JP2003183137A - Cosmetic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a cosmetic composition which has good stability of viscosity, usage properties and function properties. <P>SOLUTION: This cosmetic composition characteristically contains the components (A) and (B); the component (A) being an amphoteric polyurethane resin containing a polysiloxane chain having a structure unit derived from a compound represented by the formula (1) (wherein R<SP>1</SP>, R<SP>6</SP>-R<SP>9</SP>represent each an alkyl group; R<SP>2</SP>-R<SP>5</SP>represent each C<SB>n</SB>H<SB>2n</SB>; and R<SP>10</SP>represents methyl group or ethyl group), and/or an amphoteric polyurethane resin holding a polysiloxane compound; the components (B) being a hydrophobic modified polyether urethane represented by the formula (2): R<SP>1</SP>-ä(O-R<SP>2</SP>)<SB>k</SB>-OCONH-R<SP>3</SP>[-NHCOO-(R<SP>4</SP>-O)<SB>n</SB>-R<SP>5</SP>]<SB>h</SB>}<SB>m</SB>(wherein R<SP>1</SP>, R<SP>2</SP>and R<SP>4</SP>represent each a hydrocarbon group; R<SP>3</SP>represents a hydrocarbon group which can have a urethane bond; R<SP>5</SP>represents a hydrocarbon group, a fluorocarbon group, an alkylsilicone group and an aromatic hydrocarbon group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cosmetic composition. More specifically, it relates to a cosmetic composition suitable as a hair cosmetic or an external skin preparation.

[0002]

2. Description of the Related Art In the field of cosmetics, a film-forming agent and an aqueous thickener are blended in order to improve usability and maintain its dosage form. As the film forming agent, for example, anionic, nonionic or amphoteric acrylic polymers, vinylpyrrolidone polymers, cationic vinylpyrrolidone polymers or cellulose polymers and the like are blended. On the other hand, examples of the aqueous thickener include polysaccharides of organic compounds, casein, natural polymers such as xanthan gum, synthetic polymers such as acrylic acid polymers and carboxyvinyl polymers, and inorganic compounds such as montmorillonite. Various clay minerals, silica and the like are appropriately selected and blended according to the intended effect.

When a composition containing such a film-forming agent and an aqueous thickener is used in cosmetics, a stable viscosity can be obtained such that the dosage form can be maintained in various temperature ranges, and at the same time external application Since it is often used for the skin and hair, the feel when used, that is, the ease of use is required.

However, none of the conventional compositions containing a film-forming agent and an aqueous thickening agent have sufficiently known stability of viscosity, favorable usability and function as a cosmetic. For example, when applied to hair as a hair cosmetic, an anion-based acrylic resin, an anion / cation-based amphoteric acrylic resin that has been conventionally used,
Nonionic polyvinylpyrrolidone resin and the like, in combination with the vinyl type, cellulose type, etc., the safety is relatively high, the addition of a thickener is small, but a sticky feeling peculiar to the polymer is generated. The setting property (hair styling property) for finishing hard is good, but once a comb is passed through, the setting property may be lost and the hairstyle may not last long. When applied to the skin as an external preparation for the skin, the firmness and firmness of the skin cannot be obtained. Also,
The composition containing the film-forming agent and the clay mineral has high thixotropy and has a refreshing after-use feeling, which is preferable in terms of usability, but is likely to cause syneresis due to temperature change and is unstable. .

[0005]

The present invention has been made in view of the above circumstances, and an object thereof is to provide a cosmetic composition excellent in stability of viscosity, use characteristics, and functional characteristics.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an ampholytic urethane resin having a specific polysiloxane chain and / or an ampholytic urethane resin carrying a polysiloxane compound. It was found that the above-mentioned problems can be solved by using, together with a hydrophobically modified polyether urethane having a specific structure, the present invention has been completed.

That is, the present invention is a cosmetic composition containing the following components (A) and (B).

(A) The following general formula (1)

[0009]

[Chemical 6]

[In the formula, R ¹ represents an alkyl group having 1 to 24 carbon atoms. R ^{2 to} R ⁴ each independently represent —C _n H _2n — (where n represents an integer of 1 to 3). R ⁵ is -C _n H
_2n- (wherein n represents an integer of 3 to 5). Further, R ^{6 to} R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms. R ¹⁰ represents a methyl group or an ethyl group. m
Represents an integer of 1 to 200. ]

An ampholytic urethane resin containing a polysiloxane chain having a structural unit derived from the compound represented by
Or a polysiloxane compound-carrying amphoteric urethane resin.

(B) The following general formula (2)

[0013]

[Chemical 7]

[In the formula, R ¹ , R ² and R ⁴ each independently represent a hydrocarbon group, R ³ represents a hydrocarbon group which may have a urethane bond, and R ⁵ represents a straight chain or branched chain. Represents a chain or secondary hydrocarbon group, a fluorocarbon group, an alkyl silicone group, an aromatic hydrocarbon group, m is an integer of 2 or more, h is an integer of 1 or more, and k and n are independent of each other. 0 to
It is an integer in the range of 1,000]

A hydrophobically modified polyether urethane represented by:

Here, the polysiloxane compound is "supported".
This means that the polysiloxane compound is "constrained" by the skeleton of the amphoteric urethane resin or that the polysiloxane compound is "entangled" with the skeleton of the amphoteric urethane resin. It is not the chemical binding of compounds. Therefore, in the present invention, the term "supported" is used to mean that the polysiloxane compound is "constrained" in the skeleton of the amphoteric urethane resin, or "entangled" with the polysiloxane compound in the skeleton of the amphoteric urethane resin. . However, a part of the skeleton of the amphoteric urethane resin may be formed as a result of the polysiloxane compound, and this partially chemically bonded one is not excluded as long as the intended amphoteric urethane resin is obtained. The loading of the polysiloxane compound on the amphoteric urethane resin can be confirmed by IR spectrum or the like.

The polysiloxane chain-containing amphoteric urethane resin and / or polysiloxane compound-carrying amphoteric urethane resin used in the present invention is preferably an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule. .

The ampholytic urethane resin constituting the polysiloxane compound-carrying ampholytic urethane resin used in the present invention is
It is preferably an amphoteric urethane resin produced by reacting at least the following compounds (A) to (D). (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary A compound having at least one selected from an amino group and a secondary amino group, and a tertiary amino group

The polysiloxane compound-carrying amphoteric urethane resin preferably used is at least the following (A):
To (D) and (S) are used, (A), (B)
And a first step of reacting the compound of (C) with an isocyanate group excess condition to produce an isocyanate group-containing prepolymer, and a second step of reacting the isocyanate group-containing prepolymer with the compound of (D). Including,
And in at least one of the first step and the second step,
It is an amphoteric urethane resin produced in the presence of the compound (S). (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary Compound (S) polysiloxane compound having at least one selected from an amino group and a secondary amino group, and a tertiary amino group

Here, the presence means that the polysiloxane compound is present in the reaction system and is not intended to positively react the polysiloxane compound,
As a result, some of them may inevitably react. In addition,
The term "presence" in the formation of the amphoteric urethane resin carrying the polysiloxane compound of the present invention is all used in this sense.

The polysiloxane compound-carrying amphoteric urethane resin preferably used comprises at least the following compounds (A) to (D) and (S):
The first step of producing the isocyanate group-containing prepolymer by reacting the compounds of (B) and (D) under an excess of isocyanate groups, and reacting the isocyanate group-containing prepolymer with the compound of (C) It is an amphoteric urethane resin including the second step and produced in the presence of the compound (S) in at least one of the first step and the second step. (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary Compound (S) polysiloxane compound having at least one selected from an amino group and a secondary amino group, and a tertiary amino group

The ampholytic urethane resin constituting the polysiloxane compound-carrying ampholytic urethane resin used in the present invention is
It may be an amphoteric urethane resin produced by reacting at least the following compounds (A) to (E). (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary At least one selected from an amino group and a secondary amino group, and a compound (E) having a tertiary amino group, at least one selected from a hydroxyl group, a primary amino group, and a secondary amino group. A compound having a structural unit represented by the following general formula (3)

[0023]

[Chemical 8]

(In the formula, p is an integer of 1 to 500, and q is 0 to
Represents an integer of 400. )

The polysiloxane compound-carrying amphoteric urethane resin preferably used is at least the following (A):
~ (E) and (S) compounds are used, (A),
The first step of producing the isocyanate group-containing prepolymer by reacting the compounds (B), (C) and (E) under the condition of excess isocyanate group, and the isocyanate group-containing prepolymer as described in (D). It may be an amphoteric urethane resin which includes a second step of reacting with a compound and is produced in the presence of the compound (S) in at least one of the first step and the second step. (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary At least one selected from an amino group and a secondary amino group, and a compound (E) having a tertiary amino group, at least one selected from a hydroxyl group, a primary amino group, and a secondary amino group. A compound having a structural unit represented by the following general formula (3)

[0026]

[Chemical 9]

(In the formula, p is an integer of 1 to 500, and q is 0 to
Represents an integer of 400. )

(S) Polysiloxane compound

The polysiloxane compound-carrying amphoteric urethane resin preferably used is at least the following (A):
~ (E) and (S) compounds are used, (A),
The first step of producing the isocyanate group-containing prepolymer by reacting the compounds of (B), (D) and (E) under the condition of excess isocyanate group, and the isocyanate group-containing prepolymer of (C) It may be an amphoteric urethane resin which includes a second step of reacting with a compound and is produced in the presence of the compound (S) in at least one of the first step and the second step. (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary At least one selected from an amino group and a secondary amino group, and a compound (E) having a tertiary amino group, at least one selected from a hydroxyl group, a primary amino group, and a secondary amino group. A compound having a structural unit represented by the following general formula (3)

[0030]

[Chemical 10]

(In the formula, p is an integer of 1 to 500, and q is 0 to
Represents an integer of 400. )

(S) Polysiloxane compound

The polysiloxane compound constituting the polysiloxane compound-carrying amphoteric urethane resin used in the present invention is selected from dimethylpolysiloxane, polyether modified silicone, cyclic silicone, phenyl modified silicone, alkyl modified silicone and alkoxy modified silicone. At least one kind is preferable.

In the hydrophobically modified polyether urethane of the general formula (2), R ² and R ⁴ are preferably each independently an alkylene group having 2 to 4 carbon atoms or a phenylethylene group.

In the hydrophobically modified polyether urethane of the general formula (2), R ³ is preferably a residue of polyisocyanate represented by R ^3- (NCO) _{h + 1} .

The polyisocyanate represented by R ^3- (NCO) _{h + 1} is a polyisocyanate having a urethane bond which is obtained by reacting a divalent to octavalent polyol with a divalent to tetravalent polyisocyanate. It is preferable.

In the hydrophobically modified polyether urethane of the general formula (2), R ¹ is preferably a residue of a polyol represented by R ^1- (OH) _m .

In the hydrophobic modified polyether urethane represented by the general formula (2), R ⁵ is a straight chain, branched chain or secondary hydrocarbon group having 8 to 36 carbon atoms or a straight chain or branched chain having 4 to 24 carbon atoms. Chain or secondary hydrocarbon group or C4-24
It is preferably a straight chain, branched chain or secondary fluorocarbon group.

The hydrophobically modified polyether urethane of the general formula (2) is represented by R ¹ -[(O-R ² ) _k -OH] _m 1
Or two or more polyether polyols and R ^3- (N
CO) _{h + 1} represented by 1 or 2 or more polyisocyanates, and HO- (R ⁴ -O) _n -R ⁵ represented by 1 or 2
It can be a reactant of one or more polyether monoalcohols.

In the present invention, the cosmetic composition may be a hair cosmetic.

In the present invention, the molecular weight indicates the number average molecular weight.

[0042]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

The amphoteric urethane resin used in the present invention is
The following general formula (1)

[0044]

[Chemical 11]

[In the formula, R ¹ represents an alkyl group having 1 to 24 carbon atoms. R ^{2 to} R ⁴ each independently represent —C _n H _2n — (where n represents an integer of 1 to 3). R ⁵ is -C _n H
_2n- (wherein n represents an integer of 3 to 5). Further, R ^{6 to} R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms. R ¹⁰ represents a methyl group or an ethyl group. m
Represents an integer of 1 to 200. ]

Polysiloxane chain-containing amphoteric urethane resin having a structural unit derived from the compound represented by
Alternatively, it is a polysiloxane compound-carrying amphoteric urethane resin, and both urethane resins are novel compounds.

First, the polysiloxane chain-containing ampholytic urethane resin will be described.

The polysiloxane chain-containing ampholytic urethane resin used in the present invention is an amphoteric urethane resin having a specific polysiloxane chain, and is preferably obtained by reacting at least the following components (F) to (J). , Having a carboxyl group and a tertiary amino group in one molecule. (F) Polyol compound (G) Polyisocyanate compound (H) Compound (I) represented by the general formula (1): Compound having active hydrogen and carboxyl group (J) Compound having active hydrogen and tertiary amino group

The above-mentioned polyol compound (F component) is not particularly limited as long as it is used in the usual production of polyurethane, and examples thereof include polyol, polyester polyol, polyether polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene. Examples thereof include polyols, polyolefin polyols, and polyacrylic acid ester-based polyols, which may be used alone or in combination of two or more. Among them, polyol, polyester polyol and polyether polyol are preferably used.

