WO2020085134A1

WO2020085134A1 - Topical composition

Info

Publication number: WO2020085134A1
Application number: PCT/JP2019/040370
Authority: WO
Inventors: えりか末永; 三佳坂口
Original assignee: 三洋化成工業株式会社
Priority date: 2018-10-26
Filing date: 2019-10-15
Publication date: 2020-04-30
Also published as: JPWO2020085134A1

Abstract

The present invention is a topical composition which contains structural units (a) derived from a monofunctional ethylenic unsaturated monomer (A), structural units (b) derived from a monofunctional ethylenic unsaturated monomer (B), and structural units (c) derived from a monofunctional ethylenic unsaturated monomer (C) as essential structural units, and contains a copolymer (D) free from structural units derived from ethylenic unsaturated monomers having a functionality of 2 or higher. The monomer (A) is free from phosphorus atoms and silicon atoms in the molecule. The monomer (B) has an HLB of 0.3-5.2. The molar ratio of the structural units (a) is 2-55 mol%, the molar ratio of the structural units (b) is 0.01-10 mol%, and the molar ratio of the structural units (c) is 43-97.99 mol%. The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer (D) is 2.0-7.0. The copolymer (D) has a cation charge density of 1.2-1.6 meq/g.

Description

External composition

The present invention relates to a composition for external use.

Conventionally, various anionic surfactants and amphoteric surfactants have been compounded in external compositions such as hair and skin cleaners, hair treatment agents, cosmetics and bath agents, but these foam. However, there is a problem in that the feel during washing and rinsing and the feel after washing are inferior, and the hair is often tangled and the skin is tight.
Therefore, it is known to incorporate a cationic polymer for the purpose of improving the feel during washing and rinsing and the feel after washing (Patent Document 1). When these are diluted with water during washing and rinsing, they form a complex with the anionic surfactant contained in the detergent and precipitate to reduce friction on the hair surface and skin surface, improving the feel. can do.

By the way, when an external composition containing a conventional conditioning agent was used, the moisturizing property of the skin after use was not sufficient, and the smoothness of the finish was not satisfactory either.

JP, 2005-189919, A

An object of the present invention is to provide a composition for external use which has good moisturizing properties when used on the skin and can impart smoothness to the skin or hair when used on the skin or hair. .

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems.
That is, the present invention provides an aminium group having at least one alkyl group having 1 to 24 carbon atoms and / or at least one aralkyl group having 7 to 24 carbon atoms or at least one alkyl group having 1 to 24 carbon atoms and / or at least Structural unit (a) derived from monofunctional ethylenically unsaturated monomer (A) having a quaternary ammonium group having one aralkyl group having 7 to 24 carbon atoms, said monofunctional ethylenically unsaturated monomer In the structural unit (b) derived from the monofunctional ethylenically unsaturated monomer (B) having an alkyl group having 3 to 30 carbon atoms other than (A), and the monofunctional ethylenically unsaturated monomer (C) A composition for external use containing a copolymer (D) which has a structural unit (c) derived from it as an essential structural unit and does not have a structural unit derived from a difunctional or higher functional ethylenically unsaturated monomer.
The monofunctional ethylenically unsaturated monomer (A) does not contain a phosphorus atom and a silicon atom in the molecule,
HLB of the monofunctional ethylenically unsaturated monomer (B) is 0.3 to 5.2,
The monofunctional ethylenically unsaturated monomer (C) is (meth) acrylamide, a monoalkyl (meth) acrylamide having an alkyl carbon number of 1-2, and a dialkyl (meth) acrylamide having an alkyl carbon number of 1-2. At least one monomer selected from the group consisting of
Based on the total number of moles of the structural unit (a), the structural unit (b) and the structural unit (c) constituting the copolymer (D), the structural unit (a) constituting the copolymer (D). Is 2 to 55 mol%, and the molar ratio of the structural unit (b) constituting the copolymer (D) is 0.01 to 10 mol%, constituting the copolymer (D). The structural unit (c) has a molar ratio of 43 to 99.99 mol%,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer (D) is 2.0 to 7.0,
The composition for external use has a cationic charge density of the copolymer (D) of 1.2 to 1.6 meq / g.

When the composition for external use of the present invention is used on the skin, the moisturizing property of the skin is good, and when it is used on the skin or the hair, smoothness can be imparted to the skin or the hair.

The composition for external use of the present invention comprises an aminium group having at least one alkyl group having 1 to 24 carbon atoms and / or at least one aralkyl group having 7 to 24 carbon atoms, or at least one alkyl group having 1 to 24 carbon atoms, and / Or a structural unit (a) derived from a monofunctional ethylenically unsaturated monomer (A) having a quaternary ammonium group having at least one aralkyl group having 7 to 24 carbon atoms, a monofunctional ethylenically unsaturated monomer Structural unit (b) derived from monofunctional ethylenically unsaturated monomer (B) having an alkyl group having 3 to 30 carbon atoms other than monomer (A), and monofunctional ethylenically unsaturated monomer (C And a constitutional unit (c) derived from (4) as an essential constitutional unit, and an external composition containing a copolymer (D) which does not have a constitutional unit derived from a bifunctional or higher ethylenically unsaturated monomer. Thus, the monofunctional ethylenically unsaturated monomer (A) does not contain a phosphorus atom and a silicon atom in the molecule, and the monofunctional ethylenically unsaturated monomer (B) has an HLB of 0.3. To 5.2, the monofunctional ethylenically unsaturated monomer (C) is (meth) acrylamide, a monoalkyl (meth) acrylamide having an alkyl carbon number of 1-2, and an alkyl carbon number of 1-2. Which is at least one kind of monomer selected from the group consisting of dialkyl (meth) acrylamide, and which comprises the structural unit (a), the structural unit (b) and the structural unit (c) constituting the copolymer (D). Based on the total number of moles, the molar ratio of the structural unit (a) constituting the copolymer (D) is 2 to 55 mol%, and the structural unit (b) constituting the copolymer (D) is The molar ratio is 0.01 to 10 mol%, The molar ratio of the structural unit (c) constituting the polymer (D) is 43 to 99.99 mol%, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer (D). (Mw / Mn) is 2.0 to 7.0, and the external charge composition is such that the copolymer (D) has a cationic charge density of 1.2 to 1.6 meq / g.

In the present invention, the composition for external use is a detergent for hair (hair shampoo), a treatment agent for hair (which is used by applying to hair after washing the hair, specifically, treatment, conditioner, Hair rinse and hair pack), hair setting agent, hair coloring agent, hair perm agent, skin cleanser (body soap and face cleansing cream), cosmetics (lotion, emulsion, beauty essence and pack), bath agent, etc. It is preferably a hair cleanser, a hair treatment and a skin cleanser, and particularly preferably a hair cleanser, a hair rinse, a treatment, a conditioner and a skin cleanser.
When the external composition of the present invention is used as a hair cleaning agent, a hair treating agent, a hair setting agent, a hair coloring agent and a hair perm agent, the scalp has good moisturizing properties and provides smoothness to the scalp and hair. Can be granted.
In addition, when used as a skin cleanser, cosmetics, and bath agent, the skin has good moisturizing properties and can impart smoothness to the skin.

Further, in general, the detergent containing the cationic polymer such as the above-mentioned cationic polymer is not sufficient in detergency against foam quality and sebum stain at the time of washing, but the external composition of the present invention is Since it contains the below-mentioned copolymer (D) as a cationic polymer, it has a high cleaning property against sebum stains, and when used as a cleaning agent, it also has an effect of excellent foam quality during cleaning. Therefore, it is useful as a hair cleanser and a skin cleanser. Furthermore, when used as a skin cleanser, it also has the effect of providing a refreshing feeling during rinsing.
Further, when the external composition containing a cationic polymer such as the cationic polymer described in Patent Document 1 described above is used as a hair cleaning agent, a hair treating agent, a hair setting agent, a hair coloring agent and a hair perm agent. In addition, after the hair is dried, especially when exposed to high humidity (in rainy weather, etc.), the hair may be damaged and the hair may not be put into its original shape. That is, waviness occurs in a direction different from the original shape of the hair. On the other hand, the composition for external use of the present invention contains the below-mentioned copolymer (D) as a cationic polymer, and therefore, as a hair cleansing agent, hair treating agent, hair setting agent, hair coloring agent and hair perm agent. When used, it can sufficiently suppress the swelling after drying the hair, the smoothness of the hair during rinsing (finger passage to the hair), the softness of the hair during rinsing, and the softness of the hair after drying. is there.
Therefore, when the external composition of the present invention is used as a hair cleansing agent, the moisturizing property of the scalp after drying, the smoothness of the hair after drying, the detergency against sebum stains, the foam quality at the time of washing, and the hair after drying. It is extremely useful because it can simultaneously achieve all effects of suppressing swelling, smoothness of hair during rinsing (finger passage to the hair), softness of hair during rinsing, and softness of hair after drying. is there.
Further, the external composition of the present invention, when used as a skin cleanser, moisturizes the skin after drying, smoothness of the skin after drying, detergency against sebum stains, foam quality at the time of cleaning and refreshing at the time of rinsing. This is extremely useful because all the effects of feeling can be achieved at the same time.

The copolymer (D) in the present invention is an aminium having at least one C (C may be abbreviated as C hereinafter) 1 to C24 alkyl group and / or at least one C7 to C24 aralkyl group. Group or a structural unit derived from a monofunctional ethylenically unsaturated monomer (A) having a quaternary ammonium group having at least one C1-C24 alkyl group and / or at least one C7-C24 aralkyl group ( a), a structural unit (b) derived from a monofunctional ethylenically unsaturated monomer (B) having a C3 to C30 alkyl group other than the above monofunctional ethylenically unsaturated monomer (A), and a monofunctional The constitutional unit (c) derived from the ethylenically unsaturated monomer (C) is an essential constitutional unit.
The monofunctional ethylenically unsaturated monomer (A) in the present invention is an aminium group having at least one C1 to C24 alkyl group and / or at least one C7 to C24 aralkyl group or at least one C1 to C24 alkyl group. A monofunctional ethylenically unsaturated monomer having a quaternary ammonium group having an alkyl group and / or at least one C7 to C24 aralkyl group, which does not contain a phosphorus atom and a silicon atom in the molecule. It is the body.
The C1 to C24 alkyl group includes a C1 to C24 straight chain alkyl group and a C3 to C24 branched alkyl group. Specifically, the straight chain alkyl group (methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group and n-tetracosyl group, etc., branched alkyl group (isopropyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-, 2- or 3-methylbutyl group, 2,2- Methylpropyl group, 1-ethylpropyl group, 1-, 2-, 3- or 4-methylpentyl group, 2,2-dimethylbutyl group, 1- or 2-ethylbutyl group, 2-methylhexyl group, 2-methyl Heptyl group, 2-methyloctyl group, 2-methylnonyl group, 2-methyldecyl group, 2-methylundecyl group, 2-methyldodecyl group, 2-methyltridecyl group, 2-methyltetradecyl group, 2-methylpenta group Decyl group, 2-methylhexadecyl group, 2-methylheptadecyl group, 2-methyloctadecyl group, 2-methylnonadecyl group, 2-methylicosyl group, 2-methylhenicosyl group, 2-methyldocosyl group, 2-methyltrico Syl group, 2-ethylhexyl group, 2-ethylheptyl group, 2-ethyloctyl group, 2-ethylnonyl group, 2-ethyldecyl group 2-ethylundecyl group, 2-ethyldodecyl group, 2-ethyltridecyl group, 2-ethyltetradecyl group, 2-ethylpentadecyl group, 2-ethylhexadecyl group, 2-ethylheptadecyl group, 2- And an ethyloctadecyl group, a 2-ethylnonadecyl group, a 2-ethylicosyl group, a 2-ethylhenicosyl group, a 2-ethyldocosyl group and the like).
The C1 to C24 alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group, from the viewpoints of skin moisturizing property, skin smoothness, finger-passing property during rinsing, and refreshing feeling during rinsing. .

C7-C24 aralkyl groups include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylpropyl group, 2-phenylpropyl group, 3-phenylpropyl group, 1-naphthylmethyl group, 2- Examples thereof include a naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, a 9-anthracenylmethyl group and a 9-anthracenylethyl group.
As the C7 to C24 aralkyl group, a benzyl group is preferable from the viewpoints of skin moisturizing property, skin smoothness, finger-passing property during rinsing and refreshing feeling during rinsing.

Of the C1 to C24 alkyl groups and the C7 to C24 aralkyl groups, a methyl group, an ethyl group, and a benzyl group from the viewpoints of skin moisturizing property, skin smoothness, finger-passing property during rinsing, and refreshing feeling during rinsing. Is preferred, and a methyl group is more preferred.

As the aminium group in the monofunctional ethylenically unsaturated monomer (A), a proton is attached to a secondary amino group having one of the above alkyl groups or one of the above aralkyl groups and one substituent having an ethylenically unsaturated group. And a tertiary amino group having two alkyl groups and / or aralkyl groups in total and one substituent having an ethylenically unsaturated group, to which a proton is added. Further, the quaternary ammonium group includes a group having a total of three alkyl groups and / or the above aralkyl groups and one substituent having an ethylenically unsaturated group.
In the monofunctional ethylenically unsaturated monomer (A), examples of the ethylenically unsaturated group include a vinyl ether group, a 2-propenyl group, an isopropenyl group and a (meth) acryloyl group. In addition, "(meth) acryloyl" means "acryloyl and / or methacryloyl".
In the monofunctional ethylenically unsaturated monomer (A), examples of the counter anion of the aminium group or quaternary ammonium group include a halogen anion and a monoalkyl sulfate ester anion having a C1 to C8 alkyl group.

The constitutional unit (a) derived from the monofunctional ethylenically unsaturated monomer (A) is produced by addition polymerization of the ethylenically unsaturated group contained in the monofunctional ethylenically unsaturated monomer (A). It may be a structural unit, and after the addition polymerization of the monomer (A ′) having an amino group, the amino group in the monomer (A ′) may be cationized to form the structural unit (a).
As the structural unit (a), one type may be used alone, or two or more types may be used in combination. As the monofunctional ethylenically unsaturated monomer (A), one type may be used alone, or two or more types may be used in combination.

