JP2012232936A - Hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress creak of hair after rinsing, and to obtain fluffy voluminous feeling after drying.SOLUTION: This hair cosmetic includes a component (A) of a tertiary amine compound, a component (B) of a higher alcohol with 12-28 carbons and one hydroxy group, a component (C) of cationized hydroxypropyl cellulose, a component (D) of a branched fatty acid or its salt, and water.

Description

  The present invention relates to a hair cosmetic.

  Hair is damaged by chemical treatment with hair color, shampooing, and physical treatment with the heat of a dryer. It is well known that when hair is damaged, negative elements are generated from an aesthetic point of view, such as dryness, poorness, and loss of gloss. Therefore, in order to return the hair to a smooth feeling before the treatment, a hair cosmetic combining a tertiary amine compound and a higher alcohol is widely used as a conditioning agent.

  For example, in Patent Documents 1 to 3, a predetermined branched fatty acid is used as a higher alcohol, and an aromatic alcohol is used in combination to repair or inhibit hair damage / fatigue destruction due to chemical treatment, dryer drying, and daily hair care behavior. In addition, it is described that a good flexibility and a supple feel can be imparted from wet to dry.

JP 2007-176923 A JP 2007-176924 A JP 2008-37829 A

  However, in the techniques described in Patent Documents 1 to 3, although damaged hair has an effect on smoothness, there is a problem in terms of squeaky hair after rinsing. In addition, there has been a demand for a hair cosmetic that can prevent the hair after drying from sticking to the scalp and maintain a soft and soft hair style.

（式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に下記一般式（２）で表されるカチオン化エチレンオキシ基とプロピレンオキシ基を有する置換基を示し、ｎはアンヒドログルコースの平均重合度を示し、５０〜５０００である。） According to the present invention,
A hair cosmetic containing the following components (A), (B), (C), (D) and water is provided.
(A) Tertiary amine compound (B) Higher alcohol having 12 to 28 carbon atoms and 1 hydroxyl group (C) Cationized hydroxypropyl cellulose (derived from anhydroglucose represented by the following general formula (1) And the degree of substitution of the cationized ethyleneoxy group is 0.01 to 2.9, and the degree of substitution of the propyleneoxy group is 0.1 to 4.0)

(Wherein R ¹ , R ² and R ³ each independently represent a substituent having a cationized ethyleneoxy group and a propyleneoxy group represented by the following general formula (2), and n is an average of anhydroglucose. The degree of polymerization is 50 to 5000.)

（式中、Ｙ^１及びＹ^２は、一方が水素原子であり、他方が下記一般式（３）で表されるカチオン性基を示し、ＰＯはプロピレンオキシ基を示す。ｐは一般式（２）中に含まれるカチオン化エチレンオキシ基（−ＣＨ（Ｙ^１）−ＣＨ（Ｙ^２）−Ｏ−）の数を、ｑはプロピレンオキシ基（−ＰＯ−）の数を示し、それぞれ０又は正の整数である。ｐ及びｑがいずれも０でない場合、カチオン化エチレンオキシ基とプロピレンオキシ基の付加順序は問わず、さらにｐ及び／又はｑが２以上である場合は、ブロック結合又はランダム結合のいずれであってもよい。ただし、Ｒ^１、Ｒ^２及びＲ^３のすべてにおいて、ｐ及びｑがいずれも０になる場合を除く。）

(In the formula, ^one of Y ¹ and Y ² is a hydrogen atom, the other represents a cationic group represented by the following general formula (3), PO represents a propyleneoxy group, and p represents a general formula (2 ) Represents the number of cationized ethyleneoxy groups (—CH (Y ¹ ) —CH (Y ² ) —O—), and q represents the number of propyleneoxy groups (—PO—), each of which is 0 or positive When both p and q are not 0, the addition order of the cationized ethyleneoxy group and the propyleneoxy group is not limited, and when p and / or q is 2 or more, a block bond or a random bond (However, in all of R ¹ , R ² and R ³ , except that p and q are all 0.)

（式中、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に炭素数１〜３の直鎖又は分岐のアルキル基を示し、Ｘ⁻はアニオン性基を示す。）
（Ｄ）下記式（４）で表される分岐脂肪酸又はその塩
ＣＨ_３−ＣＨＲ^７−（ＣＨ_２）_ｒＣＯＯＨ （４）
（式中、Ｒ^７はメチル基又はエチル基を示し、ｒは３〜２６の整数を示す。）

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, and X ⁻ represents an anionic group.)
(D) Branched fatty acid represented by the following formula (4) or a salt thereof CH ₃ —CHR ⁷ — (CH ₂ ) _r COOH (4)
(In the formula, R ⁷ represents a methyl group or an ethyl group, and r represents an integer of 3 to 26.)

  According to the present invention, by using a predetermined branched fatty acid (component (D)) in the cationized hydroxypropyl cellulose (component (C)), the hair is given flexibility at the time of rinsing, and the hair after the rinsing is performed. Squeaking can be suppressed. In addition, it is possible to create a soft and soft hair style on the hair after drying.

  According to the present invention, it is possible to suppress the squeak of the hair after rinsing and to obtain a soft and voluminous finish after drying.

  Hereinafter, embodiments of the present invention will be described.

[(A) Tertiary amine compound]
The tertiary amine compound (A) can be represented by, for example, general formula (11).

In general formula (11), R ¹¹ is a linear or branched alkyl group which may be divided by a functional group represented by —OCO— or —COO— having a total carbon number of 8 to 35 or substituted with —OH. , An alkenyl group, or an aliphatic acyloxy (polyethoxy) ethyl group, R ¹² represents an alkyl group having 1 to 22 carbon atoms, or a hydroxyalkyl group, or a polyoxyethylene group having a total number of added moles of 10 or less. R ¹² may be the same or different.

  Specific examples of the tertiary amine compound (A) include at least one selected from the following tertiary amine compounds (A1), (A2), and (A3).

(A1) Hydroxy ether alkyl amine Examples include compounds represented by the following general formula (12).

In the general formula (12), R ¹³ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ¹⁴ and R ¹⁵ are the same or different and are alkyl having 1 to 6 carbon atoms. Group or — (A ¹ O) _b H (A ¹ is an alkylene group having 2 to 4 carbon atoms, b is a number of 1 to 6, b A ¹ may be the same or different, and the arrangement thereof is arbitrary. Is). a shows the number of 1-5.

  Specific examples of the tertiary amine compound (A1) include hexadecyloxy (2-hydroxypropyl) dimethylamine and octadecyloxy (2-hydroxypropyl) dimethylamine.

(A2) Etheramine Examples include compounds represented by the following general formula (13).

In General Formula (13), R ¹⁶ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ¹⁷ and R ¹⁸ are the same or different and are alkyl having 1 to 6 carbon atoms. Group or — (A ² O) _c H (A ² represents an alkylene group having 2 to 4 carbon atoms, c represents a number of 1 to 6, and c A ² may be the same or different, Is optional).

  Specifically, examples of the tertiary amine compound (A2) include N, N-dimethyl-3-hexadecyloxypropylamine and N, N-dimethyl-3-octadecyloxypropylamine.

(A3) Alkylamidoamines Examples include compounds represented by the following general formula (14).

In the general formula (14), R ¹⁹ represents an aliphatic hydrocarbon group having 11 to 23 carbon atoms, R ²⁰ is the same or different, and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, d is 2 to 2 The number 4 is shown. )

  Specifically, examples of the tertiary amine compound (A3) include N- (3- (dimethylamino) propyl) docosanamide and N- (3-dimethylamino) propyl) stearamide.

  As the component (A), (A-2) ether amine and (A-3) alkylamidoamine are preferable from the viewpoint of smoothness at the time of coating and rinsing.

  Furthermore, (A-2) etheramine is preferable, and N, N-dimethyl-3-hexadecyloxypropylamine and N, N-dimethyl-3-octadecyloxypropylamine are more preferable.

  The tertiary amine compound (A) may be used in combination of two or more. From the viewpoint of smoothness at the time of application and rinsing, good touchability, and glossiness, the content of the component (A) is preferably 0.1 to 15% by mass of the hair cosmetic composition of the present invention, 0.2 10 mass% is more preferable, and 0.5-5 mass% is further more preferable.

[(B) Higher alcohol]
The higher alcohol (B) has 12 to 28 carbon atoms and 1 hydroxyl group. Those having an alkyl group having 12 to 28 carbon atoms are preferred, those having 16 to 24 carbon atoms are more preferred, those having an alkyl group having 18 to 22 carbon atoms are further preferred, and this alkyl group is a linear alkyl group. Is preferred. Specific examples include cetyl alcohol, stearyl alcohol, aralkyl alcohol, and behenyl alcohol, and stearyl alcohol and behenyl alcohol are more preferable. The higher alcohol of the component (B) contains one hydroxyl group and does not contain two or more hydroxyl groups.

