JP6779563B2 - Moisturizer polymer - Google Patents

Description

The present invention relates to polymers for moisturizers. More specifically, the present invention relates to a moisturizer polymer useful for skin cosmetics, external preparations for skin, hair cosmetics and the like.

A moisturizer is blended in cosmetics to prevent the skin from drying out, and as conventional moisturizers, polyhydric alcohols such as glycerin and 1,3-butanediol, sodium hyaluronate and the like are known.
In addition, a film-forming polymer-type moisturizer that suppresses evaporation of water by forming a film on the skin surface of the polymer has also been developed. For example, Patent Document 1 describes a specific unit structure containing an amide group. Hydrophilic polymers having the above are disclosed. Further, Patent Document 2 describes a 50% by mass aqueous solution of the polymer having a specific structural unit, having a weight average molecular weight (Mw) of 5,000 to 150,000, and having a temperature of 30 ° C. and a relative humidity of 60%. A water-soluble (meth) acrylamide polymer for cosmetics or skin external preparations having a mass reduction rate of 25% by mass or less after being left for 6 hours is disclosed. Further, Patent Document 3 describes 0.001 to 0 as an amphipathic polymer compound composed of a copolymer containing (A) vinylpyrrolidone as a constituent unit and (B) biwa leaf extract as an extract pure content (B'). When 0.02% by mass and (C) soybean extract are contained and the extract pure content (C') of (C) soybean extract is taken, it is represented by (A) / [(B') + (C')]. The cosmetics having a mass ratio of (A), (B') and (C') of 1 to 1000 are disclosed.

Japanese Unexamined Patent Publication No. 2011-213903 Japanese Unexamined Patent Publication No. 2010-196048 International Publication No. 13/054760

As mentioned above, various moisturizers have been developed. However, conventional moisturizers such as polyhydric alcohols such as glycerin and 1,3-butanediol have insufficient hygroscopicity under low humidity, cannot sufficiently maintain moisturizing property, and further have hygroscopicity under high humidity. There was a problem that stickiness occurred because the temperature was too high. Further, Na hyaluronate is very expensive, and there is a problem that the blending amount is limited because the whole system is thickened due to the ultrahigh molecular weight.
Further, the moisturizers described in Patent Documents 1 and 2 have poor moisturizing properties, and there is room for improvement in moisturizing properties, especially under low humidity. In addition, the moisturizer described in Patent Document 3 maintains a moisturizing effect by using a loquat leaf extract or soybean extract in combination with a polymer-type moisturizer.

The present invention has been made in view of the above situation, and exhibits an excellent moisturizing effect even when used alone as a moisturizer, and is particularly excellent in maintaining moisturizing properties even in low humidity, and is inexpensive, and is a cosmetic product. It is an object of the present invention to provide a compound having less limitation on the amount to be blended with the above.

The present inventor has investigated various compounds having excellent moisturizing performance, and as a result, a polymer having a structural unit derived from an unsaturated monomer having a lactam structure and a structural unit derived from an unsaturated monomer having a specific functional group. However, even when no other moisturizing component is added, it exhibits excellent moisturizing performance by itself, is also excellent in maintaining moisturizing properties under low humidity, and this polymer can be produced at a lower cost than Na hyaluronate. We have found that, and have come up with the idea that the above problems can be solved brilliantly, and have arrived at the present invention.

That is, in the present invention, the structural unit (a) derived from the unsaturated monomer (A) having a lactam structure, the aryl group, the hydroxyl group, the ether group and the following formula (1);

(In the formula, R ¹ is a hydrogen atom, a monovalent metal atom, a divalent metal atom, a trivalent metal atom, a quaternary ammonium base, or a hydroxyl group, an alkoxy group, or a (poly) oxyalkylene as a substituent. A group represented by a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of a group, an oxo group-containing group, a halogen atom, an epoxy group and a carbonyl group). A polymer for a moisturizer having a structural unit (b) derived from an unsaturated monomer (B) having at least one group selected from the group consisting of.
The present invention will be described in detail below.
It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The polymer for a moisturizer of the present invention (hereinafter, also simply referred to as a polymer) has a structural unit (a) derived from an unsaturated monomer (A) having a lactam structure, an aryl group, a hydroxyl group, an ether group and the above formula. It has a structural unit (b) derived from an unsaturated monomer (B) having at least one group selected from the group consisting of the groups represented by (1). Since the polymer of the present invention has the above-mentioned structure, it exhibits excellent moisturizing performance by itself and is also excellent in maintaining moisturizing property under low humidity. Further, since the polymer of the present invention has an excellent balance between hydrophilicity and lipophilicity, it has low hygroscopicity under high humidity and can suppress stickiness under high humidity when used in cosmetics and the like. ..

The unsaturated monomer (A) having a lactam structure is a monomer having a lactam ring and an ethylenically unsaturated hydrocarbon group, and has the following formula (2);

(In the formula, R ² , R ³ , R ⁴ , and R ⁵ represent the same or different hydrogen atoms or alkyl groups having 1 to 10 carbon atoms or groups represented by the formula (1). X represents 0. It represents an integer of ~ 5. y represents an integer of 1 to 3).) It is preferable that the structure is represented by.
The number of carbon atoms of the alkyl group in R ^{2 to} R ⁵ is preferably 1 to 5, and more preferably 1 to 3. The alkyl group is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
R ² and R ³ are preferably hydrogen atoms. R ⁴ is preferably a hydrogen atom or a group represented by the above formula (1). When R ⁴ is a group represented by the formula (1), R ¹ in the group represented by the formula (1) is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. .. R ⁵ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
x is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and most preferably 0.
The y is preferably 1 or 2, and more preferably 1.

Examples of the compound represented by the above formula (2) include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, 1- (2-propenyl) -2-pyrrolidone, and the like. The following formula (3);

(In the formula, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) Examples thereof include compounds represented by 1 type or 2 or more types. As the unsaturated monomer having a lactam structure, an unsaturated monomer having a pyrrolidone ring is preferable, and N-vinylpyrrolidone is more preferable.

The unsaturated monomer (B) having at least one group selected from the group consisting of the above aryl group, hydroxyl group, ether group and the group represented by the above formula (1) contains at least these functional groups. It suffices to have one kind, and may have two or more kinds.

The unsaturated monomer having an aryl group is a monomer having an aryl group and an ethylenically unsaturated hydrocarbon group, and is not particularly limited as long as it has these, and is substituted with other than the aryl group. It may have a group. Examples of other substituents include alkyl groups having 1 to 10 carbon atoms such as methyl group and ethyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and carbonyl group such as aldehyde group. ..
Examples of the unsaturated monomer having an aryl group include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, tert-butylstyrene, chlorostyrene and the like.
Styrene is preferable as the unsaturated monomer having an aryl group.
When the polymer of the present invention has a structural unit derived from an unsaturated monomer having an aryl group as the structural unit (b), the lipophilicity of the polymer is improved, and the polymer is easily retained on the lipophilic skin surface. The moisturizing effect on the skin surface is further improved.

The unsaturated monomer having a hydroxyl group is a monomer having a hydroxyl group (hydroxyl group) and an ethylenically unsaturated hydrocarbon group, and is not particularly limited as long as it has these, other than the hydroxyl group. It may have other substituents. The other substituent is not particularly limited, but in addition to the above-mentioned alkyl group having 1 to 10 carbon atoms, halogen atom and carbonyl group, an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an oxyethylene group. (Poly) oxyalkylene group having 1 to 3 carbon atoms and 1 to 100 repetitions; an oxo group-containing group such as a sulfonic acid group and a phosphoric acid group; a cyclic group having 2 to 8 carbon atoms. Examples include ether-containing groups.
Examples of the unsaturated monomer having a hydroxyl group include unsaturated alcohols such as vinyl alcohol, allyl alcohol and isoprenyl alcohol; and hydroxyl group-containing unsaturated carboxylic acids such as α-hydroxyacrylic acid; 2-hydroxyethyl (meth). Hydroxy group-containing (meth) acrylates such as acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; 1-allyloxy- Examples thereof include an addition reaction product of an unsaturated monomer having an epoxy group such as 3-butoxypropan-2-ol and an alcohol.
The unsaturated monomer having an epoxy group is not particularly limited, and examples thereof include allyl glycidyl ether. The alcohol is not particularly limited, and examples thereof include methanol, ethanol, propanol, butanol and the like.
The unsaturated monomer having a hydroxyl group is preferably a hydroxyl group-containing (meth) acrylate, an addition reaction product of an unsaturated monomer having an epoxy group and an alcohol, and more preferably 2-hydroxyethyl (meth) acrylate. , 1-Aryloxy-3-butoxypropan-2-ol.

The unsaturated monomer having an ether group is a monomer having an ether group and an ethylenically unsaturated hydrocarbon group, and is not particularly limited as long as it has these, and is substituted with other than the ether group. It may have a group. The other substituent is not particularly limited, and examples thereof include a hydroxyl group and the like in addition to the unsaturated monomer having an aryl group and the unsaturated monomer having a hydroxyl group.
Examples of the unsaturated monomer having an ether group include an addition reaction product of an unsaturated alcohol such as (meth) allyl alcohol and isoprenol and an alkylene oxide and a terminal hydrophobic modified product thereof; an epoxy group such as allyl glycidyl ether. Unsaturated monomer; Addition reaction product of alcohol and unsaturated monomer having an epoxy group such as 1-allyloxy-3-butoxypropan-2-ol can be mentioned.
The unsaturated monomer having an ether group is preferably an addition reaction product of an unsaturated alcohol such as 1-allyloxy-3-butoxypropan-2-ol or isoprenol and an alkylene oxide.

Examples of the hydrocarbon group having 1 to 30 carbon atoms in R ¹ of the group represented by the above formula (1) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group and the like. Alkyl group of 1 to 30; cycloalkyl group having 3 to 30 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; carbon number of 6 such as phenyl group, benzyl group, trill group and o-xysilyl group Included are ~ 30 aromatic hydrocarbon groups. The hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms. It is more preferably an alkyl group having 1 to 20 carbon atoms, and further preferably an alkyl group having 1 to 12 carbon atoms.

The hydrocarbon group having 1 to 30 carbon atoms in R ¹ of the above formula (1) is composed of a hydroxyl group, an alkoxy group, a (poly) oxyalkylene group, an oxo group-containing group, a halogen atom, an epoxy group and a carbonyl group as substituents. It may have at least one selected from the group. The number of carbon atoms in the hydrocarbon group does not include the number of carbon atoms constituting the substituent.
Specific examples of the alkoxy group, (poly) oxyalkylene group, oxo group-containing group, halogen atom, epoxy group and carbonyl group include unsaturated monomers having an aryl group and unsaturated monomers having a hydroxyl group. As described in Substituents of.

The monovalent metal atom in R ¹ is not particularly limited, and examples thereof include alkali metal atoms such as lithium, sodium, and potassium. Preferred are sodium and potassium.
The divalent metal atom is not particularly limited, and examples thereof include alkaline earth metal atoms such as calcium and magnesium.
The trivalent metal atom is not particularly limited, and examples thereof include aluminum and iron.
The quaternary ammonium base is not particularly limited, but the following formula (4);

(In the formula, R ⁷ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) It is preferable that the group is represented by.
The R ⁷ is preferably a hydrogen atom or a monovalent metal atom.

Examples of the unsaturated monomer having a group represented by the above formula (1) include the following formula (5);

(In the formula, R ⁸ , R ⁹ , and R ¹⁰ are the same or different, and hydrogen atom, hydroxyl group, alkyl group having 1 to 10 carbon atoms,-(CH ₂ ) zCOOR ¹² (-(CH ₂ ) zCOOR ¹² ) are -COOR ¹¹ or other-(CH ₂ ) zCOOR ¹² may form an anhydride). W represents an integer of 0 to 2. z represents an integer of 0 to 2. R ¹¹ ,, R ¹² is the same or different, hydrogen atom, monovalent metal atom, divalent metal atom, trivalent metal atom, quaternary ammonium base, or hydroxyl group as substituent, alkoxy group, (poly) oxy. It represents a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of an alkylene group, an oxo group-containing group, a halogen atom, an epoxy group and a carbonyl group). It is preferably a monomer.

The alkyl groups having 1 to ¹⁰ carbon atoms of R ^{8 to} R ^{10 in} the group represented by the above formula (5) have 1 carbon number of R ^{2 to} R ⁵ and R ^{7 in} the above formulas (2) and (4). Similar to 10 to 10 alkyl groups.
The R ⁸ and R ⁹ are preferably hydrogen atoms. The R ¹⁰ is preferably a hydrogen atom, a hydroxyl group or a methyl group, and more preferably a hydrogen atom or a methyl group.
w is preferably 0 or 1, more preferably 0.
As the substituent in R ¹¹ and R ¹² , it has at least one selected from the group consisting of a hydroxyl group, an alkoxy group, a (poly) oxyalkylene group, an oxo group-containing group, a halogen atom, an epoxy group and a carbonyl group. A good hydrocarbon group having 1 to 30 carbon atoms is the same as R ¹ in the above formula (1).

The monomer represented by the above formula (5) is not particularly limited, and for example, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and α-hydroxyacrylic acid and salts thereof; maleic acid. , Itaconic acid, citraconic acid, unsaturated dicarboxylic acids such as fumaric acid, salts thereof, and anhydrides thereof; half esters and diesters of these unsaturated dicarboxylic acid-based monomers and alcohols; methyl (meth). Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) Alkyl (meth) acrylates such as acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate. Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylates and isobornyl (meth) acrylates;

α-Hydroxymethyl acrylate, α-hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyl-containing (meth) acrylates such as hydroxybutyl (meth) acrylates; (di) ethylene glycols such as ethylene glycol (meth) acrylates, ethylene glycol methoxy (meth) acrylates, diethylene glycol (meth) acrylates, and diethylene glycol methoxy (meth) acrylates. Alkoxypolyalkylene glycol (meth) acrylates such as methoxy) (meth) acrylates and alkoxypolyethylene glycol methacrylates; oxo group-containing (meth) acrylates such as sulfopropyl (meth) acrylates and (meth) acryloyloxyethyl phosphate; trifluoroethyl ( Fluoro group-containing alkyl (meth) acrylates such as meta) acrylates, tetrafluoropropyl (meth) acrylates and octafluoropentyl (meth) acrylates; glycidyl (meth) acrylates, α-methylglycidyl (meth) acrylates, glycidyl allyl ethers and the like. Epoxy group-containing (meth) acrylate; acetonyl (meth) acrylate, diacetone (meth) acrylate, 2-hydroxypropyl (meth) acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, 2- (acetoacetoxy) ethyl ( Examples thereof include carbonyl group-containing (meth) acrylates such as (meth) acrylate and (meth) acryloyloxyalkylpropenal.

Examples of the monomer represented by the above formula (4) include the above unsaturated monocarboxylic acid and salts thereof; unsaturated dicarboxylic acids, salts thereof, and anhydrides thereof; unsaturated dicarboxylic acid-based monomer. A half-ester and a diester of an alcohol having 1 to 22 carbon atoms; an alkyl (meth) acrylate having 1 to 30 carbon atoms is preferable.

The salt is not particularly limited, and examples thereof include an alkali metal salt, an alkaline earth metal salt, and a quaternary ammonium salt. The salt is preferably an alkali metal salt.

The unsaturated monomer (B) may have at least one group selected from the group consisting of an aryl group, a hydroxyl group, an ether group and a group represented by the above formula (1). When the unsaturated monomer (B) has a (poly) oxyalkylene group, it is preferably a compound having 3 to 200 carbon atoms. A compound having 7 to 200 carbon atoms is more preferable, and a compound having 7 to 100 carbon atoms is more preferable. When the unsaturated monomer (B) has a (poly) oxyalkylene group, the unsaturated monomer (B) has an isoprenyl structure represented by (CH ₃ ) ₂ C = CHCH _2-. Is preferable.
Further, the alkylene group constituting the oxyalkylene group has 1 to 5 carbon atoms, the number of repetitions of the oxyalkylene group is 1 to 100, and the number of carbon atoms in the structure other than the (poly) oxyalkylene group is 3 to 20. Is preferable. The number of carbon atoms of the alkylene group is more preferably 1 to 4, and further preferably 1 to 3. The number of repetitions of the oxyalkylene group is more preferably 1 to 90, still more preferably 1 to 80.
When the unsaturated monomer (B) does not have a (poly) oxyalkylene group, the unsaturated monomer (B) is preferably a compound having 2 to 50 carbon atoms. A compound having 2 to 40 carbon atoms is more preferable, and a compound having 2 to 30 carbon atoms is more preferable.

The polymer of the present invention has a structure derived from an unsaturated monomer having at least one group selected from the group consisting of a hydroxyl group, an ether group and a group represented by the above formula (1) as the structural unit (b). It is preferable to have a unit. When the polymer for a moisturizer has such a structural unit, the holding power of water due to hydrogen bonding is further improved, the hydrophilicity of the polymer is further improved, and the hygroscopicity is more excellent.

The structural unit (b) in the polymer of the present invention is the following formula (6);

(In the formula, R ¹³ represents a hydrogen atom or a methyl group. R ¹⁴ is a hydrogen atom, a monovalent metal atom, a divalent metal atom, a trivalent metal atom, a quaternary ammonium base, or 1 carbon number. It is more preferably a structural unit derived from a monomer represented by (representing a hydrocarbon group of ~ 30).

Specific examples and preferred examples of the monovalent metal atom, the divalent metal atom, the trivalent metal atom, the quaternary ammonium base and the hydrocarbon group having 1 to 30 carbon atoms in R ¹⁴ are as described above. ..
The R ¹⁴ is preferably a hydrogen atom, a monovalent metal atom, or a quaternary ammonium base. More preferably, it is a hydrogen atom or a monovalent metal atom.

Examples of the monomer represented by the above formula (6) include (meth) acrylic acid or salts thereof, and the above-mentioned alkyl (meth) acrylate having 1 to 30 carbon atoms.

The structural unit (b) is more preferably a structural unit derived from (meth) acrylic acid or a salt thereof.

The polymer for a moisturizer of the present invention may have a structural unit (e) derived from a monomer (E) other than the structural unit (a) and (b).
The other monomer (E) is not particularly limited, and examples thereof include acrylamide and the like.

The moisturizer polymer of the present invention preferably has a structural unit (a) ratio of 30 to 99% by mass with respect to 100% by mass of all structural units. It is more preferably 40 to 97% by mass, further preferably 45 to 95% by mass, and particularly preferably 50 to 90% by mass.
The moisturizer polymer preferably has a structural unit (b) ratio of 1 to 40% by mass with respect to 100% by mass of all structural units. It is more preferably 2 to 40% by mass, further preferably 3 to 30% by mass, and particularly preferably 5 to 30% by mass.
The moisturizer polymer preferably has a structural unit (e) ratio of 0 to 30% by mass with respect to 100% by mass of all structural units. It is more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, particularly preferably 0 to 8% by mass, and most preferably 0 to 5% by mass.

In the moisturizer polymer of the present invention, the ratio of the structural unit (b) is preferably 1 to 50% by mass with respect to 100% by mass of the structural unit (a). It is more preferably 2 to 40% by mass, and further preferably 3 to 30% by mass.

In particular, when the polymer has a structural unit derived from an unsaturated monomer having an aryl group as the structural unit (b), the ratio of the structural unit derived from the unsaturated monomer having an aryl group is the total structural unit. (A) It is preferably 0.1 to 40% by mass with respect to 100% by mass. More preferably, it is 1 to 30% by mass. When the ratio of the structural unit derived from the unsaturated monomer having an aryl group is within the above preferable range, the hydrophilicity and hydrophobic balance of the polymer for moisturizer of the present invention will be better.

Further, the structure derived from an unsaturated monomer in which the polymer has at least one group selected from the group consisting of a hydroxyl group, an ether group and a group represented by the above formula (1) as the structural unit (b). When having units, the ratio of these structural units is preferably 1 to 50% by mass with respect to 100% by mass of the structural unit (a). More preferably, it is 1 to 40% by mass. When the ratio of these structural units is in the above-mentioned preferable range, the balance between hydrophilicity and hydrophobicity of the polymer for moisturizer of the present invention becomes better.
When calculating the ratio of structural units in the polymer, the unsaturated monomer having an aryl group has a hydroxyl group, an ether group and a group represented by the above formula (1) as substituents. Such a monomer is classified into an unsaturated monomer having a hydroxyl group, an ether group or a group represented by the above formula (1).

The polymer of the present invention was left as a powder having an average particle size of 250 μm or less for 3 days under the conditions of 23 ° C. and a relative humidity of 50%, and further left for 1 day under the conditions of 30 ° C. and a relative humidity of 60%. The mass increase rate when the mass of the polymer is measured before and after standing is preferably 30% by mass or less with respect to 100% by mass of the mass before standing. It is more preferably 20% by mass or less, and further preferably 10% by mass or less.
The powder having an average particle size of 250 μm or less can be obtained by pulverizing the dried polymer with a lab miller until it passes through a JIS standard sieve having a mesh size of 250 μm.

The polymer of the present invention is left as a powder having an average particle size of 250 μm or less for 3 days under the conditions of 23 ° C. and a relative humidity of 50%, further left for 1 day under the conditions of 30 ° C. and a relative humidity of 60%, and then further. The mass reduction rate when the mass of the polymer was measured before and after standing at 30 ° C. and 40% relative humidity for 1 day was 30 mass with respect to 100 mass% of the mass before standing. % Or less is preferable. It is more preferably 20% by mass or less, further preferably 10% by mass or less, and most preferably 5% by mass or less.

The weight average molecular weight of the moisturizer polymer of the present invention is not particularly limited, but is preferably 1000 to 1000000. It is more preferably 2000 to 900,000, further preferably 3000 to 800,000, and particularly preferably 5000 to 800,000. If the weight average molecular weight of the polymer is in a preferable range, the viscosity of the entire system after the addition of the polymer for a moisturizer of the present invention can be in a preferable range. The weight average molecular weight of the polymer can be measured by the method described in Examples.

The polymer for a moisturizer of the present invention preferably has a viscosity of an aqueous solution having a solid content of 25% by mass of the polymer of 1-1000000 mPa · s. When the aqueous solution of the polymer of the present invention has the above-mentioned preferable viscosity range, when the polymer of the present invention is blended into cosmetics, the thickening of the entire system is suppressed and the limitation of the blending amount is reduced. The viscosity is more preferably 1 to 500,000 mPa · s.
The viscosity of the aqueous solution of the polymer can be measured with a B-type viscometer.

The polymer for moisturizer of the present invention is preferably water-soluble.
Here, the fact that the polymer is water-soluble means that the insoluble content is less than 0.5% by weight when 0.5 g of the polymer is dissolved in 100 g of water at 25 ° C.

The structure of the polymer for a moisturizing agent of the present invention includes a random copolymer structure, a graft structure, a block copolymer structure, a gradient copolymer structure, a star-shaped structure, a dendrimer structure, and the like. Good.

<Manufacturing method of polymer for moisturizer>
The production of the polymer for a moisturizer of the present invention is not particularly limited, but it can be produced by polymerizing a monomer component, and specific examples and preferable examples of the monomer component are as described above.

The content ratio of the unsaturated monomer (A) having a lactam structure in the monomer component which is the raw material of the polymer of the present invention is preferably 30 to 99% by mass with respect to 100% by mass of all the monomers. .. It is more preferably 40 to 97% by mass, further preferably 45 to 95% by mass, and particularly preferably 50 to 90% by mass.

An unsaturated single amount having at least one group selected from the group consisting of an aryl group, a hydroxyl group, an ether group and a group represented by the above formula (1) in the monomer component which is a raw material of the polymer of the present invention. The content ratio of the body (B) is preferably 1 to 40% by mass with respect to 100% by mass of all the monomers. It is more preferably 2 to 40% by mass, further preferably 3 to 30% by mass, and particularly preferably 5 to 30% by mass.

The ratio of the other monomer (E) in the monomer component that is the raw material of the polymer of the present invention is preferably 0 to 30% by mass with respect to 100% by mass of all the monomers. It is more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, particularly preferably 0 to 8% by mass, and most preferably 0 to 5% by mass.

The content ratio of the unsaturated monomer (B) in the monomer component which is the raw material of the polymer of the present invention is 1 to 50% by mass with respect to the total 100% by mass of the unsaturated monomer (A). Is preferable. It is more preferably 2 to 40% by mass, still more preferably 3 to 30% by mass.

When an unsaturated monomer having an aryl group is contained as a monomer component which is a raw material of the polymer of the present invention, the ratio of the unsaturated monomer having an aryl group is 100 mass by mass of the unsaturated monomer (A). It is preferably 0.1 to 40% by mass with respect to%. More preferably, it is 1 to 30% by mass.

As a monomer component which is a raw material of the polymer of the present invention, an unsaturated monomer having at least one group selected from the group consisting of a hydroxyl group, an ether group and a group represented by the above formula (1) is used. When included, the total ratio of these monomers is preferably 1 to 50% by mass with respect to 100% by mass of the unsaturated monomer (A). More preferably, it is 1 to 40% by mass.

The polymerization of the polymer for a moisturizer may be carried out in the absence of a solvent, or a solvent may be used. Examples of the polymerization method include commonly used methods such as a solution polymerization method, a suspension polymerization method, a reverse phase suspension polymerization method, a casting polymerization method, a thin film polymerization method, and a spray polymerization method.

As a method for initiating the polymerization of the above-mentioned monomer component, a method of adding a polymerization initiator, a method of irradiating UV, a method of applying heat, a method of irradiating light in the presence of a photoinitiator, or the like can be adopted. it can.
The polymer for a moisturizer is preferably produced by a method of polymerizing the above-mentioned monomer component in the presence of a polymerization initiator. When polymerizing the monomer component, a polymerization initiator can be appropriately used depending on the polymerization method. As the polymerization initiator, those usually used can be used, for example, hydrogen peroxide; persulfate such as sodium persulfate, potassium persulfate, ammonium persulfate; dimethyl 2,2'-azobis (2-). Methylpropionate), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) ) -2-Methylpropionamidine] hydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (2-imidazolin-2-yl) ) Propane] Azobisisobutyate, 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride and other azo compounds; benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t -Organic peroxides such as butyl peroxide and cumene hydroperoxide; oxidizing agents and reducing agents such as ascorbic acid and hydrogen peroxide, sodium sulfoxylate and t-butyl hydroperoxide, persulfate and metal salts, etc. An oxidation-reduction type initiator or the like that generates radicals in combination is suitable. Among these polymerization initiators, hydrogen peroxide, persulfate, and azo compounds are preferable, and azo compounds are most preferable, because the residual monomer tends to decrease.
The polymerization initiator is not limited to these examples. Each of these polymerization initiators may be used alone, or two or more kinds thereof may be used in combination.

The amount of the polymerization initiator used is not particularly limited as long as it can initiate the polymerization of the monomer component, but is usually 0.01 to 30 parts by mass with respect to 100 parts by mass of all the monomer components. , Preferably 0.02 to 20 parts by mass, more preferably 0.05 to 10 parts by mass.

In the above polymerization, a chain transfer agent may be used if necessary. Specific examples of the chain transfer agent include thiol-based chain transfer agents such as mercaptoethanol, thioglycolic acid, mercaptopropionic acid, and n-dodecyl mercaptan; halogens such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane. Compounds; Secondary alcohols such as isopropyl alcohol and glycerin; Phosphorous acid (salts) such as hypophosphite and sodium hypophosphate (including hydrates thereof); Phosphorous acid and phosphorous acid Phosphorous acid (salt) such as sodium; Phosphorous acid (salt) such as sodium sulfite and potassium sulfite; Dithionite (salt) such as sodium hydrogen sulfite and potassium hydrogen sulfite; Sodium dithionite (salt) such as sodium bisulfite; Pyrophosphorous acid (salt) such as potassium pyrosulfite; and the like. The chain transfer agent may be used alone or in the form of a mixture of two or more.
The amount of the chain transfer agent used is preferably 0 g or more and 600 g or less, and more preferably 0 g or more and 500 g or less, with respect to 1 mol of the monomer (total monomer) used.

In the above polymerization step, heavy metal ions may be used for the purpose of promoting a reaction or the like. In the present invention, the heavy metal ion means a metal ion having a specific gravity of 4 g / cm ³ or more. By using heavy metal ions, it is possible to reduce the amount of the polymerization initiator used. The heavy metal ion is not particularly limited as long as it is contained in the form of an ion, but it is preferable to use a method using a solution obtained by dissolving a heavy metal compound because it is excellent in handleability. Examples of the heavy metal compounds, Mohr's salt _{(Fe (NH 4) 2 (} SO 4) 2 · 6H 2 O), ferrous sulfate heptahydrate, ferrous chloride, ferric chloride, manganese chloride, and Illustrated.
The amount of the heavy metal ion used is preferably 0 ppm or more and 100 ppm or less, and more preferably 0 ppm or more and 50 ppm or less, based on the total amount of the polymerization reaction solution.

In the above copolymerization method, as a method of adding the monomer component, the polymerization initiator, etc. to the reaction vessel, all the monomer components are charged in the reaction vessel, and the polymerization initiator is added into the reaction vessel. Method of performing polymerization: A part of the monomer component is charged into the reaction vessel, and the polymerization initiator and the remaining monomer component are added continuously or stepwise (preferably continuously) into the reaction vessel. Method of copolymerizing with; a method of charging a polymerization solvent in a reaction vessel and adding the entire amount of the monomer component and the polymerization initiator; one of the monomers (for example, an unsaturated monomer having a lactam structure). A method of carrying out copolymerization by charging a part of the above into a reaction vessel and adding a polymerization initiator and the remaining monomer components into the reaction vessel (preferably continuously) is preferable. Even in such a method, since the molecular weight distribution of the obtained polymer can be narrowed (sharpened), the copolymerization can be carried out by sequentially dropping the polymerization initiator and the monomer component into the reaction vessel. preferable.

The above copolymerization method can be carried out by either a batch method or a continuous method. In addition, as a solvent used as needed in the copolymerization, a solvent usually used can be used, such as water; methyl alcohol, ethyl alcohol, isopropyl alcohol (2-propanol), butanol, THF (tetra), etc. Alcohols; glycerin; polyethylene glycol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, n-heptane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide Classes: Ethers such as diethyl ether and dioxane are suitable. These may be used alone or in combination of two or more. Among these, one or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms may be used from the viewpoint of the solubility of the monomer component and the obtained copolymer. preferable. Water and lower alcohols having 1 to 4 carbon atoms are more preferable, and water and isopropyl alcohol are more preferable.
The solvent is relatively inexpensive, and the production method of the present invention is economically excellent.
In the method for producing a copolymer of the present invention, any chain transfer agent, pH adjuster, buffer, etc. can be used, if necessary.

The temperature at the time of polymerization is not particularly limited, but is usually 20 to 100 ° C, preferably 40 to 100 ° C. When the temperature at the time of polymerization is within the above range, the residual monomer component tends to decrease. It is not necessary to keep the temperature at the time of polymerization constant during the progress of the polymerization reaction. For example, the polymerization is started from room temperature and the temperature is raised to a set temperature at an appropriate temperature rise time or rate. After that, the set temperature may be maintained, or the polymerization temperature may be changed (increased or lowered) over time during the progress of the polymerization reaction depending on the dropping method of the monomer component, the initiator, or the like. May be good. Further, when the monomer component is polymerized, it is preferable to appropriately stir the monomer component so that the monomer component is polymerized uniformly.

The polymerization time is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually about 1 to 10 hours. In the present invention, the "polymerization time" represents the time during which the monomer is added.

The pressure in the reaction system may be normal pressure (atmospheric pressure), reduced pressure, or pressurized pressure. The atmosphere in the reaction system may be either an air atmosphere or an inert gas atmosphere.
The inert gas is not particularly limited, and examples thereof include nitrogen and argon, and nitrogen is preferable.

The solid content concentration in the aqueous solution (that is, the polymerized solid content concentration of the monomer) at the time when the polymerization reaction in the above polymerization reaction system is completed is preferably 10% by mass or more, more preferably 20 to 80% by mass. .. As described above, when the solid content concentration at the end of the polymerization reaction is as high as 20% by mass or more, the polymerization can be carried out at a high concentration and in one step. Therefore, the polymer of the present invention can be efficiently obtained, for example, the concentration step which is necessary in some cases in the conventional production method can be omitted. Therefore, the production efficiency can be significantly increased, and as a result, the productivity of the polymer of the present invention can be significantly improved and the increase in production cost can be suppressed.

