damage after treatment. Furthermore, since the raw material cost is lower than that of conventional poly-γ-L-glutamic acid, it can be mass-produced, and can sufficiently withstand long-term use, it is expected to greatly contribute to the industry.

Claims (8)

A hair treatment composition comprising (1) poly-γ-L-glutamic acid and / or a salt thereof, (2) an oxidizing agent comprising a salt, and (3) at least one cationic surfactant. . The poly-γ-L-glutamic acid is a poly-γ-L-glutamic acid cross-linked product characterized by having a cross-linked structure between poly-γ-L-glutamic acid molecules. Hair treatment composition. The hair treatment composition according to claim 1 or 2, wherein the average molecular weight of poly-γ-L-glutamic acid is 1,000,000 or more. 4. The hair treatment composition according to any one of claims 1 to 3, wherein the average molecular weight of poly- [gamma] -L-glutamic acid is 2 million or more. 5. The hair treatment composition according to claim 1, wherein the average molecular weight of poly-γ-L-glutamic acid is 3.5 million or more. The hair treatment composition according to any one of claims 1 to 5, wherein the water absorption capacity of poly-γ-L-glutamic acid is 10 to 5000 times. The hair treatment composition according to any one of claims 1 to 6, wherein the oxidizing agent comprising a salt is a bromate. Cationic surfactants are alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, cationized lanolin, γ-gluconamidopropyldimethylhydroxyethylammonium chloride, tri (polyoxyethylene) stearylammonium chloride, and cationized hydrolyzed polypeptide The hair treatment composition according to claim 1, wherein the composition is one or more selected from the group consisting of: