JP2007153791A - Shampoo composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a shampoo composition providing rich foam and good finger-combability at rinsing, imparting excellent touch feeling to the hair after drying, capable of inhibiting the smell of the scalp, and having temporal stability. <P>SOLUTION: The shampoo composition contains (A) an anionic surfactant, (B) an ampholytic and/or semipolar surfactant, (C) one or more kinds of cationic macromolecular compounds selected from a cationized cellulose, a cationized guar gum, and a copolymer of a monomer mixture containing a vinylic monomer having a hydroxy group and an amide group, and a vinylic monomer having a cationic group, (D) a polylysine and/or a salt thereof, and (E) an organic acid. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a shampoo composition, and in particular, it is easy to follow a finger when rinsing with rich foam, is excellent in the feel of hair after drying, can suppress the smell of the scalp, and is stable over time in the color and smell of the composition The present invention relates to an excellent shampoo composition.

  Various efforts have been made to improve the goodness of the hair when shampooing is rinsed, and as a typical example, a combination of cationic water-soluble polymer compounds such as cationized cellulose and cationized guar gum Have been proposed (see Japanese Patent Application Laid-Open No. 11-236320, Japanese Patent Application Laid-Open No. 04-234309). However, such a cationic polymer compound cannot obtain a sufficient effect even if it is added in a small amount, and it is necessary to add a large amount in order to exhibit these effects. As a result, the hair may become stiff or sticky due to the film-forming properties of the cationic polymer compound. In addition, depending on the type of the cationic polymer compound, there is a problem of deterioration in color tone or significant change in odor over time (especially stored at 40 to 50 ° C. which is an accelerated test condition). there were.

  On the other hand, an unpleasant odor caused by microorganisms living on the surface of the scalp (hereinafter referred to as skin resident bacteria) is also generated. In order to suppress this unpleasant odor of the scalp, masking of unpleasant odors by fragrances, growth suppression of skin resident bacteria by antibacterial agents, and the like are performed.

  However, masking with a fragrance may cause the odor of the fragrance to mix with an unpleasant odor, resulting in a bad odor. Conventional antibacterial agents are heavy metal antibacterial agents such as silver and copper, and organic synthetic antibacterial agents. Therefore, there has been a demand for improving safety. As means for solving this problem, there are proposals for blending ε-polylysine, which is a natural antibacterial agent, into cosmetics (Patent Document 3: Japanese Patent Laid-Open No. 2003-40724, Patent Document 4: Japanese Patent Laid-Open No. 2004-35461). Although it has been made, it was insufficient in terms of suppressing the scalp odor generated after drying.

JP-A-11-236320 Japanese Patent Laid-Open No. 04-234309 JP 2003-40724 A JP 2004-35461 A

  The present invention has been made in view of the above circumstances, and is a shampoo composition that is excellent in fingering when rinsing with rich foam, excellent in the feel of hair after drying, can suppress the smell of the scalp, and has excellent stability over time. The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventor has (A) an anionic surfactant, (B) an amphoteric surfactant and / or a semipolar surfactant, (C) a cationized cellulose, One or two or more cationic properties selected from a copolymer of a cationized guar gum and a monomer mixture containing a vinyl monomer having a hydroxyl group and an amide bond and a vinyl monomer having a cationic group A shampoo composition comprising a polymer compound, (D) polylysine and / or a salt thereof, and (E) an organic acid is easy to follow during rinsing, has excellent hair feel after drying, and has a scalp odor. It has been found that the composition can be suppressed and the composition has excellent stability over time, and the present invention has been made.

Therefore, the present invention
(A) an anionic surfactant,
(B) amphoteric surfactant and / or semipolar surfactant,
(C) One kind selected from a copolymer of a cationized cellulose, a cationized guar gum, and a monomer mixture containing a vinyl monomer having a hydroxyl group and an amide bond and a vinyl monomer having a cationic group Or two or more cationic polymer compounds,
(D) polylysine and / or a salt thereof,
(E) A shampoo composition containing an organic acid is provided.

  The shampoo composition of the present invention is good in fingering during rinsing, has excellent hair feel after drying, can suppress the smell of the scalp, and has excellent stability over time.

  (A) component of this invention is an anionic surfactant, and can be used individually by 1 type or in combination of 2 or more types. Examples of the anionic surfactant include carboxylic acid type, sulfonic acid type, sulfuric acid type, and phosphoric acid type, but linear alkylbenzene sulfonate, α-sulfo fatty acid methyl ester salt, α-olefin sulfonate, alkane. Sulfuric acid types such as sulfonic acid salts, and sulfuric acid types such as alkyl sulfate esters and polyoxyalkylene alkyl ether sulfates are preferred. Of these, α-olefin sulfonates are preferable for the sulfonic acid type, and alkyl sulfate ester salts and polyoxyalkylene alkyl ether sulfate ester salts are preferable for the sulfuric acid type.

  The α-olefin sulfonate is preferably an alkyl group having 10 to 18 carbon atoms, particularly tetradecene sulfonate having 14 carbon atoms. In the alkyl sulfate ester salt, an alkyl group having 10 to 18 carbon atoms is preferable, and 12 to 14 carbon atoms are particularly preferable. In the polyoxyalkylene alkyl ether sulfate ester salt, those having 10 to 18 carbon atoms in the alkyl group are preferable, and those having 12 to 14 carbon atoms are particularly preferable. The alkylene moiety is preferably polyoxyethylene or polyoxypropylene, and particularly preferably polyoxyethylene. Moreover, the range of the ethylene total average added mole number is preferably 2-4. These counter ions include alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolamine salts and the like.