In the method for producing a polymer for a moisturizer of the present invention, an aging step may be provided for the purpose of increasing the polymerization rate of the monomer after the addition of all the raw materials used is completed. The aging time is usually 1 to 240 minutes, preferably 1 to 180 minutes, and more preferably 1 to 120 minutes. If the aging time is less than 1 minute, the monomer component may remain due to insufficient aging, and toxicity and odor caused by the residual monomer become a problem.

The temperature of the polymer solution preferable in the aging step is in the same range as the above-mentioned polymerization temperature. Therefore, the temperature here may be maintained at a constant temperature (preferably the temperature at the time when the dropping is completed), or the temperature may be changed over time during aging.

The method for producing a crosslinked polymer of the present invention preferably includes a step of drying the obtained crosslinked polymer.
The drying temperature and time are not particularly limited, but it is preferably performed at 80 to 250 ° C., and the drying time is preferably 30 minutes to 3 hours.
The drying step is preferably performed in a time range of 80 ° C. to 250 ° C. for 50% or more of the total time of the drying step. When the drying temperature and time are in the above ranges, the physical properties of the polymer tend to be further improved. More preferably, it is carried out at the above temperature through virtually all drying steps. The drying temperature is specified by the heat medium temperature, but if it cannot be specified by the heat medium temperature such as microwave, it is specified by the material temperature. The drying method is not particularly limited as long as the drying temperature is within the above range, and hot air drying, no wind drying, vacuum drying, infrared drying, microwave drying and the like can be preferably used. Above all, it is more preferable to use hot air drying. When hot air drying is used, the dry air volume is preferably in the range of 0.01 to 10 m / sec, more preferably 0.1 to 5 m / sec. The drying temperature range is more preferably 110 ° C. to 220 ° C., and even more preferably 120 ° C. to 200 ° C. Further, the drying may be performed at a constant temperature or may be performed by changing the temperature, but it is preferable that substantially all the drying steps are performed within the above temperature range.

When the polymer is dried in the above production method, it is preferable that the dried polymer is pulverized and / or classified. More preferably, both pulverization and classification are performed.
The above crushing can be performed by a commonly used method, for example, a roll crusher such as a roll mill, a hammer crusher such as a hammer mill, an impact crusher, a cutter mill, a turbo grinder, a ball mill, a flash mill. , A method of pulverizing using a jet mill or the like. Among these, it is more preferable to use a roll mill to control the particle size distribution. In order to control the particle size distribution, it is more preferable to grind two or more times continuously, and it is further preferable to grind three times or more continuously. Further, when crushing twice or more, each crusher may be the same or different. It is also possible to use different types of crushers in combination.

The crushed powder can be classified by a commonly used method, and a sieve having a specific opening may be used. The classifier used for classifying with a sieve is not particularly limited, but for example, a vibrating sieve (unbalanced weight drive type, resonance type, vibrating motor type, electromagnetic type, circular vibration type, etc.), an in-plane motion sieve. (Horizontal motion type, horizontal circular-linear motion type, three-dimensional circular motion type, etc.), movable net type sieve, forced stirring type sieve, net surface vibration type sieve, wind force sieve, sonic sieve, etc. Be done. A vibrating sieve and an in-plane motion sieve are preferably used.

The present invention is also a moisturizer containing the polymer for the moisturizer of the present invention.
The content ratio of the polymer for the moisturizer in the moisturizer is not particularly limited, but is preferably 1 to 100% by mass with respect to 100% by mass of the moisturizer. More preferably, it is 5 to 100% by mass.

The moisturizer polymer of the present invention is preferably used for skin cosmetics, external preparations for skin, or hair cosmetics.
The skin cosmetics are not particularly limited, but for example, basic cosmetics such as facial cleansers, creams, milky lotions, and beauty liquids; makeup cosmetics such as liquid foundations, foundation milky lotions, teak colors, eye shadows, mascara, and lipsticks; Cleaning cosmetics such as cleansing creams, facial cleansing foams, and liquid wash pigments; cosmetics such as sunscreen cosmetics (including non-medicinal products); bath cosmetics such as bathing agents. Examples of external preparations for skin include external preparations such as liniment agents, lotions and ointments.
The hair cosmetics are not particularly limited, and examples thereof include shampoo, conditioner, treatment, wax, spray, gel, and mist.

The present invention is also a skin cosmetic, an external preparation for skin or a hair cosmetic containing the polymer for moisturizer of the present invention.
The content ratio of the moisturizer polymer in the skin cosmetics, external preparations for skin or hair cosmetics is not particularly limited, but is 0.01 to 10 mass with respect to 100% by mass of the skin cosmetics, external preparations for skin or hair cosmetics. % Is preferable. More preferably, it is 0.05 to 5% by mass.

In addition, the cosmetics and skin external preparations of the present invention include, if necessary, water and additive components generally blended in cosmetics and skin external preparations, such as oily bases, moisturizers, feel improvers, and surface activity. Agents, polymers, thickening / gelling agents, solvents, propellants, antioxidants, reducing agents, oxidizing agents, preservatives, antibacterial agents, chelating agents, pH adjusters, acids, alkalis, powders, inorganic salts , UV absorbers, whitening agents, vitamins and their derivatives, anti-inflammatory agents, anti-inflammatory agents, hair growth agents, blood circulation promoters, stimulants, hormones, anti-wrinkle agents, anti-aging agents, tightening agents, cold sensation agents , Warming agent, wound healing promoter, irritation palliative, pain reliever, cell activator, plant / animal / microbial extract, antipruritic, keratin exfoliating / dissolving agent, antiperspirant, refreshing agent, astringent, enzyme, nucleic acid , Perfume, pigment, colorant, dye, pigment, water and the like can be blended.

Examples of these additive components include cetanol, myristyl alcohol, oleyl alcohol, lauryl alcohol, cetostearyl alcohol, stearyl alcohol, araquil alcohol, behenyl alcohol, jojoba alcohol, chimil alcohol, ceracyl alcohol, and bacillus as oily bases. Higher alcohols such as alcohols, hexyldecanols, isostearyl alcohols, 2-octyldodecanols, dimerdiols; aralkyl alcohols and derivatives such as benzyl alcohols; lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, undecylene Acids, 12-hydroxystearic acid, palmitooleic acid, oleic acid, linoleic acid, linoleic acid, erucic acid, docosahexaenoic acid, eikosapentaenoic acid, isohexadecanoic acid, anteisohenicosanic acid, long-chain branched fatty acids, dimeric acid , Higher fatty acids such as hydrogenated dimeric acid and metal soaps such as aluminum salt, calcium salt, magnesium salt, zinc salt and potassium salt, and nitrogen-containing derivatives such as amide; liquid paraffin (mineral oil), heavy Liquid isoparaffin, light liquid isoparaffin, α-olefin oligomer, polyisobutene, hydrogenated polyisobutene, polybutene, squalane, olive-derived squalane, squalane, vaseline, carbides such as solid paraffin; candelilla wax, carnauba wax, rice wax, Waxes such as wood wax, honey wax, montan wax, ozokelite, selecin, paraffin wax, microcrystallin wax, petrolatum, Fishertropsh wax, polyethylene wax, ethylene / propylene copolymer; palm oil, palm oil, palm kernel oil, saflower oil , Olive oil, castor oil, avocado oil, sesame oil, tea oil, evening primrose oil, wheat germ oil, macadamia nut oil, hazelnut oil, kukui nut oil, rosehip oil, meadowfoam oil, persic oil, tea tree oil, peppermint oil, corn oil, Plants such as rapeseed oil, sunflower oil, wheat germ oil, flaxseed oil, cotton seed oil, soybean oil, peanut oil, rice bran oil, cacao butter, shea butter, hydrogenated palm oil, hydrogenated castor oil, jojoba oil, hydrogenated jojoba oil, etc. Fats and oils; Animal fats and oils such as beef fat, milk fat, horse fat, egg yolk oil, mink oil, turtle oil; Animal waxes such as whale wax, lanolin, orange raffy oil;

Liquid lanolin, reduced lanolin, adsorption purified lanolin, acetate lanolin, acetate liquid lanolin, hydroxylanolin, polyoxyethylene lanolin, lanolin fatty acid, hard lanolin fatty acid, lanolin alcohol, lanolin acetate, acetic acid (cetyl lanolin) ester and other lanolins Sphingolin lipids such as lecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingomyelin, phospholipids such as phosphatidic acid, lysolecithin; hydrogenated soybean phospholipids, partially hydrogenated soybean phospholipids, hydrogen Phosphorlipid derivatives such as added egg yolk phospholipids and partially hydrogenated egg yolk phospholipids; sterols such as cholesterol, dihydrocholesterol, lanosterol, dihydrolanosterol, phytosterol, cholic acid; sapogenins; saponins; cholesteryl acetate, cholesteryl nonanoate, Cholesteryl stearate, cholesteryl isostearate, cholesteryl oleate, di-lauroyl-L-glutamate (cholesteryl / behenyl / octyldodecyl), di-lauroyl-L-glutamate (cholesteryl / octyldodecyl), N-lauroyl-L- Acylsarcosin alkyl esters such as diglutamate (phytosteryl / behenyl / octyldodecyl), di-lauroyl-L-glutamate (phytosteryl / octyldodecyl), N-lauroylsarcosin isopropyl, cholesteryl 12-hydroxystearate, macadamia nut oil fatty acid cholesteryl, Macademia nut oil fatty acid phytosteryl, phytosteryl isostearate, soft lanolin fatty acid cholesteryl, hard lanolin fatty acid cholesteryl, long-chain branched fatty acid cholesteryl, long-chain α-hydroxy fatty acid cholesteryl and other sterol esters; phospholipid-cholesterol complex, phospholipid-phytosterol complex Lipid complex such as body;

Octyldodecyl myristate, hexyldecyl myristate, octyldodecyl isostearate, cetyl parimitinate, octyldodecyl palmitate, cetyl octanate, hexyldecyl octanoate, isotridesyl isononanoate, isononyl isononanoate, octyl isononanoate Isodecyl acid, isotridecyl neopentate, isostearyl neopentate, octyldodecyl neodecanoate, oleyl oleate, octyldodecyl oleate, octyldodecyl ricinoleate, octyldodecyl lanolin fatty acid, hexyldecyl dimethyloctanoate, octyldodecyl erucate Himasi oil, ethyl oleate, ethyl avocado oil fatty acid, isopropyl myristate, isopropyl palmitate, octyl palmitate, isopropyl isostearate, isopropyl lanolin fatty acid, diethyl sebatate, diisopropyl sebatate, dioctyl sebatate, diisopropyl adipate, sebatic acid Monoalcohol carboxylic acid esters such as dibutyloctyl, diisobutyl adipate, dioctyl succinate, triethyl citrate; oxyacid esters such as cetyl lactate, diisostearyl malate, hydrogenated castor oil monoisostearate;

Glyceryl trioctanoate, glyceryl trioleate, glyceryl triisostearate, glyceryl diisostearate, tri (capric acid / capric acid) glyceryl, tri (capric acid / capric acid / myristic acid / stearic acid) glyceryl, hydrogenated rosin triglyceride (hydrogen) Additive ester gum), rosin triglyceride (ester gum), glyceryl dicosanate behate, trimethylol propane trioctanoate, trimethylolpropane triisostearate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, 2-butyl dioctanoate- 2-Ethyl-1,3-propanediol, propylene glycol dioleate, pentaerythrityl tetraoctanoate, hydrogenated rosin pentaerythrityl, ditrimethylol propane triethylhexanoate, ditrimethylol propane (isostearic acid / sebacic acid), triethylhexane Pentaerythrityl acid, (hydroxystearic acid / stearic acid / logonic acid) dipentaerythrityl, diglyceryl diisostearate, polyglyceryl tetraisostearate, polyglyceryl nonaisostearate-10, deca (erucic acid / isostearic acid / ricinoleic acid) polyglyceryl-8, Polyhydric alcohol fatty acid esters such as (hexyldecanoic acid / sebacic acid) diglyceryl oligoester, glycol distearate (ethylene glycol distearate);

Diisopropyl dimergylinolate, diisostearyl dimerserinolate, dimerserylinolate (isostearyl / phytosteryl), dimergylinolic acid (phytosteryl / behenyl), dimerserinolic acid (phytosteryl / isostearyl / cetyl / stearyl /) Dimericicic acid or dimer such as behenyl), dimerdilinoleic acid dimerdilinoleyl, diisostearate dimergylinoleil, dimergylinoleil hydrogenated rosin condensate, dimergylinol acid-hardened castor oil, hydroxyalkyl dimerdilinoleyl ether, etc. Derivatives of diols; palm oil fatty acid monoethanolamide (cocamide MEA), palm oil fatty acid diethanolamide (cocamide DEA), lauric acid monoethanolamide (lauramide MEA), lauric acid diethanolamide (lauramide DEA), lauric acid monoisopropanolamide ( Lauramide MIPA), palmitate monoethanolamide (partamide MEA), palmitate diethanolamide (partamide DEA), coconut oil fatty acid methylethanolamide (cocamidomethyl MEA) and other fatty acid alkanolamides; dimethicone (dimethylpolysiloxane), highly polymerized dimethicone (Highly polymerized dimethylpolysiloxane), cyclomethicone (cyclic dimethylsiloxane, decamethylcyclopentasiloxane), phenyltrimethicone, diphenyldimethicone, phenyldimethicone, stearoxypropyldimethylamine, (aminoethylaminopropylmethicone / dimethicone) copolymer, dimethiconol , Dimethiconol crosspolymer, silicone resin, silicone rubber, amino-modified silicone such as aminopropyl dimethicone and amodimethicone, polyether-modified silicone such as cation-modified silicone and dimethicone copolypoly, polyglycerin-modified silicone, sugar-modified silicone, carboxylic acid-modified silicone. , Phosphate-modified silicone, sulfuric acid-modified silicone, alkyl-modified silicone, fatty acid-modified silicone, alkylether-modified silicone, amino acid-modified silicone, peptide-modified silicone, fluorine-modified silicone, cationic-modified and polyether-modified silicone, amino-modified and polyether-modified silicone. , Alkyl-modified and polyether-modified silicones, silicones such as polysiloxane / oxyalkylene copolymer; perfluorodecane, pa -Fluorine-based oils such as fluorooctane and perfluoropolyether are preferable.

Moisturizers / feeling improvers include glycerin, 1,3-butylene glycol, propylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, Polyols such as trimethylolpropane, pentaerythritol, hexylene glycol, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymers and their polymers; diethylene glycol monoethyl ether Glycolalkyl ethers such as (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether; sugar alcohols such as sorbitol, xylitol, erythritol, mannitol, martitol; glucose, fructose, galactose, mannose , Treose, xylose, arabinose, fucose, ribose, deoxyribose, maltose, trehalose, lactose, raffinose, gluconic acid, glucuronic acid, cyclodextrins (α-, β-, γ-cyclodextrin, and maltosylated, hydroxyalkyl Modifications such as cyclodextrin), β-glucan, chitin, chitosan, heparin and derivatives, pectin, arabinogalactan, dextrin, dextran, glycogen, ethyl glucoside, glucosyl methacrylate polymer or copolymer and other sugars and their derivatives. Derivatives; hyaluronic acid, sodium hyaluronate; sodium chondroitin sulfate; mucoitin sulfate, caronine sulfate, keratosulfate, dermatan sulfate; white jellyfish extract, white jellyfish polysaccharide; fucoidan; tuberose polysaccharide, naturally occurring polysaccharide; citric acid, tartrate, Organic acids such as lactic acid and salts thereof; urea; salts such as 2-pyrrolidext-5-carboxylic acid and sodium thereof;

Betain (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, tyrosine, β-alanine, threonine, glutamate, glutamine, asparagine, aspartic acid, cysteine, cystine, methionine, leucine, isoleucine, Amino acids such as valine, tryptophan, histidine, taurine and salts thereof; collagen, fish-derived collagen, atelocollagen, gelatin, elastin, collagen-degrading peptide, hydrolyzed collagen, hydroxypropylammonium chloride hydrolyzed collagen, elastin-degrading peptide, keratin-degrading peptide , Hydrolyzed keratin, conchiolin-degraded peptide, hydrolyzed conchiolin, silk proteolytic peptide, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soybean proteolytic peptide, wheat proteolytic peptide, hydrolyzed wheat protein, casein-degraded peptide, acylated peptide And other protein peptides and derivatives thereof; acylated peptides such as palmitoyl oligopeptide, palmitoyl pentapeptide, palmitoyl tetrapeptide; silylated peptides; lactic acid bacteria culture solution, yeast extract, eggshell membrane protein, bovine submandibular gland mutin, etc. Hippotaurine, sesame lignan glycoside, glutathione, albumin, lactose; choline chloride, phosphorylcholine; placenta extract, aerastin, collagen, aloe extract, hamamelis water, hechima water, chamomile extract, kanzo extract, confree extract, silk extract, Animal / plant extracts such as Izayoibara extract, Seiyo-no-kogirisou extract, Eucalyptus extract, Merilot extract, natural ceramides (types 1, 2, 3, 4, 5, 6), hydroxyceramides, pseudo-ceramides, sphingoglycolipids, ceramides and Ceramides such as sugar ceramide-containing extracts are preferred.