Examples of the monomer (A ') having an amino group are those in which the ethylenically unsaturated group is a vinyl ether group (2-dimethylaminoethyl vinyl ether, etc.), those in which it is a 2-propenyl group [2- (2-propenyloxy ) Ethyldimethylamine, ethyl (2-propenyl) amine, etc.], those having an isopropenyl group (2-dimethylamino-1-propene, etc.), those having a (meth) acryloyl group (for example, a monomer described later ( A1 ′) etc.) and the like.

Specific examples of the monofunctional ethylenically unsaturated monomer (A) are those in which the ethylenically unsaturated group is a vinyl ether group {[2- (vinyloxy) ethyl] trimethylammonium chloride, ethyl [2- (vinyloxy) ethyl. ] Dimethylaminium chloride, etc.}, 2-propenyl group [2- (2-propenyloxy) ethyltrimethylaminium chloride, etc.], isopropenyl group ({2-[(1-methylethenyl) oxy] Examples thereof include ethyl} trimethylaminium chloride, etc., and a (meth) acryloyl group (for example, a monomer (A1) described later) and the like.

As the structural unit (a), the structural unit (a1) represented by the following general formula (1) is preferable.

[In the general formula (1), R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ each independently represent a C1 to C24 alkyl group; R ⁴ is a hydrogen atom, a C1 to C24 alkyl group Or represents a C7 to C24 aralkyl group; X ⁻ represents a halogen anion or a monoalkyl sulfate ester anion having a C1 to C8 alkyl group; n represents an integer of 1 to 10; Y represents NH or O. ]

R ¹ in the general formula (1) is a hydrogen atom or a methyl group.
R ² and R ³ in the general formula (1) each independently represent a C1 to C24 alkyl group.
R ⁴ in the general formula (1) represents a hydrogen atom, a C1 to C24 alkyl group or a C7 to C24 aralkyl group.

R ² and R ³ are preferably a methyl group and an ethyl group, and more preferably a methyl group, from the viewpoints of moisturizing property of skin, smoothness of skin, finger-passing property during rinsing, and refreshing feeling during rinsing. Is.
R ⁴ is preferably a hydrogen atom, a methyl group, an ethyl group or a benzyl group from the viewpoints of moisturizing properties of skin, smoothness of skin, finger-passing properties during rinsing and a refreshing feeling during rinsing, and more preferred. Is a hydrogen atom and a methyl group.

X ⁻ in the above general formula (1) is a halogen anion or a monoalkyl sulfate anion having a C1 to C8 alkyl group.
Examples of the halogen anion include fluorine anion (F ⁻ ), chlorine anion (Cl ⁻ ), bromine anion (Br ⁻ ), iodine anion (I ⁻ ), and the like.
Of these, chlorine anions and bromine anions are preferred from the viewpoints of skin moisturizing properties, skin smoothness, foam quality during washing, and softness of hair during rinsing, and more preferred are chlorine anions. .
Examples of the monoalkyl sulfate ester anion having a C1 to C8 alkyl group include monomethyl sulfate ester anion, monoethyl sulfate ester anion, monopropyl sulfate ester anion, monobutyl sulfate ester anion, monopentyl sulfate ester anion, monohexyl sulfate ester anion, monoheptyl sulfate. Examples thereof include ester anions and monooctyl sulfate ester anions.
Among these, from the viewpoints of moisturizing property of skin, smoothness of skin, softness of hair during rinsing and foam quality during washing, monomethyl sulfate ester anion (CH ₃ SO ₄ ⁻ ) and monoethyl sulfate ester anion are preferable. (CH ₃ CH ₂ SO ₄ ⁻ ).
As X ⁻ , a chlorine anion and a monomethylsulfate anion are preferable from the viewpoint of appropriately adjusting the SP value of the structural unit (a) or the monofunctional ethylenically unsaturated monomer (A). When X ⁻ is a chlorine anion and a monomethylsulfate anion, the moisturizing properties of the skin, the smoothness of the skin, the softness of the hair during rinsing and the foam quality during washing are particularly good.

In the general formula (1), n is the number of methylene groups and is an integer of 1 to 10.
As n, an integer of 2 or 3 is preferable from the viewpoints of moisturizing property of skin, smoothness of skin, easiness of incorporation into a cleaning composition and a refreshing feeling at the time of rinsing, and more preferably 2 Is.

Y in the general formula (1) is NH or O.
Y is preferably O from the viewpoints of the moisturizing property of the skin, the smoothness of the skin, the softness of hair during rinsing, and the refreshing feeling during rinsing.
As the structural unit (a1), one type may be used alone, or two or more types may be used in combination.

In the copolymer (D) of the present invention, the structural unit (a) is represented by the following general formula (3) as a monofunctional ethylenically unsaturated monomer (A) from the viewpoint of shortening the time required for cationization. It is preferably a structural unit obtained by polymerization of the monomer (A1).
The polymerization method may be radical polymerization, cationic polymerization or anionic polymerization.

In the general formula (3), R ¹ , R ² , R ³ , R ⁴ , n, X ⁻ and Y are respectively R ¹ , R ² , R ³ , R ⁴ and n in the general formula (1). , X ⁻ and Y are the same groups, and the preferred groups are also the same.

As the monomer (A1), the following amino group-containing (meth) acrylate (A1 ′) and an inorganic acid (hydrochloric acid, hydrobromic acid, hydroiodic acid, etc.) or a quaternizing agent (methyl chloride, ethyl chloride) , Dimethylsulfate, diethylsulfate, benzyl chloride, hexadecyl chloride, octadecyl chloride, etc.) and reacting to produce a monomer having an amino group cationized.

As the amino group-containing (meth) acrylate (A1 ′), N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N , N-dioctylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate.
Examples of the monomer (A1) include N, N, N-trimethyl-N- (2-acryloyloxyethyl) ammonium chloride, N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, N , N, N-Trimethyl-N- (2-methacryloyloxyethyl) ammonium methyl sulfate, N-benzyl-N, N-dimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, N, N-dimethyl-N- Ethyl-N- (2-methacryloyloxyethyl) ammonium chloride, N, N-dimethyl-N-ethyl-N- (2-methacryloyloxyethyl) ammonium ethyl sulfate, N, N-dimethyl-N-ethyl-N- ( 2-methacryloyloxypropyl) ammonium chloride N, N, N-trimethyl-N- (3-acryloylaminopropyl) ammonium chloride, N, N, N-triethyl-N- (2-acryloylaminoethyl) ammonium chloride N, N, N-trimethyl-N- ( 3-methacryloylaminopropyl) ammonium chloride, N, N, N-trimethyl-N- (3-acryloylaminopropyl) ammonium methyl sulfate, N, N, N-trimethyl-N- (3-methacryloylaminopropyl) ammonium methyl sulfate , N, N, N-trimethyl-N- (2-acryloyloxyethyl) ammonium methylsulfate and N-benzyl-N, N-dimethyl-N- (2-methacryloyloxyethyl) ammonium methylsulfate.
Among the monomers (A1), N, N, N-trimethyl-N- (3 is preferable from the viewpoints of moisturizing property of skin, smoothness of skin, finger-passing property during rinsing and refreshing feeling during rinsing. -Acryloylaminopropyl) ammonium chloride, N, N, N-trimethyl-N- (3-methacryloylaminopropyl) ammonium chloride, N, N, N-trimethyl-N- (3-acryloylaminopropyl) ammonium methyl sulfate, N , N, N-trimethyl-N- (3-methacryloylaminopropyl) ammonium methyl sulfate, N, N, N-trimethyl-N- (2-acryloyloxyethyl) ammonium chloride, N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, N, N, N-to Methyl-N- (2-acryloyloxyethyl) ammonium methyl sulfate, N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium methyl sulfate, N-benzyl-N, N-dimethyl-N- (2 -Methacryloyloxyethyl) ammonium chloride and N-benzyl-N, N-dimethyl-N- (2-methacryloyloxyethyl) ammonium methylsulfate.
As the monomer (A1), one type may be used alone, or two or more types may be used in combination.

The structural unit (b) in the present invention is a monomer other than the monofunctional ethylenically unsaturated monomer (A), has a C3 to 30 alkyl group, and has an HLB of 0.3 to 5. A constituent unit obtained by polymerization of the monofunctional ethylenically unsaturated monomer (B) of 2 is included.
The C3-30 alkyl group includes a C3-30 straight-chain alkyl group and a C3-30 branched alkyl group. Specifically, the straight-chain alkyl group (n-propyl group, n-butyl group, n -Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, pentacosil Group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, etc.), branched alkyl group (isopropyl group, isobutyl group, tert-group) Chill group, sec-butyl group, 1-, 2- or 3-methylbutyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, 1-, 2-, 3- or 4-methylpentyl group, 2, 2-dimethylbutyl group, 1- or 2-ethylbutyl group, 2-methylhexyl group, 2-methylheptyl group, 2-methyloctyl group, 2-methylnonyl group, 2-methyldecyl group, 2-methylundecyl group, 2 -Methyldodecyl group, 2-methyltridecyl group, 2-methyltetradecyl group, 2-methylpentadecyl group, 2-methylhexadecyl group, 2-methylheptadecyl group, 2-methyloctadecyl group, 2-methylnonadecyl group , 2-methylicosyl group, 2-methylhenicosyl group and 2-methyldocosyl group, 2-methyltricosyl group, 2-ethylhexyl group, 2-ethyl Butyl group, 2-ethyloctyl group, 2-ethylnonyl group, 2-ethyldecyl group, 2-ethylundecyl group, 2-ethyldodecyl group, 2-ethyltridecyl group, 2-ethyltetradecyl group, 2-ethylpenta group Decyl group, 2-ethylhexadecyl group, 2-ethylheptadecyl group, 2-ethyloctadecyl group, 2-ethylnonadecyl group, 2-ethylicosyl group, 2-ethylhenicosyl group, 2-ethyldocosyl group, 2-ethyltrico Syl group, 2-ethyltetracosyl group, 2-ethylpentacosyl group, 2-ethylhexacosyl group, 2-ethylheptacosyl group, 2-ethyloctacosyl group, etc.) and the like.
Of these, a C3 to C12 alkyl group is preferable, and a C4 to C8 alkyl group is more preferable, from the viewpoints of moisturizing properties of the skin, smoothness of the skin, softness of hair after drying and a refreshing feeling upon rinsing. is there.

In the monomer (B), examples of the ethylenically unsaturated group include a vinyl ether group, a 2-propenyl group, an isopropenyl group and a (meth) acryloyl group.

The monomer (B) is a monomer having HLB of 0.3 to 5.2.
In the present invention, HLB is a measure showing a balance between hydrophilicity and lipophilicity, and higher HLB means higher inorganicity. For example, “Introduction to Surfactants, 2007, Sanyo Chemical Industries Co., Ltd. It is known as a value calculated by the Oda method described in “Company Issued by Takehiko Fujimoto, p. 212” and not a value calculated by the Griffin method. The HLB value can be calculated from the ratio of the organic value and the inorganic value of the organic compound.
HLB = 10 × inorganic / organic The organic value and the inorganic value for deriving HLB can be calculated using the values in the table on page 213 of “Introduction to Surfactants”.
HLB of the monomer (B) includes skin moisturizing properties, skin smoothness, foam quality during washing, detergency against sebum stains, reduction of swelling after hair drying, finger-passing property to hair during rinsing, From the viewpoint of the softness of hair during rinsing, the softness of hair after drying, the feeling of freshness during rinsing and the moisturization of skin after drying, 1 to 5 is preferable, and 2 to 4.2 is more preferable.

Specific examples of the monomer (B) are those in which the ethylenically unsaturated group is a vinyl ether group [propyl vinyl ether (HLB = 2.2), octyl vinyl ether (HLB = 1.1), triacontyl vinyl ether (HLB). = 0.34), etc.], a 2-propenyl group [3-propoxypropan-1-ene (HLB = 2), allyl octyl ether (HLB = 1.05), allyl triacontyl ether (HLB = 0.40). 34) etc.], those having an isopropenyl group [2-propoxy-1-propene (HLB = 2), isopropenyl octyl ether (HLB = 1.05), isopropenyl triacontyl ether (HLB = 0.34), etc. ], A (meth) acryloyl group [propyl acrylate (HLB = 5.17), methacrylic acid pro (HLB = 4.77), n-butyl acrylate (HLB = 4.43), n-butyl methacrylate (HLB = 4.13), n-octyl acrylate (HLB = 2.82), methacrylic acid n-octyl (HLB = 2.7), 2-ethylhexyl acrylate (HLB = 2.8), n-dodecyl acrylate (HLB = 2.07), n-dodecyl methacrylate (HLB = 2.03), acrylic Acid n-triacontyl (HLB = 0.94), n-triacontyl methacrylate (HLB = 0.93), etc.] and the like.
As the structural unit (b), one type may be used alone, or two or more types may be used in combination. As the monomer (B), one type may be used alone, or two or more types may be used in combination.

The structural unit (b) is preferably a structural unit (b1) represented by the following general formula (2).

[In the general formula (2), R ⁵ represents a hydrogen atom or a methyl group; -Z- represents -C (O) O- or -O-; R ⁶ represents a C3-C30 alkyl group. ]

R ⁵ in the general formula (2) is a hydrogen atom or a methyl group.
In the general formula (2), -Z- represents -C (O) O- or -O-.

R ⁶ in the general formula (2) represents a C3 to C30 alkyl group.

R ⁶ is preferably a C3 to C12 alkyl group, more preferably C4 to C8, from the viewpoints of moisturizing properties of the skin, smoothness of the skin, softness of hair after drying and a refreshing feeling upon rinsing. It is an alkyl group.
As the structural unit (b1), one type may be used alone, or two or more types may be used in combination.

In the copolymer (D) of the present invention, the structural unit (b) includes a structural unit obtained by polymerizing the monomer (B1) represented by the following general formula (4).
The polymerization method may be radical polymerization, cationic polymerization or anionic polymerization.
As (B), one type may be used alone, or two or more types may be used in combination.

In the general formula (4), R ⁵ , R ⁶ and -Z- are the same groups as R ⁵ , R ⁶ and -Z- in the general formula (2), respectively, and preferred ones are also the same.