  (A) The anionic surfactant is a main base of the shampoo composition of the present invention, and the blending amount thereof is preferably 1 to 50% by mass, more preferably 3 to 40% by mass in the shampoo composition. %, More preferably 5 to 30% by mass. If it is less than 1% by mass, the detergency and foaming power may be insufficient, and if it exceeds 50% by mass, the viscosity of the composition may remarkably increase and it may be difficult to remove from the container.

  (B) component of this invention is an amphoteric surfactant and / or a semipolar surfactant, and can be used individually by 1 type or in combination of 2 or more types. Examples of amphoteric surfactants include betaine type, imidazoline type, and amino acid type, but betaine type and imidazoline type are preferred, betaine type is preferably alkylaminoacetic acid betaine and alkylamidopropylbetaine, and imidazoline type is 2-alkyl- N-carboxymethyl-N-hydroxyethyl imidazolinium betaine is preferred. In alkylaminoacetic acid betaine, the alkyl group preferably has 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms. In particular, palm oil fatty acid aminoacetic acid betaine, palm oil fatty acid aminoacetic acid betaine, and laurylaminoacetic acid betaine are preferable. In the alkylamidopropyl betaine, the alkyl group preferably has 6 to 20 carbon atoms, more preferably 8 to 18 carbon atoms, particularly coconut oil fatty acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine, lauric acid. Amidopropyl betaine is preferred. In 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, the alkyl group preferably has 8 to 18 carbon atoms, and more preferably has 10 to 16 carbon atoms. In particular, the alkyl group is preferably an alkyl group derived from coconut oil fatty acid, palm oil fatty acid and lauric acid.

  Examples of the semipolar surfactant include amine oxide type and amidoamine oxide type, but amine oxide type is preferable, and alkylamine oxide such as lauryldimethylamine oxide is particularly preferable. These amphoteric surfactants and semipolar surfactants moderate the action on the skin, prevent rough skin, and enhance foaming.

  (B) As for the compounding quantity of an amphoteric surfactant and / or a semipolar surfactant, 0.1-30 mass% is preferable in a shampoo composition, More preferably, it is 0.5-20 mass%, More preferably, it is 1-. 10% by mass. If it is less than 0.1% by mass, the thickening effect and the detergency may be insufficient. If it exceeds 30% by mass, the viscosity of the composition may be remarkably increased or the solution stability may be deteriorated.

  Component (C) of the present invention is a copolymer of a monomer mixture containing cationized cellulose, cationized guar gum, and a vinyl monomer having a hydroxyl group and an amide bond and a vinyl monomer having a cationic group. It is 1 type, or 2 or more types of cationic polymer compounds chosen from these. These materials can be used as raw materials obtained by evaporating water to form powders or granules, and can also be used after being swollen and dissolved in a solvent such as water or alcohol.

  The cationized cellulose is obtained by adding a cationic functional group to cellulose, and is O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose (display name: polyquaternium) represented by the following formula (1). -10).

（式中、Ｒは水素原子又は下記一般式（ｉ）で表される基を示し、分子中少なくとも一般式（ｉ）で表される基を有する。ｐ，ｑは０〜５の数であり、ｎは５００〜２０，０００である。）

（式中、Ｚ^-は陰イオンであり、Ｃｌ^-が好ましい。）

(In the formula, R represents a hydrogen atom or a group represented by the following general formula (i), and has at least a group represented by the general formula (i) in the molecule. P and q are 0 to 5 numbers. , N is 500 to 20,000.)

(In the formula, Z ⁻ is an anion, and Cl ⁻ is preferable.)

  The cation degree of the cationized cellulose varies depending on the degree of addition of the cation group, but the cation degree is preferably in the range of 0.1 meq / g to 3.0 meq / g, and 0.5 meq / g to 1.7 meq / g. Is most preferred. The cation degree is preferably in the above range from the viewpoint of good finger passage when rinsing hair, excellent hair feel after drying, and excellent stability over time.

  The weight average molecular weight of the cationized cellulose is preferably in the range of 100,000 to 3,000,000, more preferably in the range of 300,000 to 2,000,000. The weight average molecular weight is preferably within the above range from the viewpoint of good fingering when rinsing hair, excellent feel of hair after drying, and excellent stability over time.

  Specific examples of the cationized cellulose include Leogard LP, GP, MGP, XE-511K (manufactured by Lion Corporation), UCARE LR-30M, JR-400, JR-30M (Dow Chemical), Kachinal HC-100 (Toho Chemical Industry Co., Ltd.).

  The cationized guar gum is obtained by adding a cationic functional group to guar gum, and O- [2-hydroxy-3- (trimethylammonio) propyl] guar gum represented by the following formula (2) (display name: guar hydroxy) Propyltrimonium chloride).

（式中、Ｒ´は水素原子又は下記一般式（ｉ）で表される基を示し、分子中少なくとも一般式（ｉ）で表される基を有する。ｍは４〜５，０００である。）

（式中、Ｚ^-は陰イオンであり、Ｃｌ^-が好ましい。）

(In the formula, R ′ represents a hydrogen atom or a group represented by the following general formula (i), and has at least a group represented by the general formula (i) in the molecule. M is 4 to 5,000. )

(In the formula, Z ⁻ is an anion, and Cl ⁻ is preferable.)