Examples of the polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, and the like. Examples include spiroglycol, trimethylolpropane, 1,4-cyclohexanedimethanol and the like.

Examples of the polyester polyol include at least one dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, maleic acid, fumaric acid, phthalic acid and terephthalic acid. Polyvalent ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, spiroglycol, trimethylolpropane, etc. Examples thereof include those obtained by polycondensing at least one kind of alcohol and those obtained by ring-opening polymerization of lactone acid.

Examples of the polyether polyol include polyhydric alcohols used in the synthesis of the polyester polyol, phenols such as bisphenol A, or primary amines such as ethylene oxide, propylene oxide, oxetane, and tetrahydrofuran. The compound obtained by ring-opening addition polymerization of the above cyclic ether can be used, and polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, bisphenol A are subjected to ring-opening addition polymerization of at least one of propylene oxide and ethylene oxide. (In the case of a copolymer, either a block copolymer or a random copolymer may be used).

The polyisocyanate compound (component G)
Are not particularly limited, and examples thereof include organic diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds, and these may be used alone or in combination of two or more.

Examples of the aliphatic diisocyanate compound include ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-
Hexamethylene diisocyanate and the like can be mentioned. Examples of the alicyclic diisocyanate compound include hydrogenated 4,4′-diphenylmethane diisocyanate,
1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate and the like can be mentioned. Examples of the aromatic diisocyanate compound include 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate. Among these, in terms of excellent light resistance and low price,
1,6-hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate and the like are preferable.

The polyisocyanate compound (component G)
The molar ratio of G component / (F + H + I + J component) = 2 /
It is preferable to set in the range of 0.8 to 2 / 1.8,
Particularly preferably G component / (F + H + I + J component) = 2 /
It is 1-2 / 1.8.

The compound (H component) used together with the polyol compound (F component) and the polyisocyanate compound (G component) has a structure represented by the following general formula (1).

[0057]

[Chemical 12]

[In the formula, R ¹ represents an alkyl group having 1 to 24 carbon atoms. R ^{2 to} R ⁴ each independently represent —C _n H _2n — (where n represents an integer of 1 to 3). R ⁵ is -C _n H
_2n- (wherein n represents an integer of 3 to 5). Further, R ^{6 to} R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms. R ¹⁰ represents a methyl group or an ethyl group. m
Represents an integer of 1 to 200. ]

In the general formula (1), the alkyl group having 1 to 24 carbon atoms represented by R ¹ may be linear or branched, but is preferably linear. The number of carbon atoms is preferably 1-10. Further, in the general formula (1), the alkyl group having 1 to 20 carbon atoms represented by R ^{6 to} R ⁹ may be linear or branched, but a linear one is preferable, and an alkyl group The carbon number of is preferably 1 to 10. Furthermore, the number of repetitions m in the general formula (1)
Is preferably set such that the molecular weight of the compound (H component) represented by the general formula (1) is in the range of 500 to 12,000, and more preferably the molecular weight of the compound (H component) is 700 to 10 It is set to be in the range of 1,000.

The compound (H component) represented by the general formula (1) includes the following structural formula (4) or structural formula (5).
Compounds represented by are preferred. m is the general formula (1)
Is the same as in.

[0061]

[Chemical 13]

[0062]

[Chemical 14]

The compound (H component) represented by the general formula (1) can be produced, for example, by the hydrosilylation reaction shown below.

[0064]

[Chemical 15]

[In the reaction formula, R ¹¹ represents —C _n H _2n — (where n represents an integer of 1 to 3), and other symbols are the same as those in the general formula (1). ]

As the catalyst, a hydrosilylation catalyst such as platinum or chloroplatinic acid is used.

The molar ratio of the compound (H component) represented by the general formula (1) is H component / G component = 0.01 / 2 to 0.2.
It is preferable to set it in the range of 5/2, and particularly preferably in the range of H component / G component = 0.01 / 2 to 0.3 / 2.

The compound having active hydrogen and a carboxyl group (component I) is not particularly limited as long as it is a compound having at least one active hydrogen and at least one carboxyl group in the molecule. The compound represented by 6) is preferable.

[0069]

[Chemical 16]

[In the formula, R ¹² represents an alkyl group having 1 to 24 carbon atoms. R ¹³ and R ¹⁴ are each independently -C _n H _2n-.
(However, n represents an integer of 1 to 3.). ]

In particular, a carbon number of 3 to 2 having a dialkylol group such as dimethylol, diethanol and dipropanol.
6, preferably 3 to 12 carboxylic acids are mentioned as suitable examples. Specific examples include dimethylolpropionic acid (DMPA) and dimethylolbutanoic acid. Further, a carboxyl group-containing polycaprolactone diol is also preferably used. These may be used alone or in combination of two or more.

The compound having active hydrogen and a tertiary amino group (component J) is not particularly limited as long as it is a compound having at least one active hydrogen and at least one tertiary amino group in the molecule. However, a compound represented by the following general formula (7) is preferable.

[0073]

[Chemical 17]

[In the formula, R ¹⁵ represents an alkyl group having 1 to 24 carbon atoms. R ¹⁶ and R ¹⁷ are each independently -C _n H _2n-.
(However, n represents an integer of 1 to 3.). ]

Particularly, for example, N-methyldiethanolamine, N having the same dialkylol group as the above-mentioned component I, N
Preferred examples include N-alkyl dialkanolamine compounds such as -butyldiethanolamine, dimethylaminoethanol and the like. The alkyl group of N-alkyl preferably has 1 to 24 carbon atoms, and particularly preferably 1 to 8 carbon atoms. These may be used alone or in combination of two or more.

As the polysiloxane chain-containing amphoteric urethane resin, one having a structural unit derived from alkylene oxide (hereinafter, also referred to as “RO”) in the structure is used in the cosmetic composition. It is preferable from the viewpoint of improving stability and characteristics. Examples of the structural unit derived from the RO include ethylene oxide (hereinafter,
Also called "EO". ) Units, propylene oxide (hereinafter also referred to as “PO”) units, and the like, and preferably EO units.

The polysiloxane chain-containing ampholytic urethane resin may have both EO units and PO units. The ratio of the EO unit to the PO unit is based on mass,
The range of EO unit / PO unit = 10/0 to 2/8 is preferable, and particularly preferable is EO unit / PO unit 10/0 to 4 /.
It is 6.

The repeating number n of EO units is preferably set in the range of 3 to 300, and particularly preferably 20 to.
120. That is, when n is less than 3, the EO units introduced into the amphoteric urethane resin are too small to impart sufficient hydrophilicity, and conversely, when n exceeds 300, the hydrophilicity of the amphoteric urethane resin itself. Is too strong, which may adversely affect the moisture resistance and the like. Also,
The number m of repeating PO units is also preferably set in the range of m = 3 to 300, and particularly preferably m = 20 to 12
It is 0. When it has both the EO unit and the PO unit, it is preferable to set it in the range of n + m = 3 to 300, and particularly preferably n + m = 20 to 120.

The compound having a structural unit derived from RO in the above structure is not particularly limited as long as the structural unit derived from EO can be introduced into the structure of the polysiloxane chain-containing ampholytic urethane resin. However, it may overlap with the polyether polyol in the F component. For example, polyethylene glycol (PE
G), polyoxyethylene polyoxypropylene glycol (EO / PO block copolymer) and the like,
Polyethylene glycol is preferably used. In addition, what induces a polyalkylene oxide group includes both types of OH group introduction type, both ends NH ₂ group introduction type, one end OH group introduction type, and one end NH ₂ group introduction type of polyalkylene oxide. It may be a derivative. When the both-end OH group-introduced type or both-end NH ₂ group-introduced type is used, EO
An amphoteric urethane resin having units in the main chain is obtained. Further, when the one-end OH group-introduced type or the one-end NH ₂ group-introduced type is used, an amphoteric urethane resin having an EO unit in its side chain or terminal is obtained.

The molecular weight of the polyalkylene oxide derivative is preferably in the range of 200 to 20,000, and particularly preferably 1,000 to 10,000.

In the present invention, the polyol compound (F
Component), a polyisocyanate compound (G component), a compound (H component) represented by the general formula (1), a compound having active hydrogen and a carboxyl group (I component), and optionally other than the F component. The polyalkylene oxide derivative of 1 is reacted with excess isocyanate groups to produce an isocyanate group-containing prepolymer, and then this isocyanate group-containing prepolymer and a compound having active hydrogen and a tertiary amino group (component J) Can be produced by reacting Alternatively, in the polysiloxane chain-containing ampholytic urethane resin, the reaction order of the specific I component and J component is exchanged, that is, the F component and G component are exchanged.
After reacting the component, the H component, the J component, and optionally a polyalkylene oxide derivative other than the F component in excess of the isocyanate group to produce an isocyanate group-containing prepolymer, the isocyanate group-containing prepolymer, It can also be produced by reacting with the specific I component. In addition, in the above-mentioned manufacturing method, a specific I component and J
When both components are reacted at the same time, the carboxyl group in the component I and the tertiary amino group in the component J first form a salt and become insoluble in the reaction system. Therefore, the desired amphoteric urethane resin cannot be produced. Further, the polyalkylene oxide derivative other than the F component, which is added as necessary, may be added after the isocyanate group-containing prepolymer is prepared.

When an isocyanate group-containing prepolymer is prepared by using each of the above-mentioned components, a chain extension or molecular weight inhibitor is used for the purpose of adjusting various properties of the polysiloxane chain-containing ampholytic urethane resin as the final product. Can be used. The chain extender is not particularly limited, and examples thereof include low molecular weight polyols and amines. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, spiroglycol, cyclohexyldimethanol,
Hydrogenated bisphenol A, neopentyl glycol,
Examples thereof include bis (β-hydroxyethoxy) benzene, glycols such as xylylene glycol, and triols such as trimethylolpropane and glycerin. Examples of the amines include ethylenediamine, propylenediamine, piperazine, hydrazine, isophoronediamine, methylene (bis-o-chloroaniline), polypropylene glycol containing amino groups at both ends, and the like.
Examples of the molecular weight suppressor include polypropylene glycol containing an amino group at one end.

In producing the polysiloxane chain-containing amphoteric urethane resin, a solvent can be used if necessary. For example, it is preferable to use an organic solvent that dissolves both the raw material and the polyurethane produced. . Examples of the organic solvent include amides such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and cellosolve acetate and cellosolve ether.

When the polysiloxane chain-containing ampholytic urethane resin is produced, it is dispersed in water by neutralizing the carboxyl group or the tertiary amino group incorporated in the molecule with a neutralizing agent. It is possible to impart sex. Examples of the neutralizing agent for the carboxyl group include triethylamine, trimethylamine, 2-amino-2-methyl-1-propanol, triethanolamine, potassium hydroxide, sodium hydroxide and the like. For example, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, dimethyl sulfuric acid and the like can be mentioned.

When producing the polysiloxane chain-containing amphoteric urethane resin, a polymerization catalyst well known in the field of polyurethane can be used. For example, a tertiary amine catalyst or an organometallic catalyst can be used. You can Examples of the tertiary amine catalyst include [2,2,2] diazabicyclooctane (DABCO), tetramethylenediamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like. Examples of the organometallic catalyst include dibutyltin dilaurate and the like.

Hereinafter, specific production examples of the polysiloxane chain-containing amphoteric urethane resin will be described. [Production Example 1; Amphoteric urethane resin (A)] Isophorone diisocyanate (IPD) was added to a glass four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser.
I) 70 g, polyester polyol (1,6-hexanediol adipate, molecular weight 2,000) 220 g,
8 g of the compound represented by the structural formula (4) (OH group with one terminal introduced, molecular weight of about 1,000) and 14 g of dimethylolbutanoic acid (DMBA) were added, 50 g of ethyl acetate was added as a solvent, and an oil bath was used. And heated to 80 ° C. and reacted for 4 hours. Then, 2 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate
Is added, and the reaction is further performed at 80 ° C. for 2 hours, and NCO
A prepolymer having a residual group was obtained. The NCO group-remaining prepolymer was cooled to 50 ° C., 900 g of water containing 9 g of triethylamine was added and dispersed therein under high-speed stirring, and further chain extension reaction was carried out at 50 ° C. for 3 hours to increase the molecular weight. It was The ethyl acetate was recovered from the obtained aqueous liquid to obtain an aqueous liquid of a polysiloxane chain-containing amphoteric urethane resin containing substantially no solvent. The amphoteric urethane resin has a structure in which both grafted alkyl groups on the particular carbon atom constituting the main chain of the urethane resin (tetravalent) and (-C ₂ H ₅₎ polysiloxane chain.