The ethylenically unsaturated monomer (C) is a group consisting of (meth) acrylamide, a monoalkyl (meth) acrylamide having 1 to 2 carbon atoms in the alkyl, and a dialkyl (meth) acrylamide having 1 to 2 carbon atoms in the alkyl. It is at least one kind of monomer selected from In addition, "(meth) acrylic" means "acrylic and / or methacrylic".
The copolymer (D) in the present invention has the constituent unit (c) derived from the monomer (C), and the monomer (C) is an essential constituent monomer.
As the structural unit (c), one type may be used alone, or two or more types may be used in combination.
Among the monomers (C), those having (meth) acrylamide and alkyl having 1 to 10 carbon atoms are preferable from the viewpoints of skin moisturizing property, skin smoothness, finger-passing property during rinsing and refreshing feeling during rinsing. 2 is a dialkyl (meth) acrylamide.

In the present invention, the molar ratio of the structural unit (a), the structural unit (b) and the structural unit (c) constituting the copolymer (D) is such that the moisturizing property of the skin, the smoothness of the skin, and the foam quality at the time of washing. From the viewpoints of the detergency against sebum stains, the ability to pass through fingers during rinsing, the softness of hair after drying, the refreshing feeling during rinsing and the moisture of the skin after drying, the structural unit (a), the structural unit (b) and Based on the total number of moles of the structural unit (c), the structural unit (a) is 2 to 55 mol%, the structural unit (b) is 0.01 to 10 mol%, and the structural unit (c) is 43 to 97.99. Mol%.
The molar ratio of the structural unit (a) is from 10 to 30 mol% from the viewpoint of skin moisturizing property, skin smoothness, foam quality during washing, softness of hair after drying and moisture of skin after drying. It is more preferably 10 to 20 mol%.
The molar ratio of the constituent unit (b) is such that skin moisturizing property, skin smoothness, foam quality during washing, detergency against sebum stain, softness of hair after drying, refreshing feeling during rinsing and skin after drying. From the viewpoint of moisture content, 0.1 to 5 mol% is preferable, and 0.2 to 5 mol% is more preferable.
The molar ratio of the structural unit (c) is preferably 60 to 89.99 mol%, more preferably 65, from the viewpoint of moisturizing property of skin, smoothness of skin, foam quality during washing and finger-passing property during rinsing. ˜89.9 mol%, and more preferably 75˜89.8 mol%.

The copolymer (D) is a copolymer containing the above structural unit (a), structural unit (b) and structural unit (c) as essential structural units, and is a bifunctional or higher functional ethylenically unsaturated monomer. It is a copolymer having no derived constitutional unit.
The copolymer (D) contains the monofunctional ethylenically unsaturated monomer (A), the monofunctional ethylenically unsaturated monomer (B) and the monofunctional ethylenically unsaturated monomer (C). It is preferably a polymer of a monomer component.
The molar ratio of the monomer (A) in the monomer component is from the viewpoint of moisturizing the skin, smoothness of the skin, foam quality during washing, softness of hair after drying and moisture of the skin after drying. The amount is preferably 2 to 55 mol%, more preferably 10 to 30 mol%, and particularly preferably 10 to 20 mol%, based on the total number of moles of the above monomer components.
The molar ratio of the monomer (B) in the monomer component is such as skin moisturizing property, skin smoothness, foam quality during washing, detergency against sebum stains, softness of hair after drying, and rinsing From the viewpoint of a refreshing feeling and the moisturization of the skin after drying, 0.01 to 10 mol% is preferable, and 0.1 to 5 mol% is more preferable, based on the total number of moles of the above-mentioned monomer components. It is preferably 0.2 to 5 mol%.
The molar ratio of the monomer (C) in the monomer components is the sum of the above monomer components from the viewpoints of skin moisturizing properties, skin smoothness, foam quality during washing, and finger-passing properties during rinsing. Based on the number of moles, 43 to 99.99 mol% is preferable, 60 to 89.99 mol% is more preferable, 65 to 89.9 mol% is still more preferable, and 75 to 89 is particularly preferable. It is 0.8 mol%.

The weight average molecular weight of the copolymer (D) measured by gel permeation chromatography (GPC) is preferably 650,000 to 2,000,000.
When the weight average molecular weight of the copolymer (D) is 650,000 or more, foam quality during washing, detergency against sebum stains, reduction of waviness after hair drying, fingerability during rinsing, hair during rinsing The softness of the hair, the softness of the hair after drying, the refreshing feeling at the time of rinsing, and the moisture of the skin after drying become good. When it is 2,000,000 or less, the transparency after blending the detergent composition is good.
The weight average molecular weight of the copolymer (D) is from the viewpoint of skin moisturizing property, skin smoothness, foam quality at the time of washing, finger combability at the time of rinsing, refreshing feeling at the time of rinsing and moisture of the skin after drying. , And more preferably 1,000,000 to 2,000,000.

In the chromatogram of the copolymer (D) measured by gel permeation chromatography (GPC), the area (M ₁ ) of the region having a molecular weight of less than 3,000 and the area of the region having a molecular weight of 3,000 to 10,000,000 are measured. The area ratio (M ₁ / M ₂ ) with respect to the area (M ₂ ) is from the viewpoint of moisturizing property of skin, smoothness of skin, foam quality at the time of washing, finger-passing property at the time of rinsing, and refreshing feeling at the time of rinsing. It is preferably 10/90 to 30/70, more preferably 10/90 to 20/80.
When the area ratio (M ₁ / M ₂ ) is 10/90 or more, the moisturizing property of the skin and the smoothness of the skin are improved. Further, when the area ratio (M ₁ / M ₂ ) is 30/70 or less, a refreshing feeling at the time of rinsing is good.
The area ratio (M ₁ / M ₂ ) can be adjusted by the length of aging time during synthesis.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer (D) is 2.0 to 7.0.
When Mw / Mn of the copolymer (D) is 2.0 or more, the production of the copolymer (D) is easy and the detergency for sebum stains is good. When it is 7.0 or less, the smoothness of the skin is good, and the foam quality at the time of washing, the detergency against sebum stains, the reduction of the swelling after the hair is dried, the fingerability of the hair at the time of rinsing, and the easiness of the hair at the time of rinsing Good softness, softness of hair after drying, refreshing feeling during rinsing, and moisturizing of skin after drying.
The Mw / Mn of the copolymer (D) is more preferably 2.0 to 5.0 from the viewpoint of further suppressing the moisturizing properties of the skin, the smoothness of the skin and the swelling of hair after drying.

In the present invention, the area of the region where the molecular weight is less than 3,000 (M ₁ ), the area of the region where the molecular weight is 3,000 to 10,000,000 (M ₂ ), the number average molecular weight (hereinafter abbreviated as Mn), and The weight average molecular weight (hereinafter abbreviated as Mw) is measured by gel permeation chromatography (hereinafter abbreviated as GPC). The measurement shall comply with the following measurement conditions.
<GPC measurement conditions>
GPC model: HLC-8120GPC, Tosoh Corporation column: TSKgel GMHXL 2 + TSKgel Multipore HXL-M, Tosoh Corporation solvent: Tetrahydrofuran (THF)
Detector: Refractive index detector Reference substance: Standard polystyrene (TSK standard POLYSTYRENE), manufactured by Tosoh Corporation

The cationic charge density (meq / g) of the copolymer (D) is 1.2 to 1.6.
When the cationic charge density (meq / g) of the copolymer (D) is less than 1.2, the moisturizing property of the skin, the smoothness of the skin, the foam quality at the time of washing, the detergency against sebum stains, and after hair drying The swelling is reduced, the ability to pass through the hair during rinsing, the softness of hair during rinsing, the softness of hair after drying, the feeling of freshness during rinsing, and the moisture of the skin after drying are deteriorated. When it exceeds 1.6, the moisturizing property of the skin, the smoothness of the skin, the transparency after blending the detergent composition and the refreshing feeling upon rinsing are deteriorated.
The cationic charge density is (D) the equivalent number of cationic charges per unit weight, and can be calculated by the following method.
As described above, the copolymer (D) is a copolymer having a plurality of structural units [the structural unit (a), the structural unit (b), the structural unit (c), etc.].
Here, the above-mentioned cation charge density refers to “charge density ei (meq) for each structural unit [for example, 1,000 meq in the case of the structural unit (a), structural unit (b) and structural unit] In the case of the unit (c), 0 meq] "," molecular weight mi of each constitutional unit ", and" molar ratio xi of each constitutional unit to the total number of moles of all constitutional units constituting the copolymer (D) ". Can be obtained by the following mathematical expression (1).

Note that the cation charge density can be adjusted by the molar ratio of the structural unit (a) constituting the copolymer (D). For example, the cationic charge density of the copolymer (D) can be reduced by reducing the molar ratio of the monomer (A) in the monomers constituting the copolymer (D). The cationic charge density of the copolymer (D) can be increased by increasing the molar ratio of the monomer (A) in the monomers constituting the copolymer (D).

The above-mentioned copolymer (D) is a known solution polymerization (adiabatic polymerization described in JP-A-55-133413) using a radical polymerization initiator (d) and optionally a chain transfer agent for radical polymerization (e). , Thin film polymerization, spray polymerization, etc.) and known reverse phase suspension polymerization (such as those described in JP-B-54-30710, JP-A-56-26909 and JP-A-1-5808). [Photopolymerization (such as those described in JP-B-6-804), precipitation polymerization (such as those described in JP-A-61-2123610) and reverse phase emulsion polymerization (JP-A-58-197398]). Etc.] and the like], etc.].
Of the above-mentioned polymerization methods, solution polymerization, reverse phase suspension polymerization, photopolymerization and reverse phase emulsion polymerization are preferable from the industrial viewpoint, and solution polymerization is more preferable.

As the radical polymerization initiator (d), an azo compound [water-soluble one [azobisamidinopropane (salt) and azobiscyanovaleric acid (salt), etc.]] and oil-soluble one [azobisdimethylvaleronitrile, azobisisobutyrate] Ronitrile and azobiscyclohexanecarbonitrile, etc.]]; and peroxides [water-soluble [peracetic acid, t-butyl peroxide, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, etc.] and oil-soluble [Benzoyl peroxide, cumene hydroxyperoxide, etc.] and the like.

Examples of the salt in the azo compound include inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts, alkali metal (lithium, sodium, potassium, etc.) salts, ammonium salts, and the like.
The peroxide may be used as a redox initiator in combination with a reducing agent, and as the reducing agent, bisulfite (sodium bisulfite, potassium bisulfite, ammonium bisulfite, etc.), a reducing metal salt [iron sulfate (II Etc.], amine complexes of transition metal salts [pentamethylenehexamine complex of cobalt (III) chloride and diethylenetriamine complex of copper (II) chloride, etc.] and organic reducing agents [ascorbic acid and tertiary amines [dimethylaminobenzoic acid ( Salt) and dimethylaminoethanol, etc.] and the like.
The azo compound, the peroxide and the redox initiator may be used alone or in combination of two or more.

Among the above radical polymerization initiators (d), azo compounds are preferable from the viewpoint of reducing the water-insoluble content of the resulting copolymer (D).
The amount of (d) used is preferably 100 to 8,000 ppm, based on the total weight of the monomers constituting (D), from the viewpoint of appropriately adjusting the molecular weight of the copolymer (D). , And more preferably 1,000 to 6,000 ppm.

The chain transfer agent for radical polymerization (e) is not particularly limited, and a compound having one or two or more hydroxyl groups in the molecule [including a compound having a molecular weight of 32 or more and Mn of 50,000 or less for the polymer, Include methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol (molecular weight of 100 or more and Mn of 50,000 or less) and polyethylene polypropylene glycol (molecular weight of 100 or more and Mn50 of polymer). Etc.], ammonia, compounds having one or more amino groups in the molecule [including amines (including C1 to C30, methylamine, dimethylamine, triethylamine, propanolamine, etc. Etc.], compounds having one or more thiol groups in the molecule described in JP-A-2005-189919, (hypo) phosphorous acid compounds [phosphorous acid, hypophosphorous acid, and these [Alkali metal (Na and K etc.) salts and the like], and derivatives thereof, and the like.
Of these, dipropylene glycol is preferable from the viewpoint of controlling the molecular weight of the copolymer (D).

The amount of the chain transfer agent (e) used for radical polymerization is preferably 0.01 based on the total weight of the monomers constituting (D), from the viewpoint of appropriately adjusting the molecular weight of the copolymer (D). It is ˜20 wt%, and more preferably 0.1 ˜20 wt%.
In addition, among the chain transfer agents for radical polymerization (e), compounds that also correspond to the solvent (f) described below are the chain transfer agents for radical polymerization in the calculation of the amount of the chain transfer agent for radical polymerization (e) used. Calculated by treating it as corresponding to the agent (e).

Among the methods for producing the copolymer (D), examples of the solution polymerization method include the following methods.
A solvent (f) and, if necessary, a chain transfer agent for radical polymerization (e) are charged in a polymerization tank and heated to 40 to 100 at a predetermined polymerization temperature (from the viewpoint of appropriately adjusting the Mw of the copolymer (D). C., preferably 40 to 80.degree. C.), and then the inside of the tank is sufficiently replaced with an inert gas (such as nitrogen).
On the other hand, a monomer solution containing the monomer (A), the monomer (B), the monomer (C), the radical polymerization initiator (d) and the solvent (f) was prepared and sufficiently replaced with an inert gas. After that, the mixture is put into a polymerization tank with stirring and polymerized while being suspended.
The monomer solution may be charged either all at once or dropwise. In that case, the monomer solution may be a uniform solution of the monomer (A), the monomer (B), the monomer (C), the radical polymerization initiator (d) and the solvent (f), The solutions may be prepared separately and then mixed immediately before the dropping, or may be simultaneously dropped separately. However, from the viewpoint of adjusting Mw and Mn of the copolymer (D) within the above range, a solution of the monomer (A), the monomer (B), the monomer (C) and the solvent (f). And a method in which the radical polymerization initiator (d) and the solution of the solvent (f) are separately dropped simultaneously. The dropping time of each solution is preferably 1 to 8 hours, and particularly preferably 4 to 6 hours from the viewpoint of adjusting Mw / Mn within the above range.
Examples of the method for replacing the monomer solution or the like with an inert gas include a method of bubbling an inert gas into the monomer solution or the like, a method of blending the inert gas with a static mixer in a dropping line, etc. From the viewpoint of properties, a method of blending an inert gas with a static mixer is preferable.