  Although the cation degree of the cationized guar gum varies depending on the degree of addition of the cationic group, the cation degree is preferably in the range of 0.5 meq / g to 3.0 meq / g, and 1.0 meq / g to 2.4 meq / g. Is most preferred. The cation degree is preferably in the above range from the viewpoint of good finger passage when rinsing hair, excellent hair feel after drying, and excellent stability over time.

  The weight average molecular weight of the cationized guar gum is preferably 100,000 to 3,000,000, more preferably 200,000 to 1,500,000. The weight average molecular weight is preferably in the above range from the viewpoint of good fingering when rinsing hair, excellent feel of hair after drying, solubility in shampoo compositions, and stability over time.

  Specific examples of the cationized guar gum include Laborum gum CG-M / CG-M7 / CG-M8M (Dainippon Pharmaceutical Co., Ltd.), N-Hance 3000 (Hercules Japan), Jaguar C-13S, Jaguar C- 14S, Jaguar C-17S, Jaguar C-210, Jaguar C-1620 (Rhone-Poulenc), EXCEL (Rhodia) and the like.

  The cation degree of the components of the cationized cellulose and the cationized guar gum can be easily calculated if the chemical structure is clear, but even if the structure such as the monomer ratio is unknown, the Kjeldahl method, etc. It can be calculated from the measured value of N content. In addition, the cation degree shown by this invention is computed based on the value measured by the nitrogen determination method 2nd method of the general test method of the cosmetic raw material reference | standard which is a Kjeldahl method. In addition, meq / g which is a unit of cation degree indicates the number of milliequivalents of N cation groups per 1 g of a sample.

  The weight average molecular weights of the cationized cellulose and the cationized guar gum can be measured by a method of comparing with a polymer having a known molecular weight using liquid chromatography using a general GPC column. The above-mentioned weight average molecular weight is a value measured using GPC-MALLS, and a sample solution diluted with a mobile phase having a pure polymer concentration of about 1000 ppm is used with a TSK-GELA column (manufactured by Tosoh Corporation). Using a multi-angle light scattering detector, a wavelength of about 633 nm was measured using a 0.5 mol / L sodium perchlorate solution as a mobile phase. As a standard product, polyethylene glycol having a known molecular weight was used.

  As the vinyl monomer having a hydroxyl group and an amide bond of a copolymer of a monomer mixture containing a vinyl monomer having a hydroxyl group and an amide bond and a vinyl monomer having a cationic group, It is preferable to use a hydroxyalkyl (meth) acrylamide-based monomer represented by the formula (3) (where “(meth) acryl” represents acryl and methacryl).

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は水素原子、又は炭素原子数１〜４のアルキル基もしくはヒドロキシアルキル基を示す。ａは１〜４の整数を表す。）

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. A represents an integer of 1 to 4)

  Examples of the vinyl monomer having a hydroxyl group and an amide bond represented by the general formula (3) include N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, and N, N-dihydroxyethyl (meth). Examples include N-hydroxyalkyl (meth) acrylamides such as acrylamide. Among them, N-hydroxyethyl (meth) acrylamide is particularly preferable because the solubility of the monomer in water and the solubility of the obtained polymer in water are high.

  The structural unit corresponding to the vinyl monomer having a hydroxyl group and an amide bond is preferably 20 to 90% by mass in the copolymer. More preferably, it is 30-80 mass%, Most preferably, it is 40-70 mass%. This structural unit is considered to increase the effect of adsorbing on the hair due to the action of hydrogen bonds derived from the amide bond portion. When the constitutional unit corresponding to the vinyl monomer having a hydroxyl group and an amide bond is less than 20% by mass in the copolymer, the adsorptive power to hair or the like is lowered due to the above reasons, and the smoothness and smoothness after drying. May decrease. If it exceeds 90% by mass, the content of the structural unit corresponding to the vinyl-based monomer having a cationic group decreases, and it becomes impossible to form a sufficient complex with the anionic surfactant. In some cases, the smoothness during rinsing may decrease.

  On the other hand, vinyl monomers having a cationic group include diallyl quaternary ammonium salts such as N, N-dimethyl-N, N-diallylammonium chloride, N-methacryloyloxyethyl-N, N, N-trimethyl. (Meth) acrylic ester quaternary ammonium salts such as ammonium chloride, (meth) acrylamide quaternary ammonium salts such as N-methacryloylaminopropyl-N, N, N-trimethylammonium chloride, and L-arginine and glycidyl methacrylate Amino acid-based cationic species such as reactants can be exemplified, and (meth) acrylic quaternary ammonium salt monomers represented by the general formula (4) are particularly preferable.

［式中、Ｒ³は水素原子又はメチル基を示し、Ｒ⁴及びＲ⁵はそれぞれ独立に炭素数１〜２４のアルキル基、又は炭素数６〜２４のアリール基もしくはアラルキル基を示し、Ｒ⁶は水素原子、炭素数１〜２４のアルキル基もしくはアルケニル基、炭素数６〜２４のアリール基もしくはアラルキル基、又は下記一般式（５）
−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−Ｎ⁺Ｒ⁷Ｒ⁸Ｒ⁹・Ｙ^- （５）
（式中、Ｒ⁷〜Ｒ⁹はそれぞれ独立に炭素数１〜２４のアルキル基、又は炭素数６〜２４のアリール基もしくはアラルキル基を示す。Ｙ^-は陰イオンを示す。）
で表される基である。Ｘ^-は陰イオン、ｂは０又は１、ｃは１〜１０の整数を示す。］