[Production Example 2; Amphoteric Urethane Resin (B)] In the same manner as Production Example 1 except that the compound represented by the structural formula (4) is replaced with the compound represented by the structural formula (5). As a result, an aqueous solution of a polysiloxane chain-containing ampholytic urethane resin was obtained. This amphoteric urethane resin has an alkyl group (-) at a specific carbon atom (tetravalent) constituting the main chain of the urethane resin.
It has a structure in which both C ₉ H ₁₉ ) and a polysiloxane chain are grafted.

[Production Example 3; Amphoteric urethane resin (C)] A polysiloxane chain-containing amphoteric urethane resin was produced in the same manner as in Production Example 1 except that the compounding amount of the compound represented by the structural formula (4) was increased to 16 g. An aqueous liquid of The amphoteric urethane resin has a structure in which both grafted alkyl groups on the particular carbon atom constituting the main chain of the urethane resin (tetravalent) and (-C ₂ H ₅₎ polysiloxane chain.

[Production Example 4; Amphoteric urethane resin (D)] 70 g of isophorone diisocyanate (IPDI) and polyester polyol (1) were placed in a glass four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser. , 6
-Hexanediol adipate, molecular weight 2,000) 2
20 g, a compound represented by the structural formula (4) (one terminal O
H group-introduced type, molecular weight about 1,000) 16g, trimethylolpropane 1g and dimethylolbutanoic acid (DM
BA) (14 g) was added, ethyl acetate (50 g) was added as a solvent, and the mixture was heated to 80 ° C. using an oil bath and reacted for 4 hours. Then, N-methyldiethanolamine (NM
2 g of DEtA) and 60 g of ethyl acetate are added,
Further, the mixture was reacted at 80 ° C. for 2 hours to obtain a prepolymer having NCO groups remaining. After cooling the NCO group-remaining prepolymer to 50 ° C., 9 g of triethylamine was added thereto.
900 g of water containing was added under high speed stirring to disperse, and further chain extension reaction was carried out at 50 ° C. for 3 hours to increase the molecular weight. The ethyl acetate was recovered from the obtained aqueous liquid to obtain an aqueous liquid of a polysiloxane chain-containing amphoteric urethane resin containing substantially no solvent. This amphoteric urethane resin has a structure in which both an alkyl group (—C ₂ H ₅ ) and a polysiloxane chain are grafted onto a specific carbon atom (tetravalent) constituting the main chain of the urethane resin, and a crosslinked structure is formed. Have

[Comparative Production Example 1; Amphoteric urethane resin (E)]
In place of the compound represented by the structural formula (4), a compound represented by the following structural formula (8) (one terminal OH group-introduced type,
An aqueous liquid of a polysiloxane chain-containing ampholytic urethane resin was obtained in the same manner as in Production Example 1 except that a molecular weight of about 1,000) was used. This amphoteric urethane resin has a structure in which only a polysiloxane chain is grafted onto a specific carbon atom (trivalent) constituting the main chain of the urethane resin, and an alkyl group is not grafted.

[0091]

[Chemical 18]

Next, the polysiloxane compound-carrying amphoteric urethane resin according to the present invention will be described.

The cosmetic composition of the present invention contains an amphoteric urethane resin carrying a polysiloxane compound. The preferred amphoteric urethane resin of the present invention is a polysiloxane compound-carrying amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule.

The amphoteric urethane resin which is preferably used in the present invention and which constitutes the amphoteric urethane resin carrying a polysiloxane compound carrying a polysiloxane compound and having a carboxyl group and a tertiary amino group in one molecule is at least the following. The amphoteric urethane resin produced by reacting the compounds (A) to (D) is preferable. (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary A compound having at least one selected from an amino group and a secondary amino group, and a tertiary amino group

The polyol compound used in the present invention (hereinafter, also referred to as compound (A)) is not particularly limited as long as it is a polyol compound generally used for producing a urethane resin. Examples of the compound (A) include, for example, polyester polyols, polyether polyols, low molecular weight polyols, polycarbonate polyols, polybutadiene polyols, polyisoprene polyols, polyolefin polyols, polyacrylic acid ester-based polyols, etc. Or, two or more kinds are used together. Among them, polyester polyol, polyether polyol and low molecular weight polyol are preferably used.

Examples of the polyester polyol include succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid,
At least one dicarboxylic acid such as terephthalic acid, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, Examples thereof include polyester polyols obtained by polycondensing at least one polyhydric alcohol such as 1,10-decanediol, diethylene glycol, spiroglycol, and trimethylolpropane, and polyester polyols obtained by ring-opening polymerization of lactones. To be

Examples of the polyether polyols include water and polyhydric alcohols used in the synthesis of the polyester polyols, phenols such as bisphenol A and hydrides thereof, and primary amines or secondary amines. Examples of the class include polyether polyols obtained by ring-opening addition polymerization of cyclic ethers such as ethylene oxide, propylene oxide, oxetane, and tetrahydrofuran. Further, polyoxypropylene polyol, polyoxytetramethylene polyol, and polyether polyol obtained by ring-opening addition polymerization of at least one of propylene oxide and ethylene oxide with bisphenol A (in the case of a copolymer, a block copolymer, a random copolymer) Any of the copolymers may be used).

Examples of the low molecular weight polyol include:
1,4-cyclohexanedimethanol, ethylene glycol, propylene glycol, isopropylene glycol, 1,4-butanediol, 1,3-butanediol, butylene glycol, 1,6-hexanediol,
Neopentyl glycol, 1,8-octane diol,
1,10-decanediol, diethylene glycol, dipropylene glycol, spiroglycol, trimethylolpropane, glycerin, diglycerin, triglycerin and the like can be mentioned.

The compound (A) can be used alone or in combination. Among the compounds (A), 1,4-cyclohexanedimethanol is preferable.

In the present invention, when the compound (A) overlaps with the compound (E) described later, the compound is included in the compound (E) and is not included in the compound (A). Furthermore, in the present invention, when the compound (A) overlaps with the compound (C) described later, the compound is included in the compound (C) and not included in the compound (A). In the present invention, when the compound (A) overlaps with the compound (D) described later, the compound is the compound (D).
And not included in the compound (A).

The polyisocyanate compound used in the present invention (hereinafter, also referred to as compound (B)) is not particularly limited as long as it is a polyisocyanate compound generally used for the production of urethane resin. Examples of the compound (B) include organic diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds. These may be used alone or in combination of two or more.

Examples of the aliphatic diisocyanate compound include ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 1,6-
Hexamethylene diisocyanate and the like can be mentioned.

Examples of the alicyclic diisocyanate compound include hydrogenated 4,4'-diphenylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate and norbornane diisocyanate.

Examples of the aromatic diisocyanate compound include 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, toluene diisocyanate and naphthalene diisocyanate.

Among these compounds (B), 1,6-hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate and the like are preferable because of their excellent weather resistance and low price. Compound (B)
Can be used alone or in combination.

The compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group used in the present invention and a carboxyl group (hereinafter, also referred to as compound (C)) is A compound having at least one kind selected from a hydroxyl group, a primary amino group and a secondary amino group in the molecule, and at least one carboxyl group, which is capable of obtaining a target amphoteric urethane resin. If there is, it is not particularly limited. Suitable examples of the compound (C) include carboxylic acids having a dialkylol group such as dimethylol, diethanol and dipropanol and having 3 to 26 carbon atoms, preferably 3 to 12 carbon atoms. Specific examples include dimethylolpropanoic acid (DMPA) and dimethylolbutanoic acid. Further, a carboxyl group-containing polycaprolactone diol is also used. These alone
Alternatively, they may be used in combination of two or more.

A compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group used in the present invention and a tertiary amino group (hereinafter, also referred to as compound (D)). As a compound having at least one kind selected from a hydroxyl group, a primary amino group and a secondary amino group and at least one tertiary amino group in the molecule, which is a target amphoteric urethane resin. The compound is not particularly limited as long as it can be obtained. Examples of the compound (D) include, for example, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, and N-methyldipropanolamine having the same dialkyrol group as the compound (C). And other N-alkyl dialkanolamine compounds. The N-alkyl alkyl group of the N-alkyl dialkanolamine compound preferably has 1 to 24 carbon atoms, and particularly preferably 1 to 8 carbon atoms. Furthermore, N, N-dimethylethanolamine,
Examples thereof include N, N-dialkylalkanolamine compounds such as N, N-diethylethanolamine and N, N-dibutylethanolamine, and triethanolamine. These may be used alone or in combination of two or more.

The polysiloxane compound used in the present invention (hereinafter, also referred to as compound (S)) is a polysiloxane compound that can be blended in cosmetics, and has a hydroxyl group at both ends or one end of the siloxane chain. There is no particular limitation as long as it is a polysiloxane compound that does not have at least one selected from a primary amino group and a secondary amino group, and is a compound that can obtain the target amphoteric urethane resin. Examples of polysiloxane compounds include dimethylpolysiloxane, polyether-modified silicone, cyclic silicone, phenyl-modified silicone, alkyl-modified silicone, and alkoxy-modified silicone. These polysiloxane compounds are arbitrarily selected and blended alone or in combination of two or more.

Examples of the dimethylpolysiloxane include compounds represented by the general formula (9).

[0110]

[Chemical 19]

(In the formula, n represents an integer of 1 or more.)

In the formula, n is preferably an integer of 1-100,
The integer of 1-50 is more preferable, and the integer of 3-30 is particularly preferable.

The dimethylpolysiloxane of the present invention may be a commercially available product, and examples of the commercially available product include S manufactured by Toray Dow Corning Silicone Co., Ltd.
Examples include H200 series (trade name), KF96 series (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

Examples of the polyether-modified silicone include compounds represented by the general formula (10).

[0115]

[Chemical 20]

(In the formula, m represents an integer of 0 or more, and n is 1
The above integers are represented, and R ¹⁸ represents a group represented by the following general formula (11). )

[0117]

[Chemical 21]

(In the formula, R ¹⁹ is a hydrogen atom or a carbon number of 1 to 1.
0 represents a hydrocarbon group, a represents an integer of 1 to 10, and b
Represents an integer of 1 to 300, and c represents an integer of 0 to 300. )

In the general formula (10), m is 0 to 300.
Is more preferable, the integer of 1-300 is more preferable, the integer of 1-100 is more preferable, and the integer of 1-50 is particularly preferable. n is preferably an integer of 1 to 300, and 1
The integer of -100 is more preferable, and the integer of 1-50 is especially preferable. Further, in the general formula (11), R ¹⁹ is preferably a hydrogen atom or a methyl group. a is preferably an integer of 1 to 5, and particularly preferably an integer of 2 to 4. b is preferably an integer of 2 to 50, more preferably an integer of 2 to 40, and 2
An integer of 30 is particularly preferred. c is preferably an integer of 0 to 50, more preferably an integer of 0 to 40, and particularly preferably an integer of 0 to 30.

As the compound (S) represented by the general formula (10), in the general formula (10), m is an integer of 1 to 300, n is an integer of 1 to 300, and R ¹⁸ is a general formula ( A compound represented by 11) in which a is an integer of 1 to 5, b is an integer of 2 to 50, and c is an integer of 0 to 50 is preferable.

As the compound (S) represented by the general formula (10), in the general formula (10), m is an integer of 1 to 100, n is an integer of 1 to 100, and R ¹⁸ is a general formula ( A compound represented by 11) in which a is an integer of 2 to 4, b is an integer of 2 to 40, and c is an integer of 0 to 40 is more preferable.

As the compound (S) represented by the general formula (10), in the general formula (10), m is an integer of 1 to 50, n is an integer of 1 to 50, and R ¹⁸ is a general formula ( 1
1) is a group represented by 1), wherein a is an integer of 2 to 4,
A compound in which b is an integer of 2 to 30 and c is an integer of 0 to 30 is particularly preferable.

Examples of the polyether-modified silicone represented by the general formula (10) include Toray Dow Corning
SH3746, SH3771 manufactured by Silicone Co., Ltd.
C, SH3772C, SH3773C, SH3775
C, SH3748, SH3749, SH3771M, S
H3772M, SH3773M, SH3775M (trade name), and KF351A manufactured by Shin-Etsu Chemical Co., Ltd.
KF353A, KF945A, KF352A, KF61
5A, KF6011, KF6012, KF6013, K
F6015, KF6016, KF6017 (trade name) and the like can be mentioned.

Examples of the phenyl-modified silicone include compounds represented by the general formula (12).

[0125]

[Chemical formula 22]

(In the formula, R ²⁰ and R ²¹ are each independently a hydrocarbon group having 1 to 12 carbon atoms (for example, a linear or branched saturated hydrocarbon group having 1 to 12 carbon atoms), -OSi. (C
H ₃ ) ₃ or a phenyl group. However, at least one of R ²⁰ and R ²¹ is a phenyl group. m represents an integer of 0 or more, and n represents an integer of 1 or more. )

In the general formula (12), m is 0 to 300.
Is preferred, an integer of 0-100 is more preferred,
An integer of 0 to 50 is particularly preferable. n is preferably an integer of 1 to 500, more preferably an integer of 1 to 100, and 1 to 5
An integer of 0 is particularly preferred. As the phenyl-modified silicone, in the general formula (12), R ²⁰ = CH ₃ or-
_{OSi (CH 3) 3, R} 21 = C 6 H 5, m = 0, n = 1~10
A methylphenylpolysiloxane of 0 is especially preferred.