Examples of the solvent (f) include water and hydrophilic organic solvents (C1-C4 monohydric alcohols, glycol solvents, ketone solvents, etc.) and the like, and may be a mixed solvent of water and a hydrophilic organic solvent. .
Examples of C1-C4 monohydric alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and t-butyl alcohol.
Examples of glycol solvents include glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, etc.) and glycol monoalkyl ethers (ethylene glycol monobutyl ether). , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether and dipropylene glycol monomethyl ether) and dialkyl ethers of these glycols (ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol). Isopropyl ether etc.) and the like.
Examples of the ketone solvent include acetone and methyl ethyl ketone.
Among them, dipropylene glycol is preferable from the viewpoint of adjusting Mw and Mn of the copolymer (D) within the above range.

The external composition of the present invention may contain water in addition to the copolymer (D).

The composition for external use of the present invention further comprises an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a cationic surfactant, a humectant, an emulsifier, a conditioning agent, a chelating agent, a builder, and C1 to C20. From monohydric alcohols, fatty acids, hydrocarbon oils, thickeners, setting polymers, pearling agents, fragrances, colorants, preservatives, medicinal agents, anti-inflammatory agents, bactericides, UV absorbers and antioxidants It may contain at least one additive (E) other than (D) selected from the group consisting of

As the anionic surfactant, a sulfonate having a C8 to C24 hydrocarbon group (preferably an alkyl group) [as a salt, an alkali metal salt and a C1 to C20 amine (monoethanolamine, diethanolamine and triethanolamine) A salt (sometimes abbreviated as TEA) is included, and specifically, dodecylbenzene sulfonate sodium, α-olefin (C8-C24) sodium sulfonate, etc.], a C8-C24 hydrocarbon group (preferably alkyl) Group) a phosphoric acid ester salt having an alkali metal salt (eg, an alkali metal salt and a C1 to C20 amine (monoethanolamine, diethanolamine, TEA, etc.) salt, and the like, and specifically, sodium lauryl phosphate, (poly) oxy) Ethylene (average number of moles added = 1-100) Lauryl ether phosphorus Sodium, etc.], fatty acid salt [The fatty acid is preferably C8 to C24, such as lauric acid, myristic acid, palmitic acid, stearic acid, etc. Examples of the salt include alkali metal salts and C1 to C20 amines ( Monoethanolamine, diethanolamine, TEA, etc.) salts, etc. Specifically, sodium laurate, triethanolamine laurate, etc.], C8-C24 carboxylic acid and aminocarboxylic acid amino acid (C2-C20 amino) A carboxylic acid having a group, specifically, a condensate with glycine, alanine, glutamic acid, sarcosine, or the like, or a salt thereof [as the salt, an alkali metal salt and a C1 to C20 amine (monoethanolamine, diethanolamine, and TEA, etc.) salts, etc., and acyl sarcosine salts [ Oleyl sarcosine sodium, lauryl sarcosine sodium, palmityl sarcosine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine and "new surfactant" written by Hiroshi Horiguchi (1975, published by Sankyo Publishing Co., Ltd.) p402-404. Etc.], etc., acyl glutamate [sodium oleyl glutamate, sodium lauryl glutamate, sodium palmityl glutamate, coconut oil fatty acid glutamate triethanolamine and coconut oil fatty acid glutamate sodium, etc.], acyl alanine salt [sodium lauroyl methyl-β-alanine Etc.]], C8 to C24 carboxylic acids and C2 to C10 amino sulfonic acids (C2 to C20 amino group-containing sulfonic acids, such as taurine and o- Condensation product with minobenzenesulfonic acid or the like) or a salt thereof [as the salt, alkali metal salts and C1 to C20 amine (monoethanolamine, diethanolamine, TEA, etc.) salts and the like are included, and an acylmethyl taurine salt [coconut oil Fatty acid methyl taurine sodium etc.], a condensate of a C10-18 carboxylic acid and isethionic acid or a salt thereof [acyl isethionate [coconut oil fatty acid sodium isethionate etc.] etc.], a C8-C24 hydrocarbon group (preferably Is an alkyl carboxylic acid) or a salt thereof [oxide of C2 to C4 alkylene oxide (preferably ethylene oxide) adduct of C8 to C24 aliphatic alcohol (preferably average addition mole number = 2 to 20)] And salts, eg C8-C24 alkyl groups and polyoxyethylene An alkyl ether carboxylic acid having a group (average number of added moles = 2 to 20) and a salt, and examples of the salt include an alkali metal salt and a C1 to C20 amine (monoethanolamine, diethanolamine, TEA, etc.) salt, and the like. Specifically, (poly) oxyethylene (average number of added moles = 2 to 20) sodium lauryl ether acetate, etc.], a sulfuric acid ester salt having a C8 to C24 hydrocarbon group (preferably an alkyl group) [C8 to C24 fat A sulfate ester salt of a group alcohol and a sulfate ester salt of a C2 to C4 alkylene oxide (preferably ethylene oxide) adduct (preferably an average addition mole number = 2 to 20) of a C8 to C24 aliphatic alcohol, Are alkali metal salts and C1-C20 amines (monoethanolamine, diethanolamine). And TEA), for example, a sulfuric acid ester salt having a C8 to C24 alkyl group and a polyoxyethylene group (average added mole number = 2 to 20), and specifically, sodium lauryl sulfate, (Poly) oxyethylene (average addition mole number = 2 to 20) sodium lauryl ether sulfate, (poly) oxyethylene (average addition mole number = 2 to 20) lauryl sulfate triethanolamine, (poly) oxyethylene (average addition mole number) Number = 2 to 20) sodium coconut oil fatty acid monoethanolamide sulfate], a phosphate ester salt having a C8 to C24 hydrocarbon group (preferably an alkyl group) [as the salt, an alkali metal salt and a C1 to C20 amine ( Monoethanolamine, diethanolamine, TEA, etc.) salt, and specifically, lauryl phosphate Lithium, (poly) oxyethylene (average number of moles added = 2 to 20) sodium lauryl ether phosphate, etc., sulfosuccinate [alkyl (C6 to C18) sulfosuccinate salt [di-2-ethylhexyl sulfosuccinate monosalt] And mono-2-ethylhexyl sulfosuccinate disalt, etc.] and (poly) oxyethylene (average addition mole number = 1 to 50) alkyl (C8 to C24) sulfosuccinate ester [di-polyoxyethylene (average addition Molar number = 2 to 20) lauryl sulfosuccinic acid ester monosalt and mono-polyoxyethylene (average added molar number = 2 to 20) lauryl sulfosuccinic acid ester disalt] and the like.

The amphoteric surfactant is preferably a betaine-type amphoteric surfactant [having a C8 to C24 alkyl group, and specific examples thereof include coconut oil fatty acid amide propyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, and 2-alkyl. -N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl hydroxysulfobetaine, lauroylamidoethyl hydroxyethyl carboxymethyl betaine hydroxypropyl sodium phosphate, etc.], amino acid type amphoteric surfactant [β-lauryl aminopropionate sodium Etc.] etc. are mentioned.

As the nonionic surfactant, mono-aliphatic alcohol (C8 to C24) alkylene oxide (C2 to C8) adduct (average number of added moles = 1 to 100), polyvalent (divalent to 10 valent or higher) Aliphatic alcohol (C2-C24) alkylene oxide (C2-C8) adduct (average addition mole number = 1-100) {(poly) oxyethylene (average addition mole number = 1-100) dodecylene glycol etc.}, Fatty acid (C8-C24) alkyl (C1-C10) ester (eg, isopropyl palmitate, etc.), (poly) oxyalkylene (C2-C8, average added mole number = 1-100) higher fatty acid (C8-C24) ester [ Polyethylene glycol monostearate (average number of moles added = 20), polyethylene glycol distearate (average number of moles added) 30) etc.], polyhydric (divalent to 10 valent or higher) alcohol fatty acid (C8 to C24) ester [glyceryl monostearate, ethylene glycol monostearate, sorbitan monolaurate, etc.], (poly) oxyalkylene (C2 To C8, degree of polymerization = 1 to 100, polyhydric (divalent to 10 valent or higher) alcohol fatty acid (C8 to C24) ester [(poly) oxyethylene (average addition mole number = 1 to 100) sorbitan monolauric acid Ester, polyoxyethylene (average addition mole number = 50) dioleic acid methyl glucoside, etc.], amidation product of fatty acid and alkanolamine [C8 to C24 is preferable as fatty acid, C1 to C10 as alkanolamine is preferable. Preferably, specifically, coconut oil fatty acid monoethanolamide, 1 1-type coconut oil fatty acid diethanolamide, 1: 1-type lauric acid diethanolamide, etc.], (poly) oxyalkylene (C2 to C8, average added mole number = 1 to 100) alkyl (C1 to C22) phenyl ether, (poly) Examples thereof include oxyalkylene (C2 to C8, average added mole number = 1 to 100) alkyl (C8 to C24) amino ether, and polyoxyalkylene (C2 to C4) ether (average added mole number = 1 to 50).

Cationic surfactants include those having a quaternary ammonium salt type [C8 to C40 alkyl group, and specifically, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, ethyl Lanolin sulfate fatty acid aminopropylethyldimethylammonium etc.], amine salt type [stearic acid diethylaminoethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate etc.] and the like.

Further, as the anionic surfactant, amphoteric surfactant, cationic surfactant and nonionic surfactant in the present invention, the anionic surfactants described in US Pat. No. 4,331,447 are used. , Amphoteric surfactants, cationic surfactants and nonionic surfactants.

Examples of the humectant include C1 to C6 polyhydric (preferably dihydric to hexahydric) alcohols (ethylene glycol, propylene glycol, glycerin, dipropylene glycol, sorbitol, pentanediol, etc.), C1 to C6 polyhydric (preferably Is an alkylene oxide (preferably C2 to C4) adduct to a dihydric to hexahydric alcohol (such as polyethylene glycol), sodium pyrrolidonecarboxylate and squalane.

Examples of the emulsifiers include esterified products of C1 to C6 polyhydric (preferably 2 to 6) alcohols and C8 to C24 fatty acids (polyhydric alcohols include, for example, ethylene glycol, propylene glycol, glycerin, dipropylene). Fatty acids such as glycol, sorbitol, pentanediol and the like include lauric acid, myristic acid, palmitic acid, stearic acid, coconut oil and the like, and specific examples thereof include glyceryl monostearate and glyceryl oleate.

Examples of the conditioning agent include those other than the copolymer (D) when the copolymer (D) is used as the conditioning agent, and specifically, the cationization in the range of Mw 500 to 5,000,000 is included. Cellulose, cationized guar gum, silicones, polyethylene glycol, sodium polyacrylate, (cationized) hydroxyethyl cellulose, protein derivatives, ceramides, pseudo-ceramides, linear or branched C16-C40 fatty acids (18- Methyl eicosane, etc.), hydroxy acid, panthenol and the like.

Examples of the chelating agent include sodium ethylenediaminetetraacetic acid (sometimes abbreviated as EDTA), sodium 1-hydroxyethane-1,1-diphosphonate, and the like.

Examples of the above-mentioned builders include polycarboxylic acid salts (acrylic acid homopolymers and maleic acid homopolymers, etc.), polyvalent carboxylic acid salts (citric acid, malic acid, etc.) and alkali builders (caustic soda, soda ash, ammonia, tricarboxylic acid). Ethanolamine, sodium tripolyphosphate, sodium silicate, etc.) and the like.

Examples of the C1-C20 monohydric alcohol include chain aliphatic alcohols, and specific examples thereof include ethanol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and octyldodecanol. .

The above fatty acids are preferably C8 to C24, and specific examples thereof include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, and lignoceric acid.

Examples of the above hydrocarbon oil include liquid paraffin, liquid isoparaffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, microcrystalline wax and the like.

Examples of the above thickener include cellulose derivatives, polyvinyl alcohol, sodium polyacrylate and the like.

As the above-mentioned setting polymer, polymers generally used for hair setting agents can be used, and specific examples thereof include carboxyvinyl polymer and polyvinylpyrrolidone.

As the pearling agent, glycol distearate and the like can be mentioned.

The above-mentioned fragrances, coloring agents, preservatives, anti-inflammatory agents, bactericides, ultraviolet absorbers and antioxidants are described in "Cosmetics Science" by Takeo Tamura, Japan Hair Science Association, p.150-176, published in 1976. Perfume, coloring agents described in p145 to 148, preservatives and bactericides described in p185 to 196 (for example, phenoxyethanol, etc.), anti-inflammatory agents described in p172, ultraviolet absorbers described in p177 to 183, and p199 to Examples thereof include the antioxidant described in p203.

The anti-dandruff agent and vitamin agent may be mentioned as the above-mentioned medicinal effects.

Also, the pH of the composition for external use is preferably 4 to 9 from the viewpoint of safety for the human body.

The weight ratio of the copolymer (D) in the composition for external use of the present invention is such that foam quality at the time of washing, detergency against sebum stains, reduction of waviness after hair drying, finger-passing property at rinsing, and hair rinsing at rinsing. From the viewpoint of softness, softness of hair after drying, refreshing feeling during rinsing and moisture of skin after drying, it is preferably 0.01 to 2% by weight based on the weight of the composition for external use, and It is preferably 0.1 to 1% by weight.
The weight ratio of water in the composition for external use of the present invention is preferably 34.99 to 95% by weight, more preferably 38.9 to 90% by weight, from the viewpoint of handleability.
In the composition for external use of the present invention, the ratio of the total weight of the additive (E) other than the copolymer (D) is determined from the viewpoint of handling properties of the composition for external use and basic performance as a cleaning agent such as foam quality. It is preferably from 3 to 65% by weight, more preferably from 5 to 61% by weight, based on the weight of the composition.

In the external composition of the present invention, the total content of surfactants (anionic surfactant, amphoteric surfactant, nonionic surfactant and cationic surfactant) is the foam quality and handling of the external composition. From the viewpoint of properties, it is preferably from 3 to 40% by weight, more preferably from 5 to 38% by weight, based on the weight of the composition for external use. When the amount of the surfactant is 3% by weight or more, the foam quality is sufficient, and when it is 40% by weight or less, the viscosity of the composition for external use becomes appropriate and the handleability is good.