  (B) 2 or more types of higher alcohol of a component may be used together, and the content is preferably 0.1 to 20% by mass of the hair cosmetic composition of the present invention, and smoothness at the time of application and rinsing. From the viewpoint of improving stability and the like, 0.5 to 15% by mass is more preferable, and 1 to 10% by mass is further preferable.

[(C) Cationized hydroxypropyl cellulose]
The hair cosmetic composition of the present invention has a main chain derived from anhydroglucose represented by the above general formula (1) as the component (C), and the degree of substitution (k) of the cationized ethyleneoxy group is 0. And cationized hydroxypropyl cellulose (hereinafter also referred to as “C-HPC”) having a propyleneoxy group substitution degree (m) of 0.1 to 4.0.

In general formula (1), R ¹ , R ² and R ³ are each independently a substituent represented by general formula (2), and R ¹ , R ² and R ³ may be the same. , May be different. Also, n R ¹ , n R ² , and n R ³ may be the same or different.

In General Formula (2), ^one of Y ¹ and Y ² is a hydrogen atom, the other is a cationic group represented by the following General Formula (3), and PO is a propyleneoxy group. p is the number of cationized ethyleneoxy groups (—CH (Y ¹ ) —CH (Y ² ) —O—) contained in the general formula (2), and q is the number of propyleneoxy groups (—PO—). Each of which is 0 or a positive integer. When both p and q are not 0, the addition order of the cationized ethyleneoxy group and the propyleneoxy group is not limited, and when p and / or q is 2 or more, it is either a block bond or a random bond. Also good. However, in all of R ¹ , R ² and R ³ , the case where p and q are all 0 is excluded. That is, at least one of n R ^{1 s} , n R ^{2 s,} and n R ^{3 s} , p in the general formula (2) is not 0, and at least one Q in Formula (2) is not 0.

In General Formula (3), R ⁴ , R ^5, and R ⁶ each independently represent a linear or branched alkyl group having 1 to 3 carbon atoms, and X ⁻ represents an anionic group.

  In addition, from the viewpoint of suppressing squeaking at the time of rinsing with the hair cosmetic composition of the present invention and imparting a volume feeling after drying, the average degree of polymerization n in the general formula (1) is 50 or more, and 100 or more. Is preferable, 200 or more is more preferable, and 300 or more is more preferable. Further, when rinsing with the hair cosmetic composition of the present invention, it suppresses squeaking during drying, gives a feeling of volume after drying, gives a soft finish, and is easy to manufacture, and is preferably 5000 or less, and preferably 3000 or less. 2000 or less is more preferable, and 1500 or less is more preferable. Taking these viewpoints together, the average degree of polymerization n is 50 to 5000, preferably 100 to 3000, more preferably 200 to 2000, and still more preferably 300 to 1500. In the present invention, the average degree of polymerization refers to a viscosity average degree of polymerization measured by a copper-ammonia method.

  The substituent represented by the general formula (2) has a cationized ethyleneoxy group and a propyleneoxy group as shown in the general formula (2).

  In the general formula (2), p is preferably 0 or 1 from the viewpoint of ease of production. q is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0 or 1. When a plurality of substituents represented by the general formula (2) are present in the C-HPC molecule, the values of p and q may be different between the substituents.

The total of p and q (p + q) is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and an integer of 1 to 3 from the viewpoint of ease of production. Is more preferable, and 1 or 2 is particularly preferable. When neither p nor q is 0, the addition order of the cationized ethyleneoxy group and the propyleneoxy group is not limited, but the order described in the general formula (2) is preferable from the viewpoint of ease of production. Moreover, when both p and q are not 0 and p and / or q is 2 or more, either block bonding or random bonding may be used, but from the viewpoint of ease of production, block bonding is possible. It is preferable that In n R ¹ , n R ² , and n R ³ , at least one of p in the general formula (2) is not 0, and at least one of the q in the general formula (2) Is not zero.

The cationic group represented by the general formula (3) has a structure represented by the general formula (3). In the general formula (3), R ⁴ , R ⁵ and R ⁶ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, n- A propyl group and an isopropyl group are mentioned. In these, a methyl group or an ethyl group is preferable from a water-soluble viewpoint of C-HPC, and a methyl group is more preferable. In the general formula (3), X represents an anionic group which is a counter ion of an ammonium group, and X is not particularly limited as long as X is an anionic group. Specific examples thereof include alkyl sulfate ions, sulfate ions, phosphate ions, alkyl carbonate ions, and halide ions. Among these, halide ions are preferable from the viewpoint of ease of production. Examples of halide ions include fluoride ions, chloride ions, bromide ions, and iodide ions. From the viewpoints of water solubility and chemical stability of C-HPC, chloride ions and bromide ions are preferred, and chloride ions are preferred. Product ions are more preferred.

In the C-HPC represented by the general formula (1), it is possible to reduce the squeak of the hair after washing with the hair cosmetic composition of the present invention, to give a soft and voluminous feel to the hair after drying, and to facilitate production. From the viewpoint, the substitution degree (k) of the cationized ethyleneoxy group is 2.9 or less, preferably 2.0 or less, more preferably 1.0 or less, and further preferably 0.5 or less. Moreover, from the viewpoint of reducing the squeak of the hair after washing with the hair cosmetic composition of the present invention, suppressing the sticky feeling of the hair after drying, and imparting a soft volume feeling to the hair after drying, it is 0.01 or more. .05 or more is preferable, 0.1 or more is more preferable, and 0.2 or more is more preferable. If these viewpoints are put together, it will be 0.01-2.9, 0.05-2.0 are preferred, 0.1-1.0 are more preferred, and 0.2-0.5 are still more preferred.
In the present invention, the degree of substitution (k) of the cationized ethyleneoxy group is the average number of moles of cationized ethyleneoxy groups present in the C-HPC molecule per mole of anhydroglucose unit constituting the cellulose main chain. Say.

From the viewpoints of reducing the squeaking of the hair after washing with the hair cosmetic composition of the present invention, suppressing the stickiness of the hair after drying, imparting a soft and voluminous feeling to the hair after drying, and propylene The degree of substitution (m) of the oxy group is 4.0 or less, preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.6 or less. In addition, m is 0.1 or more from the viewpoint of reducing the squeaking of the hair after washing with the hair cosmetic composition of the present invention, suppressing the sticky feeling of the hair after drying, and imparting a soft volume feeling to the hair after drying. 0.2 or more is preferable, 0.3 or more is more preferable, and 0.4 or more is more preferable. Summing up these viewpoints, m is 0.1 to 4.0, preferably 0.2 to 2.5, more preferably 0.3 to 2.0, and further 0.4 to 1.6. preferable.
In the present invention, the degree of substitution (m) of propyleneoxy groups refers to the average number of moles of propyleneoxy groups present in C-HPC molecules per mole of anhydroglucose units constituting the cellulose main chain.

  From the viewpoint of ease of production, the sum (k + m) of the substitution degree of the cationized ethyleneoxy group and the substitution degree of the propyleneoxy group is preferably 3.2 or less, more preferably 3.0 or less. It is preferably 2.0 or less, more preferably 0.11 or more from the viewpoint of improving the fingering property after drying of the hair treated with the hair cosmetic and the soft volume. More preferably, it is more preferably 0.3 or more. Taking these viewpoints together, the sum (k + m) of the substitution degree of the cationized ethyleneoxy group and the substitution degree of the propyleneoxy group is preferably 0.11 to 3.2, more preferably 0.2 to 3.0. 0.3 to 2.0 is more preferable.

  The content of C-HPC is preferably 0.01% by mass or more, and 0.02% by mass from the viewpoint of giving a soft impression after washing with the hair cosmetic composition of the present invention, and a soft finish after drying. % Or more is more preferable, 0.05 mass% or more is more preferable, and 0.1 mass% or more is further more preferable. Further, the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 2% by mass or less, and still more preferably 1% by mass or less. When these viewpoints are put together, the content of C-HPC is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, further preferably 0.05 to 2% by mass, More preferably, ˜1% by mass.

  The mass ratio of the component (C) to the component (A) ((C) / (A)) reduces the squeaking of the hair after washing with the hair cosmetic composition of the present invention, and imparts firmness and stiffness to the hair after drying. From the viewpoint of imparting a soft volume feeling, the lower limit is preferably 0.001 or more, more preferably 0.02 or more, and even more preferably 0.05 or more. The upper limit is preferably 5 or less, more preferably 3 or less, and still more preferably 2 or less. When these viewpoints are put together, 0.001 to 5 is preferable, (C) / (A) is more preferably 0.02 to 3, and further preferably 0.05 to 2.