Wherein, R ³ represents a hydrogen atom or a methyl group, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 24 carbon atoms, or an aryl group or an aralkyl group having a carbon number of 6 to 24, R ⁶ Is a hydrogen atom, an alkyl or alkenyl group having 1 to 24 carbon atoms, an aryl or aralkyl group having 6 to 24 carbon atoms, or the following general formula (5)
—CH ₂ —CH (OH) —CH ₂ —N ⁺ R ⁷ R ⁸ R ⁹ · Y ⁻ (5)
(In the formula, R ^{7 to} R ⁹ each independently represents an alkyl group having 1 to 24 carbon atoms, or an aryl group or aralkyl group having 6 to 24 carbon atoms. Y ⁻ represents an anion.)
It is group represented by these. X ⁻ represents an anion, b represents 0 or 1, and c represents an integer of 1 to 10. ]

Examples of the vinyl monomer having a cationic group represented by the general formula (4) include N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride, N- (meth) acryloyloxyethyl-N. -Ethyl-N, N-dimethylammonium = monoethyl sulfate, N- (meth) acryloyloxyethyl-N, N, N-triethylammonium = monoethyl sulfate, N- [3- {N '-(meth) acryloyloxy Ethyl-N ', N'-dimethylammonium} -2-hydroxypropyl] -N, N, N-trimethylammonium chloride, N- [3- {N'-(meth) acryloyloxyethyl-N ', N'- Diethylammonium} -2-hydroxypropyl] -N, N, N-triethylammonium chloride (Meth) acrylic acid esters having an on-group, N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride, N- (meth) acryloylaminopropyl-N-ethyl-N, N-dimethyl Ammonium = monoethyl sulfate, N- (meth) acryloylaminopropyl-N, N-diethyl-N-methylammonium chloride, N- (meth) acryloylaminopropyl-N, N-diethyl-N-methylammonium = monomethyl sulfate N- [3- {N '-(meth) acryloylaminopropyl-N', N'-dimethylammonium} -2-hydroxypropyl] -N, N, N-trimethylammonium chloride, N- [3- {N '-(Meth) acryloylaminopropyl-N', N'-diethylan Pyridinium} -2-hydroxypropyl] -N, N, N- trimethyl ammonium chloride having a cationic group of the ride, etc. (meth) acrylamides, and the like.
Of these, N- (meth) acryloyloxyethyl-N, N, N-trimethylammonium chloride and N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium chloride are preferably used. ) Acrylyloxyethyl-N, N, N-trimethylammonium chloride is preferred.

  The structure corresponding to the copolymer of vinyl monomers having a cationic group was obtained by copolymerizing a precursor of a vinyl monomer having a cationic group represented by the following general formula (6). Later, it can be obtained by converting into a structure having a corresponding cationic group with a cationizing agent.

（式中、Ｒ³〜Ｒ⁵、ｂ、ｃは前記と同義である。）

(In the formula, R ^{3 to} R ⁵ , b and c are as defined above.)

  Examples of the cationic vinyl monomer precursor include tertiary amines such as N- (meth) acryloyloxyethyl-N, N-dimethylamine and N- (meth) acryloyloxyethyl-N, N-diethylamine. (Meth) acrylamides having tertiary amines such as (meth) acrylic acid esters, N- (meth) acryloylaminopropyl-N, N-dimethylamine, N- (meth) acryloylaminopropyl-N, N-diethylamine Etc.

  Examples of the cationizing agent include alkyl halides such as methyl chloride and cation group-containing cationizing agents such as 3-chloro-2-hydroxypropyl-N, N, N-trimethylammonium chloride. The cationization reaction can be carried out, for example, by adding a cationizing agent to a polymer solution under the conditions of 20 to 100 ° C. and 1 to 20 hours. In addition, a cationic vinyl monomer or its precursor may be used individually by 1 type, or may use 2 or more types together.

  The structural unit corresponding to the vinyl monomer having a cationic group in the copolymer is preferably 10 to 80% by mass. More preferably, it is 20-70 mass%, Most preferably, it is 30-60 mass%. The structural unit corresponding to this vinyl monomer having a cationic group forms a complex with an anionic surfactant in a hair cosmetic composition, and makes the copolymer easy to adhere to the hair. It is considered a thing.

  If the structural unit corresponding to the vinyl monomer having a cationic group is less than 10% by mass, a sufficient complex cannot be formed with the anionic surfactant, and the smoothness may be lowered during rinsing during hair washing. When it exceeds 80% by mass, the structural unit corresponding to the vinyl monomer having a hydroxyl group and an amide bond decreases, and the adsorptive power to hair or the like decreases, so that the smoothness and dryness after drying may decrease. is there.

  The copolymer may further contain a structural unit derived from another vinyl monomer. However, the presence of an anionic functional group in the copolymer may hinder the formation of a complex with the anionic surfactant described above, and therefore, those having a small number of anionic functional groups are preferable (for example, all functional groups 10 mass% or less), and it is more preferable if it does not substantially contain this. Here, “substantially free” means, for example, a material that does not exhibit anionic property at pH 3-8. Other vinyl monomers include esters of alcohols having 1 to 22 carbon atoms and (meth) acrylic acid, amides of alkylamines having 1 to 22 carbon atoms and (meth) acrylic acid, ethylene glycol , Monoesters of 1,3-propylene glycol and the like with (meth) acrylic acid, further esters in which the hydroxyl groups of the monoester are etherified with methanol, ethanol or the like, and nonionic monomers such as (meth) acryloylmorpholine And semipolar monomers such as amphoteric monomers such as betaine group-containing (meth) acrylic esters, betaine group-containing (meth) acrylamides, amine oxide group-containing (meth) acrylic esters, amine oxide group-containing (meth) acrylamides Examples include the body.