Preferred examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and high molecular weight surfactants. The HLB of the surfactant is not particularly limited, and can be used from a low HLB of about 1 to a high HLB of about 20, and it is also preferable to combine a low HLB and a high HLB.
Examples of preferred surfactants include fatty acid salts such as potassium laurate and potassium myristate; alkyl sulphates such as sodium lauryl sulphate, triethanolamine lauryl sulphate and ammonium lauryl sulphate; laureth. Polyoxyethylene alkyl sulfates such as sodium sulphate and triethanolamine laures sulphate; sodium cocoyl methyl taurine, potassium cocoyl methyl taurine, sodium lauroyl methyl taurine, sodium myristyl methyl taurine, sodium lauroyl methyl alanine, sodium lauroyl sarcosin, lauroyl sarcosin triethanol. Acyl N-methyl amino acid salts such as amines and sodium methylalanine lauroyl glutamate; sodium cocoyl glutamate, triethanolamine cocoyl glutamate, sodium lauroyl glutamate, sodium myristyl glutamate, sodium stearoyl glutamate, ditriethanolamine palmitoyl aspartate, cocoylalanine triethanolamine Acyl amino acid salts such as; polyoxyethylene alkyl ether acetate salts such as sodium laureth acetate; succinic acid ester salts such as lauroyl monoethanolamide sodium succinate; fatty acid alkanolamide ether carboxylate; acyl late; polyoxyethylene fatty amine Sulfate; fatty acid alkanolamide sulfate; hardened coconut oil fatty acid fatty acid glyceride sulfate such as sodium glycerin sulfate; alkylbenzene polyoxyethylene sulfate; olefin sulfonate such as α-olefin sulfonate; sodium lauryl sulfosuccinate, sulfosuccinate Alkyl sulfosuccinates such as sodium dioctyl sulphonate; alkyl ether sulfosuccinates such as laureth disooxalate disodium, monolauroyl monoethanolamide polyoxyethylene sulfosuccinate sodium, sodium lauryl polypropylene glycol sulfosuccinate; sodium tetradecylbenzene sulfonate, tetra Alkylbenzene sulfonates such as decylbenzene sulfonic acid triethanolamine; alkylnaphthalene sulfonates; alkane sulfonates; α-sulfo fatty acid methyl ester salts; acyl isethionates; alkyl glycidyl ether sulfonates; alkyl sulfoacetates; laurethrin Alkyl ether phosphates such as sodium acid, sodium dilaures phosphate, sodium trilaureth phosphate, sodium monoolesphosphate; alkyl phosphates such as potassium lauryl phosphate; sodium caseinate; alkylaryl ether phosphate; fatty acid amide ether Phosphate; phospholipids such as phosphatidylglycerol, phosphatidylinositol, and phosphatidic acid; silicone-based anionic surfactants such as carboxylic acid-modified silicone, phosphoric acid-modified silicone, and sulfate-modified silicone;

Among nonionic surfactants, laures (polyoxyethylene lauryl ether), ceteth (polyoxyethylene cetyl ether), steares (polyoxyethylene stearyl ether), behenes (polyoxyethylene behenyl ether), isosteares (poly) Polyoxyethylene alkyl ethers with various polyoxyethylene additions such as oxyethylene isostearyl ethers) and octyldodeces (polyoxyethylene octyldodecyl ethers); polyoxyethylene alkylphenyl ethers; polyoxyethylene hydrogenated castor oil, poly Oxyethylene castor oil, polyoxyethylene cured castor oil monoisostearate, polyoxyethylene cured castor oil triisostearate, polyoxyethylene cured castor oil monopyroglutamic acid monoisostearic acid diester, polyoxyethylene cured castor oil maleic acid, etc. Polyoxyethylene phytosterol; polyoxyethylene cholesterol; polyoxyethylene cholestanol; polyoxyethylene lanolin; polyoxyethylene reduced lanolin; polyoxyethylene / polyoxypropylene cetyl ether, polyoxyethylene / Polyoxyethylene / polyoxypropylene alkyl such as polyoxypropylene 2-decyltetradecyl ether, polyoxyethylene / polyoxypropylene monobutyl ether, polyoxyethylene / polyoxypropylene hydrogenated lanolin, polyoxyethylene / polyoxypropylene glycerin ether, etc. Ether; polyoxyethylene / polyoxypropylene glycol; (poly) glycerin such as PPG-9 diglyceryl Polyoxypropylene glycol; glyceryl stearate, glyceryl isostearate, glyceryl palmitate, glyceryl myristate, glyceryl oleate, coconut oil fatty acid Glyceryl fatty acid partial esters such as glyceryl, monocotton oil fatty acid glycerin, glycerin monoercaate, glycerin sesquioleate, α, α'-glycerin pyroglutamate oleate, glycerin monostearate malic acid; polyglyceryl stearate-2, 3, 4, 5, 6, 8, 10, 10, polyglyceryl distearate-6, 10, polyglyceryl tristearate-2, polyglyceryl decastearate-10, polyglycerate isostearate Lil-2, 3, 4, 5, 5, 6, polyglyceryl diisostearate-2 (diglyceryl diisostearate), 3, 10, polyglyceryl triisostearate-2, tetraisostearic acid Polyglyceryl-2, polyglyceryl decisostearate-10, polyglyceryl oleate-2, 3, 4, 5, 6, 6, 8, polyglyceryl dioleate-6, polyglyceryl trioleate-2, decaoleic acid Polyglycerin fatty acid ester such as polyglyceryl-10; ethylene glycol monofatty acid ester such as ethylene glycol monostearate; propylene glycol monofatty acid ester such as propylene glycol monostearate; pentaerythritol partial fatty acid ester; sorbitol partial fatty acid ester; martitol moiety Fatty acid ester;

Multitoll ether; sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexylate diglycerol sorbitan, tetra -2-Polysorbate fatty acid ester such as diglycerol sorbitan ethylhexylate; Partial ester of sugar derivative such as sucrose fatty acid ester, methyl glucoside fatty acid ester, trehalose undecylate; alkyl glucoside such as caprylyl glucoside; alkyl polyglycoside; lanolin alcohol; reduction Lanorin; polyoxyethylene fatty acid mono and diesters such as polyoxyethylene distearate, polytylene glycol diisostearate, polyoxyethylene monooleate, and polyoxyethylene dioleate; polyoxyethylene / propylene glycol fatty acid ester; poly Polyoxyethylene glycerin fatty acid esters such as polyoxyethylene monooleate such as oxyethylene glycerin monostearate, polyoxyethylene glycerin monoisostearate, polyoxyethylene glycerin triisostearate; polyoxyethylene sorbitan monooleate, poly Polyoxyethylene sorbitan fatty acid esters such as oxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tetraoleate; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monooleate, polyoxyethylene sorbitol Polyoxyethylene sorbitol fatty acid esters such as pentaoleate and polyoxyethylene sorbitol monostearate; polyoxyethylene methyl glucoside fatty acid esters; polyoxyethylene alkyl ether fatty acid esters; polyoxyethylene animal and vegetable fats and oils such as polyoxyethylene sorbitol honey; Alkylglyceryl ethers such as isostearyl glyceryl ether, chimil alcohol, seraquil alcohol, bacillate alcohol; polyhydric alcohol alkyl ether; polyoxyethylene alkylamine; tetrapolyoxyethylene / tetrapolyoxypropylene-ethylenediamine condensate; saponin , Sophorolipid and other natural surfactants; polyoxyethylene fat Acid amide; coconut oil fatty acid monoethanolamide (cocamide MEA), coconut oil fatty acid diethanolamide (cocamide DEA), lauric acid monoethanolamide (lauramide MEA), lauric acid diethanolamide (lauramide DEA), lauric acid monoisopropanolamide (lauramide) MIPA), palmitate monoethanolamide (partamide MEA), palmitate diethanolamide (partamide DEA), coconut oil fatty acid methylethanolamide (cocamidomethyl MEA) and other fatty acid alkanolamides;

Alkyldimethylamine oxides such as lauramine oxide, cocamine oxide, stearamine oxide and behenamine oxide; alkylethoxydimethylamine oxides; polyoxyethylene alkyl mercaptans; polyether-modified silicones such as dimethicone copolyol, polysiloxane / oxyalkylene Silicone-based nonionic surfactants such as copolymers, polyglycerin-modified silicones, and sugar-modified silicones; among cationic surfactants, behentrimonium chloride, stealtrimonium chloride, cetrimonium chloride, and lauryltrimonium chloride. Alkyltrimethylammonium chloride such as stearyltrimonium bromide; alkyltrimethylammonium bromide such as stearyltrimonium bromide; dialkyldimethylammonium chloride such as distealyl dimonium chloride and dicocodimonium chloride; fatty acid amide amines such as stearamide propyl dimethylamine and stearamide ethyl diethylamine and The salt; alkyl ether amine such as stearoxypropyl dimethylamine and its salt or quaternary salt; ethyl sulfate long chain branched fatty acid (12-31) aminopropyl ethyl dimethyl ammonium, ethyl sulfate lanolin fatty acid fatty acid such as amino propyl ethyl dimethyl ammonium Amido-type quaternary ammonium salt; polyoxyethylene alkylamine and its salt or quaternary salt; alkylamine salt; fatty acid amide guanidium salt; alkyl ether amine monium salt; alkyltrialkylene glycol ammonium salt; benzalconium salt; benzethonium Salts; pyridinium salts such as cetylpyridinium chloride; imidazolinium salts; alkylisoquinolinium salts; dialkylmoriphonium salts; polyamine fatty acid derivatives; amino-modified silicones such as aminopropyldimethicone and amodimethicone, cation-modified silicones, cation-modified And silicone-based cationic surfactants such as polyether-modified silicones, amino-modified and polyether-modified silicones; among amphoteric surfactants, N-alkyl-N, N- such as lauryl betaine (lauryldimethylaminoacetate betaine). Dimethyl amino acid betaine; fatty acids such as cocamidopropyl betaine and lauramide propyl betaine Amidoalkyl-N, N-dimethyl amino acid betaine; imidazoline type betaine such as sodium cocoamphoacetate and sodium lauroamphoacetate; Alkyl sulfobetaine such as rudimethyltaurin; Sulfate-type betaine such as alkyldimethylaminoethanol sulfate ester; Phospholipid-type betaine such as alkyldimethylaminoethanol phosphate ester; Sphingoline such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, sphingomyelin Lipids, lysolecithin, hydrogenated soybean phospholipids, partially hydrogenated soybean phospholipids, hydrogenated egg yolk phospholipids, partially hydrogenated egg yolk phospholipids, phospholipids such as lecithin hydroxide; silicone-based amphoteric surfactants, etc .; Examples of the activator include polyvinyl alcohol, sodium alginate, starch derivative, traganth gum, acrylate / alkyl methacrylic acid copolymer; and various silicone-based surfactants are preferable.

Examples of the polymer / thickener / gelling agent include guar gum, locust bean gum, queens seed, carrageenan, galactan, arabic gum, tara gum, tamarind, farcerelan, karaya gum, trolley aoi, cara gum, tragant gum, pectin, pectic acid and sodium. Salts such as salts, salts such as alginic acid and sodium salts, mannan; starches such as rice, corn, potatoes, wheat; xanthan gum, dextran, succinoglucan, curdran, hyaluronic acid and its salts, zansan gum, purulan, gellan gum, chitin , Chitosan, agar, casso extract, chondroitin sulfate, casein, collagen, gelatin, albumin; methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and salts such as sodium thereof, methyl hydroxypropyl cellulose, sodium cellulose sulfate, dialkyldimethyl Ammonium sulfate cellulose, crystalline cellulose, cellulose powder and other cellulose and derivatives thereof; starch-based polymers such as soluble starch, carboxymethyl starch, methylhydroxypropyl starch, methyl starch, hydroxypropyltrimonium chloride starch, corn starch aluminum octenyl succinate, etc. Alginic acid derivatives such as sodium alginate and propylene glycol alginate; polyvinylpyridone (PVP), polyvinyl alcohol (PVA), vinylpidridone / vinyl alcohol copolymer, polyvinylmethyl ether; polyethylene glycol, polypropylene glycol, polyoxyethylene Polyoxypropylene copolymer; amphoteric methacrylic acid ester copolymer such as (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer, (acrelites / stearyl acrylate / ethylamine methacrylate) copolymer; (dimethicone / vinyldimethicone) cloth Polymer, (alkyl acrylate / diacetone acrylamide) copolymer, (alkyl acrylate / diacetone acrylamide) copolymer AMP; partially saponified polyvinyl acetate, maleic acid copolymer; vinylpyrrolidone / dialkylaminoalkyl methacrylate copolymer; Acrylic resin alkanolamine; polyester, water-dispersible polyester; polya Crylamide; polyacrylic acid ester copolymer such as ethyl polyacrylate, carboxyvinyl polymer, salt such as polyacrylic acid and sodium salt thereof, acrylic acid / methacrylic acid ester copolymer;

Acrylic acid / alkyl methacrylic acid copolymer; cationized cellulose such as polyquaternium-10, diallyldimethylammonium chloride / acrylamide copolymer such as polyquaternium-7, acrylic acid / diallyldimethylammonium chloride copolymer such as polyquaternium-22. , Polyquaternium-39 and other acrylic acid / diallyldimethylammonium chloride / acrylamide copolymers, acrylic acid / cationized metaacrylic acid ester copolymers, acrylic acid / cationized metaacrylic acid amide copolymers, polyquaternium-47 and the like. Acrylic acid / methyl acrylate / methacrylic acid propyltrimethylammonium copolymer, choline methacrylate polymer; cationized polysaccharides such as cationized oligosaccharide, cationized dextran, guarhydroxypropyltrimonium chloride; polyethyleneimine; Cationic polymer; polymer of 2-methacryloyloxyethyl phosphorylcholine such as polyquaternium-51 and polymer with butyl methacrylate copolymer and the like; acrylic resin emulsion, ethyl polyacrylate emulsion, polyacrylic alkyl ester emulsion, vinyl acetate Polymer emulsions such as resin emulsions, natural rubber latex, synthetic latex; nitrocellulose; polyurethanes and various copolymers; various silicones; various silicone-based copolymers such as acrylic-silicone graft copolymers; various fluoropolymers; Polymers; 12-hydroxystearic acid and salts thereof; dextrin fatty acid esters such as dextrin palmitate and dextrin myristinate; silicic anhydride, fuming silica (ultrafine anhydrous silicic acid), aluminum magnesium silicate, magnesium sodium silicate, metal Preferred are soaps, dialkyl phosphate metal salts, bentonite, hectrites, organically modified clay minerals, sucrose fatty acid esters, fructo-oligosaccharide fatty acid esters.

Examples of solvents and propellants include lower alcohols such as ethanol, 2-propanol (isopropyl alcohol), butanol, and isobutyl alcohol; glycols such as propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, and isopentyldiol. Kind: Diethylene glycol monoethyl ether (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether Glycol ethers such as: ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, glycol ether esters such as propylene glycol monoethyl ether acetate; glycol esters such as diethoxyethyl succinate and ethylene glycol disuccinate; benzyl Preferables include propellants such as alcohol, benzyloxyethanol, propylene carbonate, dialkyl carbonate, acetone, ethyl acetate, N-methylpyrrolidone; toluene; fluorocarbon, next-generation freon; LPG, dimethyl ether, and carbon dioxide.