Examples of the phenyl-modified silicone represented by the general formula (12) include SH556, SF557 and SF55 manufactured by Toray Dow Corning Silicone Co., Ltd.
8, SH559 (trade name), and KF50-100cs, KF50-1000c manufactured by Shin-Etsu Chemical Co., Ltd.
s, KF53, KF54, KF56 (trade name) and the like.

Examples of the alkyl-modified silicone include compounds represented by the general formula (13).

[0130]

[Chemical formula 23]

(In the formula, R ^{22 to} R ²⁴ each independently represent a hydrocarbon group having 1 to 50 carbon atoms, provided that R ^{22 to} R ²⁴
At least one of them is a hydrocarbon group having 5 to 30 carbon atoms. m represents an integer of 1 or more, and n represents an integer of 1 or more. )

In the general formula (13), R ^{22 to} R ²⁴ are hydrocarbon groups having 1 to 50 carbon atoms, and examples thereof include linear or branched saturated hydrocarbon groups. The hydrocarbon group preferably has 5 to 30 carbon atoms, more preferably has 5 to 20 carbon atoms, and particularly preferably has 10 to 20 carbon atoms. Further, m is preferably an integer of 1 to 300,
More preferably, it is an integer of 1 to 100, particularly preferably 1 to 50. n is preferably an integer of 1 to 300, more preferably an integer of 1 to 100, and particularly preferably an integer of 1 to 50.

Examples of the alkyl-modified silicone represented by the general formula (13) include SF8416 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., and KF-412 and KF-413 manufactured by Shin-Etsu Chemical Co., Ltd.
KF-414 (trade name) and the like can be mentioned.

Examples of the alkoxy-modified silicone include compounds represented by the general formula (14).

[0135]

[Chemical formula 24]

(In the formula, R ^{25 to} R ²⁷ each independently represent a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 50 carbon atoms, provided that at least one of R ^{25 to} R ²⁷ is present. Is an alkoxy group having 1 to 50 carbon atoms, m represents an integer of 0 or more, and n represents an integer of 1 or more.)

In the general formula (14), R ^{25 to} R ²⁷ are
Although it is a hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 50 carbon atoms, a linear or branched saturated hydrocarbon group can be exemplified as the hydrocarbon group having 1 to 12 carbon atoms. As the alkoxy group of 1 to 50, a linear or branched alkoxy group can be exemplified. The alkoxy group having 1 to 50 carbon atoms preferably has 1 to 30 carbon atoms, and
25 is more preferable, and 1 to 20 is particularly preferable. In addition, m is preferably an integer of 0 to 500, more preferably an integer of 1 to 500, and 1
More preferably, it is an integer of -100, and particularly preferably an integer of 1-50. n is preferably an integer of 1 to 100, more preferably an integer of 1 to 80, and particularly preferably an integer of 1 to 50.

Examples of the alkoxy-modified silicone represented by the general formula (14) include KF-851 and X-22-801B (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.

Examples of the cyclic silicone include compounds represented by the general formula (15).

[0140]

[Chemical 25]

(In the formula, R ²⁸ represents a hydrocarbon group having 2 to 12 carbon atoms, and each repeating unit may be the same or different. M is an integer of 1 or more, and n is n.
Represents an integer of 0 or more, and m + n = 3 to 10. )

In the general formula (15), R ²⁸ is a hydrocarbon group having 1 to 12 carbon atoms, and may be a linear or branched saturated hydrocarbon group. R ²⁸ has 2 to 10 carbon atoms.
Is preferred, more preferably 2-8,
Particularly preferably, it is 2-5. In addition, m is preferably an integer of 1 to 8, more preferably an integer of 3 to 8, and further preferably an integer of 4 to 8.
An integer of 6 is particularly preferred. n is preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and particularly preferably an integer of 0 to 3. m + n is 3
It is preferable that it is -8, it is more preferable that it is 4-8, and it is especially preferable that it is 4-6.

Examples of the cyclic silicone represented by the general formula (15) include SH244, SH344, SH245 and DC manufactured by Toray Dow Corning Silicone Co., Ltd.
Examples include 345, DC246 (trade name), KF994, KF995, and KF9937 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.

The general formula (10) and the general formula (1)
The repeating unit portion of the compounds represented by 2) to (15) may be in any polymerization form such as random polymerization or block polymerization.

Viscosity of compound (S) at 25 ° C. (kinematic viscosity)
Is preferably either a 1~5,000mm ² / s, more preferably from 1~2,000mm ² / s, particularly preferably from 1~1,000mm ² / s. As the compound (S), dimethylpolysiloxane and polyether-modified silicone are preferable. Compound (S)
Can be used alone or in combination.

The preferred polysiloxane compound-carrying amphoteric urethane resin in the present invention is an amphoteric urethane resin produced by reacting at least the compounds (A) to (D) in the presence of the compound (S). In producing the polysiloxane compound-carrying amphoteric urethane resin according to the present invention, at least the compounds (A) to (D) are used.
And (S) are used to react the compounds (A), (B) and (C) under conditions of excess isocyanate group to produce an isocyanate group-containing prepolymer, and the isocyanate group-containing A second step of reacting the prepolymer with the compound (D), and in at least one of the first step and the second step, the compound (S)
Can be present. It can also be produced by changing the reaction order of the compound (C) and the compound (D).

Compound (S) and the above compound (A),
Mass ratio with (B), (C) and (D), ie (S)
/ ((A) + (B) + (C) + (D)) is 0.1 / 1
It is preferably from 00 to 30/100, and 0.5 / 10
0 to 25/100 is more preferable, and 1/100
It is especially preferable that it is ˜20 / 100.

Further, the compound (B) and the compound (A),
Molar ratio with (C) and (D), ie (B) /
((A) + (C) + (D)) is 2.0 / 1.8 to 2.
It is preferably 0 / 0.8, and 2.0 / 1.8 to 2.
0 / 1.0 is more preferable, and 2.0 / 1.8 to
It is particularly preferable that it is 2.0 / 1.2.

The reaction in the first step and the second step can be carried out by appropriately using a polymerization catalyst under the reaction conditions usually used in the production of polyurethane. As the polymerization catalyst, a polymerization catalyst usually used for producing a urethane resin can be used. The polymerization catalyst is not particularly limited as long as it can obtain the target amphoteric urethane resin. As the polymerization catalyst, for example, a tertiary amine catalyst, an organometallic catalyst or the like can be used. Examples of the tertiary amine catalyst include [2,
2,2] diazabicyclooctane (DABCO), tetramethylenediamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like can be mentioned. Examples of the organic metal catalyst include dibutyltin (tin) dilaurate and the like.

When producing the amphoteric urethane resin,
If necessary, an organic solvent can be used in the reaction of the first step and the second step, for example, an organic solvent that dissolves both the compounds (A) to (D) and the amphoteric urethane resin to be formed. Is preferred. Examples of such an organic solvent include amides such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, ketones such as acetone and methylethylketone, esters such as ethyl acetate, and other cellosolve acetate and cellosolve ether. .

Further, after the second step, it is preferable that the reaction product of the second step is mixed with water to carry out a chain extension reaction. After the second step, the reaction product of the second step is mixed with basic water to carry out a chain extension reaction. Alternatively, it is more preferable to add a basic compound to the reaction product of the second step and then mix with water to carry out a chain extension reaction. Among these, it is particularly preferable to carry out the chain extension reaction by mixing the reaction product of the second step with basic water after the second step. In the present invention, after carrying out the reaction of the first step and the second step in an organic solvent, the reaction mixture of the second step is mixed with basic water, and then the chain extension reaction is carried out in water. Is preferred. In this manner, the embodiment in which the reaction mixture after the second step is mixed with basic water and then the chain length extension reaction is carried out in water is preferable because a high molecular weight amphoteric urethane resin can be easily obtained. In the production method of this aspect, it is preferable to set the production conditions such that the reaction mixture after the second step is a prepolymer having an isocyanate group at the terminal.

The basic water is water in which a basic substance is dissolved in water to exhibit basicity, and examples thereof include triethylamine, triethanolamine, ammonia, potassium hydroxide, sodium hydroxide and 2- Water in which amino-2-methyl-1-propanol and the like are dissolved can be exemplified.

A chain extender can be used in the chain extension reaction in the production of the polysiloxane compound-carrying amphoteric urethane resin according to the present invention, and the polysiloxane compound-supported finally obtained by the chain extender can be used. The characteristics of the amphoteric urethane resin can be adjusted. The chain extender is a compound used in the chain extension reaction, and examples thereof include low molecular weight polyols, amines and water.
Examples of the low-molecular polyol include glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, spiroglycol, bis (β-hydroxyethoxy) benzene, and xylylene glycol. , Triols such as trimethylolpropane and glycerin. Examples of the amines include methylene (bis-o-chloroaniline) and the like.

In the present invention, the use of a polysiloxane compound-carrying amphoteric urethane resin having a structural unit derived from RO in the resin structure improves the stability and characteristics of the cosmetic composition. Is preferred. RO
Examples of the structural unit derived from include an EO unit, a PO unit, and the like, and an EO unit is preferable.

The compound having a structural unit derived from RO in its structure is not particularly limited as long as the structural unit derived from RO can be introduced into the structure of the polysiloxane compound-carrying amphoteric urethane resin. Absent.

Preferred compounds having a structural unit derived from RO in the structure include at least one selected from a hydroxyl group, a primary amino group and a secondary amino group,
A compound having a structural unit represented by the following general formula (3) (hereinafter, also referred to as compound E).

[0157]

[Chemical formula 26]

(In the formula, p is an integer of 1 to 500, and q is 0 to
Represents an integer of 400. )

In the general formula (3), when q is 0, C
_{It is} a polymer of ₂ H ₄ O (polyoxyethylene), and when q is not 0, it is a copolymer of C ₂ H ₄ O and C ₃ H ₆ O. In the case of this copolymer, it may be a random copolymer or a block copolymer.

In the general formula (3), p is an integer of 1 to 500. Furthermore, even if q is not 0, 0
Even in the case of, p is preferably 3 to 250, and 3 to
120 is more preferable, and 3 to 50 is particularly preferable. When p is less than 1, EO units introduced into the amphoteric urethane resin are too small to impart sufficient hydrophilicity, and when the polysiloxane compound-carrying amphoteric urethane resin is used as a hair styling agent, for example, Insufficient hydrophilicity results in poor hair washability. On the other hand, when n exceeds 500, the hydrophilicity of the amphoteric urethane resin itself when carrying the polysiloxane compound becomes too strong, which adversely affects the moisture resistance and the like.

Further, in the general formula (3), the repeating number q of the PO unit is an integer of 0 to 400, and preferably q = 0. When q is not 0, q is preferably set in the range of 3 to 200, more preferably 3 to 1
00. Particularly preferably, it is 3-40. Note that q
Whether p is non-zero or zero
It is preferable to set in the range of q = 3 to 300, and more preferably p + q = 10 to 120. Particularly preferably, p + q = 3 to 50.

Whether q is not 0 or 0, the ratio of EO unit to PO unit is EO unit / PO unit = 10/0 to 2/8 on a mass basis. The range is preferable, and more preferably EO unit / PO unit 10 /
It is 0 to 3/7. Particularly preferably, the EO unit / PO unit is 10/0 to 4/6.

The compound (E) is preferably of both-terminal OH group-introduced type, both-terminal NH ₂ group-introduced type, one-terminal OH group-introduced type, or one-terminal NH ₂ -group-introduced type. When the both-end OH group-introduced type or both-end NH ₂ group-introduced type is used, an amphoteric urethane resin having the structural unit represented by the general formula (3) in the main chain is obtained. Further, when the one-end OH group-introduced type or the one-end NH ₂ group-introduced type is used, an amphoteric urethane resin having a structural unit represented by the general formula (3) in the side chain or terminal is obtained.

The mass average molecular weight of the compound (E) is 2
The range of 00 to 20,000 is preferable, and the range of 200 to 5,000 is more preferable. Particularly preferably 500-
It is 2,000.

Examples of the compound (E) include polyethylene glycol (PEG), polyethylene polypropylene glycol, polyethylene polypropylene block copolymer and the like. Of these, polyethylene glycol is preferred. The compound (E) can be used alone or in combination.

The polysiloxane compound-carrying amphoteric urethane resin when compound (E) is added is an amphoteric urethane resin produced by reacting at least the compounds (A) to (E) in the presence of the compound (S). Is preferred.