  The content of structural units derived from other vinyl monomers can be determined as appropriate within the scope of the present invention. For example, it can be appropriately determined within a range that does not hinder the solubility of the water-soluble resin or the conditioning effect when used for hair cosmetics. Therefore, 30 mass% or less in a copolymer is preferable.

The content of the structural unit corresponding to the vinyl monomer having a hydroxyl group and an amide bond and the vinyl monomer having a cationic group in the copolymer is determined by IR absorption of the hydroxyl group or the amide bond site. Alternatively, it can be measured by hydroxyl group, amide bond site, ¹ H-NMR of a methyl group adjacent to a cation group, or ¹³ C-NMR thereof.

  In addition, this copolymer can form an aqueous solution having a concentration of 5% by mass at 25 ° C., that is, the transmittance (550 nm, 10 mm glass cell) of the aqueous solution having a concentration of 5% by mass is 80% or more, and the aqueous solution is uniform And it is preferable that it is stable. What can form the 10 mass% concentration aqueous solution at 25 degreeC is further more preferable.

  The copolymer of the present invention is prepared by mixing monomers that give respective structural units or precursors thereof, copolymerizing them by a method such as solution polymerization, suspension polymerization, emulsion polymerization, and then cationizing as necessary. It can manufacture by performing reaction.

  The polymerization reaction is preferably performed in a hydrophilic solvent. Examples of the hydrophilic solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and sec-butanol, water, and the like. Is mentioned. These may be used alone or in combination of two or more. Usually, an alcohol solvent or water is used.

  As polymerization initiators, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2 ' -Azo compounds such as azobis (2-methyl-N- (2-hydroxyethyl) -pripionamide), 2,2'-azobis (2-amidinopropane) dihydrochloride, benzoyl peroxide, dicumyl peroxide, A peroxide such as di-t-butyl peroxide and lauroyl peroxide, a persulfate, or a redox system thereof can be used without particular limitation. The polymerization initiator is usually used in the range of 0.01 to 5% by mass with respect to all monomers.

  The polymerization reaction is usually performed at 30 to 120 ° C., preferably 40 to 100 ° C. for 1 to 30 hours in an inert gas atmosphere such as nitrogen or argon. After completion of the polymerization, the produced copolymer is isolated from the reaction solution by an appropriate means such as solvent distillation or addition of a poor solvent. This copolymer can be used as it is or after further purification to produce the hair cosmetic composition according to the present invention. Purification can be carried out by combining appropriate means such as reprecipitation, solvent washing, membrane separation and the like as necessary.

  The copolymer preferably has a weight average molecular weight of 5,000 to 5,000,000. More preferably, it is 10,000-2 million, More preferably, it is 20,000-1 million. If the weight average molecular weight is less than 5,000, the feeling at the time of rinsing is deteriorated, and the conditioning effect may be lowered. If it exceeds 5,000,000, the viscosity becomes too high and handling in production may be difficult. The weight average molecular weight of the copolymer was determined by gel permeation chromatography (device: manufactured by Tosoh Corporation, SC8010, SD8022, RI8020, CO8011, PS8010, column: Wakopak Industries, Ltd. Wakopak (Wakobeads G-50), Developing solvent: water / methanol / acetic acid / sodium acetate = 6/4 / 0.3 / 0.41). As the copolymer, a copolymer of methacryloyloxyethyltrimethylammonium chloride and N- (2-hydroxyethyl) acrylamide is particularly preferable. As a specific example of the copolymer, Diasleek C-801 (Mitsubishi Chemical ( Co., Ltd.).

  (C) The compounding quantity of a component is 0.01-10 mass% normally in a shampoo composition, Preferably it is 0.05-5 mass%, More preferably, it is 0.1-2 mass%. If it is less than 0.01% by mass, good rinsing properties, foam quality and foam amount may not be obtained. If it exceeds 10% by mass, the finished feeling after drying may be lowered.

  Component (D) of the present invention is polylysine and / or a salt thereof, and is a polymer of L-lysine, which is an essential amino acid. Examples of polylysine include α-polylysine and ε-polylysine, and ε-polylysine represented by the following general formula (7) in which L-lysine is bonded in a straight chain is preferable.

（式中、ｎは５〜５００の整数を示す。）

(In the formula, n represents an integer of 5 to 500.)

  ε-Polylysine may be obtained by any method. Specifically, Streptomyces alpras subspecies lysinopolymeras described in Japanese Patent No. 1245361, glycerin 5% by mass, yeast Extract 0.5% by weight, ammonium sulfate 1% by weight, dipotassium hydrogen phosphate 0.08% by weight, potassium dihydrogen phosphate 0.136% by weight, magnesium sulfate heptahydrate 0.05% by weight, zinc sulfate. Culturing in a medium adjusted to 0.004 mass% heptahydrate, 0.03 mass% iron sulfate heptahydrate, pH 6.8, and separating and collecting ε-polylysine from the resulting culture Can be obtained by:

  Furthermore, ε-polylysine is not only commercially available (manufactured by Chisso Corporation), but can be synthesized by a solid phase method or the like commonly used for peptide synthesis, and can also be synthesized by a commercially available peptide synthesizer or the like. can do. In addition, by using a gene encoding the amino acid sequence of a lysine peptide, it can be produced in large quantities in microbial cells, plant cells, and animal cells using genetic engineering techniques. The crude synthetic peptide obtained here can be further purified by means commonly used for protein / peptide purification such as gel filtration, normal phase, reverse phase HPLC, and ion exchange column purification.