In the additive (E), the preferable range of the addition amount of the additives other than the surfactant varies depending on the use of the external composition of the present invention.
Addition of moisturizers, emulsifiers, conditioning agents, chelating agents, builders, C1 to C20 monohydric alcohols, fatty acids, hydrocarbon oils, thickeners, setting polymers, pearlizing agents, medicinal agents and anti-inflammatory agents. The amount is preferably 0 to 20% by weight, and more preferably 0.1 to 15% by weight, based on the weight of components other than water in the composition for external use, from the viewpoint of foam quality and feel during rinsing.
From the viewpoint of safety, the amount of each of the fragrance, the colorant, the preservative, the bactericide, the ultraviolet absorber and the antioxidant added is 0 to 5% by weight based on the weight of the components other than water in the composition for external use. %, More preferably 0.01 to 3% by weight.
From the viewpoint of foam quality, feel at the time of rinsing and safety, the total amount of additives other than these surfactants is 0 to 25% by weight based on the weight of components other than water in the composition for external use. %, More preferably 0.01 to 18% by weight.

The external composition of the present invention can be produced, for example, by heating and dissolving the above-mentioned copolymer (D), water, and, if necessary, the additive (E) at 40 to 90 ° C.

The external composition of the present invention can also be used as a household cleaning agent such as dishwashing detergent and clothing detergent.

Preferred examples of the hair cleansing agent (hair shampoo) comprising the external composition of the present invention are shown below.
In the hair cleansing composition of the present invention, the surfactant is preferably a combination of an anionic surfactant, an amphoteric surfactant and a nonionic surfactant from the viewpoint of foam quality during cleaning and detergency against sebum stains. . From the viewpoint of the ability to pass through the hair during rinsing, it is more preferable to use an alkyl ether carboxylate having a C8 to C24 alkyl group and a polyoxyethylene group (average number of added moles = 2 to 20), C8 to C24 alkyl. Ester salt having a group and a polyoxyethylene group (average number of added moles = 2 to 20), a sulfonate having a C8 to C24 hydrocarbon group, a condensation of a C8 to C24 carboxylic acid and an aminocarboxylic acid amino acid Having at least one anionic surfactant selected from the group consisting of a salt of a product, a salt of a condensate of a C8 to C24 carboxylic acid and a C2 to C10 aminosulfonic acid, and a C8 to C24 alkyl group. A combination of a betaine-type amphoteric surfactant and an amidation product of a C8 to C24 fatty acid and a C1 to C10 alkanolamine. . From the viewpoint of the ability to pass through the hair during rinsing, polyoxyethylene (average addition mole number = 2 to 20) lauryl ether acetate, polyoxyethylene (average addition mole number = 2 to 4) alkyl (C8 To C24) ether sulfate ester salt, C8 to C24 alkyl sulfonate (preferably sodium salt as a salt), a salt of a condensate of a C8 to C18 carboxylic acid and a C2 to C5 aminocarboxylic acid amino acid, and C8 To at least one anionic surfactant selected from the group consisting of a salt of a condensate of a C18 carboxylic acid and a C3 aminosulfonic acid (preferably aminosulfonic acid is taurine) (preferably sodium salt as a salt); , A betaine-type amphoteric surfactant having a C8-C18 alkyl group, a C8-C18 fatty acid and ethanol A combination of the amidated product of the emissions. More preferably, polyoxyethylene (average added mole number = 2 to 20) sodium lauryl ether acetate, polyoxyethylene (average added mole number = 2 to 4) alkyl (C8-C24) sodium ether sulfate, α-olefin (C8) To C24) sodium sulfonate, salts of condensates of C8 to C18 fatty acids with aminocarboxylic acid amino acids (alanine, methyl-β-alanine and glutamic acid) (sodium salt and triethanolamine salt), and C8 to C18 At least one anionic surfactant selected from the group consisting of sodium salts of condensates of fatty acids and taurine, betaine-type surfactants having a C8 to C18 alkyl group, C8 to C18 fatty acids and ethanolamine It is a combination with and an amidation product.

In the hair cleaning composition (hair shampoo) of the present invention, the weight ratio of the copolymer (D) is 0.01 based on the weight of the hair cleaning composition from the viewpoint of the finger-passing property to the hair during rinsing. It is preferably from 2 to 2% by weight, more preferably from 0.1 to 0.5% by weight.

In the hair cleansing composition (hair shampoo) of the present invention, the weight ratio of the surfactants (the total of anionic surfactants, amphoteric surfactants, nonionic surfactants and cationic surfactants) is From the viewpoint of the foam quality, the amount is preferably 3 to 35% by weight, more preferably 5 to 30% by weight, based on the weight of the hair cleaning agent.

Preferred examples of the skin cleanser (body cleanser among skin cleansers: body soap) comprising the external composition of the present invention are shown below.
In the body soap of the present invention, the surfactant is preferably a combination of an anionic surfactant, an amphoteric surfactant and a nonionic surfactant, from the viewpoint of foam quality during washing and detergency against sebum stains. An alkyl ether carboxylate having a C8 to C24 alkyl group and a polyoxyethylene group (average number of added moles = 2 to 20), a C8 to C24 alkyl group, from the viewpoint of a refreshing feeling at time and the moisture of the skin after drying And at least one anionic surfactant selected from the group consisting of a sulfate ester salt having a polyoxyethylene group (average added mole number = 2 to 20), and a C8 to C24 fatty acid salt, and a C8 to C24 alkyl Of a betaine-type amphoteric surfactant having a group, a C8-C24 fatty acid and a C1-C10 alkanolamine It is a combination of a monster. From the viewpoint of detergency against foam quality and sebum stains during washing, more preferably polyoxyethylene (average number of added moles = 2 to 20) lauryl ether acetate and / or polyoxyethylene group (average number of added moles = 2 to 20). 20) Alkyl group (C8-C24) ether sulfate ester salt, C8-C24 fatty acid salt, betaine-type amphoteric surfactant having a C8-C24 alkyl group, C8-C24 fatty acid and C1-C10 It is a combination with an amide compound with an alkanolamine. Particularly preferably, polyoxyethylene (average number of added moles = 2 to 20) sodium lauryl ether acetate and / or polyoxyethylene (average number of added moles = 2) sodium alkyl (C8-C24) ether sulfate, and C12-C14 fatty acid In combination with a salt (preferably an alkali metal salt and / or a triethanolamine salt), a betaine-type amphoteric surfactant having a C8 to C18 alkyl group, and an amidated product of a C8 to C18 fatty acid and ethanolamine. is there.

In the body soap of the present invention, the weight ratio of the copolymer (D) is preferably 0.01 to 2% by weight based on the weight of the body soap from the viewpoint of moisturizing the skin after drying, and more preferably Is 0.1 to 0.5% by weight.
In the body soap of the present invention, the weight ratio of the surfactant (the total of anionic surfactant, amphoteric surfactant, nonionic surfactant and cationic surfactant) is from the viewpoint of foam quality during washing. The amount is preferably 3 to 35% by weight, more preferably 5 to 30% by weight, based on the weight of the body soap.

Preferable examples of the skin cleansing agent (of the skin cleansing agents: face cleansing agent: face cleansing cream) comprising the composition for external use of the present invention are shown below.
In the facial cleansing cream of the present invention, the surfactant is preferably an anionic surfactant, and more preferably a C8 to C24 fatty acid salt, particularly from the viewpoint of the detergency against foaminess and sebum stains during washing. A salt of a C12 to C18 fatty acid (preferably a potassium salt) is preferable.
In the facial cleansing cream of the present invention, the combination of the additive (E) is preferably a combination of an anionic surfactant, an emulsifier and a moisturizing agent from the viewpoint of a refreshing feeling during rinsing and moisturizing of the skin after drying. More preferably, it is a combination of a C8 to C24 fatty acid salt, an emulsifier (C1 to C6 polyhydric alcohol and C8 to C24 fatty acid ester), and a moisturizer (C1 to C6 polyhydric alcohol), and particularly preferably. It is a combination of a C12 to C18 fatty acid salt, glyceryl monostearate, and a C3 to C6 dihydric to hexahydric alcohol.

In the facial cleansing cream of the present invention, the weight ratio of the copolymer (D) is 0.01 to 2% by weight, and more preferably 0, from the viewpoint of moisturizing the skin after drying. 0.1 to 1.0% by weight.

In the facial cleansing cream of the present invention, the weight ratio of the surfactants (the total of anionic surfactants, amphoteric surfactants, nonionic surfactants and cationic surfactants) is from the viewpoint of foam quality during washing. The amount is preferably 3 to 40% by weight, more preferably 5 to 38% by weight, based on the weight of the face cleansing cream.

Preferable examples of hair treatment agents (treatments, conditioners, hair rinses and hair packs) comprising the external composition of the present invention are shown below.
In the hair treatment agent of the present invention, a preferable combination of the additive (E) is a cationic surfactant, a C1 to C20 monohydric alcohol, from the viewpoint of the finger-passing property to the hair during rinsing. A combination of nonionic surfactants, hydrocarbon oils and humectants is preferred. In the treatment agent for hair of the present invention, from the viewpoint of softness of hair during rinsing and smoothness of hair after drying, more preferably, a quaternary ammonium salt having a C18 to C22 alkyl group and C10 to C18 are used. It is a combination of a chain aliphatic alcohol, a fatty acid (C8-C24) alkyl ester, a hydrocarbon oil, and a C1-C6 dihydric-hexahydric alcohol. Particularly preferably, alkyl (C18-C22) trimethyl ammonium chloride, C16-C18 chain aliphatic alcohol, fatty acid (C16-C18) alkyl (C1-C3) ester, liquid paraffin, and C3-C6 2 It is a combination with a hexahydric alcohol.

In the hair treatment agent of the present invention, the weight ratio of the copolymer (D) is 0.01 to 2% by weight based on the weight of the hair treatment agent from the viewpoint of the finger-passing property to the hair during rinsing. Is preferable, and more preferably 0.1 to 1.0% by weight.

In the hair treatment agent of the present invention, the total content of the cationic surfactant, the C1 to C20 monohydric alcohol, the nonionic surfactant, the hydrocarbon oil, and the moisturizing agent is such that the finger to the hair during rinsing From the viewpoint of passability, it is preferably from 3 to 35% by weight, more preferably from 5 to 30% by weight, based on the weight of the hair treatment agent.

The preferred examples of the cosmetics (of the cosmetics, lotion and beauty essence) composed of the composition for external use of the present invention are shown below.
In the lotion and the beauty essence of the present invention, a preferable combination of the additive (E) is a C1 to C20 monohydric alcohol from the viewpoints of familiarity during application, moisture during application, and non-stickiness during application. A combination of a moisturizer and a nonionic surfactant is preferable. More preferably, a C2 to C18 monohydric alcohol, a C1 to C6 polyhydric (2 to 6 valent) alcohol, and a (poly) oxyalkylene (C2 to C8, degree of polymerization = 1 to 100) polyhydric (dihydric to Alcohol fatty acid (C8-C24) ester in combination with a 10-valent or higher valent alcohol. Particularly preferably, a C2-18 aliphatic alcohol, a C3-C6 divalent hexahydric alcohol, and a (poly) oxyethylene (average added mole number = 1-100) polyhydric (divalent hexavalent) alcohol. Combination with fatty acid (C8-C18) ester.
The lotion and beauty essence of the present invention may contain a carboxyvinyl polymer or the like as a thickener.

In the lotion and the beauty essence of the present invention, the weight ratio of the copolymer (D) is 0 based on the weight of the lotion or the beauty essence from the viewpoint of moisture after coating and drying and non-stickiness after coating and drying. It is preferably 0.01 to 4% by weight, and more preferably 0.1 to 2.0% by weight.

In the lotion and the beauty essence of the present invention, the total content of the monohydric alcohol, the moisturizer and the nonionic surfactant is based on the weight of the lotion or the beauty essence from the viewpoint of non-stickiness after coating and drying. The amount is preferably 10 to 30% by weight, more preferably 15 to 30% by weight.

A preferred example of the cosmetic (emulsion among cosmetics) comprising the composition for external use of the present invention is shown below.
In the emulsion of the present invention, a preferable combination of the additive (E) is a humectant, a nonionic surfactant, a fatty acid (C8 to C24), and C1 to C20 in terms of familiarity at the time of application. A combination of a dihydric alcohol and a hydrocarbon oil is preferred. From the viewpoints of moisture during application and non-stickiness during application, more preferably C1-C6 polyhydric (2-6-hydric) alcohols and / or C1-C6 polyhydric (2-6-hydric) alcohols ethylene oxide. A combination of an adduct, a C12 to C24 fatty acid, a C12 to C20 aliphatic alcohol, a C3 to C6 polyhydric (preferably 2 to 6) alcohol and / or polyethylene glycol, and squalane.

In the emulsion of the present invention, the weight ratio of the copolymer (D) is preferably 0.01 to 4% by weight, based on the weight of the emulsion, from the viewpoint of moisture after coating and drying and no stickiness after coating and drying. , And more preferably 0.1 to 2.0% by weight.

In the emulsion of the present invention, the total content of the humectant, the nonionic surfactant, the fatty acid, the C1 to C20 monohydric alcohol and the hydrocarbon oil is based on the weight of the emulsion from the viewpoint of non-stickiness after coating and drying. Is preferably 10 to 30% by weight, more preferably 15 to 25% by weight.

Preferred examples of the bath agent comprising the composition for external use of the present invention are shown below.
The bath agent of the present invention contains a moisturizing agent from the viewpoints of adsorptivity to the skin after bathing, dryness of the skin after bathing, moisturizing effect on the skin after bathing, and familiarity between the skin and water after bathing. C1 to C6 polyhydric (2 to 6 valent) alcohols are preferable, and C3 to C6 aliphatic polyhydric (2 to 6 valent) alcohols are particularly preferable.

In the bath agent of the present invention, the weight ratio of the copolymer (D) depends on the adsorptivity to the skin after bathing, the dry feeling of the skin after bathing, the moisturizing effect on the skin after bathing, the skin and water after bathing. From the viewpoint of familiarity with the bath agent, it is preferably 0.01 to 5% by weight, and more preferably 0.05 to 3.5% by weight, based on the weight of the bath additive.