C-HPC can be obtained, for example, by the following production methods (1) to (3).
(1) A method in which cellulose, a large amount of water, and a large excess of alkali metal hydroxide are mixed in a slurry state and reacted with a cationizing agent and propylene oxide.
(2) A method in which dimesylacetamide containing lithium chloride is used as a solvent, an amine or an alcoholate catalyst is further added to dissolve cellulose, and a cationizing agent and propylene oxide are reacted.
(3) A method of reacting powdered, pellet-shaped or chip-shaped cellulose, a cationizing agent, and propylene oxide in the presence of a base without using excessive water or a solvent as in the above (1) or (2).

In the production methods (1) to (3), either the reaction with the cationizing agent or the reaction with propylene oxide may be performed first or simultaneously. Among these production methods, the production method (3) is preferable from the viewpoint of ease of production. The production method (3) preferably has the following two steps.
First step: Adding a cationizing agent to the pulp and performing low crystallization by pulverizing treatment, then adding a base and reacting the pulp with the cationizing agent while performing low crystallization by pulverizing treatment to produce a cation Step of obtaining cationized cellulose Step 2: Step of obtaining cationized hydroxypropylcellulose by reacting the cationized cellulose obtained in the first step with propylene oxide Hereinafter, the production method of (3) is specifically described. To do.

  Since cellulose for producing C-HPC generally has low reactivity at the crystalline part, low-crystalline powdery cellulose with reduced crystallinity and pulp with high crystallinity are suitably used as the raw material cellulose. . Hereinafter, a C-HPC production example (production method (3) -1) using low crystalline powdered cellulose with reduced crystallinity, and a C-HPC production example using high-crystallinity pulp ( A manufacturing method (3) -2) is demonstrated.

<Manufacturing method (3) -1>
Low crystalline powdered cellulose can be prepared from sheet-like or roll-like pulp with high cellulose purity obtained as a general-purpose raw material. The method for preparing the low crystalline powder cellulose is not particularly limited. For example, methods described in JP-A-62-236801, JP-A-2003-64184, JP-A-2004-331918 and the like can be mentioned. Among these, it is more preferable to use low crystalline or non-crystalline powdered cellulose obtained by mechanochemical treatment (hereinafter collectively referred to as “low crystalline powdered cellulose”).

Here, the “low crystallinity” of the low crystalline powdered cellulose means a state in which the ratio of the amorphous part is large in the crystal structure of cellulose. Specifically, a powdery cellulose having a crystallinity of preferably 30% or less, more preferably 20% or less, and still more preferably 10% or less is preferable, and particularly the crystallinity is approximately 0%. It is most preferable to use a completely amorphous cellulose.
Crystallinity (%) = [(I _22.6 -I _18.5 ) / I _22.6 ] × 100 (I)
_{(Wherein, I 22.6,} the lattice plane in X-ray diffraction (002 plane) indicates the diffraction intensity of the (diffraction angle 2θ = 22.6 _{°), I 18.5} is amorphous portion (angle of diffraction 2 [Theta] = 18 .5 °) diffraction intensity.)

  Examples of the method for producing low crystalline powdered cellulose by mechanochemical treatment include a method by treating chip-like pulp obtained by roughly pulverizing sheet pulp with a pulverizer. It is also possible to treat the chip-like pulp with an extruder before the treatment with the pulverizer.

  Examples of the extruder used in this method include a single-screw or twin-screw extruder, preferably a twin-screw extruder. From the viewpoint of applying a strong compressive shear force, a so-called kneading is applied to any part of the screw. A thing provided with a disk part is preferred. Although there is no restriction | limiting in particular as a processing method using an extruder, The method of throwing a chip-form pulp into an extruder and processing continuously is preferable.

  As a pulverizer used in this method, a high pressure compression roll mill, a roll mill such as a roll rotation mill, a vertical roller mill such as a ring roller mill, a roller race mill or a ball race mill, a rolling ball mill, a vibration ball mill, a vibration rod mill, Container drive medium mill such as vibrating tube mill, planetary ball mill or centrifugal fluidizing mill, tower crusher, stirring tank mill, medium stirring mill such as flow tank mill or annular mill, high-speed centrifugal roller mill, ang mill, etc. A compacted shear mill, a mortar, or a mortar. Among these, from the viewpoint of efficiency in reducing the crystallinity and from the viewpoint of productivity, a container-driven medium mill or a medium stirring mill is preferable, a container-driven medium mill is more preferable, a vibration ball mill, a vibration rod mill, and a vibration A vibration mill such as a tube mill is more preferable, and a vibration ball mill and a vibration rod mill are particularly preferable.

The processing method may be either a batch type or a continuous type. The filling ratio of the medium such as balls and rods varies depending on the type of pulverizer, but is preferably 10 to 97%, more preferably 15 to 95%. When the filling rate is within this range, the contact frequency between the raw pulp and the medium is improved, and the grinding efficiency can be improved without hindering the movement of the medium.
Here, the filling rate refers to the apparent volume of the medium relative to the volume of the stirring unit of the pulverizer. In the case of a ball mill, the material of the ball used as the medium is not particularly limited, and examples thereof include iron, stainless steel, alumina, zirconia and the like. The outer diameter of the ball is preferably from 0.1 to 100 mm, more preferably from 1 to 50 mm, from the viewpoint of efficiently low crystallization of cellulose.

  Further, from the viewpoint of efficiently reducing the crystallinity of cellulose, the processing time of the pulverizer is preferably 5 minutes to 72 hours, more preferably 10 minutes to 30 hours. In the pulverizer treatment, the treatment is preferably performed at a temperature of preferably 250 ° C. or lower, more preferably 5 to 200 ° C. from the viewpoint of minimizing denaturation and deterioration due to generated heat.

  The rod used as the medium of the pulverizer is a rod-shaped medium, and a rod having a cross section of a polygon such as a quadrangle or a hexagon, a circle, or an ellipse can be used. The outer diameter of the rod is preferably in the range of 0.5 to 200 mm, more preferably 1 to 100 mm, and still more preferably 5 to 50 mm. The length of the rod is not particularly limited as long as it is shorter than the length of the crusher container. If the size of the rod is in the above range, desired pulverization force can be obtained and cellulose can be efficiently crystallized low. There are no particular limitations on the treatment time and treatment temperature of the vibration mill filled with the rod, but the treatment can be carried out at the same treatment time and treatment temperature as the above ball mill.

  According to the above method, the molecular weight can be controlled, and powder cellulose having a high degree of polymerization and low crystallinity, which is generally difficult to obtain, can be easily prepared. The average degree of polymerization of the low crystalline powdered cellulose is preferably 100 to 2000, more preferably 250 to 1900, and still more preferably 350 to 1800.

  The average particle size of the low crystalline powdered cellulose is not particularly limited as long as the powder has good fluidity, but the upper limit is preferably 300 μm or less, more preferably 150 μm or less, and even more preferably 50 μm or less. In addition, from a viewpoint of the handleability improvement of powdered cellulose, 20 micrometers or more are preferable and a minimum is more preferable 25 micrometers or more. However, in order to avoid the incorporation of a minute amount of coarse particles due to aggregation or the like, it is preferable to use an under-sieving product using a sieve having an opening of about 300 to 1000 μm for the reaction as necessary.

  The low crystalline powdery cellulose obtained as described above is cationized by reacting with a glycidyl trialkylammonium salt in the presence of a base to produce cationized cellulose (first step).

  Examples of the glycidyltrialkylammonium salt used as the cationizing agent include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyltrimethylammonium bromide, glycidyltriethylammonium bromide and the like, and glycidyltrimethylammonium chloride is preferable from the viewpoint of availability. The amount of glycidyl trialkylammonium salt added from the viewpoint of imparting firmness and firmness after drying of hair washed with hair cosmetics, improving the soft and voluminous finish, and suppressing stickiness The amount is usually 0.01 to 3.0 times mol, preferably 0.02 to 2 times mol, more preferably 0.04 to 1.0 times mol, per mol of anhydroglucose unit.

  Examples of the base to be present at the time of cationization include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. From the viewpoint of availability, versatility, and economy, sodium hydroxide, water Barium oxide is more preferred. The amount of base added varies depending on the type of cellulose and the like, but is usually 0.05 to 1.0 times mol, preferably 0.1 to 0.5 times mol for 1 mol of cellulose anhydroglucose unit. .

  The water content in the reaction system is preferably 100% by mass or less based on the cellulose used as a raw material. If the moisture content with respect to cellulose is within this range, the cellulose can be reacted in a fluid powder state without excessive aggregation. In this respect, 80% by mass or less is more preferable, and 5 to 50% by mass is even more preferable.

  The reaction temperature is usually 10 to 85 ° C, preferably 15 to 80 ° C.

  C-HPC can be produced by reacting the cationized cellulose obtained as described above with propylene oxide for hydroxypropylation (second step).