  The number average molecular weight of ε-polylysine used in the present invention is usually 500 to 100,000, preferably 1,000 to 50,000, more preferably 2,000 to 20,000. The above range is preferable from the viewpoint of the effect of suppressing the smell of the scalp and the feeling of finish when dried.

The number average molecular weight is the number average molecular weight Mn given by Mn = ΣMiNi / ΣNi when there are Ni molecules having a molecular weight Mi. The measurement methods include osmotic pressure method, boiling point increase method, freezing point decrease And GPC (Gel Permeation Chromatography) method. The GPC method measures the molecular weight distribution. The molecular weight is converted into a standard substance such as polystyrene, the low angle light scattering method (LALLS), and the multi-angle light scattering method (MALLS). GPC-LALLS method and GPC-MALLS method. GPC is also called SEC (Size Exclusion Chromatography). The method for measuring the number average molecular weight is not particularly limited, but is measured, for example, under the following conditions.
GPC-LALLS method column: Tosoh Biosep G5000 PWXL, 7.8 mm × 30 cm
Moving layer: 0.1 mol / L sodium phosphate buffer (pH 7.0)
Flow rate: 0.5 mL / min
Column temperature: 40 ° C

  In the present invention, ε-polylysine may be free or a polylysine salt. As polylysine salts, inorganic acid salts of ε-polylysine formed with inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid and ε-polylysine, acetic acid, propionic acid, fumaric acid, malic acid, citric acid, maleic acid, adipine Organic acid salts of ε-polylysine formed from organic acids such as acid, gluconic acid and lactic acid and ε-polylysine, medium chain and long chain saturated fatty acids such as caproic acid, lauric acid and stearic acid, and ε-polylysine Ε-polylysine saturated fatty acid, ε-polylysine unsaturated fatty acid salt formed from ε-polylysine and other medium and long chain unsaturated fatty acids such as oleic acid, linoleic acid and arachidonic acid Of the mixture. As polylysine salt and / or its salt, these can be used individually by 1 type or in combination of 2 or more types as appropriate.

  (D) The compounding quantity of polylysine salt and / or its salt is 0.001-5 mass% in a shampoo composition as (epsilon) -polylysine, Preferably it is 0.005-1 mass%, More preferably, it is 0.01. It is -0.5 mass%. If it is less than 0.001% by mass, a sufficient scalp odor suppressing effect may not be exhibited, and if it exceeds 5% by mass, the feeling of finish when dried may be deteriorated.

  The component (E) of the present invention is an organic acid and can be used alone or in combination of two or more. Examples of the organic acid include citric acid, malic acid, tartaric acid, lactic acid, succinic acid, acetic acid, glycolic acid, and α-hydroxy acid. From the viewpoint of the effect of suppressing the odor of the scalp and the effect of suppressing the odor change of the composition, α-hydroxy acid and citric acid are preferred.

  (E) The compounding quantity of organic acid is 0.001-10 mass% normally in a shampoo composition, 0.01-5 mass% is preferable, More preferably, it is 0.1-3 mass%. If the amount is less than 0.001% by mass, the effect of suppressing the scalp odor is not sufficient, and if it exceeds 10% by mass, the composition may be easily separated and the stability may be deteriorated.

  The pH at 25 ° C. of the shampoo composition of the present invention was adjusted by adding alkali such as triethanolamine, triisopropanolamine, potassium hydroxide, potassium hydroxide, etc., if necessary after blending these organic acids. The pH is preferably in the range of 4.0 to 6.0 from the viewpoint of suppressing the smell of the scalp and ensuring the storage stability of the preparation.

  The pH of the shampoo composition can be measured by inserting a pH meter electrode directly into the composition and reading the pH value after stabilization using the method defined in the general test method of cosmetic raw material standards.

  It is preferable that the shampoo composition of the present invention contains a plant extract alone or in combination of two or more. Examples of plant extracts include Roman chamomile extract, Japanese horse chestnut extract, hop extract, pine extract, lemon extract, rosemary extract, hypericum extract, Hypericum perforatum extract, chamomile extract, eucalyptus flower extract, carp daisy flower extract, cornflower extract, etc. . When mix | blending a plant extract, the compounding quantity is 0.001-1 mass% in a shampoo composition.

  In the shampoo composition of the present invention, in addition to the essential components, water and optional components, components used in ordinary shampoo compositions within a range that does not impair the effects of the present invention, such as ethanol, isopropanol, etc. Lower alcohols, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, sorbitol, polyethylene glycol, etc., POE (20) hardened castor oil, lauric acid monoethanolamide can be used as a foam stabilizer and viscosity modifier . Furthermore, thickeners such as carboxymethyl cellulose, hydroxyethyl cellulose, anhydrous sodium sulfate, chelating agents such as EHDP and EDTA, opacifying agents such as ethylene glycol diisostearate and fish scales, mica pieces, pigments, antiseptic / antifungal agents, It can mix | blend suitably as needed.