The production of this resin can be carried out in the same manner as in the production method when compound (E) is not added. That is, at least the compounds (A) to (E) and (S) are used, and the compounds (A), (B) and (C) are used.
And (E) are reacted under conditions of excess isocyanate groups to produce an isocyanate group-containing prepolymer, and the isocyanate group-containing prepolymer,
It can be produced by including the second step of reacting with the compound (D), and in the presence of the compound (S) in at least one of the first step and the second step. It can also be produced by changing the reaction order of the compound (C) and the compound (D).

Compound (S) and the above compound (A),
Mass ratio with (B), (C), (D) and (E), ie (S) / ((A) + (B) + (C) + (D) +
(E)) is preferably 0.1 / 100 to 30/100, more preferably 0.5 / 100 to 25/100, and particularly preferably 1/100 to 20/100. .

Further, the compound (B) and the compound (A),
Molar ratio with (C), (D) and (E), ie (B)
/ ((A) + (C) + (D) + (E)) is 2.0 /
It is preferably 1.8 to 2.0 / 0.8, and 2.0 /
More preferably, it is 1.8 to 2.0 / 1.0.
It is particularly preferable that it is 0 / 1.8 to 2.0 / 1.2.

Further, in the reaction in the first step and the second step, as in the case where the compound (E) is not added, the reaction conditions usually used in the production of urethane resin are used, and a polymerization catalyst is appropriately used. Can be implemented. The same applies to the polymerization catalyst, organic solvent, chain extension reaction and the like. As described above, even when the compound (E) is added, it is more preferable to perform the first step and the second step in an organic solvent and carry out the chain extension reaction in water.

The polysiloxane compound-carrying amphoteric urethane resin of the present invention has a carboxyl group and a tertiary amino group in one molecule. Ratio of carboxyl group to tertiary amino group (ratio of the number of both functional groups), carboxyl group /
The tertiary amino group is preferably 1/50 to 50/1, and 1
/ 1 to 50/1 is more preferable, and 1/1 to 25/1 is particularly preferable. The ratio of the carboxyl groups to the tertiary amino groups in the polysiloxane compound-carrying amphoteric urethane resin is 1 /
In the case of 50 to 50/1, using a hair styling agent in which a polysiloxane compound-carrying amphoteric urethane resin is used, the hair will have a better texture. In the reaction, the ratio (molar ratio) of the compound (C) and the compound (D), the ratio of the compound (C) / the compound (D), is 1/50 to 50.
/ 1 is preferable, 1/1 to 50/1 is more preferable, and 1
/ 1 to 25/1 is particularly preferable.

The polysiloxane compound-carrying amphoteric urethane resin according to the present invention does not necessarily contain the polysiloxane chain of the polysiloxane compound in its skeleton through a covalent bond, but the polysiloxane compound is supported by the skeleton of the amphoteric urethane resin. A polysiloxane chain is contained when the skeleton of the "restraining" or amphoteric urethane resin is physically entangled with the polysiloxane chain of the polysiloxane compound. This restraint or entanglement
It is considered that the progress of the polymerization reaction of the amphoteric polyurethane makes it more complicated and makes it difficult to separate the polysiloxane compound from the obtained amphoteric urethane resin.

In the present invention, the state in which the skeleton of the amphoteric urethane resin and the polysiloxane compound are bound or entangled with each other is referred to as a state in which the skeleton of the amphoteric urethane resin "supports" the polysiloxane compound. Here, "support" differs depending on whether the amphoteric urethane resin is in the form of an aqueous solution or a water dispersion. The skeleton of the amphoteric urethane resin is
Although it is usually a linear structure, it may have a branched structure or a crosslinked structure. When the amphoteric urethane resin is in the form of "aqueous solution", it is considered that the polysiloxane chain is inserted between the skeletons of the amphoteric urethane resin. .

On the other hand, when the amphoteric urethane resin is in the form of "water dispersion", the amphoteric urethane resin is considered to be in the form of particles dispersed in water, and the polysiloxane chain is bound to the particles. Can take several forms. First, the first form is a form in which the whole or part of the polysiloxane chain is wrapped inside the particles.
The second form is a form in which the end of the polysiloxane chain is wrapped inside the particle. Get up. The third form is a form in which polysiloxane chains are attached to the surface of the particles. The first to third forms all correspond to "restraint", and the first to third forms
Those in which the third forms are mixed are also considered to be "restraint".

As described above, the skeleton of the polysiloxane compound-carrying amphoteric urethane resin according to the present invention carries the polysiloxane compound. Therefore, it is considered that the polysiloxane chain has a property of relatively easy movement, but the polysiloxane compound is difficult to separate from the amphoteric urethane resin.

Production examples of the polysiloxane compound-carrying amphoteric urethane resin used in the present invention and other urethane resins for comparison will be described below.

[Production Example 5: Amphoteric urethane resin (F)] Stirring
Four equipped with equipment, thermometer, nitrogen inlet tube and reflux condenser
Isophorone diisocyanate (IPD
I) 70 g, polypropylene glycol (PPG, mass
Average molecular weight 1,000) 63 g, 1,4-cyclohexa
7 g of dimethanol (CHDM), dimethylpolysiloxane
Sun (viscosity at 25 ℃ is 10 mm ²/ S, Toray Da
SH200C-1 manufactured by Ukoning Silicone Co., Ltd.
8 g of 0cs (trade name) and dimethylolbutanoic acid (DM
BA) 20 g, and ethyl acetate 50 g as a solvent
Well, use an oil bath to heat to 80 ° C and react for 3 hours.
Let Then, N-methyldiethanolamine (NMD
2 g of EtA) and 60 g of ethyl acetate are added, and
Remaining at 80 ° C for 3 hours to leave isocyanate groups
The obtained prepolymer was obtained. Remaining of this isocyanate group
After cooling the prepared prepolymer to 50 ° C, potassium hydroxide was added.
Disperse by stirring at high speed in 700 g of water containing 10 g of um,
Furthermore, a chain extension reaction is performed at 50 ° C for 3 hours to obtain a high molecular weight
Made into The ethyl acetate was recovered from the obtained aqueous liquid.
And supports a polysiloxane compound that contains substantially no solvent
An aqueous liquid of amphoteric urethane resin was obtained.

[Production Example 6; Amphoteric Urethane Resin (G)] In the production method described in Production Example 5, instead of 8 g of dimethylpolysiloxane, a polyether-modified silicone (2
SH3775C manufactured by Toray Dow Corning Silicone Co., Ltd. with a viscosity of 1600 mm ² / s at 5 ° C.
An aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin was obtained in the same manner as in Production Example 5 except that 8 g of (trade name) was used.

[Production Example 7: Amphoteric Urethane Resin (H)] In the production method described in Production Example 5, instead of 8 g of dimethylpolysiloxane, cyclic silicone (viscosity at 25 ° C. is 4 mm ² / s, Toray Dow Corning An aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin was obtained in the same manner as in Production Example 5, except that SH245 (trade name) manufactured by Silicone Co., Ltd. was used.

[Production Example 8: Amphoteric urethane resin (I)] In the production method described in Production Example 5, phenyl-modified silicone (25 ° C) was used instead of 8 g of dimethylpolysiloxane.
In the same manner as in Production Example 5, except that a viscosity of 22 mm ² / s, and 8 g of SH556 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd. were used, an aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin was prepared. Got

[Production Example 9: Amphoteric urethane resin (J)] In the production method described in Production Example 5, instead of 8 g of dimethylpolysiloxane, an alkyl-modified silicone (25 ° C.) was used.
In the same manner as in Production Example 5, except that a viscosity of 500 mm ² / s, and 8 g of KF-412 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. were used, an aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin was prepared. Obtained.

[Production Example 10; Amphoteric Urethane Resin (K)] In the production method described in Production Example 5, instead of 8 g of dimethylpolysiloxane, an alkoxy-modified silicone (2
A viscosity of 80 mm ² / s at 5 ° C., except that 8 g of KF-851 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. was used,
An aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin was obtained in the same manner as in Production Example 5.

[Production Example 11: Amphoteric urethane resin (L)] In the production method described in Production Example 5, instead of 8 g of dimethylpolysiloxane, dimethylpolysiloxane (25
SH200C-10cs manufactured by Toray Dow Corning Silicone Co., Ltd. with a viscosity of 10 mm ² / s at ℃
An aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin was obtained in the same manner as in Production Example 5 except that 20 g of (trade name) was used.

[Production Example 12: Amphoteric urethane resin (M)] In the production method described in Production Example 5, instead of 8 g of dimethylpolysiloxane, a polyether-modified silicone (viscosity at 25 ° C .: 1600 mm ² / s, Toray. SH3775C made by Dow Corning Silicone Co., Ltd.
An aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin was obtained in the same manner as in Production Example 5 except that 20 g of (trade name) was used.

[Production Example 13: Amphoteric urethane resin (N)] 4 equipped with a stirrer, a thermometer, a nitrogen introducing pipe and a reflux condenser
Isophorone diisocyanate (IPD
I) 70 g, polypropylene glycol (PPG, mass average molecular weight 1,000) 55 g, polyethylene glycol (PEG, mass average molecular weight 1,000) 8 g, 1,4
-Cyclohexanedimethanol (CHDM) 7 g, dimethylpolysiloxane (viscosity at 25 ° C is 10 mm ²
/ S, Toray Dow Corning Silicone Co., Ltd. SH200C-10cs (brand name) 8g and dimethylol butanoic acid (DMBA) 20g are put, ethyl acetate 50g is added as a solvent, and it heats at 80 degreeC using the oil bath. And reacted for 3 hours. Then, 2 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate
Was further added, and the mixture was further reacted at 80 ° C. for 3 hours to obtain a prepolymer in which an isocyanate group remained. After cooling the prepolymer with the remaining isocyanate groups to 50 ° C., it is dispersed in 700 g of water containing 10 g of potassium hydroxide by high-speed stirring to disperse the polymer, and further subjected to chain extension reaction at 50 ° C. for 3 hours to increase the molecular weight. It was The ethyl acetate was recovered from the obtained aqueous liquid to obtain an aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin containing substantially no solvent.

[Production Example 14: Amphoteric Urethane Resin (O)] In the production method described in Production Example 13, instead of 8 g of dimethylpolysiloxane, a polyether-modified silicone (viscosity at 25 ° C .: 1600 mm ² / s, Toray. SH3775C made by Dow Corning Silicone Co., Ltd.
An aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin was obtained in the same manner as in Production Example 13 except that 8 g of (trade name) was used.

[Production Example 15; Amphoteric Urethane Resin (P)] In the production method described in Production Example 13, dimethylpolysiloxane (2
SH200C-10cs manufactured by Toray Dow Corning Silicone Co., Ltd. with a viscosity of 10 mm ² / s at 5 ° C.
An aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin was obtained in the same manner as in Production Example 13 except that 20 g of (trade name) was used.

[Production Example 16: Amphoteric Urethane Resin (Q)] In the production method described in Production Example 13, instead of 8 g of dimethylpolysiloxane, a polyether-modified silicone (viscosity at 25 ° C .: 1600 mm ² / s, Toray. SH3775C made by Dow Corning Silicone Co., Ltd.
An aqueous liquid of a polysiloxane compound-carrying amphoteric urethane resin was obtained in the same manner as in Production Example 13 except that 20 g of (trade name) was used.

[Comparative Production Example 2; Amphoteric urethane resin (R)]
An aqueous liquid of an amphoteric urethane resin was obtained in the same manner as in Production Example 5 except that dimethylpolysiloxane was not used in the production method described in Production Example 5.

[Comparative Production Example 3; Amphoteric urethane resin (S)]
A four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser was charged with isophorone diisocyanate (IP
DI) 70 g, polypropylene glycol (PPG, mass average molecular weight 1,000) 63 g, 1,4-cyclohexanedimethanol (CHDM) 7 g and dimethylolbutanoic acid (DMBA) 20 g are added, ethyl acetate 50 g is added as a solvent, and oil is added. It heated at 80 degreeC using the bath, and was made to react for 3 hours. Thereafter, 2 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added, and the mixture was further reacted at 80 ° C. for 3 hours to obtain a prepolymer in which isocyanate groups remained. After cooling the prepolymer with the remaining isocyanate groups to 50 ° C., it is dispersed in 700 g of water containing 10 g of potassium hydroxide by high-speed stirring to disperse the polymer, and further subjected to chain extension reaction at 50 ° C. for 3 hours to increase the molecular weight. It was After recovering the ethyl acetate from the obtained aqueous liquid to obtain an aqueous liquid of the amphoteric urethane resin containing substantially no solvent, dimethylpolysiloxane (25
SH200C-10cs manufactured by Toray Dow Corning Silicone Co., Ltd. with a viscosity of 10 mm ² / s at ℃
8 g of (trade name) was added to obtain an aqueous liquid of an amphoteric urethane resin.

When the amphoteric urethane resin of the present invention is blended with the cosmetic composition of the present invention, it is preferably used as an aqueous liquid. In the present invention, the term “aqueous liquid” includes not only an aqueous solution state in which an amphoteric urethane resin is completely dissolved in water but also an aqueous dispersion state in which an amphoteric urethane resin is dispersed in water (water dispersion, microemulsion, etc.). Is. Incidentally, the aqueous liquid of the amphoteric urethane resin,
It is also possible to add a crosslinking agent such as a silane coupling agent to impart crosslinkability. Further, it is also possible to add various additives in order to impart storage stability, for example,
Examples thereof include protective colloid agents, antibacterial agents, antifungal agents and the like.