  Here, the amount of propylene oxide used is cellulose from the viewpoint of imparting firmness and stiffness after drying of hair washed with hair cosmetics, improving the finish with a soft and voluminous feel, and suppressing stickiness. The amount is preferably 0.01 to 5.0 times mol, more preferably 0.1 to 3.0 times mol, and further preferably 0.5 to 2.5 times mol per mol of anhydroglucose unit in the molecule.

  A base or an acid can be used as a catalyst for hydroxypropylation. Base catalysts include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, trimethylamine, triethylamine, triethylenediamine and the like. Tertiary amines can be mentioned. Examples of the acid catalyst include Lewis acid catalysts such as lanthanide triflate. In these, a base catalyst is preferable from a viewpoint of suppressing the fall of the polymerization degree of raw material cellulose, An alkali metal hydroxide is more preferable, Sodium hydroxide and potassium hydroxide are further more preferable. These catalysts can be used alone or in combination of two or more. The amount of the catalyst used is not particularly limited, but is usually 0.05 to 1.0 times mol, preferably 0.1 to 0.8 times mol per mol of anhydroglucose unit in the cellulose molecule, .2 to 0.5 times mole is more preferable.

  There are no particular restrictions on the method of adding propylene oxide. For example, (a) a method in which propylene oxide is added dropwise after adding a catalyst to cationized cellulose, (b) propylene oxide is added to cationized cellulose all at once, and then a catalyst is added. Although the method of adding and reacting gradually is mentioned, Method (a) is more preferable.

  The water content in the reaction system is preferably 100% by mass or less based on the cellulose used as a raw material. If the water content with respect to cellulose is within this range, the cationized cellulose can be reacted in a fluid powder state without excessive aggregation. In this respect, 80% by mass or less is preferable, and 5 to 50% by mass is more preferable.

  In the present invention, it is preferable to react the cationized cellulose, the catalyst and propylene oxide in a fluid powder state. However, the cationized cellulose powder and the catalyst are preliminarily mixed with a mixer, a shaker, or a mixing mill. For example, propylene oxide may be added and reacted after uniformly mixing and dispersing as required.

  The reaction temperature for hydroxypropylation is preferably 0 to 150 ° C., but is preferably 10 to 100 ° C., more preferably 20 to 80 ° C., from the viewpoint of avoiding polymerization of propylene oxides and abrupt reaction. Is more preferable. The reaction can be carried out at normal pressure. Moreover, it is preferable to carry out in inert gas atmosphere, such as nitrogen, from a viewpoint of avoiding the fall of the molecular weight by cleavage of the cellulose chain during reaction.

  After completion of the reaction, the unreacted propylene oxide is removed, followed by neutralization treatment, purification treatment, etc., if necessary, followed by drying to obtain the C-HPC of the present invention. The neutralization treatment can be performed by a conventional method. For example, when a base catalyst is used as the catalyst, it can be carried out by adding an acid solution such as acetic acid, a mixed solution of an acid and an inert organic solvent, or an acid aqueous solution. The type of the acid is not particularly limited, and may be appropriately selected in consideration of the corrosion of the apparatus. The purification treatment can be performed by washing with a solvent such as water-containing isopropanol or water-containing acetone solvent and / or water or a dialysis membrane.

  The order of the reaction of cationization and hydroxypropylation in the above production method (3) -1 may be carried out after the hydroxypropylation of the raw material cellulose, or may be carried out at the same time. From the viewpoint of controlling the degree of substitution of the oxy group and the propyleneoxy group, it is preferable to cationize the raw material cellulose and then perform hydroxypropylation. In the first step and the second step of the production method (3) -1, since the cleavage of the cellulose skeleton as the main chain does not substantially occur, the average degree of polymerization of the obtained C-HPC is low crystallization treatment. It can be approximated by the average degree of polymerization of the powdered cellulose later.

<Manufacturing method (3) -2>
When using a highly crystalline pulp without using the aforementioned low crystalline powdered cellulose as the raw material cellulose, it is preferable to perform low crystallization during cationization in order to improve the reactivity of the pulp. Specifically, a cationizing agent is added to the pulp and low crystallization is performed by a pulverizer treatment, and then a base is added and the pulp and the cationizing agent are reacted while performing low crystallization by a pulverizer treatment. Or by adding a base to the pulp and performing low crystallization by a pulverizer treatment, and then adding a cationizing agent and performing a reaction between the pulp and the cationizing agent while performing low crystallization by a pulverizer treatment. Cellulose can be obtained. From the viewpoint of water solubility of C-HPC obtained through this cationization, in the cationization of cellulose, first, a cationizing agent is added to the pulp, and low crystallization is performed by a pulverizer treatment, and then a base. It is preferable to carry out the reaction between the pulp and the cationizing agent while adding a low crystallization by a pulverizer treatment.

  The shape of the pulp used as the raw material cellulose is not particularly limited as long as the introduction into the production apparatus is not hindered, but from the viewpoint of operation, the pellets obtained by cutting or coarsely pulverizing sheet pulp or sheet pulp or It is preferable to use chip-like pulp or powdered cellulose obtained by pulverization. There is no limitation on the crystallinity of the pulp used as the raw material cellulose. However, since the treatment for decreasing the crystallinity of cellulose usually involves a decrease in molecular weight accompanying the cleavage of the cellulose chain, in order to obtain a higher molecular weight cationized cellulose, a cellulose having a lower molecular weight and higher crystallinity. Is preferably used. On the other hand, it is difficult to obtain cellulose having a crystallinity of 95% or higher and a crystallinity of 95%. Therefore, from the viewpoint of the degree of polymerization and availability, the crystallinity of the raw material cellulose represented by the calculation formula (I) is preferably 10 to 95%, more preferably 30 to 90%, and further preferably 60 to 80%.

  The average degree of polymerization of the raw material cellulose is not limited, but in order to obtain a higher molecular weight cationized cellulose, it is preferable to use raw material cellulose having a higher degree of polymerization. From this viewpoint, the average degree of polymerization of the raw material cellulose is preferably 100 to 2000, more preferably 300 to 1500, and still more preferably 350 to 1350.

  Preferred embodiments such as the kind and amount of the cationizing agent, the kind of base, the kind of pulverizer, the low crystallization method and the conditions are the above production method (3) except for the processing time of the pulverizer for low crystallization. It is the same as that described in -1. The processing time of the pulverizer for low crystallization is preferably 1 minute to 5 hours, more preferably 2 minutes to 3 hours, and particularly preferably 5 minutes to 2 hours. If the amount of the base is 0.01 equivalent or more per mol of anhydroglucose unit of the raw material cellulose, the reaction between the cellulose and the cationizing agent proceeds rapidly. The yield of the reaction is high. In this respect, 0.05 to 0.8 equivalent is preferable, 0.1 to 0.7 equivalent is more preferable, 0.2 to 0.6 equivalent is more preferable, and 0 to 0.7 equivalent per mole of anhydroglucose unit of the raw material cellulose. .3 to 0.5 equivalent is particularly preferred.

  Cationization proceeds at the time of low crystallization after addition of a cationizing agent and a base, but when the reaction is insufficient, preferably aging at 10 to 100 ° C, more preferably 30 to 80 ° C, The reaction can proceed. The moisture content at the time of ripening and its preferred mode are the same as in the case of cationization of the low crystalline powdered cellulose described above except that pulp is used instead of the low crystalline powdered cellulose as a raw material. Moreover, it is preferable to carry out in inert gas atmosphere, such as nitrogen, from a viewpoint of avoiding the fall of the molecular weight by cleavage of the cellulose chain | strand during reaction (1st process).

  The amount of propylene oxide, catalyst, reaction conditions, treatment after completion of the reaction and preferred modes thereof used in the second step in the production method (3) -2 are the same as those in the second step in the production method (3) -1. is there.

  As a method for producing C-HPC used in the present invention, from the viewpoint of imparting firmness and stiffness after drying of hair washed with the hair cosmetic composition of the present invention and improving the finish with a soft and voluminous feel, The production method (3) -2 is preferred in which low crystallization is carried out at the time of crystallization, and the resulting cationic cellulose is subjected to hydroxypropylation.

[(D) Branched fatty acid or salt thereof]
The branched fatty acid (D) is a branched fatty acid represented by the following formula (4) or a salt thereof.
^{_{CH 3 -CHR 7 - (CH 2}} ) r COOH (4)
(In the formula, R ⁷ represents a methyl group or an ethyl group, and r represents an integer of 3 to 26.)
For example, LIPIDS, vol. 23, no. 9, 878-881 (1988), it can be separated and extracted from hair or the like, but can also be synthesized according to Patent Document 2, WO 98/30532. The branched fatty acid is represented by the general formula (4), and the total carbon number is preferably 7 to 30, more preferably 10 to 24, and still more preferably 16-22. Specifically, 18-methyleicosanoic acid, 14-methylpentadecanoic acid, 14-methylhexadecanoic acid, 16-methylheptadecanoic acid, 16-methyloctadecanoic acid, 18-methylnonadecanoic acid, and 20-methylheneicosanoic acid are included. Can be mentioned. The branched fatty acid salts include alkali metal salts such as sodium salt, lithium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; ammonium salt; triethanolamine salt, diethanolamine salt and monoethanol. Organic amine salts such as amine salts; basic amino acid salts such as lysine salts and arginine salts.