Antioxidants include tocopherol derivatives such as tocopherol (vitamin E) and tocopherol acetate; BHT, BHA; bisulfite derivatives such as propyl bisulfite; vitamin C (ascorbic acid) and / or its derivatives; erythorbic acid and its derivatives; Sulfites such as sodium sulfite; hydrogen sulfites such as sodium hydrogen sulfite; thiosulfites such as sodium thiosulfite; metahydrosulfites; thiotaurine, hypotaurine; thioglycerol, thiourea, thioglycolic acid, cysteine hydrochloride are preferable. Is listed as. As the reducing agent, thioglycolic acid, cysteine, cysteamine and the like are preferable. As the oxidizing agent, hydrogen peroxide solution, ammonium persulfate, sodium bromate, percarbonate and the like are preferable.

Examples of preservatives and antibacterial agents include hydroxybenzoic acids such as methylparaben, ethylparaben, propylparaben and butylparaben and salts thereof or esters thereof; salicylic acid; sodium benzoate; phenoxyethanol; 1,2-pentanediol, 1,2-hexane. 1,2-diols such as diols; isothiazolinone derivatives such as methylchloroisothiazolinone and methylisothiazolinone; imidazolinium urea; dehydroacetic acid and salts thereof; phenols; halogenated bisphenols such as triclosan, acid amides , Tertiary ammonium salts; trichlorocarbanide, zincpyrythion, benzalkonium chloride, benzethonium chloride, sorbic acid, chlorhexidine, chlorhexidine gluconate, halocarban, hexachlorophenol, hinokithiol; phenol, isopropylphenol, cresol, timol, parachlorophenol, Other phenols such as phenylphenol and sodium phenylphenol; phenylethyl alcohol, photosensitizers, antibacterial zeolite, and silver ion are preferable. Examples of the chelating agent include edetates (ethylenediaminetetraacetate) such as EDTA, EDTA2Na, EDTA3Na, and EDTA4Na; hydroxyethylethylenediaminetriacetate such as HEDTA3Na; pentetate (diethylenetriaminepentaacetate); phytate; ethidroic acid and the like. Phosphonic acid and salts such as sodium salt thereof; sodium oxalate; polypolyamino acids such as polyaspartic acid and polyglutamic acid; sodium polyphosphate, sodium metaphosphate, phosphate; sodium citrate, citric acid, alanine, dihydroxyethylglycine , Gluconic acid, ascorbic acid, succinic acid, tartrate acid are preferred. Acids / acids / alkalis include citric acid, sodium citrate, lactic acid, sodium lactate, glycolic acid, succinic acid, acetic acid, sodium acetate, malic acid, tartaric acid, fumaric acid, phosphoric acid, hydrochloric acid, sulfuric acid, monoethanol. Amine, diethanolamine, triethanolamine, isopropanolamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, arginine, hydroxide Preferred are sodium, potassium hydroxide, aqueous ammonia, guanidine carbonate and ammonium carbonate.

Powders include mica, talc, kaolin, sericite, montmorillonite, kaolinite, mica, white mica, gold mica, synthetic mica, red mica, black mica, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, cay. Barium acid, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, bentonite, smectite, clay, mud, Metal soap (eg zinc myristate, calcium palmitate, aluminum stearate), calcium carbonate, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, dark blue, carbon black, titanium oxide, fine and ultrafine titanium oxide, zinc oxide , Fine particles and ultrafine zinc oxide, alumina, silica, fumigant silica (ultrafine anhydrous silicic acid), mica titanium, fish scale foil, boron nitride, photochromic pigment, synthetic fluorine gold mica, fine particle composite powder, gold, aluminum, etc. Inorganic powders of various sizes and shapes, and these are treated with silicones such as hydrogen silicone and cyclic hydrogen silicone or other surface treatment agents such as silane or titanium coupling agents to make them hydrophobic or Inorganic powders such as hydrophilized powders; starch, cellulose, nylon powder, polyethylene powder, polymethylmethacrylate powder, polystyrene powder, styrene and acrylic acid copolymer resin powder, polyester powder, benzoguanamine resin powder, polyethylene terephthalate. -Polymethylmethacrylate laminated powder, polyethylene terephthalate, aluminum, epoxy laminated powder, etc., urethane powder, silicone powder, Teflon (registered trademark) powder, and other organic powders and surface treatment powders of various sizes and shapes, organic and inorganic Composite powders are preferred. Inorganic salts include sodium chloride-containing salts such as salt, normal salt, rock salt, sea salt, and natural salt; potassium chloride, aluminum chloride, calcium chloride, magnesium chloride, ginger, zinc chloride, ammonium chloride; sodium sulfate, aluminum sulfate, etc. Aluminum / potassium sulfate (myoban), aluminum / ammonium sulfate, barium sulfate, calcium sulfate, potassium sulfate, magnesium sulfate, zinc sulfate, iron sulfate, copper sulfate; sodium phosphates such as 1Na / 2Na / 3Na phosphate, phosphate Potassiums, calcium phosphates, magnesium phosphates are preferred.

Examples of the ultraviolet absorber include paraaminobenzoic acid, paraaminobenzoic acid monoglycerin ester, N, N-dipropoxyparaaminobenzoic acid ethyl ester, N, N-diethoxyparaaminobenzoic acid ethyl ester, N, N-dimethylparaaminobenzoate ethyl. Benzophenone-based UV absorbers such as esters, N, N-dimethylparaaminobenzoic acid butyl esters, N, N-dimethylparaaminobenzoic acid ethyl esters; Anthranilic acid-based UV absorbers such as homomentyl-N-acetylanthranilate; salicylic acid And salicylic acid-based UV absorbers such as sodium salts, amilsalicylate, menthyl salicylate, homomentyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate; octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl. -2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, isopropyl-p-methoxy cinnamate, isoamyl-p-methoxy Synnamete, 2-ethylhexyl p-methoxycinnamate (octyl paramethoxysilicate), 2-ethoxyethyl-p-methoxycinnamate (sinoxate), cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenyl Ceramic acid-based UV absorbers such as cinnamates, 2-ethylhexyl α-cyano-β-phenyl cinnamates (octocrine), glycerylmono-2-ethylhexanoyl-diparamethoxycinnamates, ferulic acid and derivatives thereof; 2, 4-Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy- 4-methoxybenzophenone (oxybenzophenone-3), 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4' Benzophenones such as −phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone Non-ultraviolet absorber; 3- (4'-methylbenziliden) -d, l-phenyl, 3-benziliden-d, l-phenyl; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy- 5-Methylphenylbenzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole; 2- (2'-hydroxy-5'-methylphenylbenzotriazole; dibenzalazine; dianisoilmethane; 5- (3,3-Dimethyl-2-norbornylidene) -3-pentan-2-one; dibenzoylmethane derivatives such as 4-t-butylmethoxydibenzoylmethane; octylriazone; urocanic acid such as urocanic acid and ethyl urocanate Derivatives; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 1- (3,4-dimethoxyphenyl) -4,4-dimethyl-1,3-pentandione, dimethoxybenzilidendioxoimidazolidinepropion Preferable examples include hydantin derivatives such as 2-ethylhexyl acid, phenylbenzimidazole sulfonic acid, terephthalylidene dicanfursulfonic acid, drometrizole trisiloxane, methyl anthranilate, rutin and its derivatives, oryzanol and its derivatives. ..

Examples of the whitening agent include hydroquinone glycosides such as arbutin and α-arbutin and their esters; ascorbic acid, ascorbic acid phosphate ester salts such as ascorbic acid, ascorbic acid phosphate sodium salt and ascorbic acid phosphate ester magnesium salt, and ascorbic acid. Ascorbic acid fatty acid ester such as tetraisopalmitic acid ester, ascorbic acid alkyl ether such as ethyl ether ascorbic acid, ascorbic acid glucoside such as ascorbic acid-2-glucoside and its fatty acid esters, ascorbic acid sulfate ester, tocopheryl ascorbyl phosphate Ascorbic acid derivatives such as: kodiic acid, ellagic acid, tranexamic acid and its derivatives, ferulic acid and its derivatives, placenta extract, glutathione, orizanol, butylresorcinol, oil-soluble chamomile extract, oil-soluble kanzo extract, Nishikawayanagi extract, Yukinoshita extract Etc. Plant extracts are preferred.

Examples of vitamins and their derivatives include vitamin A such as retinol, retinol acetate, and retinol palmitate; thiamine hydrochloride, thiamine sulfate, riboflavin, riboflavin acetate, pyridoxin hydrochloride, pyridoxin dioctanoate, and pyridoxin dipalmitate. Vitamin B group such as flavin adenine dinucleotide, cyanocobalamine, folic acid, nicotinic acid such as nicotinic acid amide / benzyl nicotinate, vitamin B group such as choline; vitamin C group such as salt such as ascorbic acid and sodium thereof; vitamin D; α, Vitamin Es such as β, γ, δ-tocopherol; other vitamins such as pantothenic acid and biotin; ascorbic acid phosphate ester salts such as ascorbic acid phosphate sodium salt and ascorbic acid phosphate ester magnesium salt, tetra ascorbate Ascorbic acid fatty acid ester such as ascorbyl isopalmitic acid ester, ascorbyl stearate, ascorbyl palmitate, ascorbyl dipalmitate, alkyl ether ascorbic acid such as ethyl ascorbic acid, ascorbic acid glucoside such as -2-glucoside ascorbic acid and its fatty acid ester , Ascorbic acid derivatives such as tocopheryl ascorbyl phosphate; vitamin derivatives such as tocopherols such as tocopherol nicotinate, tocopherol acetate, tocopherol linoleate, ascorbyl palmitate, tocopherol phosphate ester, tocotrienol, and various other vitamin derivatives are preferable. Is listed as.

Anti-inflammatory and anti-inflammatory agents include glycyrrhizinic acid and its derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokithiol, guaiazulene, allantoin, indomethacin, zinc oxide, hydrocortisone acetate, prednisone, diphedramine hydrochloride, chlorpheniramine maleate; peach leaf extract. , Plant extracts such as Honoha extract are preferred.

As hair growth agents, blood circulation promoters, and stimulants, plant extracts and tinctures such as senburi extract, togarashi tincture, ginger tincture, ginger extract, and cantarist tincture; capsaicin, nonylate valenylamide, gingerone, ictamol, and tannic acid. , Borneol, cyclanderate, cinnaridine, trazoline, acetylcholine, verapamil, cepharanthin, γ-orizanol, cepharanthin, vitamin E and derivatives such as tocopherol nicotinate / tocopherol acetate, γ-orizanol, nicotinic acid and nicotinic acid amide / benzyl nicotinate Derivatives such as ester inositol hexanicotinate and nicotine alcohol, allantin, photosensitizer 301, photosensitizer 401, capronium chloride, pentadecanoic acid monoglyceride, flavanonol derivative, stigmasterol or stigmasterol and its glycoside, minoxidil are preferable. Is listed as. As the hormones, estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, prednisone and the like are preferable.

Other medicinal agents such as anti-wrinkle agents, anti-aging agents, tightening agents, cold sensitizers, warming agents, wound healing promoters, irritation palliatives, analgesics, cell activators, etc. include retinols, retinoic acids, retinoins. Tocopheryl acid; derivatives such as lactic acid, glycolic acid, gluconic acid, fruit acid, salicylic acid and its glycosides / esterified products, hydroxycapric acid, long-chain α-hydroxy fatty acid, long-chain α-hydroxy fatty acid cholesteryl and other α- or β-Hydroxy acids and their derivatives; γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid; carnitine; creatin; ceramides, sphingosines; caffeine, xanthin and its derivatives; coenzyme Q10, carotene, lycopene, astaxanthin Antioxidants and active oxygen scavengers such as α-lipoic acid; catechins; flavones such as quercetin; isoflavones; gallic acid and ester sugar derivatives; polyphenols such as tannin, sesamine, protoanthocyanidin, chlorogenic acid, apple polyphenols Derivatives such as rutin and glycosides; Derivatives such as hesperidin and glycosides; Lignan glycosides; Kanzo extract-related substances such as glabridin, glabrene, liquiritin, isoliquiritin; lactoferrin; gingerol, gingerol; menthol, camphor, sedrol Perfume substances and derivatives thereof; capsaicin, vanillin and the like and derivatives; insect repellents such as diethyl toluamide; complexes of physiologically active substances and cyclodextrins are preferred.

Plant / animal / microbial extracts include iris extract, acitaba extract, asunaro extract, asparagus extract, avocado extract, flaxseed extract, almond extract, altea extract, arnica extract, aloe extract, apricot extract, apricot kernel extract, ginkgo extract. , Inchikou extract, Uikyo extract, Ukon extract, Woolong tea extract, Uwaurushi extract, Agetsu extract, Echinashi leaf extract, Enmeisou extract, Ogon extract, Oubaku extract, Ouren extract, Omugi extract, Otanenjinjin extract, Otogirisou extract, Odori kosou extract, Ononis extract , Dutch mustard extract, orange extract, dried seawater, seaweed extract, oyster leaf extract, oyster extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, cucumber extract, chamomile extract, oil-soluble chamomile extract, carrot extract, kawarayomogi Extract, crow wheat extract, calcade extract, kanzo extract, oil-soluble kanzo extract, kiwi extract, kiou extract, kikurage extract, kina extract, cucumber extract, kiri leaf extract, guanosine, guava extract, kujin extract, kuchinashi extract, kumazasa extract, clara extract, walnut Extract, chestnut extract, grapefruit extract, clematis extract, black rice extract, brown sugar extract, black vinegar, chlorella extract, quail extract, gentiana extract, gennoshouko extract, tea extract, yeast extract, koboku extract, coffee extract, gobo extract, rice extract, rice Fermented extract, fermented rice bran extract, rice germ oil, comfrey extract, collagen, moss peach extract, saishin extract, psycho extract, saitai extract, saffron extract, salvia extract, sabonsou extract, sasa extract, sanzashi extract, sansha extract, sansho Extract, Shiitake extract, Jio extract, Shikon extract, Shiso extract, Shinanoki extract, Shimotsukesou extract, Jatoba extract, Shakuyaku extract, Shokyu extract, Shobu root extract, Shirakaba extract, White chrysanthemum extract, Sugina extract, Stevia extract, Stevia fermented product, Nishikawayanagi extract, Seiyoukizuta extract, Seiyousanzashi extract, Seiyouniwatoko extract, Seiyounokogirisou extract, Seiyouhakka extract, Sage extract, Zeniaoi extract, Senkyu extract, Senburi extract, Souhakuhi extract, Daiou extract, Dai Zu extract, Taisou extract, Thyme extract, Dandelion extract, Local clothing extract, Tea extract, Chouji extract, Chigaya extract, Chinpi extract, Tea tree oil, Jincha extract, Togarashi extract, Touki extract, Tokinsenka extract, Tounin extract, Tohi extract, Dokudami extract, Tomato Extract, Natto extract, Carrot extract, Carrot extract, Novara extract, Hibiscus extract, Bakumondou extract, Hass extract, Parsley extract, Birch extract, Honey, Hamamelis extract, Paris etalia extract, Hikiokoshi extract, Bisaborol, Hinoki extract, Bifizus bacterium extract, Biwa extract, Fukitanpopo extract, Fukinotou extract, Bukuryo extract, Butcher bloom extract, Grape extract, Grape seed extract, Propolis, Hechima extract, Benibana extract, Peppermint extract, Bodaiju extract, Button extract, Hop extract, Maikaika extract, Pine extract, Maronie extract , Mizubasho extract, Mukuroji extract, Melissa extract, Mozuku extract, Peach extract, Yagurumagiku extract, Eucalyptus extract, Yukinoshita extract, Yuzu extract, Yuri extract, Yokuinin extract, Yomogi extract, Lavender extract, Green tea extract, Eggshell membrane extract, Apple extract, Louis Boss tea extract , Reishi extract, lettuce extract, lemon extract, lotus extract, lotus extract, rose extract, rosemary extract, roman chamomile extract, royal jelly extract, crackle extract and the like are preferable.

Examples of the antipruritic agent include diphenhydramine hydrochloride, chlorpheniramine maleate, camphor, substance-P inhibitor and the like. Examples of the exfoliating / dissolving agent include salicylic acid, sulfur, resorcin, selenium sulfide, pyridoxine and the like.
Examples of the antiperspirant include chlorohydroxyaluminum, aluminum chloride, zinc oxide, zinc paraphenol sulfonate and the like. Examples of the refreshing agent include menthol and methyl salicylate. Examples of the astringent include citric acid, tartaric acid, lactic acid, aluminum / potassium sulfate, tannic acid and the like. Examples of enzymes include superoxide dismutase, catalase, lysozyme chloride, lipase, papain, pancreatin, protease and the like. Preferred examples of nucleic acids include ribonucleic acid and a salt thereof, deoxyribonucleic acid and a salt thereof, and disodium adenosine triphosphate.