The preferred content of the amphoteric urethane resin used in the present invention is 0.1 to 5.0% by mass in the total amount of the cosmetic composition as an effective component. More preferably,
It is 0.5 to 4.0 mass%. If the amount is less than 0.1% by mass, the effect of the present invention cannot be sufficiently obtained, and the amount is 5.0% by mass.
This is because if the content exceeds the above range, weight and stickiness will occur.

Next, the hydrophobically modified polyether urethane as the component (B) will be described.

The hydrophobically modified polyether urethane used in the present invention is represented by the following general formula (2).

[0195]

[Chemical 27]

[In the formula, R ¹ , R ² and R ⁴ each independently represent a hydrocarbon group, R ³ represents a hydrocarbon group which may have a urethane bond, and R ⁵ represents a straight chain or branched chain. Represents a chain or secondary hydrocarbon group, a fluorocarbon group, an alkyl silicone group, an aromatic hydrocarbon group, m is an integer of 2 or more, h is an integer of 1 or more, and k and n are independent of each other. 0 to
It is an integer in the range of 1,000]

In the general formula (2), R ¹ represents a hydrocarbon group, but is preferably a residue of a polyol represented by R ^1- (OH) _m .

Further, R ² and R ^{4 in} the general formula (2) each independently represent a hydrocarbon group, but preferably an alkylene group having 2 to 4 carbon atoms or a phenylethylene group.

Further, R ³ in the general formula (2) represents a hydrocarbon group which may have a urethane bond, but R ^3- (NCO)
It is preferably a residue of a polyisocyanate represented by _{h + 1} , and the polyisocyanate represented by R ^3- (NCO) _{h + 1} is a 2- to 8-valent polyol and a 2- to 4-valent polyol. A polyisocyanate having a urethane bond obtained by reacting polyisocyanate is preferable.

R ⁵ in the general formula (2) represents a straight chain, branched chain or secondary hydrocarbon group, a fluorocarbon group, an alkyl silicone group or an aromatic hydrocarbon group. Alternatively, in the case of a secondary hydrocarbon group, its carbon number is preferably 8 to 36. In the case of a fluorocarbon group, it has 4 to 24 carbon atoms.
Is preferably a linear, branched, and / or secondary fluorocarbon group. In the case of an alkyl silicone group, it is preferably an alkyl silicone having a molecular weight of 200 or more, more preferably a dimethyl silicone having a molecular weight of 500 or more. Further, in the case of an aromatic carbon group, an aromatic carbon group having 10 or more carbon atoms is preferable, and a group selected from cholesterol, cholestanol, phytosterol, phytostanol and derivatives thereof is more preferable.

Hydrophobic modified polyether urea of the general formula (2)
Tan is, for example, R¹-[(OR²)_k-OH]_mRepresented by
One or more polyether polyols and R³
-(NCO)_{h + 1}1 or 2 or more types of poly
Sociate and HO- (R^Four-O)_n-R^FiveOne kind represented by
Or by reacting with two or more kinds of polymonoalcohol
It can be obtained by In this case, in general formula (2)
R¹~ R^FiveIs R to be used ¹-[(OR²)_k-OH]_m, R³
-(NCO)_{h + 1}, HO- (R^Four-O)_n-R^FiveDetermined by
It The charging ratio of the three is not particularly limited, but
Derived from terpolyol and polyether monoalcohol
Hydroxyl group and isocyanate derived from polyisocyanate
The ratio of groups is NCO / OH = 0.8: 1 to 1.4: 1.
Is preferred.

The polyether polyol compound represented by R ¹ -[(O-R ² ) _k -OH] _m is a m-valent polyol containing alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin. It is possible by addition-polymerizing styrene oxide or the like.

Here, as the m-valent polyol, 2 to 8 are used.
Divalent alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol and neopentyl glycol; glycerin, trioxyisobutane, 1, 2,
3-butanetriol, 1,2,3-pentatriol, 2-methyl-1,2,3-propanetriol, 2
-Methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-
Propyl-3,4,5-heptanetriol, 2,4-
Trihydric alcohols such as dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane and trimethylolpropane; penta Erythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3
Tetrahydric alcohols such as 4,5-hexanetetrol; pentahydric alcohols such as adnit, arabite and xylit; hexahydric alcohols such as dipentaerythritol, sorbitol, mannite and idite; octahydric alcohols such as sucrose. Can be mentioned.

Further, an alkylene oxide to be added,
R ² is determined by styrene oxide and the like, and is particularly easily available, and in order to exert an excellent effect, alkylene oxide having 2 to 4 carbon atoms or styrene oxide is preferable.

The alkylene oxide, styrene oxide and the like to be added may be homopolymerized, two or more kinds of random polymerized or block polymerized. The addition method may be a normal method. The degree of polymerization k is 0 to 1,00.
0, preferably 1 to 500, more preferably 10
~ 50 is good. The ratio of ethylene group occupying the R ² is preferably preferably from 50 to 100 wt% of the total R ^2.

The molecular weight of R ¹ -[(O-R ² ) _k -OH] _m is preferably from 500 to 100,000, and 1.00
The thing of 0-50,000 is especially preferable.

The polyisocyanate represented by R ^3- (NCO) _{h + 1} is not particularly limited as long as it has two or more isocyanate groups in the molecule. Examples thereof include aliphatic diisocyanates, aromatic diisocyanates, alicyclic diisocyanates, biphenyl diisocyanates, phenylmethane diisocyanates, triisocyanates and tetraisocyanates.

Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate and 3-methoxy. Hexane diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate , Paraxylylene Diisocyanate, tetramethylxylylene diisocyanate, and the like.

Examples of aromatic diisocyanates include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate. , 4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate and the like.

Examples of the alicyclic diisocyanate include hydrogenated xylylene diisocyanate and isophorone diisocyanate. As the biphenyl diisocyanate, for example, biphenyl diisocyanate,
3,3'-dimethylbiphenyl diisocyanate, 3,
3'-dimethoxy biphenyl diisocyanate etc. are mentioned.

Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4'-diisocyanate, 2,2'-dimethyldiphenylmethane-4,
4'-diisocyanate, diphenyldimethylmethane-
4,4'-diisocyanate, 2,5,2 ', 5'-tetramethyldiphenylmethane-4,4'-diisocyanate, cyclohexylbis (4-isocyanatophenyl) methane, 3,3'-dimethoxydiphenylmethane-
4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, 4,
4'-diethoxydiphenylmethane-3,3'-diisocyanate, 2,2'-dimethyl-5,5'-dimethoxydiphenylmethane-4,4'-diisocyanate,
3,3'-dichlorodiphenyldimethylmethane-4,
4'-diisocyanate, benzophenone-3,3'-
Examples thereof include diisocyanate.

As the triisocyanate, for example, 1
-Methylbenzene-2,4,6-triisocyanate,
1,3,5-Trimethylbenzene-2,4,6-triisocyanate, 1,3,7-naphthalene triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate Isocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, triphenylmethane-4,4 ',
4 ''-triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4
-Isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenyl) thiophosphate, etc. are mentioned.

Further, it may be used as a dimer or trimer (isocyanurate bond) of these polyisocyanate compounds, or may be used as a biuret by reacting with an amine. Furthermore, a polyisocyanate having a urethane bond obtained by reacting a polyol with these polyisocyanate compounds can also be used. As the polyol, those having 2 to 8 valences are preferable, and the above-mentioned polyols are preferable. When trivalent or higher polyisocyanate is used as R ³ — (NCO) _{h + 1} , this polyisocyanate having a urethane bond is preferable.

The polyether monoalcohol represented by HO- (R ⁴ -O) _n -R ⁵ is finally composed of at least two hydrophobic groups separated by a hydrophilic chain portion in the hydrophobically modified polyether urethane structure. In particular, it is not particularly limited as long as it is a monohydric alcohol polyether.

Such compounds can be obtained, for example, by addition-polymerizing ethylene oxide, propylene oxide, butylene oxide, alkylene oxide such as epichlorohydrin, styrene oxide and the like with monohydric alcohol.

The residue of the monohydric alcohol, R ⁵ , is not particularly limited as long as it is a group which acts as a hydrophobic group in the final hydrophobically modified polyether urethane structure, and for example,
Examples thereof include alkyl groups, alkenyl groups, alkylaryl groups, cycloalkyl groups, cycloalkenyl groups, hydrocarbons such as aromatic hydrocarbons, fluorocarbon groups, and alkyl silicone groups.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, isostearyl, icosyl, docosyl, tetracosyl. , Triacontyl, 2-octyldodecyl, 2-dodecyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl-branched-isostearyl and the like.

Examples of the alkenyl group include vinyl,
Allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like can be mentioned.

As the alkylaryl group, phenyl,
Toluyl, xylyl, cumenyl, mesityl, benzyl,
Phenethyl, styryl, cinnamil, benzhydryl,
Trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, α
Examples include -naphthyl and β-naphthyl groups.

Examples of the cycloalkyl group and cycloalkenyl group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcyclopentenyl. Examples thereof include a heptenyl group.

Examples of aromatic hydrocarbons include cholesterol, cholestanol, phytosterols, phytostanols and their derivatives. Aromatic hydrocarbons not only have hydrophobic interactions in water solvents, but also π
It is suitable as a material for hydrophobically modified polyether urethane because it has a property of extremely strong association due to -π interaction.

Examples of the fluorocarbon group include heptadecafluoro-n-decanol and the like.

The alkyl silicone group is an alcohol residue of alkyl siloxane having one hydroxyl group in the structure. In addition, a part of the alkyl group may be replaced with a fluorocarbon group. The hydroxyl group-containing alkyl siloxane may be a commercially available product, and examples of commercially available products include Silaplane FM0411 and FM042.
1, the same FM0425 (above, manufactured by Chisso Corporation) and the like. The hydroxyl group-containing alkyl silicone preferably has a molecular weight of 200 or more, more preferably 500 or more.

In the polyether monoalcohol, the alkylene oxide, styrene oxide, etc. to be added may be homopolymerization, random polymerization of two or more kinds, or block polymerization. The method of addition may be a conventional method. The degree of polymerization n is 0 to 1,000, preferably 1 to 200, more preferably 10 to 50. The proportion of ethylene groups in R ⁴ is preferably all R ⁴
50 to 100% by mass, and more preferably 65 to 10% by mass.
When it is 0% by mass, a hydrophobically modified polyether urethane preferable for the purpose of the present invention is obtained.

In the production of the above-mentioned hydrophobically modified polyether urethane of the general formula (2), it can be obtained by a usual reaction between a polyether and an isocyanate. Moreover, it can be manufactured according to the method of Japanese Patent Publication No. 9-71766. For example, it can be obtained by heating a polyether polyol, a polyisocyanate, and a polymonoalcohol at 80 to 90 ° C. for 1 to 3 hours to cause a reaction.

It should be noted that, for example, R ¹ -[(O-R ² ) _k -O
H] _m represented by the polyether polyol (a) and the polyisocyanate represented by R ^3- (NCO) _{h + 1} (b)
And the polyether monoalcohol (c) represented by HO— (R ⁴ —O) _n —R ⁵ are reacted, a compound other than the compound having the structure of the general formula (2) is also by-produced. Sometimes. For example, when diisocyanate is used, a c-b-a-b-c-type compound represented by the general formula (2) is produced as a main product, but in addition, c-b-c-type and c- b
A compound such as-(ab) _x -abc type may be by-produced. In this case, the compound of the general formula (2) type can be used in the present invention in the form of a mixture containing the compound of the general formula (2) type without separating.

Further, in the hydrophobically modified polyether urethane according to the present invention, urea, ether, ester, amide bond or the like may be further formed in the polymer.

The production examples of the component (B) hydrophobically modified polyether urethane used in the present invention will be described below.

[Production Example 17: Hydrophobic modified polyether urethane (A)] A hydrophobic modified polyether urethane was produced using the raw materials shown in Table 1. That is, polyethylene glycol (PEG) (number average molecular weight of about 11,000) (R ¹ -[(O-R ² ) _k- ) was placed in a 1,000-mL four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer. OH] _m ) (550 parts), 2-dodecyl dodecyl alcohol 20 mol ethylene oxide (EO) adduct (HO- (R ⁴
-O) corresponding to _n -R ⁵⁾ was charged 198 parts, followed by 80
Hexamethylene diisocyanate (HMD
I) (corresponding to R ^3- (NCO) _{h + 1} ) (29.6 parts) was added, and the mixture was reacted at 80 to 100 ° C. for 2 hours under a nitrogen stream, and it was confirmed that the isocyanate content was 0%. A solid reaction product was obtained.