  Examples of the extract include an extract from lanolin, that is, lanolin fatty acid. Lanolin fatty acid contains about 50% by mass of methyl branched long chain fatty acid called iso fatty acid or anteiso fatty acid. Specifically, 18MEA [Crode Japan Co., Ltd.], Scriro [Crode Japan Co., Ltd.], FA-NH [Nippon Seika Co., Ltd.] can be mentioned.

  (D) The branched fatty acid of the component or its salt may use 2 or more types together. Moreover, you may mix and use a synthetic product and an extract. The content thereof is preferably in the range of 0.005 to 15% by mass, more preferably 0.01 to 10% by mass in the hair cosmetic composition of the present invention, from the viewpoint that the squeaking at the time of rinsing can be remarkably reduced. 0.05 to 5% by mass is more preferable.

  The mass ratio of the component (C) to the component (D) ((C) / (D)) reduces the squeaking of the hair after washing with the hair cosmetic composition of the present invention and imparts firmness and stiffness to the hair after drying. From the viewpoint, the lower limit is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1 or more, and even more preferably 1.5 or more. The upper limit is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, and even more preferably 15 or less. From these viewpoints, (C) / (D) is preferably from 0.1 to 100, more preferably from 0.5 to 50, still more preferably from 1 to 30, and even more preferably from 1.5 to 15.

[(E) Silicones]
The hair cosmetic composition of the present invention may contain (E) silicones. (E) As silicones, the dimethylpolysiloxane represented by General formula (21) is mentioned, for example.
^{_{R 5 (CH 3) 2 SiO}} - [(CH 3) 2 SiO] e -Si (CH 3) 2 R 5 (21)
Wherein, ^{R 5} represents a methyl group or a hydroxyl group, e is the number of 10 to 20,000. ]
When R ⁵ is a methyl group, a is preferably 500 to 10,000, particularly preferably 1000 to 5,000.

(E) Although various dimethylpolysiloxanes can be used as silicones, commercially available products include DOW CORNING TORAY BY11-026, BY22-060 (manufactured by Toray Dow Corning), KF-9008, KF-9003 (Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd.). Specifically, it is shown by the following formula (22).
_{(CH 3) 3 SiO - [} (CH 3) 2 SiO] e -Si (CH 3) 3 (22)
[In formula, e shows the number of 100-20000. ]

  As the dimethylpolysiloxane, those dissolved or dispersed in liquid oil (for example, low-polymerized polydimethylsiloxane oil, liquid silicone oil such as cyclic silicone, or liquid hydrocarbon oil such as isoparaffin) can be used.

  The content of dimethylpolysiloxane is preferably 0.01% by mass or more and 15% by mass or less, and more preferably 0.1 to 10% by mass in the hair cosmetic composition of the present invention from the viewpoint of giving slipping to the hair after drying. . Among these, 1 to 5% by mass is more preferable.

(F) Surfactant The hair cosmetic composition of the present invention may contain a surfactant other than the component (A). Specific examples include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants. When used in conditioners, hair rinses, treatments, etc., it is preferable to use cationic surfactants. .

  Examples of the cationic surfactant other than the component (A) include the following compounds (F1), (F2), and (F3) from the viewpoint of improving the fingering property after washing and drying with hair cosmetics and the feeling of unity. preferable.

(F1) Alkyltrimethylammonium salt For example, the compound represented by the following general formula (23) is mentioned.
^{_{R 31 -N + (CH 3)}} 3 A - (23)
[In the formula, R ³¹ represents an alkyl group having 12 to 22 carbon atoms, and A ⁻ represents a halogen (chlorine or bromine) ion or an alkyl sulfate ion having 1 to 2 carbon atoms. ]

  Among these, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride are particularly preferable.

(F2) Alkoxytrimethylammonium salt Examples include compounds represented by the following general formula (24).
R ³² —O—R ³³ —N ⁺ (CH ₃ ) ₃ A ⁻ (24)
[Wherein, R ³² represents an alkyl group having 12 to 22 carbon atoms, R ³³ represents an ethylene group or a propylene group, and A ⁻ is the same as above. ]

(F3) Dialkyldimethylammonium salt For example, the compound represented by the following general formula (25) is mentioned.
(R ³⁴ ) ₂ N ⁺ (CH ₃ ) ₂ A ⁻ (25)
[Wherein, R ³⁴ represents an alkyl group having 12 to 22 carbon atoms, and A ⁻ is the same as described above. ]

  The component (F) cationic surfactant may be used in combination of two or more thereof, and from the viewpoint of improving good flexibility, slipperiness and volume feeling after drying, the content thereof is hair makeup. 0.01-5 mass% in a raw material is preferable, 0.05-3 mass% is more preferable, 0.1-1 mass% is further more preferable.

  In addition, the hair cosmetic composition of the present invention contains an organic acid selected from hydroxymonocarboxylic acid and dicarboxylic acid in order to obtain the effect of neutralizing component (A) or imparting firmness and stiffness to the hair after drying. You can also. Specific examples of the hydroxy monocarboxylic acid include glycolic acid, lactic acid, glyceric acid, gluconic acid, pantothenic acid and the like. Specific examples of the dicarboxylic acid include malic acid, oxalic acid, malonic acid, maleic acid, succinic acid, glutaric acid and the like. In particular, glycolic acid, lactic acid, and malic acid are preferable from the viewpoint of providing a soft and voluminous finish after drying. The content in the hair cosmetic is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and 0.5 to 2% by mass from the viewpoint of sufficiently enhancing the elasticity and stiffness after drying. Is more preferable.

  The hair cosmetic composition of the present invention has a pH (when diluted to 20 mass times with water, 25 ° C.) of 2 to 2 from the viewpoint of improving the gloss, soft finish and volume feeling after drying. 5 and more preferably pH 3 to 4.5.

In the hair cosmetic composition of the present invention, in addition to the components (A) to (F), other components used as ordinary cosmetic raw materials can be contained. Examples of such an optional component include polymer compounds such as cationized cellulose, hydroxylated cellulose, and highly polymerized polyethylene oxide other than the component (C); humectants such as glycerin, propylene glycol, and dipropylene glycol; zinc pyrithione, chloride Anti-dandruff agents such as benzalkonium; other chelating agents, touch improvers, thickeners, fragrances, UV absorbers, visible light absorbers, chelating agents, antioxidants, coloring agents, preservatives, pH adjusters, viscosity Examples thereof include a regulator, a pearl brightener, and a wetting agent. The hair cosmetic composition of the present invention is produced by mixing the components (A) to (F) and these other components and dissolving them in water.
50 mass% or more and 98 mass% or less are preferable in the hair cosmetics of this invention, and, as for content of water, 60 mass% or more and 95 mass% or less are more preferable.

  The hair cosmetic composition of the present invention can be suitably used for a dosage form that is applied to hair after shampooing the hair, for example, hair rinse, hair conditioner, hair treatment and the like.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

  In the following Examples and Comparative Examples, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise specified. Moreover, the measuring method of various physical properties is as follows.

(1) Measurement of moisture content of pulp and powdered cellulose The moisture content of pulp and powdered cellulose was measured using an infrared moisture meter ("FD-610", manufactured by Kett Scientific Laboratory). The point at which the mass change rate for 30 seconds was 0.1% or less at a measurement temperature of 120 ° C. was defined as the measurement end point.
(2) Calculation of crystallinity of pulp and powdered cellulose From the peak intensity of the diffraction spectrum measured under the following conditions using “Rigaku RINT 2500VC X-RAY diffractometer” manufactured by Rigaku Corporation, the above formula (I) Based on the calculation.
X-ray source: Cu / Kα-radiation, tube voltage: 40 kV, tube current: 120 mA
Measurement range: 2θ = 5-45 °
Measurement sample: created by compressing pellets with an area of 320 mm ² × thickness 1 mm X-ray scanning speed: 10 ° / min When the obtained crystallinity has a negative value, the crystallinity is 0%. did.