  Since the shampoo composition of the present invention can suppress the smell of the scalp, it can reduce the amount of paraben such as methyl paraoxybenzoate and ethyl paraoxybenzoate. The amount of paraben can be 0.1% by mass or less in the shampoo composition, and can also be free of parabens (unblended). Therefore, it is suitable for sensitive skin.

  Furthermore, the fragrance | flavor and fragrance | flavor composition used for the shampoo composition of this invention are the fragrance | flavor components described in Unexamined-Japanese-Patent No. 2003-300121 [0021]-[0035] etc., and also for the fragrance | flavor described in the same [0050]. A solvent etc. are mentioned. The amount of the perfume solvent used is 0.1 to 99% by mass, preferably 1 to 50% by mass in the perfume composition.

  Examples of the fragrance stabilizer include dibutylhydroxytoluene, butylhydroxyanisole, vitamin E and its derivatives, catechin compounds, flavonoid compounds, polyphenol compounds and the like, and 0.0001 to 10% by mass in the fragrance composition. However, Preferably, 0.001 to 5 mass% is mix | blended. Among these, a preferable stabilizer is dibutylhydroxytoluene.

  The fragrance composition is a mixture composed of the above fragrance components, a solvent, a fragrance stabilizer and the like. The shampoo composition of the present invention contains 0.005 to 40% by mass of the fragrance composition in the shampoo composition, preferably 0.01 to 10% by mass.

  The shampoo composition of this invention is manufactured by mixing and stirring each component in accordance with a normal method. At this time, the component (A) is preferably used as an aqueous anionic surfactant solution having a concentration of 20 to 70% by mass previously diluted with purified water or ethanol. In addition, the components (B), (C), (D), (E) and other components may be added as water-soluble ones or in an aqueous solution, and oil-soluble ones may be used as other components. The oily component may be dissolved or dispersed in the oil component.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” of the composition is mass%, and the numerical value is a value (AI) converted to a pure component.

[Examples 1-14, Comparative Examples 1-6]
Shampoo compositions having the compositions shown in Tables 1 to 3 were prepared on the basis of conventional methods, and evaluated according to the methods shown below. The results are shown in the table.

Evaluation Method (1) Performance Evaluation For 30 women in their 20s and 30s who have been coloring continuously at least once every two months (hair length: semi-long to long), actual use evaluation was performed. After using each composition for one week continuously, we evaluated the “goodness of fingers when rinsing” and “smoothness of hair after drying” based on the following criteria, and the number of people who answered that the results were good Shown in the evaluation.
<Standard>
Better than everyday shampoo Equivalent to everyday shampoo Better than everyday shampoo <Evaluation>
◎: 25 or more out of 30 respondents: ○: 15-24 out of 30 respondents △: 5-14 out of 30 respondents: × Less than 5 out of 30

(2) Scalp odor 20 females in their 20s and 30s (hair length: semi-long to long) were evaluated for actual use. After 8 hours from the shampooing, a sensory evaluation was performed by a specialized paneler based on the following scores, and the results were shown by the following evaluation based on an average of 20 people.
<Score>
3 points: No smell 2 points: Slight smell 1 point: Smell <Evaluation>
◎: Average point is 2.5 points or more ○: Average point is 2 points or more and less than 2.5 points △: Average point is 1 point or more and less than 2 points ×: Average point is less than 1 point

(3) Color tone and smell of the composition 200 ml of each composition was filled in a PP (polypropylene) container, stored in a thermostatic chamber at 50 ° C. for 1 month, and then allowed to stand in an environment at 22 to 27 ° C. for 3 days. The thing was evaluated. Evaluation was performed by sensory evaluation by a specialized paneler based on the following scores, using a standard product stored in a thermostatic chamber at -5 ° C for 1 month and then left in an environment at 22-27 ° C for 3 days. The results are shown in the following evaluation.
<Score>
5 points: Equivalent to standard product 4 points: Slight difference compared to standard product 3 points: Difference compared to standard product, but no problem in quality 2 points: Standard product There is a large difference in comparison and there is a problem in quality. 1 point: A significant difference is recognized compared to the standard product. The composition of the standard product is shown below.
<Evaluation>
◎: 4 points or more ○: 3 points or more and less than 4 points △: 2 points or more and less than 3 points ×: Less than 2 points

[Example 15]
A shampoo composition having the following composition was prepared.
Composition%
Sodium polyoxyethylene lauryl ether sulfate (2EO) 15
Lauric acid amidopropyl betaine 3
Palm oil alkylbetaine 1
Cationized cellulose (2) 0.2
Cationized guar gum (2) 0.1
Dimethyldiallylammonium chloride / acrylamide copolymer solution 0.2
Sodium tetradecene sulfonate 1
ε-polylysine 0.3
Lauryldimethylamine oxide 0.5
POE (20) hydrogenated castor oil 1
Stearic acid monoglyceride 0.5
POE stearyl ether 0.5
Polyoxyethylene lauric acid monoethanolamide 1.5
Hydroxypropyl cellulose 0.1
Bentonite 0.1
Glycerin 0.5
Sorbitol 1.5
Amodimethicone 0.15
(Aminoethylaminopropylsiloxane / dimethylsiloxane copolymer)
Ethylene glycol distearate 1.5
Roman chamomile extract 0.05
Horsetail extract 0.05
Hop extract 0.05
Pine extract 0.03
Lemon extract 0.05
Rosemary extract 0.05
Hypericum extract 0.05
Hypericum perforatum extract 0.05
Chamomile extract 0.05
Tokakinka extract 0.05
Fuyubodaiju Flower Extract 0.05
Cornflower extract 0.03
Yellow No. 203 0.001
Red No. 106 0.001
Green No. 3 0.00025
Sodium benzoate 0.1
Salicylic acid 0.05
Arginine 0.1
Glutamic acid 0.1
Fragrance B 0.3
Citric acid appropriate amount (adjusted to pH = 4.2)
Purified water balance
Total 100.0%