[Production Examples 18 to 23; Hydrophobic Modified Polyether Urethanes (B) to (G)] In the same manner as in Production Example 17,
Hydrophobic modified polyether urethanes (B) to (G) shown in Table 1 were prepared.

[0231]

[Table 1]

* 1: Silaplane FM0411 (molecular weight 1,000) (Chisso) * 2: Silaplane FM0421 (molecular weight 5,000)
0) (Chisso)

As the hydrophobically modified polyether urethane of the present invention, commercially available products can be used, and examples of the commercially available products include Adecanol UH140S and UH-4.
20, same UH-438, same UH-750, same GT-70
0 (above, Asahi Denka Kogyo), Serad-FX110
0, FX1010, FX1035 (above, manufactured by HULS), Rheolate205, 208, 204,
225, 278, 244 (Rheox), DW1206F, 1206J, 1206G
(Above, manufactured by Rohm & Haas), Dapral-T
212 (manufactured by Akzo), Borchigel-LW4
4, L75N (above, manufactured by Borchers) and the like.

The content of the hydrophobically modified polyether urethane in the present invention is preferably 0.1 to 10.0% by mass. If the content is less than 0.1% by mass, the effect of addition may not be observed, and if it exceeds 10% by mass, the viscosity becomes too high, which causes inconvenience in handling during production. In some cases, work efficiency may be reduced, inconvenience may occur when the container is taken out from the container during actual use, and the spread during application to the skin or hair may be poor.

The cosmetic composition of the present invention may contain other components usually used in cosmetics, pharmaceuticals and the like, in addition to the components described above, within the range not impairing the effects of the present invention.
For example, oil components, powder components, surfactants, moisturizers, water-soluble polymers, thickeners, film agents, ultraviolet absorbers, sequestering agents, sugars, amino acids, organic amines, pH adjusters,
Skin nutrients, vitamins, antioxidants, fragrances, water and the like can be mentioned.

Examples of oils include beeswax, candelilla wax, carnauba wax, lanolin and its derivatives,
Wax such as liquid lanolin, liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalane, petrolatum, microcrystalline wax, wax, hydrocarbons, myristic acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid Higher fatty acids such as cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, cetostearyl alcohol and other higher alcohols, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristin Acid myristyl, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, isocetyl stearate, iso Monoester oil such as stearic acid isocetyl,

Di-2-ethylhexyl succinate, neopentyl glycol di2-ethylhexanoate, neopentyl glycol dicaprate, di2-heptylundecyl adipate, di2-ethylhexyl sebacate, diisostearyl malate, diisostearate. Diester oils such as polyglyceryl, trimethylolpropane triisostearate, trimethylolpropane tri-2-ethylhexanoate, polyglyceryl triisostearate, triester oils such as glyceryl tri-2-ethylhexanoate,
Tetraester oil such as pentaerythritate tetra-2-ethylhexanoate, polyglyceryl polyisostearate, dimethylpolysiloxane, chain polysiloxane such as methylphenylpolysiloxane, diphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane , Silicones such as cyclic polysiloxanes such as dodecamethylcyclohexanesiloxane, amino-modified polysiloxanes, polyether-modified polysiloxanes, alkyl-modified polysiloxanes, modified polysiloxanes such as fluorine-modified polysiloxanes, polyalkylene glycol polyethers and their carboxylic acids Examples thereof include oligoester compounds and terpene hydrocarbons.

Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene cholesteryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl fatty acid ester, polyoxyethylene hydrogenated castor oil, Nonionic activators such as polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyether modified silicone, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, cetyl pyridinium chloride, etc. Cationic activator, sodium cetyl sulfate, sodium polyoxyethylene lauryl ether sulfate Umm, sodium lauryl sulfate,
Examples thereof include anionic activators such as potassium coconut oil fatty acid and sodium coconut oil fatty acid methyl taurine.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin, sorbitol, polyethylene glycol and the like.

Examples of the humectant include hyaluronate, chondroitin sulfate, pyrrolidonecarboxylate and the like.

Examples of the polymers include acrylic resins, silicone resins, polyvinylpyrrolidone polymers and the like.

Examples of the protein or protein hydrolyzate include soybean protein, gelatin, collagen, silk fibroin, elastin and the like.

Examples of antiseptics include ethylparaben, butylparaben and the like.

Examples of the activator include various amino acids,
Examples include biotin and pantothenic acid derivatives.

Examples of antiseborrheic agents include γ-oryzanol, sodium dextran sulfate, vitamin E and the like.

Examples of the diluent include ethanol, isopropanol, tetrachlorodifluoroethane and the like.

Examples of the thickener include carboxyvinyl polymer and the like.

The dosage form of the present invention is arbitrary and may be, for example, a solubilizing system, an emulsifying system, an oil-water two-layer system, or the like.

In the present invention, the amphoteric urethane resin and the hydrophobically modified polyether urethane can be blended as components of the cosmetic composition to obtain a cosmetic composition by a conventional method. According to the present invention, a cosmetic composition having excellent stability over time such as viscosity stability can be obtained, and in terms of use characteristics,
Cosmetics that have no sticky feel on the hands when used, and have a good feeling of use when applied to hair, and a good feeling of familiarity when applied to skin. A cosmetic composition which is excellent in functional properties, such as a composition for obtaining a hair cosmetic having a natural elastic hairstyle and a skin external preparation excellent in firmness and elasticity of the skin. Can be obtained.

[0250]

EXAMPLES The present invention will be specifically described with reference to the following examples. The blending amount is% by mass. Further, “%” means “mass%” unless otherwise specified. Prior to the description of the examples, the evaluation method used in the present invention will be described.

(1) Viscosity stability Samples after the prepared cosmetic composition was filled in a 50 ml transparent glass tube and stored in respective thermostats at 50 ° C, 37 ° C, 25 ° C and 0 ° C, and after 6 months passed Was observed (viscosity). For the viscosity, an apparent viscosity at 25 ° C. and 100 s ⁻¹ was obtained by using a cone plate or a double cylinder type viscometer. The evaluation was performed as follows.

(Evaluation Criteria) A: The change in viscosity of each temperature sample is the initial viscosity (25 ° C.).
It is 10% or less compared with. B: The viscosity change of each temperature sample is the initial viscosity (25 ° C)
Is more than 10% and 20% or less. C: The viscosity change of each temperature sample is the initial viscosity (25 ° C)
Is more than 20% and 30% or less. D: Change in viscosity of each temperature sample is the initial viscosity (25 ° C)
Is over 30% compared to.

(2) Transparency Each test product was measured by measuring the transmittance at 900 nm with an ultraviolet absorption measuring device, and evaluated according to the following evaluation criteria. ◯: transmittance of 80% or more Δ: transmittance of 50% or more and less than 80% ×: transmittance of less than 50%

(3) Test of Use Characteristics For each test product, a panel of 30 men and women and 60 people in total judged the feeling of use. Regarding the feeling of use, items such as "feeling of stickiness on the hands", "ease of application to the hair during application" in the case of hair cosmetics, and "ease of conforming to the skin" in the case of external preparation for skin evaluated. Judgment was made based on the number of panels that felt these feelings of use, and the feeling of use of each test product was determined according to the following criteria.

(Evaluation criteria for stickiness of hands) ◎: More than 45 people felt that their hands were not sticky ○: 30 to 44 people felt that the hands were not sticky Δ: 16 to 29 people felt that the hands were not sticky ×: 15 people or less felt the stickiness of the hand

(Evaluation Criteria for Ease of Spreading on Hair at Application) ◎: 45 or more people who felt easy to spread ◯: 30 to 44 people who felt easy to spread Δ: Extend 16 to 29 people felt easy: 15 or less felt easy to spread

(Evaluation Criteria for Familiarity with Skin) ◎: More than 45 people felt that they were familiar with the skin ○: 30 to 44 people felt that they were familiar with the skin Δ: 16 to 29 people felt familiar with the skin ×: 15 or less people felt familiar with the skin

(4) Functional characteristic test For each test product, a cosmetic function was evaluated by a use test by a panel of 30 men and women and a total of 60 people. In the case of a hair cosmetic, it is “persistence of hairstyle”, and in the case of an external preparation for skin, it is “skin firmness and elasticity”. The functional characteristics of each test product were judged according to the following criteria, based on the number of panel members who felt these functions.

(Evaluation Criteria for Holding Hairstyle) ◎: 4 hours after application, 4 people felt holding hairstyle
5 people or more ○: 6 hours after application, 3 people felt that they had a hairstyle
0 to 44 people △: 6 hours after application, 1 person felt that he had a hairstyle
6 to 29 people x: 1 person who felt that he / she had a hairstyle 6 hours after application
5 or less

(Evaluation criteria for firmness and elasticity of skin) ◎: More than 45 people felt firmness and elasticity of skin ○: 30 to 44 people felt the elasticity and firmness of the skin Δ: 16 to 29 people felt the elasticity and firmness of the skin ×: 15 people or less felt the elasticity and stiffness of the skin

(Examples 1 to 20, Comparative Examples 1 to 5) Table 2
A cosmetic composition having the composition shown in 4 was prepared by a conventional method. These cosmetic compositions were gel-like. The evaluation results are shown in the same Tables 2-4.

[0262]

[Table 2]

(* 1) Hibiswako 104 (manufactured by Wako Pure Chemical Industries, Ltd.)

[0264]

[Table 3]

[0265]

[Table 4]

As is clear from Tables 2-4, Examples 1-
The cosmetic composition of 20 shows little change in viscosity over time,
It has excellent viscosity stability. It has excellent usability in terms of stickiness to the hands, easy spreadability on hair, and easy adaptability to the skin. In terms of functionality, it has long-lasting hairstyle and firmness and elasticity. It can be seen that it is an excellent transparent gel-like cosmetic composition having excellent properties.

On the other hand, as shown in Comparative Examples in Table 2, Comparative Examples 1 to 3 in which an amphoteric urethane resin outside the scope of the present invention was mixed in place of the amphoteric urethane resin of the present invention, the amphoteric urethane resin of the present invention Comparative Example 4 in which polyvinylpyrrolidone has been used in place of the conventional, and Comparative Example 5 in which polyvinylpyrrolidone and a carboxyvinyl polymer have been added instead of the combination of the amphoteric urethane resin and the hydrophobically modified polyether urethane are both It is understood that the effect of the present invention cannot be exhibited.

The cosmetic compositions of the present invention having various formulations were prepared by a conventional method, and the examples will be shown below. In addition, when the above-mentioned effect test was performed on these, all were excellent in viscosity stability, use characteristics, and functional characteristics. The cosmetic compositions of Examples 21 to 28 were all excellent in transparency.

[0269] [Example 21] Hair styling gel       Ingredient amount (% by mass) (1) Amphoteric urethane resin (C) (Production Example 3) 5.0                           (20 mass% aqueous dispersion) (2) Glycerin 2.5 (3) 1,3-butylene glycol 2.5 (4) Polyoxyethylene hydrogenated castor oil (40EO) 0.5 (5) Dimethylpolysiloxane (1,000 mPa · s) 1.0 (6) Sodium hydroxide (adjusted to pH 7.5) (7) Ethanol 20.0 (8) Polyoxyethylene octyldodecyl ether 0.1 (9) Perfume 0.1 (10) Trisodium edetate 0.03 (11) Deionized water residual (12) Hydrophobic modified polyether urethane (B) (Production Example 18) 1.0

[0270] [Example 22] Hair styling gel       Ingredient amount (% by mass) (1) Amphoteric urethane resin (H) (Production Example 7) 6.0                           (20 mass% aqueous dispersion) (2) Amphoteric urethane resin (L) (Production Example 11) 6.0                           (20 mass% aqueous dispersion) (3) Glycerin 2.5 (4) 1,3-butylene glycol 2.5 (5) Polyoxyethylene hydrogenated castor oil (40EO) 0.5 (6) Dimethylpolysiloxane (1,000 mPa · s) 1.0 (7) Sodium hydroxide (adjusted to pH 7.5) (8) Ethanol 20.0 (9) Polyoxyethylene octyldodecyl ether 0.1 (10) Perfume 0.1 (11) Trisodium edetate 0.03 (12) Residual ion-exchanged water (13) Hydrophobic modified polyether urethane (D) (Production Example 20) 3.0

[0271] [Example 23] Hair styling gel       Ingredient amount (% by mass) (1) Amphoteric urethane resin (I) (Production Example 8) 8.0                           (20 mass% aqueous dispersion) (2) Amphoteric urethane resin (J) (Production Example 9) 2.0                           (20 mass% aqueous dispersion) (3) Glycerin 2.5 (4) 1,3-butylene glycol 2.5 (5) Polyoxyethylene hydrogenated castor oil (40EO) 0.5 (6) Dimethylpolysiloxane (1,000 mPa · s) 1.0 (7) Sodium hydroxide (adjusted to pH 7.5) (8) Ethanol 20.0 (9) Polyoxyethylene octyldodecyl ether 0.1 (10) Perfume 0.1 (11) Trisodium edetate 0.03 (12) Residual ion-exchanged water (13) Hydrophobic modified polyether urethane (F) (Production Example 22) 4.5 (14) Hydrophobic modified polyether urethane (Note 1) 0.5   (Note 1) ADEKA NOL UH-420 (made by Asahi Denka Co., Ltd.)