In the bath agent of the present invention, the weight ratio of the moisturizer is 1 to 30 weight based on the weight of the bath agent from the viewpoint of the moisturizing effect on the skin after bathing, the feel of hot water during bathing, and the handleability of the bath agent. %, More preferably 5 to 20% by weight.

Preferred examples of the hair setting agent (of the hair setting agents, hair gel) comprising the composition for external use of the present invention are shown below.
In the hair gel of the present invention, a preferable combination of the additive (E) is a C1 to C20 monohydric alcohol, a moisturizing agent, and a setting agent from the viewpoint of gloss of the hair after application and the condition of the hair after application. A combination with a polymer is preferred. More preferably, it is a combination of a C1 to C4 aliphatic alcohol, a C1 to C6 divalent to polyhydric aliphatic alcohol, a carboxyvinyl polymer and / or polyvinylpyrrolidone, and particularly preferably ethanol and glycerin. And a carboxyvinyl polymer and polyvinylpyrrolidone.

In the hair gel of the present invention, the weight ratio of the copolymer (D) is 0.01 to 5% by weight based on the weight of the hair gel, from the viewpoint of the gloss of the hair after application and the condition of the hair after application. It is more preferably 0.1 to 1% by weight.

In the hair gel of the present invention, the weight ratio of the C1 to C20 monohydric alcohol is preferably 1 to 30% by weight, more preferably 5 to 20% by weight, based on the weight of the hair gel, from the viewpoint of the condition of the hair after application. %.
In the hair gel of the present invention, the weight ratio of the moisturizer is preferably 1 to 20% by weight, and more preferably 2 to 10% by weight, based on the weight of the hair gel, from the viewpoint of the condition of the hair after application.
In the hair gel of the present invention, the weight ratio of the setting polymer is preferably 1 to 15% by weight, and more preferably 1 to 5% by weight, based on the weight of the hair gel, from the viewpoint of the condition of the hair after application.

Representative examples of the composition of the hair cleansing composition (hair shampoo) comprising the external composition of the present invention are shown below.
Polyoxyethylene (average number of moles added = 3) sodium lauryl ether acetate: 5 to 15% by weight
Palm oil fatty acid methyl taurine sodium: 5 to 15% by weight
Coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine: 1 to 5% by weight
2-Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine: 1 to 5% by weight
Coconut oil fatty acid monoethanolamide: 1-5% by weight
Dodecylene glycol 1 mol adduct of ethylene oxide: 1 to 5% by weight
Moisturizer (glycerin, etc.): 0-5% by weight
Copolymer (D): 0.1 to 0.7% by weight
Conditioning agents other than (D) (cationized cellulose, etc.): 0 to 0.5% by weight
Pearling agents (ethylene glycol distearate, etc.): 0-2% by weight
Chelating agent (EDTA, etc.): Proper amount pH adjuster (citric acid, triethanolamine, etc.): Proper amount UV absorber: Proper amount Preservative: Proper amount Purified water: Remaining amount (total 100% by weight)

Representative examples of the composition of the skin cleanser (body soap) comprising the external composition of the present invention will be given below.
Polyoxyethylene (average number of moles added = 3) sodium lauryl ether acetate: 1 to 3% by weight
Polyoxyethylene (average number of moles added = 2.0) sodium lauryl ether sulfate: 1 to 5% by weight
Potassium laurate: 5-10% by weight
Potassium myristate: 5-10% by weight
Coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine: 1 to 5% by weight
Copolymer (D): 0.1 to 0.7% by weight
Coconut oil fatty acid monoethanolamide: 1-5% by weight
Dodecylene glycol 1 mol adduct of ethylene oxide: 1 to 5% by weight
Moisturizer (glycerin, etc.): 0-5% by weight
Pearling agents (ethylene glycol distearate, etc.): 0-3% by weight
Conditioning agents other than (D) (cationized cellulose, etc.): 0 to 0.5% by weight
pH adjuster (citric acid, triethanolamine, etc.): appropriate amount Preservative: appropriate amount Purified water: residual amount (total 100% by weight)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Unless otherwise specified, all parts below refer to parts by weight.

<Production Example 1>
7 parts of dipropylene glycol and 180 parts of water were charged into a reaction vessel equipped with two dropping funnels, stirring, a nitrogen introducing tube, a cooling tube and a temperature control function. Into the dropping funnel, 19 parts of a 78% by weight aqueous solution of N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, 0.5 part of 2-ethylhexyl acrylate, 59 parts of an aqueous solution of 50% acrylamide and dipropylene glycol. A monomer solution was prepared by charging 1 part and 3 parts of water and stirring until uniform. Charge another dropping funnel with 0.1 part of 2,2'-azobis (2-amidinopropane) dihydrochloride, 29 parts of water and 1 part of dipropylene glycol and stir until homogeneous to prepare an initiator solution. did. The reaction vessel is stirred until it becomes a homogeneous solution, the temperature of the contents is adjusted to 50 ° C in a constant temperature bath of 50 ° C, and the inside of the reaction system is sufficiently replaced with nitrogen (gas phase oxygen concentration 50 ppm or less), 5 The monomer solution and the initiator solution were simultaneously dropped into the reaction vessel from the dropping funnel over a period of time, and the reaction and aging were continued for 2 hours. After completion of the polymerization, 300 parts of a polymer was obtained by reacting at 70 ° C. for 4 hours to decompose the remaining initiator (Mw 1, 200,000, Mw / Mn = 3.0, molecular weight in chromatogram was 3,). The area ratio (M ₁ / M ₂ ) of the area (M ₁ ) of the region of less than 000 and the area (M ₂ ) of the region having a molecular weight of 3,000 to 10,000,000 is 10/90). This was used as a copolymer (D-1).

<Production Examples 2 to 15>
Copolymers (D-2) to (D-15) were prepared in the same manner as in Production Example 1 except that the monomers shown in Table 1 were used in the amounts shown in Table 1 and the reaction times shown in Table 1 were used. A containing solution was obtained.

<Comparative Production Example 1>
54 parts of isopropanol and 300 parts of water were charged into a reaction vessel equipped with two dropping funnels, stirring, a nitrogen introducing tube, a cooling tube and a temperature control function. A dropping funnel was charged with 39 parts of a 78 wt% aqueous solution of N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, 0.9 part of 2-ethylhexyl acrylate, and 147 parts of a 40 wt% aqueous solution of acrylamide to prepare a uniform solution. The mixture was stirred until it became transparent to prepare a monomer solution. Another dropping funnel was charged with 0.04 part of 2,2′-azobis (2-amidinopropane) dihydrochloride and 53 parts of water and stirred until uniform, to prepare an initiator solution. Stir until the solution becomes a homogeneous solution in the reaction vessel, adjust the temperature of the contents to 40 ° C in a constant temperature bath of 40 ° C, and after thoroughly replacing the inside of the reaction system with nitrogen (gas phase oxygen concentration of 10 ppm or less) The temperature was adjusted to 40 to 50 ° C., and the monomer solution and the initiator solution were simultaneously dropped into the reaction vessel from the dropping funnel over 2 hours, and the reaction and aging were continued for 2 hours. After the completion of the polymerization, the content was taken out, shredded, dried at 80 ° C. for 10 hours in a circulating air dryer, and further pulverized with a mixer to obtain 187 parts of a particulate copolymer (D′-1). (Mw 1,200,000, Mw / Mn = 10.0, area of the region where the molecular weight is less than 3,000 in the chromatogram (M ₁ ) and area of the region where the molecular weight is 3,000 to 10,000,000 (M ₂ ) area ratio (M ₁ / M ₂ ) of 10/90, solid content concentration 100% by weight).

<Comparative Production Examples 4 and 5>
Copolymers (D'-4), (D'-) were prepared in the same manner as in Comparative Production Example 1 except that the monomers shown in Table 1 were used in the amounts shown in Table 1 and the reaction times shown in Table 1 were used. 187 parts of 5) were obtained (solid content concentration 100% by weight).

<Comparative Production Examples 2, 3, 6>
Copolymers (D'-2), (D'-3 ) And (D′-6) (a solid content concentration of 18% by weight) was obtained.

The following monomers were used as the monomers used in Production Examples 1 to 15 and Comparative Production Examples 1 to 6.
-N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride [78% by weight aqueous solution, manufactured by Sanyo Chemical Industry Co., Ltd.]
N, N, N-trimethyl-N- (3-acryloylaminopropyl) ammonium chloride [75 wt% aqueous solution, manufactured by Merck]
N-benzyl-N, N-dimethyl-N- (2-methacryloyloxyethyl) ammonium chloride [95 wt% aqueous solution, manufactured by BOC Sciences]
・ Butyl methacrylate [Tokyo Chemical Industry Co., Ltd.]
・ 2-Ethylhexyl acrylate [manufactured by Mitsubishi Chemical Corporation]
・ Dodecyl acrylate [Tokyo Chemical Industry Co., Ltd.]
-Acrylamide [40 wt% aqueous solution, manufactured by Mitsui Chemicals, Inc.]
・ Dimethylacrylamide [Tokyo Chemical Industry Co., Ltd.]
・ Propyl acrylate [Fujifilm Wako Pure Chemical Industries, Ltd.]
Triacyl vinyl ether: obtained in Production Example 16 below

<Production Example 16>
Production of triacontyl vinyl ether Into a continuous reaction distillation apparatus equipped with a reaction vessel having an internal capacity of 10 L and a distillation column having 10 theoretical plates, 3476 g of 1-triacontanol and 107 g of potassium hydroxide were weighed and heated at 120 ° C. It dehydrated under reduced pressure and the potassium alcoholate catalyst was prepared. Next, acetylene (20 kPa, 22 g / h) and 1-triacontanol (484 g / h) were continuously supplied and reacted at 137 ° C. to obtain triacontyl vinyl ether (484 g / h) from the top of the distillation column. It was

<Production Example 17>
Production of polyoxyethylene (average number of moles added = 2.0) sodium lauryl ether acetate In a stainless steel autoclave equipped with stirring and temperature control functions, 186 parts (1 mole) of lauryl alcohol, 0.32 part of magnesium perchlorate and After 0.03 part of magnesium hydroxide was added and the inside of the mixed system was replaced with nitrogen, dehydration was performed at 120 ° C. for 1 hour under reduced pressure (2.67 kPa). Then, 88 parts (2 mol) of ethylene oxide (EO) was introduced at 150 ° C. so that the gauge pressure was 98.07 to 294.21 kPa. The time required for addition polymerization of EO was 10 hours.
A glass reaction vessel was charged with 1920 parts (0.75 mol) of the above product, 97 parts (0.83 mol) of sodium monochloroacetate and 293 g of toluene, and the degree of pressure reduction was gradually increased while maintaining the temperature at 50 ° C. to 10.00 kPa. And Then, 38 parts (0.94 mol) of granular sodium hydroxide was charged for 2 hours while dehydrating under reduced pressure. Further aging was carried out for 6 hours. The reaction rate (etherification degree) measured by liquid chromatography was 96%. After adding 300 parts of water, the mixture was acidified with hydrochloric acid, allowed to stand still, desalted by liquid separation, and then desulfurized. Sodium hydroxide 30 parts (0.75 mol) was dissolved in water 700 parts, the above-mentioned ether carboxylic acid was added at 60 ° C. to adjust the pH to 6.5, and polyoxyethylene (average added mole number = 2.0) lauryl A 30% by weight aqueous solution of sodium ether acetate was obtained.

<Production Example 18>
Production of polyoxyethylene (average number of moles added = 20) sodium lauryl ether acetate In a stainless steel autoclave equipped with stirring and temperature control functions, 186 parts (1 mole) of lauryl alcohol, 0.32 parts of magnesium perchlorate and hydroxylation were added. After 0.03 part of magnesium was added and the inside of the mixed system was replaced with nitrogen, dehydration was performed at 120 ° C. for 1 hour under reduced pressure (2.67 kPa). Next, 88 parts of EO (2 mol) was introduced at 150 ° C. so that the gauge pressure was 98.07 to 294.21 kPa. The time required for addition polymerization of EO was 10 hours. Further, 1.3 parts of potassium hydroxide was added to the obtained product, and 792 parts (18 mol) of EO was reacted at 130 ° C.
A glass reaction vessel was charged with 1920 parts (0.75 mol) of the above product, 97 parts (0.83 mol) of sodium monochloroacetate and 293 g of toluene, and the degree of pressure reduction was gradually increased while maintaining the temperature at 50 ° C. to 10.00 kPa. And Then, 38 parts (0.94 mol) of granular sodium hydroxide was charged for 2 hours while dehydrating under reduced pressure. Further aging was carried out for 6 hours. The reaction rate (etherification degree) measured by liquid chromatography was 96%. After adding 300 parts of water, the mixture was acidified with hydrochloric acid, allowed to stand still, desalted by liquid separation, and then desulfurized. 30 parts of sodium hydroxide (0.75 mol) is dissolved in 700 parts of water, the above-mentioned ether carboxylic acid is added at 60 ° C. to adjust the pH to 6.5, and polyoxyethylene (average added mole number = 20) lauryl ether acetic acid. A 30% by weight aqueous solution of sodium was obtained.

<Production Example 19>
Production of sodium polyoxyethylene (average number of moles added = 2.0) alkyl (C8) ether sulfate In a stainless steel autoclave equipped with a stirring and temperature control function, 138 parts (1 mole) of octyl alcohol and magnesium perchlorate of 0.1. After 32 parts and 0.03 part of magnesium hydroxide were charged and the inside of the mixed system was replaced with nitrogen, dehydration was carried out at 120 ° C. for 1 hour under reduced pressure (2.67 kPa). Next, 88 parts of EO (2 mol) was introduced at 150 ° C. so that the gauge pressure was 98.07 to 294.21 kPa. The time required for addition polymerization of EO was 10 hours.
The alkylene oxide adduct (AOA product) was transferred to a glass container equipped with a stirring, temperature control function and dropping funnel, and 120 parts (1.03 mol) of chlorosulfonic acid was gradually added dropwise while maintaining the temperature at 20 ° C. . After dehydrochlorination at the same temperature for 2 hours, the sulfated product was neutralized (end point pH = 6.5) with an aqueous solution in which 41.2 parts (1.03 mol) of sodium hydroxide was dissolved in 1,110 parts of water. An aqueous anionic surfactant solution containing 28% by weight of the active ingredient was obtained.