As fragrances, acetylsedrene, amylcinnamaldehyde, allylamylglycolate, β-ionone, isoe super, isobutylquinolin, iris oil, iron, indole, ylang ylang oil, undecanal, undecenal, γ-undecalactone, Estragor, Eugenol, Oak Moss, Opoponax Resinoid, Orange Oil, Eugenol, Oranthiol, Galaxolid, Carbachlor, L-Carbon, Kamfer, Cannon, Carrot Seed Oil, Clove Oil, Methyl Silica, Geraniol, Geranyl nitrile , Isobornyl acetate, Geranyl acetate, Dimethylbenzylcarvinyl acetate, Styralyl acetate, Cedril acetate, Telepinel acetate, pt-butylcyclohexyl acetate, Vetiberyl acetate, benzyl acetate, Linaryl acetate, Isopentyl salicylate, benzyl salicylate, Sandalwood oil, Santa Roll, cyclamenaldehyde, cyclopentadecanolide, methyl dihydrojasmonate, dihydromilsenol, jasmine absolute, jasmine lactone, cis-jasmon, citral, citronenol, citroneral, cinnamon bark oil, 1,8-cineole, cinnamaldehyde, Stylux resinoid, cedarwood oil, sedrene, sedrol, celery seed oil, thyme oil, damascon, damasenon, timol, tuberose absolute, decanal, decalactone, terpineol, γ-terpinen, triplar, nerol, nonanar, 2,6-nonadienol, nonalactone , Pacholi alcohol, vanilla absolute, vanillin, basil oil, pachori oil, hydroxycitronellal, α-pinene, piperitone, phenethyl alcohol, phenylacetaldehyde, petitgrain oil, hexyl cinnamaldehyde, cis-3-hexenol, peruvian balsam, vetiver oil , Vetiberol, peppermint oil, pepper oil, heliotropin, bergamot oil, benzylbenzoate, borneol, milresinoid, muskketone, methylnonylacetaldehyde, γ-methylyonone, menthol, L-menthol, L-menthon, eucalyptus oil, β-yonone, Synthetic fragrances and naturals such as lime oil, lavender oil, D-limonen, linalol, lylar, lilial, lemon oil, rose absolute, rose oxide, rose oil, rosemary oil, various essential oils Fragrances and various blended fragrances are preferred.

As pigments / colorants / dyes / pigments, brown 201, black 401, purple 201, purple 401, blue 1, blue 2, blue 201, blue 202, blue 203, blue 204 , Blue 205, Blue 403, Blue 404, Green 201, Green 202, Green 204, Green 205, Green 3, Green 401, Green 402, Red 102, Red 104-1 , Red No. 105-1, Red No. 106, Red No. 2, Red No. 201, Red No. 202, Red No. 203, Red No. 204, Red No. 205, Red No. 206, Red No. 207, Red No. 208, Red No. 213 , Red 214, Red 215, Red 218, Red 219, Red 220, Red 221, Red 223, Red 225, Red 226, Red 227, Red 228, Red 230-1 , Red 230-2, Red 231, Red 232, Red 3, Red 401, Red 404, Red 405, Red 501, Red 502, Red 503, Red 504, Red 505 , Red No. 506, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 205, Orange No. 206, Orange No. 207, Orange No. 401, Orange No. 402, Orange No. 403, Yellow No. 201, Yellow No. 202-1 , Yellow 202-2, Yellow 203, Yellow 204, Yellow 205, Yellow 4, Yellow 401, Yellow 402, Yellow 403-1, Yellow 404, Yellow 405, Yellow 406, Yellow Legal dyes such as No. 407 and Yellow No. 5; other acidic dyes such as Acid Red 14;

Basic dyes such as Arianor Sienna Brown, Arianor Madder Red, Arianor Steel Blue, and Arianor Straw Yellow; HC Yellow 2, HC Yellow 5, HC Red 3, 4-hydoxy color-Nyliploid-2- Nitro dyes such as 2-nitro-p-phenylenediamine, HC Blue 2, Basic Blue 26; Disperse dyes; Inorganic white pigments such as titanium dioxide and zinc oxide; Inorganic red pigments such as iron oxide (Bengala) and iron titanate; Inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as yellow iron and ocher; inorganic black pigments such as black iron oxide and lower titanium oxide; inorganic purple pigments such as mango violet and cobalt violet; Inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate; Inorganic blue pigments such as ultramarine and dark blue; Titanium oxide coated mica, Titanium oxide coated bismuth oxychloride, Titanium oxide coated talc, Colored titanium oxide coated mica, Pearl pigments such as bismuth oxychloride and fish scale foil; metal powder pigments such as aluminum powder, copper powder and gold; surface-treated inorganic and metal powder pigments; red 201, red 202, red 204, red 205, red 220 No., Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401, Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Organics such as zirconium, barium or aluminum lakes such as red 230, red 401, red 505, orange 205, yellow 4, yellow 5, yellow 202, yellow 203, green 3 and blue 1. Pigments; Surface-treated organic pigments: Anthracinones such as astaxanthin and alizarin, anthocyanidins, β-carotene, catenal, capsantine, chalcone, calsamine, quercetin, closin, chlorophyll, curcumin, cochineal, ciconin and other naphthoquinones, bixins, flavones, Natural pigments and dyes such as betacyanidine, henna, hemoglobin, lycopene, riboflavin, rutin; p-phenylenediamine, toluene-2,5-diamine, o-, m-, or p-aminophenol, m-phenylenedia Oxidation dye intermediates and couplers such as min, 5-amino-2-methylphenol, resorcin, 1-naphthol, 2,6-diaminopyridine and salts thereof; autoxidation dyes such as indoline; dihydroxyacetone is preferred. Can be mentioned.

As the water, in addition to normal water and purified water, hard water, soft water, natural water, deep ocean water, electrolytic alkaline ionized water, electrolytically acidic ionized water, ionized water, and cluster water are preferable.
In addition to these, cosmetic raw material standards, compounding ingredient standards by cosmetic type, Japan Cosmetic Industry Association ingredient display name list, INCI dictionary (The International Cosmetic Ingredient Dictionary and Handbook), quasi-drug raw material standards, Japanese pharmacy, pharmaceutical additives Ingredients described in standards, official standards for food additives, etc., and the international patent classification IPC is described in Japanese and foreign patent gazettes and patent publication gazettes (including publication gazettes and republishing) belonging to the A61K7 classification. It is possible to contain known cosmetic ingredients, quasi-drug ingredients, food ingredients, etc. in known combinations, blending ratios, and blending amounts.

The type of the cosmetic / skin external preparation of the present invention is not particularly limited except for the hair conditioner, but includes hair cosmetics, basic cosmetics, makeup cosmetics, aromatic cosmetics, body cosmetics, ointments, etc. External skin preparations are preferred. The cosmetic / skin external preparation of the present invention can be produced according to a usual method.

Explaining the types of cosmetics and external preparations for skin of the present invention in more detail, basic cosmetics include soft lotions, astringent cleansers, cleansing cleansers, multi-layer cleansers and the like; emollient lotions and moistures. Lotion, Milky Lotion, Nourishing Lotion, Nourishing Milk, Skin Moisture, Moisturizer Emulsion, Massage Lotion, Cleansing Lotion, Protect Emulsion, Sun Protect, Sun Protector, UV Care Milk, Sun Screen, Makeup Lotion, Horny Smoother, Elbow Emulsion such as lotion, hand lotion, body lotion; emollient cream, nutrition cream, nourishing cream, vanishing cream, moisture cream, night cream, massage cream, cleansing cream, makeup cream, base cream, pre-makeup cream, sunscreen cream, Creams such as suntan cream, hair removal cream, deodorant cream, shaving cream, keratin softening cream; gels such as moisturizing gel; essences such as moisturizing essence, whitening essence, UV protection essence; liposome cosmetics such as liposome beauty liquid and liposome lotion Types: Peel-off packs, powder packs, washing packs, oil packs, cleansing masks and other packs and masks; cleansing foams, cleansing creams, cleansing milks, cleansing lotions, cleansing gels, cleansing oils, cleansing masks, powders, facial cleansing powders, etc. Cleansers; soaps such as facial cleansers, clear soaps, medicated soaps, liquid soaps, shaving soaps, and synthetic cosmetic soaps are preferred.

Preferred makeup cosmetics include white powder / dusting powder, foundations, lipsticks, lip gloss, blusher, eyeliner, mascara, eye shadow, eyebrow, eyebrow, nail enamel, enamel remover, and nail treatment. Preferred examples of the aromatic cosmetics include perfume, perfume, parfum, eau de parfum, eau de toilette, cologne, perfume paste, fragrance powder, perfume soap, body lotion, and bath oil.
Body cosmetics include body cleaning agents such as body shampoo; deodorant cosmetics such as deodorant lotion, deodorant powder, deodorant spray, and deodorant stick; depilatory, depilatory / depilatory; bathing agent; insect repellent spray, etc. Repellers are preferred.

Hair cosmetics include oil shampoos, cream shampoos, conditioning shampoos, indulgence shampoos, hair coloring shampoos, rinse-integrated shampoos, and other shampoos; for rinses, treatments, hair packs, color lotions, split hair coats, and permanent waves. Agents, straight perm agents, oxidative hair dyes, hair bleach, hair color pretreatment, hair color aftertreatment, perma pretreatment, perma aftertreatment, hair manicure, hair tonic, and hair restorer are preferred.

As the external preparation for skin, it can also be used as a dosage form such as an ointment, a patch, a lotion, a liniment, and a liquid coating agent. It can also be used as an oral cosmetic such as toothpaste and mouthwash.
The dosage form of the cosmetic or external preparation for skin of the present invention includes emulsification of oil-in-water (O / W) type, water-in-oil (W / O) type, W / O / W type, O / W / O type and the like. Molded cosmetics, oil-based cosmetics, solid cosmetics, liquid cosmetics, paste-like cosmetics, stick-shaped cosmetics, volatile oil-based cosmetics, powdered cosmetics, jelly-like cosmetics, gel-like cosmetics, paste-like Dosage forms such as cosmetics, emulsified polymer-type cosmetics, sheet-like cosmetics, mist-like cosmetics, and spray-type cosmetics are preferable.

The polymer for a moisturizer of the present invention has the above-mentioned structure, exhibits an excellent moisturizing effect even when the polymer is used alone as a moisturizer, and is particularly excellent in maintaining moisturizing properties under low humidity. Therefore, it can be suitably used for skin cosmetics, skin external preparations, hair cosmetics and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "part by weight" and "%" means "mass%".

<Measurement conditions for polymerization average molecular weight>
Equipment: Tosoh HLC-8320GPC
Detector: RI
Column: Tosoh TSK-GEL ALPHA-M, ALPHA-2500
Column temperature: 40 ° C
Flow velocity: 0.8 ml / min.
Calibration curve: TSKgel standard Poly (ethylene oxide)
Eluent: A solution in which acetonitrile and a 0.2 M aqueous sodium nitrate solution are mixed at a ratio of 1: 4.

<Polymerization reaction rate, polymer composition analysis>
The polymerization reaction rates of Synthesis Examples 1 to 3 were determined by measuring the amount of unreacted monomers in the obtained polymerization reaction mixture using gas chromatography (6890N manufactured by Agilent Technologies) under the following conditions.
Device: Agilent "GC6890N"
Column: Agilent "J & W DB-WAX"
Temperature condition: Injection port temperature 280 ° C Detector temperature: 320 ° C,
Column conditions: Hold at 50 ° C for 5 minutes Heat up at 10 ° C / min Hold at 240 ° C for 6 minutes

The reaction rate during the polymerization reaction of Synthesis Examples 4 and 5 was determined by measuring the amount of unreacted monomers in the obtained polymerization reaction mixture using the following apparatus under the following conditions.
Equipment: Shiseido "NANOSPACE SI-2"
Column: Shiseido "CAPCELLPAK C18 UG120", 20 ° C
Eluent: Methanol for LC (manufactured by Wako Pure Chemical Industries, Ltd.) / Ultrapure water = 1/24 (mass ratio), sodium 1-heptane sulfonate 0.4% by mass Addition flow rate: 100 μL / min

<Synthesis Example 1> (Synthesis of NVP / St-based polymer)
2-Propanol (hereinafter, also referred to as "IPA") 55.5 in a glass reaction vessel equipped with a two-paddle type stirring blade, a glass lid, a stirring device with a stirring seal, a nitrogen introduction tube, and a temperature sensor. A mass portion and 35.6 parts by mass of N-vinylpyrrolidone (hereinafter, also referred to as “NVP”) were charged, and the mixture was stirred under a nitrogen stream at 100 rpm and heated to reflux. As a monomer solution, a solution was prepared by adding 35.6 parts by mass of IPA to 1.9 parts by mass of styrene (hereinafter, also referred to as “St”). Add 20.3 parts by mass of IPA to 1.1 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter also referred to as "V-601") as an initiator solution. The solution was prepared. The monomer solution prepared above and the initiator solution were continuously added dropwise for 180 minutes while maintaining reflux. 30 minutes after the completion of the dropping, add 3 parts by mass of 5% by mass of the IPA solution of V-601, and 90 minutes after the completion of the dropping, add 3 parts by mass of the IPA solution of 5% by mass of V-601 and reflux for 60 minutes. The polymerization reaction was completed by keeping it. The consumption rate of NVP after the completion of polymerization was 99%, and the consumption rate of St was 100%. The mass ratio of NVP to St contained in the copolymer (A-1) obtained from the above was 95: 5. A part of the IPA was distilled off, and then the mixture was dried under reduced pressure and pulverized with a lab miller to obtain a powder of the desired copolymer (A-1). The weight average molecular weight of the obtained copolymer (A-1) was 42,000.

<Synthesis Example 2> (Synthesis of NVP / PAB-based polymer)
649.1 g of industrial butanol (hereinafter, also referred to as "BuOH") and 15.6 g of a 48% sodium hydroxide aqueous solution are charged into a 1 L capacity four-necked flask equipped with a thermometer and a reflux condenser, and a magnetic stirrer is used. The temperature was raised to 60 ° C. with stirring. Next, 100.0 g of allyl glycidyl ether (hereinafter, also referred to as “AGE”) was added dropwise at a constant velocity over 120 minutes into the reaction system maintained at 60 ° C. under stirring, and then further 180 minutes at 60 ° C. The reaction was terminated by maintaining (aging). After cooling the reaction solution to 30 ° C., the reflux cooling tube was removed from the flask, and a Liebig condenser, a 1 L receiver, and a nitrogen input tube were attached. After reducing the pressure of the reaction system to 6.7 kPa, the reaction solution was heated, and unreacted BuOH and water were distilled off until the temperature of the solution reached 100 ° C. Next, while maintaining the reaction solution at 100 ° C., nitrogen gas was added to the AGE used in the reaction at 6 mol% / hour for 270 minutes, and unreacted BuOH and water were further distilled off.
In this way, a monomer composition (1) containing 81.0% by mass of 1-allyloxy-3-butoxypropan-2-ol (hereinafter, also referred to as “PAB”) was obtained. The monomer composition (1) contained as impurities a compound in which AGE was further added to PAB and a compound in which water was added to AGE.
IPA 90.0 parts by mass and the above-mentioned monomer composition (1) in a glass reaction vessel equipped with a two-paddle type stirring blade, a glass lid, a stirring device with a stirring seal, a nitrogen introduction tube, and a temperature sensor. 1.9 parts by mass was charged, stirred at 100 rpm under a nitrogen stream, and heated to reflux.
As a monomer solution, 35.6 parts by mass of NVP was prepared.
As an initiator solution, 1.1 parts by mass of V-601 was added with 21.4 parts by mass of IPA to prepare a solution.
The monomer solution and the initiator solution prepared above were continuously added dropwise for 120 minutes while maintaining reflux. After completion of dropping, add 1.1 parts by mass of 5% by mass of IPA solution of V-601, and 60 minutes after completion of dropping, add 1.1 parts by mass of 5% by mass of IPA solution of V-601 and reflux for 60 minutes. The polymerization reaction was completed by keeping it. The residual amounts of NVP and PAB after completion of the polymerization were 1.2% by mass and 0.7% by mass, respectively, with respect to the obtained copolymer. Therefore, the mass ratio of NVP and PAB contained in the obtained copolymer (A-2) was 95: 5. A part of IPA was distilled off, and then the mixture was dried under reduced pressure and pulverized with a lab miller to obtain a powder of the desired copolymer (A-2). The weight average molecular weight of the obtained copolymer (A-2) was 37,900.