(3) Calculation of substitution degree of cationized ethyleneoxy group and propyleneoxy group of C-HPC After purifying C-HPC obtained in the production example described later with a dialysis membrane (fraction molecular weight 1000), the aqueous solution was freeze-dried. As a result, purified C-HPC was obtained. The chlorine content (%) of the obtained purified C-HPC was measured by elemental analysis, and the number of cationic groups contained in C-HPC and the number of counter ions as chloride ions were approximated. From the following formula (II), the amount of cationized ethyleneoxy group (—CH (Y ¹ ) —CH (Y ² ) O—) contained in the C-HPC unit mass (x (mol / g)) Asked.
x (mol / g) = chlorine content obtained from elemental analysis (%) / (35.5 × 100) (II)
The hydroxypropoxy group content (%) was measured according to “Analytical method of hydroxypropyl cellulose” described in the Japanese Pharmacopoeia, except that the object of analysis was not purified hydroxypropyl cellulose but purified C-HPC. From the following formula (III), the hydroxypropoxy group content [formula (OC ₃ H ₆ OH = 75.09)] (y (mol / g) was determined.
y (mol / g) = hydroxypropoxy group content (%) / (75.09 × 100) determined from gas chromatography analysis (III)
The degree of substitution (k) of the cationized ethyleneoxy group and the degree of substitution (m) of the propyleneoxy group were calculated from the obtained x and y and the following formulas (II) and (III).
x = k / (162 + k × K + m × 58) (IV)
y = m / (162 + k × K + m × 58) (V)
[Wherein, k and K represent the degree of substitution of the cationized ethyleneoxy group and the formula weight, respectively, and m represents the degree of substitution of the propyleneoxy group. ]

(5) Measurement of average degree of polymerization (copper ammonia method)
(5-1) Measurement of viscosity average degree of polymerization of pulp and powdered cellulose (i) Preparation of measuring solution Add 0.5 g of cuprous chloride and 20-30 mL of 25% aqueous ammonia to a measuring flask (100 mL), and completely After dissolution, 1.0 g of cupric hydroxide and 25% aqueous ammonia were added to make the amount up to one dimension before the marked line. This was stirred for 30-40 minutes to completely dissolve. Thereafter, precisely weighed cellulose was added to fill the ammonia water up to the marked line. It sealed so that air might not enter, and it stirred and melt | dissolved with the magnetic stirrer for 12 hours, and prepared the solution for a measurement. The amount of cellulose to be added was changed in the range of 20 to 500 mg to prepare measurement solutions having different concentrations.
(Ii) Measurement of viscosity average degree of polymerization After the measurement solution (copper ammonia solution) obtained in (i) above was placed in an Ubbelohde viscometer and allowed to stand in a thermostatic bath (20 ± 0.1 ° C.) for 1 hour. The flow rate of the liquid was measured. From the flow time (t (seconds)) of the copper ammonia solution having various cellulose concentrations (g / dL) and the flow time (t ₀ (seconds)) of the copper ammonia aqueous solution without addition of cellulose, the relative viscosity is expressed by the following formula (VI). η _r was determined.
η _r = t / t ₀ (VI)
Next, the reduced viscosity (η _sp / c) at each concentration was determined by the following formula.
η _sp / c = (η _r −1) / c (VII)
(C: Cellulose concentration (g / dL))
Furthermore, the reduced viscosity was extrapolated to c = 0 to determine the intrinsic viscosity [η] (dL / g), and the viscosity average polymerization degree (DP) was determined according to the following formula (VIII).
DP = 2000 × [η] (VIII)

(5-2) Measurement of viscosity average degree of polymerization of C-HPC (iii) Preparation of measurement solution Measurement solution of (i) above, except for using precisely weighed C-HPC instead of precisely weighed cellulose A measurement solution was prepared in the same manner as in the above.
(Iv) Measurement of viscosity average degree of polymerization The measurement was carried out in the same manner as the measurement of the viscosity average degree of polymerization in (ii) above, except that a cellulose equivalent concentration (g / dL) was used as the concentration of the measurement solution.
Here, the cellulose equivalent concentration (c _cell ) refers to the mass (g) of the cellulose skeleton part contained in 1 dL of the measurement solution, and is defined by the following calculation formula (IX).
c _cell = u × 162 / (162 + k × K + m × 58) (IX)
[In the formula, u represents the mass (g) of the precisely weighed C-HPC used in the preparation of the measurement solution, and k, K, and m represent the same meanings as the above-described calculation formulas (IV) and (V), respectively. . ]

Production Example 1 [Production of C-HPC (1)]
(1) Chip forming step Sheet wood pulp [Biofloc HV10, manufactured by Tenbeck Co., Ltd., average polymerization degree 1508, crystallinity 74%, moisture content 7.6%] was formed into a sheet pelletizer (“SGG-220” manufactured by Horai Co., Ltd.). ) To form chips of 3 to 5 mm square.
(2) Cationization reaction step To 2100 g of the chip-like pulp obtained in the above step (1), an aqueous glycidyltrimethylammonium chloride solution (manufactured by Sakamoto Pharmaceutical Co., Ltd., water content 20%, purity 90% or more) (hereinafter "GMAC" 1170 g [0.52 mole equivalent per mole of cellulose anhydroglucose unit (hereinafter referred to as “AGU”)] was mixed in a plastic bag, and then a batch vibration mill (“FV-” manufactured by Chuo Kako Co., Ltd.). 20 ": The total volume of the container was 69 L, and the rods were loaded into a rod of φ30 mm, a length of 600 mm, and 114 SUS304 rods having a circular cross-sectional shape (filling rate 71%). A pulverization process (frequency: 60 Hz, amplitude: 8 mm, temperature: 10 to 40 ° C.) was performed for 12 minutes to obtain a powdery mixture of cellulose and GMAC.
Further, 284 g of granular sodium hydroxide (equivalent to 0.6 mole per mole of AGU) was charged into the vibration mill. The pulverization process was performed for 120 minutes on the same conditions, and the cationized cellulose was obtained.
(3) Hydroxypropylation reaction step 170 g of cationized cellulose obtained in the above step (2) was charged into a 1 L kneader (Irie Shokai Co., Ltd., PNV-1 type) equipped with a reflux tube, and heated to 70 ° C. Then, 51.0 g of propylene oxide (2.0 mol equivalent per 1 mol of AGU, manufactured by Kanto Chemical Co., Ltd., special grade reagent) was added dropwise with stirring, and the reaction was performed for 6 hours until the propylene oxide was consumed and the refluxing stopped.
The reaction completed mixture was taken out of the kneader to obtain 220 g of light brown crude C-HPC powder. 10.0 g of this crude C-HPC powder was collected and neutralized with lactic acid. In order to determine the degree of substitution of propyleneoxy groups and cationized ethyleneoxy groups, the neutralized product was purified by a dialysis membrane (fractional molecular weight 1000), and then the aqueous solution was lyophilized to obtain purified C-HPC (1). .
From elemental analysis of the obtained purified C-HPC (1), the chlorine element content was 3.8%. Further, the hydroxypropoxy group content by the “analysis method of hydroxypropylcellulose” was 36.5%. Tables 1 and 2 show the average degree of polymerization, the degree of substitution of the cationized ethyleneoxy group (k), and the degree of substitution of the propyleneoxy group (m) of the purified C-HPC (1) obtained.

Production Example 2 [Production of C-HPC (2)]
(1) Chip forming step Sheet wood pulp [Biofloc HV +, manufactured by Tenbeck Co., Ltd., average degree of polymerization 1770, crystallinity 74%, moisture content 7.0%] sheet pelletizer (“SGG-220” manufactured by Horai Co., Ltd.) ) To form chips of 3 to 5 mm square.
(2) Cationization reaction process GMAC58.5g (Equivalent 0.2 mol per mol of AGU) was mixed in a mortar with 100 g of the chip-like pulp obtained in the above step (1), and then a batch vibration mill (Chuo Chemical). “MB-1” manufactured by Kikai Co., Ltd .: The total volume of the container was 3.5 L, and the rods were placed in φ30 mm, length 218 mm, 13 SUS304 rods with a circular cross-sectional shape, filling rate 57%). A pulverization treatment (frequency 20 Hz, amplitude 8 mm, temperature 30 to 70 ° C.) was performed for 12 minutes to obtain a powdery mixture of cellulose and GMAC.
The obtained powder mixture was mixed with 10.3 g of a 48% aqueous sodium hydroxide solution (corresponding to 0.23 mol per mol of AGU) in a mortar, and then charged into the batch type vibration mill. The pulverization process was performed for 60 minutes on the same conditions, and the cationized cellulose was obtained.
(3) Hydroxypropylation reaction step 127 g of the cationized cellulose obtained in the above step (2) was charged into a 1 L kneader equipped with the reflux tube used in Production Example 1, heated to 70 ° C., and 27.0 g of propylene oxide. (Equivalent to 2.8 mol per mol of AGU) was added dropwise with stirring, and the reaction was carried out for 6 hours until propylene oxide was consumed and refluxing stopped.
The reaction-terminated mixture was taken out of the kneader to obtain 181.0 g of a light brown crude C-HPC powder.
This crude C-HPC powder was neutralized, purified and lyophilized in the same manner as in Production Example 1 to obtain purified C-HPC (2). The results are shown in Tables 1 and 2.