[Example 16]
A shampoo composition having the following composition was prepared.
Composition%
Sodium polyoxyethylene lauryl ether sulfate (3EO) 1
Amidopropyl betaine laurate 15
Palm oil fatty acid acyl-L-glutamic acid triethanolamine 1
Methacryloyloxyethyltrimethylammonium chloride / N- (2-hydroxyethyl) acrylamide copolymer 0.3
Lauryldimethylamine oxide 1
Hydroxypropyl methylcellulose 0.2
Behenyl alcohol 5
Dimethyl silicone (10 million mm ² / s) emulsion 1
Propylene glycol 3
ε-polylysine 0.5
Polyoxyethylene behenyl ether 0.1
Diglucosyl gallic acid 0.001
Hydroxyethane diphosphonic acid 0.1
Fragrance C 1.0
Malic acid: appropriate amount (adjusted to pH = 4.8)
Purified water balance
Total 100.0%

[Example 17]
The following shampoo compositions were prepared.
Composition%
Sodium polyoxyethylene lauryl ether sulfate (2E.O.) 12
Lauric acid amidopropyl betaine 3
Cationized cellulose (1) 0.1
Lauryldimethylamine oxide 3
POE (20) hydrogenated castor oil 1
Polyoxyethylene lauric acid monoethanolamide 2
Dimethicone emulsion 1
ε-polylysine 0.1
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer 0.1
Dimethyldiallylammonium chloride / acrylamide copolymer solution 0.1
Glycerin 0.5
Sorbitol 1.5
Ethylene glycol distearate 1.5
Sodium benzoate 0.3
Green No. 3 0.0004
Fragrance D 0.5
Glycolic acid appropriate amount (adjusted to pH = 5.5)
Purified water balance
Total 100.0%

  All of the shampoo compositions prepared in Examples 15 to 17 were rich in foaming, good in fingering during rinsing, excellent in the feel of hair after drying, and could suppress the smell of the scalp. The shampoo compositions prepared in Examples 15 to 17 were filled in the following containers, stored for 1 month in a thermostatic chamber at 50 ° C., and then left in an environment at 22 to 27 ° C. for 3 days. The entire amount was transferred to a petri dish and the appearance and smell were evaluated. The evaluation was made by comparing with a standard product that was stored in a thermostatic chamber at -5 ° C for one month and then left in an environment at 22-27 ° C for 3 days. As a result, no layer separation, significant discoloration, generation of foreign substances such as crystals, and significant odor change were observed in any storage container.

<Bottle container>
(1) Bottle part: Material PP Cap: Material PP
(2) Bottle: Material HDPE Cap: Material PP
(3) Bottle part: Material PET Cap: Material PP
(4) Bottle part: Material PP / HDPE Cap: Material PP
<Pump container>
(5) Bottle part: Material PP Dispenser part: Used material PP, PE and SUS304
(6) Bottle part: HDPE Dispenser part: Materials PP, PE and SUS304 used
(7) Bottle part: PET Dispenser part: Materials PP, PE and SUS304 used
(8) Bottle part: PP / HDPE Dispenser part: Materials PP, PE and SUS304 used
<Pouch container>
(9) Material: Aluminum-deposited polyethylene pouch PE is polyethylene, PP is polypropylene, PET is polyethylene terephthalate, and HDPE is high-density polyethylene.

The raw materials used in Examples and Comparative Examples are shown below.
[Preparation Example: Preparation Method of Polyoxyethylene (C12,13) Ether Sodium Sulfate (2EO)]
A 4 liter autoclave was charged with 400 g of lauryl alcohol and 0.4 g of a composite metal oxide Lewis acid sintered solid catalyst composed of Al / Mg / Mn, and the autoclave was purged with nitrogen and heated with stirring. Thereafter, 54 g of ethylene oxide was introduced while maintaining a temperature of 180 ° C. and a pressure of 0.3 mPa to obtain a reaction product. Next, 274 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, and after substitution with nitrogen, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the target sodium polyoxyethylene (C12,13) ether sulfate (2EO).

Claims (2)

(A) an anionic surfactant,
(B) amphoteric surfactant and / or semipolar surfactant,
(C) One kind selected from a copolymer of a cationized cellulose, a cationized guar gum, and a monomer mixture containing a vinyl monomer having a hydroxyl group and an amide bond and a vinyl monomer having a cationic group Or two or more cationic polymer compounds,
(D) polylysine and / or a salt thereof,
(E) A shampoo composition containing an organic acid. (A) component is α-olefin sulfonate, polyoxyalkylene alkyl ether sulfate or alkyl sulfate, (B) component is alkylamidopropyl betaine, alkylaminoacetic acid betaine, 2-alkyl-N-carboxyl (E) methyl-N-hydroxyethylimidazolinium betaine or alkylamine oxide, and (C) component is a copolymer of methacryloyloxyethyltrimethylammonium chloride and N- (2-hydroxyethyl) acrylamide; The shampoo composition according to claim 1, wherein the component is citric acid or glycolic acid.