<Synthesis Example 3> (Synthesis of NVP / HEMA-based polymer)
A glass reaction vessel equipped with a two-paddle type stirring blade, a glass lid, a stirring device with a stirring seal, a nitrogen introduction tube, and a temperature sensor is charged with 55.5 parts by mass of IPA and 30 parts by mass of NVP under a nitrogen stream. The mixture was stirred at 100 rpm and heated to reflux. As a monomer solution, a solution was prepared by adding 35.6 parts by mass of IPA to 7.5 parts by mass of 2-hydroxyethyl methacrylate (hereinafter, also referred to as “HEMA”).
A solution was prepared by adding 20.3 parts by mass of IPA to 1.1 parts by mass of V-601 as an initiator solution.
The monomer solution prepared above and the initiator solution were continuously added dropwise for 180 minutes while maintaining reflux. 30 minutes after the completion of the dropping, add 3 parts by mass of 5% by mass of the IPA solution of V-601, and 90 minutes after the completion of the dropping, add 3 parts by mass of the IPA solution of 5% by mass of V-601 and reflux for 60 minutes. The polymerization reaction was completed by keeping it. The consumption rate of NVP after the completion of polymerization was 99%, and the consumption rate of HEMA was 100%. Therefore, the mass ratio of NVP and HEMA contained in the obtained copolymer (A-3) was 80:20.
A part of the IPA was distilled off, and then the mixture was dried under reduced pressure and pulverized with a laboratory mixer to obtain a powder of the desired copolymer (A-3). The weight average molecular weight of the obtained copolymer (A-3) was 52000.

<Examples 1 to 3 and Comparative Examples 1 to 4>
The copolymer powders obtained in Synthesis Examples 1 to 3 and PVP K-30 (polyvinylpyrrolidone manufactured by Nippon Shokubai) and Aquaric FH (Na polyacrylate manufactured by Nippon Shokubai), 1,3-butanediol, propylene. The glycol was left for 3 days in an environment of 23 ° C. and 50% relative humidity.
Then, each sample was placed in an environment of 30 ° C. and 60% RH for 1 day, and the change in mass before and after leaving was measured at 30 ° C. and 60% RH.
The powders of the copolymers (A-1) to (A-3) obtained in Synthesis Examples 1 to 3 were designated as Examples 1 to 3, respectively, and PVP K-30 (polyvinylpyrrolidone manufactured by Nippon Shokubai) was compared. Example 1, Aquaric FH (manufactured by Nippon Shokubai, Na polyacrylate) was designated as Comparative Example 2, 1,3-butanediol was designated as Comparative Example 3, and propylene glycol was designated as Comparative Example 4, and the results are shown in Table 1.
The mass increase rate after being left for 1 day was evaluated as follows (Test 1).
20% or more: ×
10% or more and less than 20%: ○
Less than 10%: ◎
Further, the same sample left at 23 ° C. and 50% relative humidity for 3 days and at 30 ° C. and 60% RH for 1 day was further placed in an environment of 30 ° C. and 40% RH for 1 day, and the change in mass was measured. The mass loss rate after being left for 1 day was evaluated as follows (Test 2).
15% or more: ×
10% or more and less than 15%: △
5% or more and less than 10%: ○
Less than 5%: ◎

As a result of the above evaluation, it was clarified that the copolymers of Examples 1 to 3 have a smaller mass increase rate under high humidity than the compounds of Comparative Examples 1 to 4, and can suppress stickiness under high humidity. .. Further, 1,3-butanediol and propylene glycol, which are currently used as cosmetic moisturizers, have a large mass reduction rate and low water retention under low humidity, whereas the copolymers of Examples 1 to 3 have low water retention. It was clarified that the mass loss rate was small and the water retention was high even under low humidity.

<Synthesis Example 4> (Synthesis of polymer of NVP / SA = 80/20)
A glass reaction vessel equipped with a two-paddle type stirring blade, a glass lid, a stirring device with a stirring seal, a nitrogen introduction tube, and a temperature sensor is charged with 490 g of pure water and stirred at 100 rpm under a nitrogen stream. The temperature was raised to 80 ° C. 200 parts by mass of NVP was prepared as the monomer solution 1. Next, as the monomer solution 2, a solution was prepared by adding 114.9 parts by mass of pure water to 135.14 parts by mass of sodium acrylate (hereinafter, also referred to as “SA”) having a solid content of 37%. As an initiator solution, dimethyl 2,2'-azobis (2-methylpropion amidine) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter also referred to as "V-50") 6.25 parts by mass of pure water 56.25 A solution was prepared by adding parts by mass.
The monomer solution 1 prepared above and the initiator solution were continuously added dropwise for 120 minutes.
For the monomer solution 2, 237.5 parts by mass was added dropwise in 120 minutes, and the rest was added dropwise in 30 minutes.
Thirty minutes after the completion of the dropping, 2.5 parts by mass of a 10% by mass aqueous solution of V-50 was added, and 2 parts by mass of pure water was added as washing water. After further holding at 80 ° C. for 60 minutes, the polymerization reaction was completed. The consumption rate of NVP after the completion of polymerization was 99.9%, the consumption rate of SA was 100%, and the weight average molecular weight of the obtained copolymer was 33,000. Next, the obtained polymer was dried at 120 ° C. for 2 hours, then dried under reduced pressure and pulverized with a lab miller until it passed through a JIS standard sieve having a mesh size of 250 μm to obtain the powder of the target copolymer (B-1). Got

<Synthesis Example 5> (Synthesis of polymer of NVP / SA = 70/30)
A glass reaction vessel equipped with a two-paddle type stirring blade, a glass lid, a stirring device with a stirring seal, a nitrogen introduction tube, and a temperature sensor is charged with 400 g of pure water and stirred at 100 rpm under a nitrogen stream. The temperature was raised to 80 ° C. As the monomer solution 1, 175 parts by mass of NVP was prepared. Next, as the monomer solution 2, a solution was prepared by adding 172.3 parts by mass of pure water to 202.7 parts by mass of SA with a solid content of 37%. The initiator solution was prepared by adding 56.25 parts by mass of pure water to 6.25 parts by mass of V-50. The monomer solution 1 prepared above and the initiator solution were continuously added dropwise for 120 minutes. For the monomer solution 2, 237.5 parts by mass was added dropwise in 120 minutes, and the rest was added dropwise in 30 minutes. Thirty minutes after the completion of the dropping, 2.5 parts by mass of a 10% by mass aqueous solution of V-50 was added, and 2 parts by mass of pure water was added as washing water. After further holding at 80 ° C. for 60 minutes, the polymerization reaction was completed. The consumption rate of NVP after the completion of polymerization was 99.9%, the consumption rate of SA was 100%, and the weight average molecular weight was 40,800. Next, the obtained polymer was dried at 120 ° C. for 2 hours, dried under reduced pressure, and pulverized with a lab miller until it passed through a JIS standard sieve having a mesh size of 250 μm to obtain the powder of the target copolymer (B-2). Got

<Examples 4 and 5 and Comparative Example 5>
The obtained polymer powder was left in an environment of 23 ° C. and a relative humidity of 50% for 2 days, and then placed in an environment of 23 ° C. and a relative humidity of 40% or 55% for 24 hours, and the increase or decrease in mass was measured.

In the above evaluation, the point where the increase in mass after being left for 24 hours becomes zero is defined as the critical humidity, and the lower the critical humidity, the higher the hygroscopicity at low humidity, so it can be said that the material has high moisturizing power.
From the results in Table 2, the mass of polyvinylpyrrolidone as a comparative example decreased in an environment of 40% relative humidity, the critical humidity was 40% or more, and the moisturizing power was low, whereas in Example 4 and It was clarified that the mass of the copolymer in No. 5 increased even under low humidity, the critical humidity was 40% or less, and the moisturizing power was high.

<Examples 6 to 10 and Comparative Example 6> Moisturizing Toners Examples 6 to 10 and the copolymers A-1 to 3, B-1, 2 obtained in Synthesis Examples 1 to 5, respectively, and Sorbitol as Comparative Example 6. To prepare a moisturizing lotion according to the formulation shown in Table 3 below.
(Preparation method)
Ingredient No. in Table 3 Nos. 1 to 6 In addition to No. 11, the mixture was uniformly stirred and mixed (part A). Next, No. No. 9 to 10 After dissolving in 8, No. 7 was added and dispersed (part B). Part A was added to part B with stirring to make it uniform.

ＢＧ：１，３−ブチレングリコール

BG: 1,3-butylene glycol

The above-mentioned moisturizing lotion (Examples 6 to 10) containing the copolymers A-1 to 3, B-1, and 2 obtained in the present invention has an excellent feeling of use and moisturizing, and makes the skin soft and fresh. It kept the skin smooth and moisturized, and these effects lasted for a long time. On the other hand, the above-mentioned moisturizing lotion containing sorbitol of Comparative Example 6 lacked durability during use and was inferior in usability.

<Examples 11 to 15 and Comparative Example 7> Tightening lotion (Astringent lotion)
Using the copolymers A-1 to 3, B-1, 2 obtained in Synthesis Examples 1 to 5 as Examples 11 to 15, and sorbitol as Comparative Example 7, the tightening lotion according to the formulation shown in Table 4 below was applied. Prepared.
(Preparation method)
Ingredient No. in Table 4 Nos. 1 to 7 In addition to No. 11, the mixture was uniformly stirred and mixed (Part A). Next, No. No. 9 to 10 It was dissolved in 8 (part B). Part A was added to part B with stirring to make it uniform.

The above-mentioned tightening lotion (Examples 11 to 15) containing the copolymers A-1 to 3, B-1, and 2 obtained in the present invention has excellent usability and moisturizing feeling, and makes the skin soft and moisturized. A refreshing feel was obtained while maintaining smooth and moisturized skin, and these effects lasted for a long time. On the other hand, the above-mentioned tightening lotion containing sorbitol of Comparative Example 7 did not maintain moisture.

<Example 16> Using the copolymer B-1 obtained in Emulsion Synthesis Example 4, an emulsion according to the formulation shown in Table 5 below was prepared.
(Preparation method)
Ingredient No. in Table 5 15 is a part of No. In addition to 18, it was stirred to make a viscous liquid (part A). No. 16 is a part of No. After adding to 18 and stirring, No. 17 was added to prepare a viscous liquid (part B). Next, No. 1 to 8 were heated to about 70 ° C. and dissolved (part C). No. 9-14, the remaining No. 18 was heated to about 70 ° C. and dissolved (part D). Part D was added to part C with stirring, emulsified, cooled to about 50 ° C., parts A and B were added, and the mixture was stirred until uniform. This milky lotion was excellent in the effect of imparting a moist feeling.

<Examples 17 to 21 and Comparative Example 8> Copolymers A-1 to 3, B-1, 2 obtained in Synthesis Examples 1 to 5 as beauty essence Examples 17 to 21, respectively, and sorbitol as Comparative Example 8. Was used to prepare a beauty essence with the formulation shown in Table 6 below.
(Production method)
Part A was dissolved at room temperature. Part C was gradually added to part B while stirring to make a viscous liquid, and then parts A and D were added and stirred to make the liquid uniform.

The above-mentioned beauty essence (Examples 17 to 21) containing the copolymers A-1 to 3, B-1, and 2 obtained in the present invention has a high moisturizing effect, softens the skin, and is fresh and smooth. While maintaining moisturized skin, a feeling of use such as a smooth feel was obtained, and these effects lasted for a long time. On the other hand, the above-mentioned beauty essence containing sorbitol of Comparative Example 8 lacked smoothness at the time of use and was inferior in moisture.

<Example 22> Using the copolymer B-1 obtained in Massage Cream Synthesis Example 4, a massage cream having the formulation shown in Table 7 below was prepared.
(Preparation method)
Ingredient No. in Table 7 1 to 17 were heated to about 70 ° C. and uniformly dissolved (part A). Next, No. 18 to 22 were heated to about 70 ° C. and uniformly dissolved (part B). Part B was added to part A with stirring, emulsified, and then cooled.
This massage cream had a high massage effect and was excellent in the effect of imparting a moist feeling.

<Example 23> Using the compound A-2 obtained in Synthesis Example 2 of emollient cream, an emollient cream having the formulation shown in Table 8 below was prepared.
(Preparation method)
Ingredient No. in Table 8 1 to 10 were added, and the mixture was heated to about 80 ° C. and dissolved (part A). No. in a separate container. 11 to 15 were taken and heated to about 80 ° C. to uniformly dissolve them (Part B). Part B was added to part A, emulsified with a homomixer, and then cooled to 40 ° C.
This emollient cream was a cream having an excellent effect of imparting a moisturizing feeling.

<Example 24> Anti-aging cream The copolymer A-3 obtained in Synthesis Example 3 was used to prepare an anti-aging cream having the formulation shown in Table 9 below.
(Production method)
A was heated to about 80 ° C. and uniformly dissolved (part A). C was heated to about 80 ° C. and dissolved (part C). While stirring with a homomixer at about 80 ° C., part C was gradually added to part A, and after emulsification, the mixture was uniformly mixed, cooled to about 40 ° C., B was added, and the mixture was uniformly mixed.
This cream spreads well and has an excellent effect of imparting a moist feeling.

<Example 25> Sunscreen agent The copolymer A-1 obtained in Synthesis Example 1 was used to prepare a sunscreen agent having the formulation shown in Table 10 below.
(Preparation method)
Ingredient No. in Table 10 No. 13 Part 1 and 2, No. 3 was added and kneaded with a mill (part A). No. in a separate container. The rest of 2, No. 4 to 6 were added, and the mixture was heated to about 150 ° C. and dissolved (part B). No. in a separate container. The rest of 1, No. 7 to 12 were added, and the mixture was heated to about 80 ° C. and dissolved (part C). No. in a separate container. 14 and 15 were added, and the mixture was heated to about 80 ° C. and dissolved (part D). Part C was added to part B, mixed, and then added to part A and mixed uniformly. Then, part D was added, the mixture was stirred, and after emulsification, the mixture was cooled to 40 ° C.
This sunscreen agent was a cream that suppresses collapse due to sweat and has a moist feeling.

<Example 26> Using the copolymer A-3 obtained in Synthesis Example 3 of the base cream, a base cream having the formulation shown in Table 11 below was prepared.
(Preparation method)
Ingredient No. in Table 11 Nos. 16 and 17, respectively. It was dissolved in 18 to make a viscous liquid (2%) (part A). No. in a separate container. 1 to 10 were added, and the mixture was heated to about 80 ° C. and dissolved (part B). No. in a separate container. 11-15, No. The rest of 18 was added, and the mixture was heated to about 80 ° C. and dissolved (part C). After adding part C to part B and emulsifying, part A was added and mixed uniformly. After stirring, the mixture was cooled to 40 ° C.
This foundation cream was a foundation cream that spreads well, has a foundation, has a long-lasting feel, and can give a silky feel.

<Example 27> A foundation having the formulation shown in Table 12 below was prepared using the copolymer B-1 obtained in Foundation Synthesis Example 4.
(Preparation method)
Each component was stirred at high speed and mixed uniformly.
This foundation had excellent color development and a moist feel.

<Example 28> Using the copolymer B-1 obtained in Lipstick Synthesis Example 4, lipsticks having the formulations shown in Table 13 below were prepared.
(Preparation method)
Ingredient No. in Table 13 Nos. 11-14 Kneaded in 1 and 2 (part A). No. in a separate container. 3 to 10 were added, and the mixture was heated to about 80 ° C. and dissolved (part B). Part A was added to part B at about 80 ° C., dissolved, and then rapidly cooled. This lipstick was fresh and had high adhesion.

<Example 29> Using the copolymer A-1 obtained in Lip Gloss Synthesis Example 1, lip glosses having the formulations shown in Table 14 below were prepared.
(Preparation method)
Ingredient No. of Table 14 1 and 2 were heated to 100 to 110 ° C. and dissolved uniformly. Next, No. 3 to 6 were added and dissolved uniformly at about 80 ° C. This lip gloss was fresh and had high adhesion.