[0272] [Example 24] Hair styling gel       Ingredient amount (% by mass) (1) Amphoteric urethane resin (K) (Production Example 10) 2.5                           (20 mass% aqueous dispersion) (2) Glycerin 2.5 (3) 1,3-butylene glycol 2.5 (4) Polyoxyethylene hydrogenated castor oil (40EO) 0.5 (5) Dimethylpolysiloxane (1,000 mPa · s) 1.0 (6) Sodium hydroxide (adjusted to pH 7.5) (7) Ethanol 20.0 (8) Polyoxyethylene octyldodecyl ether 0.1 (9) Perfume 0.1 (10) Trisodium edetate 0.03 (11) Deionized water residual (12) Hydrophobic modified polyether urethane (C) (Production Example 19) 1.5 (13) Hydrophobic modified polyether urethane (Note 1) 1.5   (Note 1) ADEKA NOL UH-750 (made by Asahi Denka Co., Ltd.)

[0273] [Example 25] Hair styling gel       Ingredient amount (% by mass) (1) Amphoteric urethane resin (P) (Production Example 15) 12.0                           (25% by mass aqueous dispersion) (2) Glycerin 2.5 (3) 1,3-butylene glycol 2.5 (4) Polyoxyethylene hydrogenated castor oil (40EO) 0.5 (5) Dimethylpolysiloxane (1,000 mPa · s) 1.0 (6) Sodium hydroxide (adjusted to pH 7.5) (7) Ethanol 20.0 (8) Polyoxyethylene octyldodecyl ether 0.1 (9) Perfume 0.1 (10) Trisodium edetate 0.03 (11) Deionized water residual (12) Hydrophobic modified polyether urethane (E) (Production Example 21) 1.0

[0274] [Example 26] Hair styling gel       Ingredient amount (% by mass) (1) Amphoteric urethane resin (M) (Production Example 12) 6.0                           (20 mass% aqueous dispersion) (2) Amphoteric urethane resin (Q) (Production Example 16) 6.0                           (20 mass% aqueous dispersion) (3) Glycerin 2.5 (4) 1,3-butylene glycol 2.5 (5) Polyoxyethylene hydrogenated castor oil (40EO) 0.5 (6) Dimethylpolysiloxane (1,000 mPa · s) 1.0 (7) Sodium hydroxide (adjusted to pH 7.5) (8) Ethanol 20.0 (9) Polyoxyethylene octyldodecyl ether 0.1 (10) Perfume 0.1 (11) Trisodium edetate 0.03 (12) Residual ion-exchanged water (13) Hydrophobic modified polyether urethane (Note 1) 0.5   (Note 1) ADEKA NOL GT-700 (made by Asahi Denka Co., Ltd.)

[0275] [Example 27] Whitening skin cream       Ingredient amount (% by mass) (1) Cetyl alcohol 5.0 (2) Stearic acid 3.0 (3) Squalane 10.0 (4) Glycerol tri-2-ethylhexanoate 7.0 (5) Dipropylene glycol 5.0 (6) Glycerin 5.0 (7) Propylene glycol monostearate 1.5 (8) POE (20) cetyl alcohol ether 1.5 (9) Triethanolamine Suitable amount (10) Ascorbic acid glucoside 2.0 (11) Potassium 4-methoxysalicylate 3.0 (12) Hydrophobic modified polyether urethane (G) (Production Example 23) 1.0 (13) Preservative suitable amount (14) Antioxidant proper amount (15) Perfume proper amount (16) Residual ion-exchanged water (17) Amphoteric urethane resin (D) (Production Example 4) 2.5                             (20 mass% aqueous dispersion) (18) Amphoteric urethane resin (N) (Production Example 13) 2.5                             (20 mass% aqueous dispersion)

[0276] [Example 28] Whitening skin cream       Ingredient amount (% by mass) (1) Cetyl alcohol 5.0 (2) Stearic acid 3.0 (3) Squalane 10.0 (4) Glycerol tri-2-ethylhexanoate 7.0 (5) Dipropylene glycol 5.0 (6) Glycerin 5.0 (7) Propylene glycol monostearate 1.5 (8) POE (20) cetyl alcohol ether 1.5 (9) Triethanolamine Suitable amount (10) Ascorbic acid glucoside 2.0 (11) Potassium 4-methoxysalicylate 3.0 (12) Hydrophobic modified polyether urethane (Note 1) 2.0 (13) Preservative suitable amount (14) Antioxidant proper amount (15) Perfume proper amount (16) Residual ion-exchanged water (17) Amphoteric urethane resin (G) (Production Example 6) 5.0                             (20 mass% aqueous dispersion)   (Note 1) ADEKA NOL GT-700 (made by Asahi Denka Co., Ltd.)

[0277]

As described above in detail, according to the present invention,
A cosmetic composition having good viscosity stability and excellent use characteristics and functional characteristics can be obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Katsunori Yoshida             2-2-1 Hayabuchi, Tsuzuki Ward, Yokohama City, Kanagawa Prefecture             Shiseido Research Center (Shin-Yokohama)             Within F term (reference) 4C083 AB032 AC022 AC072 AC102                       AC122 AC182 AC242 AC392                       AC422 AC432 AC472 AC482                       AC532 AC542 AD042 AD071                       AD072 AD152 AD161 AD162                       AD642 CC01 CC05 CC31                       CC32 DD01 DD41 EE16 EE28

Claims (16)

[Claims] 1. A cosmetic composition comprising the following components (A) and (B): (A) The following general formula (1): [In the formula, R ¹ represents an alkyl group having 1 to 24 carbon atoms. R ²
To R ⁴ are each independently —C _n H _2n — (where n is 1 to
Represents an integer of 3. ) Represents. R ⁵ is -C _n H _2n - (where, n is an integer of 3-5.) Represents the. Also, R ⁶ ~
R ^9's each independently represent an alkyl group having 1 to 20 carbon atoms. R ¹⁰ represents a methyl group or an ethyl group. m is 1-2
Represents an integer of 00. ] A polysiloxane chain-containing ampholytic urethane resin having a structural unit derived from the compound represented by the above formula and / or a polysiloxane compound-carrying ampholytic urethane resin. (B) The following general formula (2): [In the formula, R ¹ , R ² and R ⁴ each independently represent a hydrocarbon group, R ³ represents a hydrocarbon group which may have a urethane bond, and R ⁵ represents a straight chain, a branched chain or 2 Hydrocarbon groups,
It represents a fluorocarbon group, an alkyl silicone group, or an aromatic hydrocarbon group, m is an integer of 2 or more, h is an integer of 1 or more, and k and n are each independently in the range of 0 to 1,000. Which is an integer]. 2. The makeup according to claim 1, wherein the polysiloxane chain-containing amphoteric urethane resin and / or the polysiloxane compound-carrying amphoteric urethane resin is an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule. Composition. 3. The cosmetic according to claim 1, wherein the amphoteric urethane resin constituting the polysiloxane compound-carrying amphoteric urethane resin is an amphoteric urethane resin produced by reacting at least the following compounds (A) to (D). Composition. (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary A compound having at least one selected from an amino group and a secondary amino group, and a tertiary amino group 4. The polysiloxane compound-carrying amphoteric urethane resin uses at least the following compounds (A) to (D) and (S), wherein the compounds (A), (B) and (C) are used as isocyanates. The method includes a first step of producing an isocyanate group-containing prepolymer by reacting under an excess of groups, and a second step of reacting the isocyanate group-containing prepolymer with the compound (D), and the first step and the second step. The cosmetic composition according to claim 1, which is an amphoteric urethane resin produced by allowing the compound (S) to exist in at least one of the two steps. (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary Compound (S) polysiloxane compound having at least one selected from an amino group and a secondary amino group, and a tertiary amino group 5. The polysiloxane compound-carrying amphoteric urethane resin uses at least the following compounds (A) to (D) and (S), wherein the compounds (A), (B) and (D) are replaced with isocyanates: The method comprises a first step of producing an isocyanate group-containing prepolymer by reacting under a group excess condition, and a second step of reacting the isocyanate group-containing prepolymer with the compound (C), and The cosmetic composition according to claim 1, which is an amphoteric urethane resin produced by allowing the compound (S) to exist in at least one of the two steps. (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary Compound (S) polysiloxane compound having at least one selected from an amino group and a secondary amino group, and a tertiary amino group 6. The makeup according to claim 1, wherein the amphoteric urethane resin constituting the polysiloxane compound-carrying amphoteric urethane resin is an amphoteric urethane resin produced by reacting at least the following compounds (A) to (E). Composition. (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary At least one selected from an amino group and a secondary amino group, and a compound (E) having a tertiary amino group, at least one selected from a hydroxyl group, a primary amino group, and a secondary amino group. A compound having a structural unit represented by the following general formula (3): (In the formula, p represents an integer of 1 to 500, and q represents an integer of 0 to 400.) 7. The polysiloxane compound-carrying amphoteric urethane resin uses at least the following compounds (A) to (E) and (S), and comprises (A), (B), (C) and (E): Compound, the first step of producing an isocyanate group-containing prepolymer by reacting under conditions of excess isocyanate group, as well as the isocyanate group-containing prepolymer,
The cosmetic according to claim 1, which comprises a second step of reacting with the compound of (D), and is an amphoteric urethane resin produced in the presence of the compound of (S) in at least one of the first step and the second step. Composition. (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary At least one selected from an amino group and a secondary amino group, and a compound (E) having a tertiary amino group, at least one selected from a hydroxyl group, a primary amino group, and a secondary amino group. A compound having a structural unit represented by the following general formula (3): (In the formula, p represents an integer of 1 to 500 and q represents an integer of 0 to 400.) (S) Polysiloxane compound 8. The polysiloxane compound-carrying amphoteric urethane resin uses at least the following compounds (A) to (E) and (S), and (A), (B), (D) and (E) Compound, the first step of producing an isocyanate group-containing prepolymer by reacting under conditions of excess isocyanate group, as well as the isocyanate group-containing prepolymer,
The cosmetic according to claim 1, which is an amphoteric urethane resin produced in the presence of the compound (S) in at least one of the first step and the second step, which comprises a second step of reacting with the compound (C). Composition. (A) Polyol compound (B) Polyisocyanate compound (C) Compound (D) hydroxyl group having at least one selected from hydroxyl group, primary amino group and secondary amino group, and carboxyl group, primary At least one selected from an amino group and a secondary amino group, and a compound (E) having a tertiary amino group, at least one selected from a hydroxyl group, a primary amino group, and a secondary amino group. A compound having a structural unit represented by the following general formula (3): (In the formula, p represents an integer of 1 to 500 and q represents an integer of 0 to 400.) (S) Polysiloxane compound 9. The polysiloxane compound constituting the polysiloxane compound-supporting ampholytic urethane resin is at least one selected from dimethylpolysiloxane, polyether-modified silicone, cyclic silicone, phenyl-modified silicone, alkyl-modified silicone and alkoxy-modified silicone. The cosmetic composition according to any one of claims 1 to 8, wherein 10. The hydrophobically modified polyether urethane of the general formula (2), wherein R ² and R ⁴ are each independently an alkylene group having 2 to 4 carbon atoms or a phenylethylene group. The cosmetic composition according to any one of 1 to 9. 11. The hydrophobically modified polyether urethane of the general formula (2), wherein R ³ is a residue of a polyisocyanate represented by R ^3- (NCO) _{h +} 1. 11. The cosmetic composition according to any one of items 1 to 10. 12. A polyisocyanate represented by R ³ — (NCO) _{h + 1} having a urethane bond obtained by reacting a divalent to octavalent polyol with a divalent to tetravalent polyisocyanate. The cosmetic composition according to claim 11, wherein 13. The hydrophobic modified polyether urethane of the general formula (2), wherein R ¹ is a residue of a polyol represented by R ^1- (OH) _m.
The cosmetic composition according to any one of 2. 14. The hydrophobically modified polyether urethane of the general formula (2), wherein R ⁵ is a straight chain, branched chain or secondary hydrocarbon group having 8 to 36 carbon atoms or a straight chain having 4 to 24 carbon atoms,
The makeup according to any one of claims 1 to 13, which is a branched or secondary hydrocarbon group or a linear, branched or secondary fluorocarbon group having 4 to 24 carbon atoms. Composition. 15. The hydrophobically modified polyether urethane represented by the general formula (2) is represented by R ¹ -[(OR ² ) _k —OH] _m 1.
Or two or more polyether polyols and R ^3- (N
CO) _{h + 1} represented by 1 or 2 or more polyisocyanates, and HO- (R ⁴ -O) _n -R ⁵ represented by 1 or 2
The cosmetic composition according to any one of claims 1 to 9, which is a reaction product of one or more polyether monoalcohols. 16. The cosmetic composition according to claim 1, wherein the cosmetic composition is a hair cosmetic composition.