Production Example 3 [Production of C-HPC (3)]
(1) Chip forming step Sheet wood pulp [Biofloc HV +, manufactured by Tenbeck Co., Ltd., average degree of polymerization 1770, crystallinity 74%, moisture content 7.0%] sheet pelletizer (“SGG-220” manufactured by Horai Co., Ltd.) ) To form chips of 3 to 5 mm square.
(2) Cationization reaction step After mixing 23.4 g of GMAC (equivalent to 0.2 mol per mol of AGU) in 100 g of the chip-like pulp obtained in the above step (1) in a mortar, a batch type vibration mill (Chuo Chemical) “MB-1” manufactured by Kikai Co., Ltd .: The total volume of the container was 3.5 L, and the rods were placed in φ30 mm, length 218 mm, 13 SUS304 rods with a circular cross-sectional shape, filling rate 57%). A pulverization treatment (frequency 20 Hz, amplitude 8 mm, temperature 30 to 70 ° C.) was performed for 12 minutes to obtain a powdery mixture of cellulose and GMAC.
The obtained powder mixture was mixed with 10.3 g of a 48% aqueous sodium hydroxide solution (corresponding to 0.23 mol per mol of AGU) in a mortar, and then charged into the batch type vibration mill. The pulverization process was performed for 60 minutes on the same conditions, and the cationized cellulose was obtained.
(3) Hydroxypropylation reaction step 127 g of the cationized cellulose obtained in the above step (2) was charged into a 1 L kneader equipped with the reflux tube used in Production Example 1, heated to 70 ° C, and 53.9 g of propylene oxide. (Equivalent to 2.8 mol per mol of AGU) was added dropwise with stirring, and the reaction was carried out for 6 hours until propylene oxide was consumed and refluxing stopped.
The reaction-terminated mixture was taken out of the kneader to obtain 181.0 g of a light brown crude C-HPC powder.
This crude C-HPC powder was neutralized, purified and lyophilized in the same manner as in Production Example 1 to obtain purified C-HPC (3). The results are shown in Tables 1 and 2.

Examples 1 to 10 and Comparative Examples 1 to 4 (Manufacture and evaluation of hair cosmetics)
The hair cosmetics shown in Table 3 were prepared by a conventional method and evaluated by the following evaluation methods. The results are shown in Table 3. The pH is a value obtained by diluting each composition 20 times by mass with water and measuring at 25 ° C.

Evaluation method The hair of a Japanese woman that has been treated once with straight perm and twice with bleach is treated as damaged hair, each having 20 g (length 15-20 cm, average diameter 80 μm) hair bundle, and 5 panelists are as follows. Sensory evaluation was performed while processing.

  After applying 2 g of the hair cosmetics shown in Table 3 to the hair bundle washed with 2 g of the standard shampoo having the following formulation and thoroughly blending the entire hair, it is rinsed under running water of about 40 ° C. for about 30 seconds, Next, towel drying was performed, and after drying with a dryer, evaluation after drying was performed. The evaluation was performed by five people, and the integrated value was obtained.

・ Standard shampoo formulation (pH 7.0)
25% polyoxyethylene (2.5) sodium lauryl ether sulfate 62.0% by mass
Lauric acid diethanolamide 2.3% by mass
Edetate disodium 0.15% by mass
Sodium benzoate 0.5% by mass
Sodium chloride 0.8 mass%
75% phosphoric acid appropriate amount Fragrance, methylparaben appropriate amount Purified water remaining

Evaluation criteria (1) No squeak when rinsing 4: Feel no squeak 3: Do not feel too squeak 2: Feel slightly squeak 1: Feel very squeak

(2) No creaking after drying 4: No squeaking 3: No squeaking 2: Slight squeaking 1: Very squeaking

(3) Smooth feeling 4: Very smooth 3: Slightly free 2: Not very free 1: Not free

(4) Harikishi 4: Very harsh 3: Slightly harsh 2: No harshness 1: No harshness

(5) Soft feeling 4: Very soft 3: Slightly soft 2: Not very soft 1: Not soft

(6) Volume feeling 4: Very volume 3: There is a little volume 2: There is not much volume 1: There is no volume

In addition, the raw material name and manufacturer of each component in Table 3 are as follows.
N, N-dimethyl-3-octadecyloxypropylamine (raw material name) Farmin DM E-80 (manufacturer) Kao Corporation N- (3- (dimethylamino) propyl) docosanamide (raw material name) AMIDET APA-22 (Manufacturer) Kao Spain Stearyl Alcohol (Raw Material) Calcoal 8098 (Manufacturer) Kao Corporation C-HPC (1)
In the C-HPC represented by the general formula (1), the degree of substitution (k) of the cationized ethylene oxide group is 0.3, and the degree of substitution (m) of the propyleneoxy group is 1.3 (described in Table 2).
・ C-HPC (2)
In the C-HPC represented by the general formula (1), the degree of substitution (k) of the cationized ethylene oxide group is 0.31, and the degree of substitution (m) of the propyleneoxy group is 0.62, (described in Table 2).
・ C-HPC (3)
In the C-HPC represented by the general formula (1), the degree of substitution (k) of the cationized ethylene oxy group is 0.11, and the degree of substitution (m) of the propyleneoxy group is 1.53 (described in Table 2).
18-methyleicosanoic acid (raw material name) 18MEA (manufacturer) Croda Japan Co., Ltd. Lanolin fatty acid (raw material name) FA-NH (manufacturer) Nippon Seika Co., Ltd. Lactic acid (90% solution)
・ Dipropylene glycol ・ HPC (hydroxypropylcellulose)
(Raw material name) HPC-M (Manufacturer) Nippon Soda Co., Ltd. C-HEC (cationized hydroxyethyl cellulose)
(Raw material name) Poise C-80M (Manufacturer) Kao Corporation, Dimethylpolysiloxane (Raw material name) BY11-039 (Manufacturer) Toray Dow Corning

Examples 11-13
A hair cosmetic composition having the following composition was prepared and evaluated by a conventional method. The pH is a value obtained by diluting each composition 20 times by mass with water and measuring at 25 ° C.

Example 11 Hair conditioner (pH 3.0)
(mass%)
N, N-dimethyl-3-octadecyloxypropylamine 2.0
(Farmin DM E-80, manufactured by Kao Corporation)
Stearyl alcohol 5.0
(Calcoal 8098, manufactured by Kao Corporation)
C-HPC (1) (Production Example 1) 0.1
Benzyl alcohol 0.5
Dipropylene glycol 5.0
Hydroxy stearic acid hydrogenated castor oil 0.1
(Technol MH, manufactured by Yokoseki Oil & Fat Co., Ltd.)
Dimethylpolysiloxane 2.5
(BY11-039, manufactured by Toray Dow Corning)
18-methyleicosanoic acid 0.3
(18MEA, made by Croda Japan Co., Ltd.)
Lactic acid (90% solution) 2.0
Fragrance 0.4
Sodium hydroxide Appropriate amount Ion exchange water Remaining amount

  The above conditioner suppressed hair squeaking during rinsing, added elasticity and firmness to the hair after drying, and made a hair style with a soft finish and volume.

Example 12 Hair Conditioner (pH 3.8)
(mass%)
N, N-dimethyl-3-octadecyloxypropylamine 2.0
(Farmin DM E-80, manufactured by Kao Corporation)
Behenyl alcohol 5.0
(Calcoal 220-80, manufactured by Kao Corporation)
C-HPC (3) (Production Example 3) 0.3
Benzyl alcohol 0.3
Dipropylene glycol 3.0
Sunflower oil 0.5
(High oleic sunflower oil, manufactured by Yokoseki Oil & Fat Co., Ltd.)
18-methyleicosanoic acid 0.3
(18MEA, made by Croda Japan Co., Ltd.)
Lactic acid (90% solution) 2.0
Fragrance 0.4
Sodium hydroxide Appropriate amount Ion exchange water Remaining amount

  The above conditioner suppressed hair squeaking during rinsing, added elasticity and firmness to the hair after drying, and made a hair style with a soft finish and volume.

Example 13 Hair Treatment (pH 4.5)
(mass%)
N, N-dimethyl-3-octadecyloxypropylamine 0.5
(Farmin DM E-80, manufactured by Kao Corporation)
Stearic acid dimethylaminopropylamide 2.0
(NIKKOL Amidoamine MPS, manufactured by Nikko Chemicals Corporation)
Stearyl alcohol 7.0
(Calcoal 8098, manufactured by Kao Corporation)
C-HPC (2) (Production Example (2)) 0.3
Dipropylene glycol 1.0
Benzyl alcohol 0.5
Phenoxyethanol 0.1
Isopropyl palmitate 1.0
Glycerin 5.0
Dimethylpolysiloxane mixture 2.5
(Silicone KHS-3, manufactured by Shin-Etsu Chemical Co., Ltd.)
16-methylheptadecanoic acid 0.5
Lactic acid (90% solution) 2.2
Fragrance 0.4
Sodium hydroxide Appropriate amount Ion exchange water Remaining amount

  The above conditioner suppressed hair squeaking during rinsing, added elasticity and firmness to the hair after drying, and made a hair style with a soft finish and volume.