<Example 30> Using the copolymer A-3 obtained in Mascara Synthesis Example 3, a mascara having the formulation shown in Table 15 below was produced.
(Preparation method)
Ingredient No. in Table 15 No. 9 After adding 1 and dispersing with a homomixer, No. 3 was added and heated to maintain the temperature at 70 ° C. (aqueous phase). Other components were mixed and heated to keep at 70 ° C. (oil phase). An aqueous phase was added to the oil phase, and the mixture was uniformly emulsified and dispersed with a homomixer to obtain the desired mascara. This mascara had good adhesion, had a good usability, and had good stability.

<Example 31> Using the copolymer B-2 obtained in Eye Shadow Synthesis Example 5, an eye shadow having the formulation shown in Table 16 below was produced.
(Preparation method)
Ingredient No. of Table 16 1 to 3 were mixed with a blender and then treated with a crusher (powder part). No. 11 to 16 were heated and dissolved at 70 to 75 ° C. (aqueous phase portion). No. 4 to 10 were heated and dissolved at 70 to 80 ° C. (oil phase portion). The powder part was added to the aqueous phase part, and the mixture was stirred and mixed. The oil phase portion was added to this with stirring, dispersed by a homomixer, and stirred and cooled to room temperature to obtain the desired eye shadow. This emulsified eye shadow had good adhesion, had a good usability, and had good emulsification stability.

<Examples 32 to 36 and Comparative Example 9> Copolymers A-1 to 3, B-1, 2 obtained in Synthesis Examples 1 to 5 as Shampoo Examples 32 to 36 and 1,3- as Comparative Example 9. Shampoos with the formulations shown in Table 17 below were prepared using butylene glycol.
(Preparation method)
Ingredient No. in Table 17 1 to 5 were heated to about 80 ° C. and uniformly dissolved (part A). Next, No. 6 to 8 were heated to about 80 ° C. and uniformly dissolved (part B). Part B was added to part A, stirred and mixed at about 80 ° C. until uniform, and then cooled. In addition, No. The prescription excluding only 1 was used as a blank.

Ten panelists evaluated the feel of the hair after using the shampoo. The evaluation was performed on two items, a slippery feeling and a moist feeling. The results are shown in Table 18 below. In the table,
◎: 8 or more out of 10 answered that it was better than blank,
◯: 6 or more out of 10 answered that it was better than blank,
Δ: 4 or more out of 10 responded that it was better than blank,
X: Less than 4 out of 10 responded that it was better than blank.
As shown in Table 18 below, the shampoos containing the product of the present invention (Examples 32 to 36) can give the hair a moist feeling and smooth finger passage as compared with the non-blended products, and are also excellent as a fattening agent. You can see that there is. On the other hand, the shampoo containing 1,3-butylene glycol of Comparative Example 9 was inferior in moist feeling.

<Example 37> Treatment The copolymer A-1 obtained in Synthesis Example 1 was used to prepare a treatment according to the formulation shown in Table 19 below.
(Preparation method)
Ingredient No. in Table 19 1 to 6 were heated to about 80 ° C. and uniformly dissolved (part A). Next, No. 7 to 11 were heated to about 80 ° C. and uniformly dissolved (part B). Part B was added to part A, and the mixture was uniformly stirred and mixed, and then cooled to room temperature.
This treatment was able to give the hair a moist and soft feeling.

<Example 38> Moistrins Synthesis Using the copolymer B-2 obtained in Example 5, moistrins according to the formulation shown in Table 20 below were prepared.
(Preparation method)
Ingredient No. in Table 20 1 to 12 were heated to about 80 ° C. and dissolved (part A). No. in a separate container. 14 to 15 were heated to about 80 ° C. and dissolved (part B). While stirring part B in part A, gradually add and mix uniformly, and then No. After adding 13 and stirring, the mixture was rapidly cooled.
This moisturizing conditioner was a rinse that was not sticky, gave the hair a moist feeling, and was able to give smooth finger passage.

<Example 39> Straight perm agent (cation type)
Using the copolymer A-2 obtained in Synthesis Example 2, liquids 1 and 2 of the straight perm agent (cation type) formulated in Tables 21 and 22 below were prepared.
(Preparation method: 1 liquid)
Ingredient No. in Table 21 Most of 15 were heated to about 80 ° C. (Part A). No. in a separate container. 1 to 8 were added and heated to dissolve (part B). No. in a separate container. The rest of 15, No. 9 to 13 were added and dissolved uniformly (part C). Part B was added to part A, mixed and stirred, and part C was added at around 45 ° C. and mixed uniformly. After cooling to room temperature, No. 14 was added.
(Preparation method: 2 liquids)
Ingredient No. in Table 22 1 to 7 were added, and the mixture was heated to about 70 ° C. and dissolved (part A). No. in a separate container. Take most of 11 and heat to about 70 ° C. 8 and 9 were added and dissolved (part B). No. in a separate container. Take the rest of No. 11 and heat it to about 60 ° C. 10 was added and dissolved (part C). Part B was added to part A at about 70 ° C., and the mixture was stirred until the viscosity became high. The mixture was cooled to 60 ° C., part C was added with stirring, and the mixture was uniformly mixed. After the temperature dropped to about 50 ° C., it was rapidly cooled. This straight perm solution has high adhesion to hair and has a setting force, so that the straight perm solution can be applied firmly.

<Example 40> Hair bleaching agent (two-agent type)
Using the copolymer A-3 obtained in Synthesis Example 3, a hair bleaching agent (two-agent type) according to the formulations shown in Tables 23 and 24 below was prepared.
(Preparation method: 1 agent)
Each component was uniformly stirred and mixed.
(Preparation method: 2 agents)
Each component was uniformly mixed and the pH was adjusted to 3.5-4.0 with citric acid.
(Mixing ratio)
1 agent: 2 agents = 1: 7
This hair bleaching agent (two-agent type) is a bleaching agent that can reduce the feeling of damage to the hair after bleaching and give the hair a good feel such as flexibility, moistness, and slipperiness by applying it to the hair. there were.

<Example 41> Oxidation Hair Dyeing Agent The copolymer A-3 obtained in Synthesis Example 3 was used to prepare an oxidative hair dyeing agent having the formulations shown in Tables 25 and 26 below.
(Preparation method: 1 agent)
Each component was mixed uniformly.
(Preparation method: 2 agents)
Each component was uniformly mixed and the pH was adjusted to 3.5-4.0 with citric acid.
(Mixing ratio)
1 agent: 2 agents = 1: 1
This oxidative hair dye is an oxidative hair dye that can reduce the feeling of damage to the hair after dyeing and give the hair a good feel such as flexibility, moistness, and slipperiness by applying it to the hair. It was.

<Example 42> Curling agent Using the copolymer B-1 obtained in Synthesis Example 4, curling agents having the formulations shown in Tables 27 and 28 below were produced.
(Preparation method: 1 liquid)
Ingredient No. in Table 27 No. 16 is part of 16 (20%). Add 1 to 3 to dissolve, and in a separate container in advance, No. No. 16 is part of 16 (10%). 14 and 15 were added and dissolved, and the mixture was added at about 40 ° C. and dissolved uniformly (part A). In another container, No. The rest of 16 was heated to about 75 ° C. (Part B). No. in another container. 8 to 13 were taken and heated to about 75 ° C. to dissolve them (Part C). Part B was added to part C, emulsified and mixed well, then cooled to 40 ° C., part A was added and the mixture was uniformly stirred. Next, No. 7 was added and stirred, and then No. Add 5 and 6 and add No. 4 was added, and the mixture was uniformly stirred and mixed to adjust the pH to 9.0 to 9.5 to obtain one desired curling agent solution.
(Preparation method: 2 liquids)
Ingredient No. of Table 28 4 to 7 were heated to about 80 ° C. and dissolved (part A). No. in another container. Part of 9 (70%) and No. 1 and 8 were added, and the mixture was heated to about 80 ° C. and dissolved (part B). In yet another container, No. The rest of 9 and No. A few were added and heated to about 50 ° C. to dissolve (Part C). After adding part B to part A and mixing and stirring uniformly to emulsify, add part C when the temperature reaches 40 ° C and mix well, and adjust the pH to 6.5 to 6.8 at room temperature to obtain the desired content. Two curling agents were obtained.
By using the curling agents 1 and 2 thus produced for hair, it was possible to curl with good flexibility, slippery feeling, moist texture, and good finish feeling.

<Example 43> Using the copolymer B-2 obtained in Hair Cream Synthesis Example 5, a hair cream having the formulation shown in Table 29 below was prepared.
(Preparation method)
Ingredient No. in Table 29 1 to 6 were heated to about 80 ° C. and dissolved (part A). No. in a separate container. 7 to 10 were added, and the mixture was heated to about 80 ° C. and dissolved (part B). Part B was added to part A and stirred and mixed.
This hair cream was glossy, non-greasy, able to retain moisture in the hair and give it a smooth feel.

<Example 44> Leave-on treatment Using the copolymer A-2 obtained in Synthesis Example 2, a leave-on treatment (for hair) according to the formulation shown in Table 30 below was prepared.
(Preparation method)
Ingredient No. in Table 30 1 to 7 were heated to about 80 ° C. and dissolved (part A). No. in another container. 8 and 9 were taken and heated to about 80 ° C. to dissolve them (Part B). Part B was gradually added to part A and mixed uniformly. This leave-on treatment (for hair) had a silky feel and was able to give the hair a feeling of softness and slipperiness. The stability was also good.

<Example 45> Using the copolymer A-2 obtained in Hair Essence Synthesis Example 2, hair essences having the formulations shown in Table 31 below were prepared.
(Preparation method)
Ingredient No. of Table 31 1 to 7 were heated to about 80 ° C. and dissolved (part A). No. in another container. 8 and 9 were taken and heated to about 80 ° C. to dissolve them (Part B). Part B was gradually added to part A and mixed uniformly. This hair essence had a refreshing feel, was not sticky, and was able to give the hair a soft and slippery feel.

<Example 46> Hair restorer The copolymer A-3 obtained in Synthesis Example 3 was used to prepare a hair restorer according to the formulation shown in Table 32 below.
(Production method)
Each component was uniformly stirred and mixed. This hair restorer was able to prevent hair loss, dandruff, and itching.

<Example 47> Perm agent The copolymer A-2 obtained in Synthesis Example 2 was used to prepare a perm agent having the formulations shown in Tables 33 and 34 below.
(Preparation method: 1 liquid)
Ingredient No. in Table 33 Most of 13 are No. No. 11 was dissolved, and then No. 12 was added little by little to dissolve it, and then No. 8 to 10 were added and dissolved (part A). No. in a separate container. Take the rest of No. 13 6 and 7 were added, and the mixture was heated and dissolved (part B). No. in a separate container. 1 to 5 were added, and the mixture was heated to about 50 ° C. and dissolved (part C). Part B was added to part A and mixed uniformly, then part C was gradually added and mixed uniformly.
(Preparation method: 2 liquids)
Ingredient No. of Table 34 Take most of 10 and heat to about 60 ° C. After adding 1 to 3 and dissolving, No. 4 was added and dissolved. Next, No. Add 5 and 6 to heat, dissolve, and slowly cool to No. 4 at around 40 ° C. 7 to 9 were added to make it uniform. The remaining No. 10 was added, mixed uniformly and cooled.
This perm agent was a perm agent that gives the hair a slippery feeling and softness by applying it to the hair.

<Example 48> Bath agent (bubble bath)
Using the copolymer A-1 obtained in Synthesis Example 1, a bath preparation according to the formulation shown in Table 35 below was prepared.
(Production method)
Dissolve A in some C to make it uniform. Add the remaining C and B and knead well. This bathing agent has effects such as moisturizing the skin and improving the gloss of the skin.

<Example 49> Cleansing oil Using the copolymer A-1 obtained in Synthesis Example 1, a cleansing oil having the formulation shown in Table 36 below was prepared.
(Preparation method)
All components were heated, dissolved and mixed.
This cleansing oil has the characteristics of being transparent, viscous, and not dripping during use, has a refreshing feel, and is well-adapted to foundations, makeup, etc., and can be quickly removed.

<Example 50> Using the copolymer A-1 obtained in Liquid Facial Cleanser Synthesis Example 1, a liquid facial cleanser according to the formulation shown in Table 37 below was prepared.
(Production method)
Ingredient No. of Table 37 3 and 10 were heated to about 80 ° C. and dissolved (part A). No. in part A 1, 2, 4 to 9, 11 to 13 were added, and the mixture was heated to about 80 ° C. to uniformly dissolve and then cooled. In addition, No. The prescription excluding only 9 was blank.
Ten panelists evaluated the feel of the skin after using the facial cleanser. The evaluation was superior to the blank in both items of slippery feeling and moist feeling.

<Example 51> Body shampoo A body shampoo having the formulation shown in Table 38 below was prepared using the copolymer A-1 obtained in Synthesis Example 1.
(Production method)
Ingredient No. in Table 38 No. 1 and a part of No. 11 were heated at about 80 ° C. and mixed uniformly (part A). No. 2-No. 10. The remaining 11 were heated at about 80 ° C. and mixed uniformly (part B). While stirring, part A was gradually added to part B and mixed uniformly. In addition, No. The prescription excluding only 8 was blank.
Ten panelists evaluated the feel of the skin after using the body shampoo. The results were superior to the blank for both the slippery feeling and the moist feeling in the evaluation.

<Examples 52 to 56> Soaps having the formulations shown in Table 39 below were prepared using the copolymers A-1 to 3, B-1, and 2 obtained in Soap Synthesis Examples 1 to 5.
(Production method)
All components are heated and dissolved at 80 ° C., cooled with stirring, poured into a mold and left to stand. In addition, the formulation excluding only the copolymers A-1 to 3, B-1, and 2 was used as a blank.
Ten panelists evaluated the feel of the skin after using the soap. The evaluation was performed on two items, a slippery feeling and a moist feeling. The results are shown in Table 40 below. In the table,
◎: 8 or more out of 10 answered that it was better than blank,
◯: 6 or more out of 10 answered that it was better than blank,
Δ: 4 or more out of 10 responded that it was better than blank,
X: Less than 4 out of 10 responded that it was better than blank.
As described below, it can be seen that the soap containing the product of the present invention can impart a moist feeling and a smooth slippery feeling to the skin as compared with the non-blended product, and is also excellent as a fattening agent.

Claims (7)

Structural unit (a) derived from unsaturated monomer (A) having a lactam structure, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, tert-butylstyrene, chlorostyrene , A hydroxyl group-containing (meth) acrylate, an addition reaction product of an unsaturated monomer having an epoxy group and an alcohol, an unsaturated monocarboxylic acid and a salt thereof, and an unsaturated dicarboxylic acid and a salt thereof. at least one kind of unsaturated monomer (B) structural units derived from (b) and the coercive having humectant polymer (however, under following formula (7);

(In the formula, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X is a hydroxyl group or an OM group (M is a group derived from an alkali metal element, an ammonium group or an organic base). (Represented), including polymers having structural units derived from monomers represented by).
-Holding humectant polymer, the proportion of the structural unit (a) is a cosmetic or a skin external preparation for moisturizer characterized in that it is a 5 0-99 wt% with respect to the total structural units 100 wt% (however, Excludes those containing graft polymers.) The moisturizer for cosmetics or skin external preparations according to claim 1, wherein the unsaturated monomer having a lactam structure is an unsaturated monomer having a pyrrolidone ring. The structural unit (b) is represented by the following formula (6);

(Wherein, R ¹³ is .R ¹⁴ is hydrogen represents a hydrogen atom or a methyl group, monovalent metal atom, a divalent metal atom, a trivalent metal atom, or represents a quaternary ammonium salt group. The moisturizing agent for cosmetics or skin external preparations according to claim 1 or 2, which is a structural unit derived from a monomer represented by). The moisturizer for cosmetics or skin external preparations according to claim 3, wherein the structural unit (b) is a structural unit derived from (meth) acrylic acid or a salt thereof. The cosmetic or skin moisturizer according to any one of claims 1 to 4, wherein the moisturizer polymer is used for skin cosmetics, skin external preparations or hair cosmetics. The moisturizer for cosmetics or skin external preparations according to any one of claims 1 to 5, wherein the moisturizer polymer is water-soluble. A skin cosmetic, an external preparation for skin, or a cosmetic for hair, which comprises the cosmetic according to any one of claims 1 to 6 or a moisturizer for external preparation for skin.