<Production Example 20>
Production of polyoxyethylene (average number of moles added = 4.0) sodium alkyl (C24) ether sulfate 355 parts of lignoceryl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) in a stainless steel autoclave equipped with a stirrer and a temperature controller (1 mol), 0.11 part of aluminum perchlorate was added, the gas phase in the mixed system was replaced with nitrogen, and then dehydration was performed at 120 ° C. for 1 hour under reduced pressure (2.67 kPa). Next, 88 parts of EO (2 mol) was introduced at 100 ° C. so that the gauge pressure was 98.07 to 294.21 kPa. The time required for addition polymerization of EO was 10 hours. Further, 1.3 parts of potassium hydroxide was added to the obtained product, and 88 parts (2 mol) of EO was reacted at 130 ° C. It cooled to 80 degreeC and obtained the AOA product.
To the above AOA product, 1.3 parts of phosphoric acid and 25.8 parts of a solution prepared by dissolving 0.8 parts of hydroxylamine sulfate in 25 parts of water were added, and the mixture was stirred at 75 to 85 ° C. for 2 hours. Then, a 30 wt% sodium hydroxide aqueous solution was added, and the mixture was stirred and neutralized (acid value at end point = 0.1 mgKOH / g). Then, dehydration was performed under reduced pressure (2.67 kPa) at 100 ° C. for about 2 hours until the water content became 0.2% by weight or less. The inorganic salt precipitated in the system and the residual hydroxylamine sulfate were removed by filtration to obtain a purified AOA product.
The purified AOA product was transferred to a glass container equipped with a stirring, temperature control function, and dropping funnel, and 120 parts (1.03 mol) of chlorosulfonic acid was gradually added dropwise while keeping the temperature at 20 ° C. After dehydrochlorination was performed at the same temperature for 2 hours, the sulfated product was neutralized (end point pH = 6.5) with an aqueous solution of 41.2 parts (1.03 mol) of sodium hydroxide dissolved in 1,110 parts of water. Thus, a 24 wt% aqueous solution of polyoxyethylene (average added mole number = 4.0) alkyl (C24) ether sodium sulfate was obtained.

<Production Example 21>
Production of sodium α-olefin (C8) sulfonate A continuous thin film type sulfonation apparatus (made of Pyrex (registered trademark) glass and having an inner diameter of 6 mm and a reactor length of 1.5 m) was used. 1-octylene (Linearene 8, manufactured by Idemitsu Kosan Co., Ltd.) 112 parts (1 mol) and SO ₃ -inert gas (nitrogen, SO ₃ concentration 2.8% by volume) 4289 parts (SO ₃ 1.5 mol) Were brought into contact with each other while flowing in parallel, and reacted at 50 ° C. The supply rate of 1-octylene is 3 g / min. The obtained sulfonated product was neutralized by adding 114 parts of a 35 wt% sodium hydroxide aqueous solution, followed by hydrolysis at 160 ° C. for 20 minutes, and then taking out unreacted oil to obtain sodium α-olefin (C8) sulfonate. 210 parts were obtained.

<Production Example 22>
Production of α-Olefin (C20-C24) Sodium Sulfonate A continuous thin film sulfonation apparatus (made of Pyrex glass, inner diameter 6 mm, reactor length 1.5 m) was used. 298 parts (1 mol) of n-α olefin (C20 to C24) (Linearene 2024, manufactured by Idemitsu Kosan Co., Ltd.) and SO ₃ -inert gas (nitrogen, SO ₃ concentration 2.8% by volume) 4289 parts (SO ₃ (1.5 mol) was contacted while flowing in parallel flow and reacted at 50 ° C. The supply rate of 1-octylene is 3 g / min. The obtained sulfonated product was neutralized by adding 114 parts of a 35 wt% sodium hydroxide aqueous solution, followed by hydrolysis at 160 ° C. for 20 minutes, and then taking out unreacted oil to obtain α-olefin (C20 to C24) sulfonic acid. 400 parts of sodium was obtained.

<Examples 1 to 21 and Comparative Examples 1 to 11>
Each component was blended in the blending amounts shown in Table 2 and Table 3 to prepare a hair cleanser (hair shampoo). Further, the transparency after blending the hair cleaning agent was evaluated by turbidity.
The turbidity was measured by a turbidimeter (COH400) manufactured by Nippon Denshoku Industries Co., Ltd. according to the method of "9.4 integrating sphere turbidity" in JIS K0101-1998.
As shown in the following criteria, the lower the score, the closer the transparency is, and the better the transparency after blending the detergent for hair, and the more preferable one is judged to be “transparent” based on the following criteria.
0 to 3 degrees (kaolin): Transparent 4 to 50 degrees (kaolin): Slight turbidity 50 degrees or more (kaolin): White turbidity

In Tables 2 and 3, the following components were used.
Copolymers (D-1) to (D-15) and (D'-1) to (D'-6): those obtained in the above Production Examples or Comparative Production Examples <anionic surfactant>
-Polyoxyethylene (average number of added moles = 2.0) sodium lauryl ether acetate: obtained in Production Example 17-Polyoxyethylene (average number of added moles = 3) sodium lauryl ether acetate (manufactured by Sanyo Chemical Industries, Ltd., "Viewlight LCA-25N")
-Polyoxyethylene (average number of added moles = 20) sodium lauryl ether sulfate: obtained in Production Example 18-Polyoxyethylene (average number of added moles = 2.0) sodium alkyl (C8) ether sulfate: In Production Example 19 Obtained product: polyoxyethylene (average number of moles added = 2.0) sodium lauryl ether sulfate (manufactured by Sanyo Kasei Co., Ltd., "Beaulite NA-25S")
-Polyoxyethylene (average number of moles added = 4.0) sodium alkyl (C24) ether sulfate: obtained in Production Example 20-α-olefin (C8) sodium sulfonate: obtained in Production Example 21-α- Sodium olefin (C14-C16) sulfonate ("ASC01416" manufactured by AK Chemtech)
-Sodium α-olefin (C20-C24) sulfonate: obtained in Production Example 22-coconut oil fatty acid alanine TEA salt (manufactured by Ajinomoto Co., Inc., "Amilite (registered trademark) ACT-12)"
・ Methyl laurate-β-alanine sodium (“SOFTIL AS-L” manufactured by NOF CORPORATION)
・ Methyl taurine sodium coconut oil fatty acid (NOF Corporation, "Diapon K-TS")
・ Palm oil fatty acid sodium glutamate ("Amisoft (registered trademark) CS-22" manufactured by Ajinomoto Co., Inc.)
-Olive oil fatty acid sodium glutamate (Kalichem, "OLIVOIL GLUTAMMATE")
<Amphoteric surfactant>
・ Palm oil fatty acid amide propyl dimethylamino acetic acid betaine (manufactured by Sanyo Kasei Co., Ltd., "Levon 2000HG")
-2-dodecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine ("Levon 105" manufactured by Sanyo Kasei Co., Ltd.)
・ Lauryl hydroxysulfobetaine ("Amhithol 20HD" manufactured by Kao Corporation)
<Nonionic surfactant>
・ Palm oil fatty acid monoethanolamide ("Profan AB-20" manufactured by Sanyo Kasei Co., Ltd.)
・ Palm oil fatty acid diethanolamide ("Profan Extra 24" manufactured by Sanyo Kasei Co., Ltd.)
<Conditioning agent>
・ Cationized hydroxyethyl cellulose (Leoguard GP, "Leoguard GP")

<Use test (other than "detergency against sebum dirt")>
A total of 20 panelists, 10 each for men and women, thoroughly wet their hair with hot water at 40 ° C., and then shampooed with 5 g of each hair cleaning agent of Examples 1 to 21 or Comparative Examples 1 to 40, After rinsing with hot water at 0 ° C., 5 g of standard conditioner prepared by the following formulation was manually applied to the hair, followed by rinsing and drying with a dryer. At that time, foam quality during washing (foam feel, fineness of foam), smoothness of hair during rinsing (finger passage), softness of hair during rinsing, moisture retention of skin after drying, after drying The items for smoothness of hair and reduction of waviness after drying (visual observation) were evaluated.
The sensory evaluation result when the panel was actually used was expressed by a score and evaluated by the total score. The results are shown in Tables 2 and 3.
(Scoring criteria)
Very good: 5 points Normal: 3 points Very bad: 1 point

(Standard conditioner prescription)
Polydimethylsiloxane: 2.0 parts Cetyl alcohol: 2.5 parts Stearyl alcohol: 2.5 parts Behenyltrimethylammonium chloride: 1.5 parts Glycerin: 4.0 parts Water: 87.5 parts

<Evaluation of "detergency against sebum dirt">
The cleaning power was evaluated according to JIS K3362 "9.2 Method for evaluating cleaning power of synthetic detergent for kitchen".
Six slide glasses were used as a set as a dirt support, and a chloroform solution of artificial dirt having the following composition was applied and used as dirt. The amount of adhered dirt per 6 slide glasses was set to be 0.140 ± 0.0010 g after air drying.
The slide glass coated with artificial dirt was washed with a 0.15% by weight aqueous solution of each of the hair cleansing agents of Examples 1 to 21 or Comparative Examples 1 to 11 as a cleaning solution, and "6 slides after application of dirt" were washed. Detergency according to the following formula from "total weight of glass (after air-drying)", "total weight of 6 slides after washing" and "total weight of dirt attached to 6 slides (after air-drying)" I asked. The detergency (%) thus obtained is shown in Tables 2 and 3.
Detergency (%) = 100 × [total weight of 6 slide glass after stain application (after air drying) (g) -total weight of 6 slide glass after cleaning (g)] / 6 slides Total weight of dirt attached to glass (after air drying) (g)

Artificial dirt component composition Beef tallow: 16.6% by weight
Soybean oil: 16.6% by weight
Monoolein: 0.4% by weight
Oil red: 0.2% by weight
Chloroform: 66.2% by weight
Total: 100.0% by weight

<Examples 22 to 37 and Comparative Examples 12 to 21>
The ingredients were blended in the blending amounts shown in Table 4 to prepare a skin cleanser (body soap).

In Table 4, the following components were used.
Copolymers (D-1) to (D-15) and (D'-1) to (D'-6): those obtained in the above Production Examples or Comparative Production Examples <anionic surfactant>
-Polyoxyethylene (average number of added moles = 2.0) sodium lauryl ether acetate: obtained in Production Example 17-Polyoxyethylene (average number of added moles = 3) sodium lauryl ether acetate (manufactured by Sanyo Chemical Industries, Ltd., "Viewlight LCA-25N")
-Polyoxyethylene (average number of added moles = 20) sodium lauryl ether acetate: obtained in Production Example 18-Polyoxyethylene (average number of added moles = 2.0) sodium alkyl (C8) ether sulfate: In Production Example 19 Obtained product: polyoxyethylene (average number of moles added = 2.0) sodium lauryl ether sulfate (manufactured by Sanyo Kasei Co., Ltd., "Beaulite NA-25S")
Polyoxyethylene (average number of moles added = 4.0) sodium alkyl (C24) ether sulfate: obtained in Production Example 20 <amphoteric surfactant>
・ Palm oil fatty acid amide propyl dimethylamino acetic acid betaine (manufactured by Sanyo Kasei Co., Ltd., "Levon 2000HG")
-2-dodecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine ("Levon 105" manufactured by Sanyo Kasei Co., Ltd.)
・ Lauryl hydroxysulfobetaine (Amhithol 20HD, manufactured by Kao Corporation)
<Nonionic surfactant>
・ Palm oil fatty acid monoethanolamide ("Profan AB-20" manufactured by Sanyo Kasei Co., Ltd.)
・ Palm oil fatty acid diethanolamide ("Profan Extra 24" manufactured by Sanyo Kasei Co., Ltd.)
<Conditioning agent>
・ Cationized hydroxyethyl cellulose (Leoguard GP, "Leoguard GP")

<Usage when cleaning the body>
10 male and 10 female panelists took 3 g of each body soap of Examples 22 to 37 and Comparative Examples 12 to 21 on their hands fully wet with water at 30 ° C, wash the inside of the upper arm, and water at 30 ° C. Rinse and wipe with a dry cotton towel. At that time, items of foam quality (foam amount, foaming speed) at the time of washing, refreshing feeling at the time of rinsing, smoothness of skin after drying, and moisturizing property of skin after drying were evaluated.
The sensory evaluation result when the panel was actually used was expressed by a score and evaluated by the total score. The results are shown in Table 4.
(Scoring criteria)
Very good: 5 points Normal: 3 points Very bad: 1 point

<Evaluation of "detergency against sebum dirt">
The evaluation of "detergency against sebum stains" was performed in the same manner as above. The results are shown in Table 4.

<Examples 38 to 53 and Comparative Examples 22 to 31>
Each component was blended in the blending amounts shown in Table 5 to prepare a face cleansing cream.

In Table 5, the following components were used.
Copolymers (D-1) to (D-15) and (D'-1) to (D'-6): those obtained in the above Production Examples or Comparative Production Examples. Glyceryl monostearate (Sanyo Kasei Co., Ltd. ("TG-C" manufactured by Co., Ltd.)
・ Cationized hydroxyethyl cellulose (Leoguard GP, "Leoguard GP")

<Usage when washing face>
10 male and 10 female panelists took 3 g of each of the facial cleansing creams of Examples 38 to 53 and Comparative Examples 22 to 31 on their hands, which were sufficiently wet with water at 30 ° C., washed their faces, and rinsed with water at 30 ° C. Wipe off the water with a dry cotton towel. At that time, items of foam quality (foam amount, foaming speed) at the time of washing, refreshing feeling at the time of rinsing, smoothness of skin after drying, and moisturizing property of skin after drying were evaluated.
The sensory evaluation result when the panel was actually used was expressed by a score and evaluated by the total score. The results are shown in Table 5.
(Scoring criteria)
Very good: 5 points Normal: 3 points Very bad: 1 point

<Evaluation of "detergency against sebum dirt">
The evaluation of "detergency against sebum stains" was performed in the same manner as above. The results are shown in Table 5.