Other aspects of the present invention are exemplified below.
<1>
A hair cosmetic comprising the following components (A), (B), (C), (D) and water.
(A) Tertiary amine compound (B) Higher alcohol (C) having 12 to 28 carbon atoms and 1 hydroxyl group (C) Cationized hydroxypropyl cellulose (derived from anhydroglucose represented by the following general formula (1) The main chain has a degree of substitution of the cationized ethyleneoxy group of 0.01 to 2.9 and a degree of substitution of the propyleneoxy group of 0.1 to 4.0)

（式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に下記一般式（２）で表されるカチオン化エチレンオキシ基とプロピレンオキシ基を有する置換基を示し、ｎはアンヒドログルコースの平均重合度を示し、５０〜５０００である。）

(Wherein R ¹ , R ² and R ³ each independently represent a substituent having a cationized ethyleneoxy group and a propyleneoxy group represented by the following general formula (2), and n is an average of anhydroglucose. The degree of polymerization is 50 to 5000.)

（式中、Ｙ^１及びＹ^２は、一方が水素原子であり、他方が下記一般式（３）で表されるカチオン性基を示し、ＰＯはプロピレンオキシ基を示す。ｐは一般式（２）中に含まれるカチオン化エチレンオキシ基（−ＣＨ（Ｙ^１）−ＣＨ（Ｙ^２）−Ｏ−）の数を、ｑはプロピレンオキシ基（−ＰＯ−）の数を示し、それぞれ０又は正の整数である。ｐ及びｑがいずれも０でない場合、カチオン化エチレンオキシ基とプロピレンオキシ基の付加順序は問わず、さらにｐ及び／又はｑが２以上である場合は、ブロック結合又はランダム結合のいずれであってもよい。ただし、Ｒ^１、Ｒ^２及びＲ^３のすべてにおいて、ｐ及びｑがいずれも０になる場合を除く。）

(In the formula, ^one of Y ¹ and Y ² is a hydrogen atom, the other represents a cationic group represented by the following general formula (3), PO represents a propyleneoxy group, and p represents a general formula (2 ) Represents the number of cationized ethyleneoxy groups (—CH (Y ¹ ) —CH (Y ² ) —O—), and q represents the number of propyleneoxy groups (—PO—), each of which is 0 or positive When both p and q are not 0, the addition order of the cationized ethyleneoxy group and the propyleneoxy group is not limited, and when p and / or q is 2 or more, a block bond or a random bond (However, in all of R ¹ , R ² and R ³ , except that p and q are all 0.)

（式中、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に炭素数１〜３の直鎖又は分岐のアルキル基を示し、Ｘ⁻はアニオン性基を示す。）

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, and X ⁻ represents an anionic group.)

(D) Branched fatty acid represented by the following formula (4) or a salt thereof CH ₃ —CHR ⁷ — (CH ₂ ) _r COOH (4)
(In the formula, R ⁷ represents a methyl group or an ethyl group, and r represents an integer of 3 to 26.)
<2>
Hair cosmetics as described in said <1> whose content of the said (C) component in hair cosmetics is 0.01-10 mass%.
<3>
<1> or <2>, wherein the mass ratio ((C) / (A)) of the component (C) to the component (A) in the hair cosmetic is in the range of 0.001 to 5. Hair cosmetics.
<4>
Any one of <1> to <3>, wherein a mass ratio ((C) / (D)) of component (C) to component (D) in the hair cosmetic is in the range of 0.1 to 100. The hair cosmetic composition according to item 1.
<5>
The hair cosmetic according to any one of <1> to <4>, wherein the content of the component (A) in the hair cosmetic is 0.1 to 15% by mass.
<6>
The hair cosmetic according to any one of <1> to <5>, wherein the content of the component (B) in the hair cosmetic is 0.1 to 20% by mass.
<7>
The hair cosmetic according to any one of <1> to <6>, wherein the content of the component (D) in the hair cosmetic is 0.005 to 15% by mass.
<8>
The content of the (A) in the hair cosmetic is 0.2 to 10% by mass, the content of the (B) component is 0.5 to 15% by mass, and the content of the (C) component is 0.05. Hair cosmetics given in any 1 paragraph of <1> thru / or <7> whose content of -2 mass% and the above-mentioned (D) ingredient is 0.01-10 mass%.
<9>
The hair cosmetic according to any one of <1> to <8>, wherein p and q are 0 or 1 in the general formula (2).
<10>
The hair cosmetic according to any one of <1> to <9>, wherein in the general formula (3), R ⁴ , R ^5, and R 6 are each independently a methyl group or an ethyl group.
<11>
The hair cosmetic according to any one of <1> to <10>, wherein the component (A) in the hair cosmetic is (A-2) ether amine and (A-3) alkylamidoamine.
<12>
The hair cosmetic according to any one of <1> to <11>, wherein the component (D) in the hair cosmetic has a total carbon number of 7 to 30 in the formula (4).
<13>
The component (C) obtained by the following steps (1) and (2), the component (A), the component (B), the component (D), the component (E) and water, The hair cosmetic according to any one of 1> to <12>.
Step (1): A cationizing agent is added to the pulp and low crystallization is performed by a pulverizer treatment. Thereafter, a base is added and the pulp and the cationizing agent are reacted while performing low crystallization by a pulverizer treatment. Step of obtaining cationized cellulose Step (2): Step of obtaining cationized hydroxypropylcellulose by reacting the cationized cellulose obtained in step (1) with propylene oxide.

Claims (9)

A hair cosmetic comprising the following components (A), (B), (C), (D) and water.
(A) Tertiary amine compound (B) Higher alcohol (C) having 12 to 28 carbon atoms and 1 hydroxyl group (C) Cationized hydroxypropyl cellulose (derived from anhydroglucose represented by the following general formula (1) The main chain has a degree of substitution of the cationized ethyleneoxy group of 0.01 to 2.9 and a degree of substitution of the propyleneoxy group of 0.1 to 4.0)

(Wherein R ¹ , R ² and R ³ each independently represent a substituent having a cationized ethyleneoxy group and a propyleneoxy group represented by the following general formula (2), and n is an average of anhydroglucose. The degree of polymerization is 50 to 5000.)

(In the formula, ^one of Y ¹ and Y ² is a hydrogen atom, the other represents a cationic group represented by the following general formula (3), PO represents a propyleneoxy group, and p represents a general formula (2 ) Represents the number of cationized ethyleneoxy groups (—CH (Y ¹ ) —CH (Y ² ) —O—), and q represents the number of propyleneoxy groups (—PO—), each of which is 0 or positive When both p and q are not 0, the addition order of the cationized ethyleneoxy group and the propyleneoxy group is not limited, and when p and / or q is 2 or more, a block bond or a random bond (However, in all of R ¹ , R ² and R ³ , except that p and q are all 0.)

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, and X ⁻ represents an anionic group.)
(D) Branched fatty acid represented by the following formula (4) or a salt thereof CH ₃ —CHR ⁷ — (CH ₂ ) _r COOH (4)
(In the formula, R ⁷ represents a methyl group or an ethyl group, and r represents an integer of 3 to 26.)   The hair cosmetic according to claim 1, wherein the content of the component (C) in the hair cosmetic is 0.01 to 10% by mass.   The hair makeup according to claim 1 or 2, wherein a mass ratio ((C) / (A)) of the component (C) to the component (A) in the hair cosmetic is in the range of 0.001 to 5. Fee.   The mass ratio ((C) / (D)) of the component (C) to the component (D) in the hair cosmetic is in the range of 0.1 to 100, according to any one of claims 1 to 3. The hair cosmetic composition described.   The hair cosmetic according to any one of claims 1 to 4, wherein the content of the component (A) in the hair cosmetic is 0.1 to 15% by mass.   The hair cosmetic according to any one of claims 1 to 5, wherein the content of the component (B) in the hair cosmetic is 0.1 to 20% by mass.   The hair cosmetic according to any one of claims 1 to 6, wherein the content of the component (D) in the hair cosmetic is 0.005 to 15% by mass.   The hair cosmetic composition according to any one of claims 1 to 7, wherein p and q are 0 or 1 in the general formula (2). The hair cosmetic according to any one of claims 1 to 8, wherein in the general formula (3), R ⁴ , R ⁵ and R 6 are each independently a methyl group or an ethyl group.