<Examples 54 to 69 and Comparative Examples 32 to 41>
Each component was blended in the blending amounts shown in Table 6 to prepare a hair rinse.

In Table 6, the following components were used.
-Copolymers (D-1) to (D-15) and (D'-1) to (D'-6): those obtained in the above Production Examples or Comparative Production Examples-behenyltrimethylammonium chloride (Sanyo Chemical Co., Ltd.) "Econor TM-22" manufactured by Co., Ltd.)
-Isopropyl palmitate ("IPP" manufactured by Higher Alcohol Industry Co., Ltd.)
・ Cetyl alcohol ("Cetanol" manufactured by High Alcohol Industry Co., Ltd.)
・ Liquid paraffin (“MORESCO”, “Liquid Paraffin”)
・ Cationized hydroxyethyl cellulose (Leoguard GP, "Leoguard GP")

<Use test>
A total of 20 panelists, 10 each for men and women, wet their hair thoroughly with hot water at 40 ° C., and then rinsed with 5 g of hair rinse of Examples 54 to 69 or Comparative Examples 32 to 41 by hand to rinse the hair. It was dried with a dryer. Familiar with hair rinse at that time, smoothness of hair during rinsing (finger passage), moisture retention of skin (scalp) after drying, smoothness of hair after drying, softness of hair after drying, and drying The items of the later hair cohesion were evaluated.
The sensory evaluation result when the panel was actually used was expressed by a score and evaluated by the total score. The results are shown in Table 6.
(Scoring criteria)
Very good: 5 points Normal: 3 points Very bad: 1 point

<Examples 70 to 85 and Comparative Examples 42 to 51>
Each component was blended in the blending amounts shown in Table 7 to prepare a lotion.

In Table 7, the following components were used.
-Copolymers (D-1) to (D-15) and (D'-1) to (D'-6): those obtained in the above Production Examples or Comparative Production Examples-Polyoxyethylene (average number of moles added) = 20) Sorbitan monococonut oil fatty acid ester (“Ionet T-20C” manufactured by Sanyo Kasei Co., Ltd.)
・ Oleyl alcohol (manufactured by High Alcohol Industry Co., Ltd., "Oleyl alcohol VP")
・ Cationized hydroxyethyl cellulose (Leoguard GP, "Leoguard GP")

<Feeling of lotion>
Panelists of 10 men and women washed their hands thoroughly with water at 30 ° C., and then wiped off the water with a dry cotton towel. Then, 3 g of the lotion of Examples 70 to 85 or Comparative Examples 42 to 51 was applied to the hands and then naturally dried for 5 minutes. At that time, the items such as the familiarity at the time of application, the moisturizing property of the skin after application drying, the smoothness of the skin after application drying, and the non-stickiness after application drying were evaluated.
The sensory evaluation result when the panel was actually used was expressed by a score and evaluated by the total score. The results are shown in Table 7.
(Scoring criteria)
Very good: 5 points Normal: 3 points Very bad: 1 point

<Examples 86 to 101 and Comparative Examples 52 to 61>
Each component was blended in the blending amounts shown in Table 8 to prepare a beauty essence.

In Table 8, the following components were used.
-Copolymers (D-1) to (D-15) and (D'-1) to (D'-6): those obtained in the above Production Examples or Comparative Production Examples-Polyoxyethylene (average number of moles added) = 20) Sorbitan monococonut oil fatty acid ester (“Ionet T-20C” manufactured by Sanyo Kasei Co., Ltd.)
・ Carboxy vinyl polymer ("AQPEC HV-501E" manufactured by Sumitomo Seika Co., Ltd.)
・ Cationized hydroxyethyl cellulose (Leoguard GP, "Leoguard GP")

<Usage of beauty essence>
Panelists of 10 men and women washed their hands thoroughly with water at 30 ° C., and then wiped off the water with a dry cotton towel. Then, 3 g of the beauty essence of Examples 86 to 101 or Comparative Examples 52 to 61 was applied to the hands, and then naturally dried for 5 minutes. At that time, the items such as the familiarity at the time of application, the moisturizing property of the skin after application drying, the smoothness of the skin after application drying, and the non-stickiness after application drying were evaluated.
The sensory evaluation result when the panel was actually used was expressed by a score and evaluated by the total score. The results are shown in Table 8.
(Scoring criteria)
Very good: 5 points Normal: 3 points Very bad: 1 point

<Examples 102 to 117 and Comparative Examples 62 to 71>
Each component was blended in the blending amounts shown in Table 9 to prepare an emulsion.

In Table 9, the following components were used.
Copolymers (D-1) to (D-15) and (D'-1) to (D'-6): those obtained in the above Production Examples or Comparative Production Examples. Polyoxyethylene (average number of moles added) = 20) Sorbitan monoisostearate, NOF Corporation, "NONION IST-221"
・ Lignoceric acid, manufactured by Tokyo Chemical Industry Co., Ltd. ・ 1-eicosanol, manufactured by Tokyo Chemical Industry Co., Ltd. ・ Squalane (manufactured by Nikko Chemicals, “NIKKOL Squalane”)
-PEG 1500 (manufactured by Sanyo Kasei Co., Ltd., polyethylene glycol (number average molecular weight 550))

<Feeling of emulsion>
Panelists of 10 men and women washed their hands thoroughly with water at 30 ° C., and then wiped off the water with a dry cotton towel. Then, 3 g of the milky lotion of Examples 102 to 117 or Comparative Examples 62 to 71 was applied to the hand, and then naturally dried for 5 minutes. At that time, the items such as the familiarity at the time of application, the moisturizing property of the skin after application drying, the smoothness of the skin after application drying, and the non-stickiness after application drying were evaluated.
The sensory evaluation result when the panel was actually used was expressed by a score and evaluated by the total score. The results are shown in Table 9.
(Scoring criteria)
Very good: 5 points Normal: 3 points Very bad: 1 point

<Examples 118 to 133 and Comparative Examples 72 to 81>
Each component was blended in the blending amounts shown in Table 10 to prepare a bath additive.

In Table 10, the following components were used.
Copolymers (D-1) to (D-15) and (D'-1) to (D'-6): those obtained in the above Production Examples or Comparative Production Examples. Cationized hydroxyethyl cellulose (Lion Co., Ltd.) Made, "Leoguard GP")

<Usage of bath salt>
Ten panelists, each of male and female, first washed their arms with soap and wiped off the water with a dry cotton towel. Next, 32 g of the bathing agent of Examples 118 to 133 or Comparative Examples 72 to 81 was mixed with 4,000 g of tap water at 40 ° C., the arm was soaked for 2 minutes, and the water was wiped off. At that time, the items of the dryness of the skin after bathing, the moisturizing property of the skin after bathing, the smoothness of the skin after bathing, and the familiarity with the moisture of the skin after bathing were evaluated.
The sensory evaluation result when the panel was actually used was expressed by a score and evaluated by the total score. The results are shown in Table 10.
(Scoring criteria)
Very good: 5 points Normal: 3 points Very bad: 1 point

<Examples 134 to 149 and Comparative Examples 82 to 91>
Each component was blended in the blending amounts shown in Table 11 to prepare a hair gel.

In Table 11, the following components were used.
-Copolymers (D-1) to (D-15) and (D'-1) to (D'-6): those obtained in the above Production Examples or Comparative Production Examples-Polyvinylpyrrolidone (manufactured by BASF, " Rubiscol VA37I ")
・ Carboxy vinyl polymer ("AQPEC HV-501E" manufactured by Sumitomo Seika Co., Ltd.)
・ Cationized hydroxyethyl cellulose (Leoguard GP, "Leoguard GP")

<Usage of hair gel>
Twenty middle-length male panelists applied the hair gels of Examples 134 to 149 or Comparative Examples 82 to 91 evenly on the hair, and brushed the hair upward from the root to the tip of the hair. After that, squeeze the hair and bend it to make it stiff, and after styling it, observe the hair and feel the luster of the hair after application, the moisturizing property of the skin (scalp) after application, the smoothness of the hair after application. Item was evaluated.
The sensory evaluation result when the panel was actually used was expressed by a score and evaluated by the total score. The results are shown in Table 11.
(Scoring criteria)
Very good: 5 points Normal: 3 points Very bad: 1 point

From the results of Tables 2 to 11, the composition for external use of the present invention has good skin moisturizing properties when used on the skin (skin, scalp, etc.), and when used on the skin or hair, It can be seen that smoothness can be imparted.
From the results of Table 2 and Table 3, the hair cleansing agents of Examples 1 to 21, which are the external use compositions of the present invention, have excellent transparency after blending, and have a detergency against foam quality and sebum stains during cleaning. It can be seen that the smoothness of hair during rinsing, the softness of hair during rinsing, the moisturizing property of the skin (scalp) after drying, the smoothness of hair after drying, and the effect of suppressing waviness after drying are high.
Further, from the results of Table 4, the skin cleansing agents of Examples 22 to 37, which are the external use compositions of the present invention, show that the foam quality at the time of washing, the detergency against sebum stains, the refreshing feeling at the time of rinsing, and the skin after drying. It can be seen that the smoothness and moisture retention of the skin after drying are high.
Similarly, from the results of Tables 5 to 11, when the composition for external use of the present invention was used as a facial cleanser, hair rinse, lotion, beauty essence, milky lotion, bath salt and hair gel, the skin had good moisturizing properties, It is also understood that smoothness can be imparted to the hair.

The external-use composition of the present invention has good skin moisturizing properties when used on the skin, and can impart smoothness to the skin or hair when used on the skin or hair. ), Hair treatment agents (treatments, conditioners, hair rinses and hair packs), hair setting agents, hair coloring agents, hair perming agents, skin cleansing agents (body soaps and face cleansing creams), cosmetics (lotions, emulsions, beauty essences) It is also useful as a bathing agent. In particular, it is useful as a hair cleansing agent, a hair treating agent, and a skin cleansing agent.
It may also be used as a household cleaning agent (clothing cleaning agent, tableware cleaning agent) and industrial cleaning agent (metal, precision parts cleaning agent).

Claims

Aminium group having at least one C1-24 alkyl group and / or at least one C7-24 aralkyl group or at least one C1-24 alkyl group and / or at least one C7 A structural unit (a) derived from a monofunctional ethylenically unsaturated monomer (A) having a quaternary ammonium group having -24 aralkyl groups, other than the monofunctional ethylenically unsaturated monomer (A) A structural unit (b) derived from a monofunctional ethylenically unsaturated monomer (B) having an alkyl group having 3 to 30 carbon atoms, and a structural unit (() derived from a monofunctional ethylenically unsaturated monomer (C). A composition for external use containing (c) and an essential constitutional unit and containing a copolymer (D) having no constitutional unit derived from a bifunctional or higher ethylenically unsaturated monomer,
The monofunctional ethylenically unsaturated monomer (A) does not contain a phosphorus atom and a silicon atom in the molecule,
HLB of the monofunctional ethylenically unsaturated monomer (B) is 0.3 to 5.2,
The monofunctional ethylenically unsaturated monomer (C) is (meth) acrylamide, a monoalkyl (meth) acrylamide having an alkyl carbon number of 1-2, and a dialkyl (meth) acrylamide having an alkyl carbon number of 1-2. At least one monomer selected from the group consisting of
Based on the total number of moles of the structural unit (a), the structural unit (b) and the structural unit (c) constituting the copolymer (D), the structural unit (a) constituting the copolymer (D). Is 2 to 55 mol%, and the molar ratio of the structural unit (b) constituting the copolymer (D) is 0.01 to 10 mol%, constituting the copolymer (D). The structural unit (c) has a molar ratio of 43 to 99.99 mol%,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer (D) is 2.0 to 7.0,
A composition for external use, wherein the cationic charge density of the copolymer (D) is 1.2 to 1.6 meq / g.
The external use according to claim 1, wherein the structural unit (a) is a structural unit represented by the following general formula (1), and the structural unit (b) is a structural unit represented by the following general formula (2). Composition.

[In the general formula (1), R 1 represents a hydrogen atom or a methyl group; R 2 and R 3 each independently represent an alkyl group having 1 to 24 carbon atoms; R 4 is a hydrogen atom, 1 to 4 carbon atoms. Represents an alkyl group having 24 carbon atoms or an aralkyl group having 7 to 24 carbon atoms; X − represents a halogen anion or a monoalkyl sulfate ester anion having 1 to 8 carbon atoms in alkyl; n represents an integer of 1 to 10; Represents NH or O. ]

[In the general formula (2), R 5 represents a hydrogen atom or a methyl group; -Z- represents -C (O) O- or -O-; R 6 represents an alkyl group having 3 to 30 carbon atoms. . ]
The weight average molecular weight of the copolymer (D) measured by gel permeation chromatography (GPC) is 650,000 to 2,000,000, and the area (M) of the region where the molecular weight is less than 3,000 in the chromatogram. 1) and according to claim 1 or 2 molecular weight area of 3,000 to 10,000,000 regions (M 2) and the area ratio of (M 1 / M 2) is 10/90 ~ 30/70 Topical composition.
The external composition according to any one of claims 1 to 3, further comprising water.
The external composition according to any one of claims 1 to 4, wherein the content of the copolymer (D) is 0.01 to 2% by weight based on the weight of the external composition.
Furthermore, anionic surfactants, amphoteric surfactants, nonionic surfactants, cationic surfactants, humectants, emulsifiers, conditioning agents, chelating agents, builders, monohydric alcohols having 1 to 20 carbon atoms, At least one selected from the group consisting of fatty acids, hydrocarbon oils, thickeners, setting polymers, pearling agents, fragrances, colorants, preservatives, medicinal agents, anti-inflammatory agents, bactericides, UV absorbers and antioxidants. Contains an additive (E) other than the one type of the copolymer (D),
The external composition according to any one of claims 1 to 5, wherein a ratio of the total weight of the additive (E) is 3 to 65% by weight based on the weight of the external composition.
7. The external composition is used as a hair cleansing agent, a hair treating agent, a skin cleansing agent, a cosmetic, a bathing agent, a hair setting agent, a hair coloring agent or a hair perm agent. The composition for external use described.