JP2000319137A - Moisturizer for hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject moisturizer which has an excellent moisturizing property for hair, by using a polymer produced by binding a water-soluble polyalkylene polyol to a comb type hydrophobic diol with a polyisocyanate. SOLUTION: This moisturizer is a polymer which has a weight-average mol.wt. of 104 to 106 (measured by GPC) and comprises repeating units of formula I in a molar ratio of 0.5 to 0.99 and repeating units of formula II A is the divalent residue of HO-A-OH which is a water-soluble polyalkylene polyol having hydroxy groups at both the molecular ends and having a number-average mol.wt. of 400 to 105; B is the divalent residue of OCN-B-NCO which is a 3 to 18C polyisocyanate compound (for example, isophorone diisocyanate or the like); D is the divalent residue of a comb type hydrophobic diol of HO-D-OH, such as a diol of formula III [R1 is a 1-20C hydrocarbon; R2, R3 are each a 4 to 21C hydrocarbon; Y, Y' are each H, methyl or the like; Z, Z' are each O, S or the like; (n), (n') are each 0 to 15]} in a molar ratio of 0.01 to 0.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel moisturizer for hair cosmetics having excellent moisturizing properties for hair.

[0002]

2. Description of the Related Art Hair cosmetics such as hair conditioners, hair gels, hair foams, shampoos, and rinses require a humectant consisting of a water-soluble polymer to give the hair a crisp feel. Water-soluble polymers such as polyethylene glycol (PEG) and various cellulose ethers are widely used. However, polyethylene glycol has a problem in that the hair is sticky and lacks a crisp feeling. In addition, cellulose ethers such as hydroxyethyl cellulose (HEC) have a problem that the hair becomes hard and lacks a feeling of tightness.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide PE
An object of the present invention is to provide a new hair moisturizing agent for hair cosmetics which is excellent in water retention and firmness for hair, replacing G and cellulose ethers.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a moisturizer for hair cosmetics comprising a novel soluble polyurethane having a comb-shaped hydrophobic diol as a hydrophobic group. Thus, the present invention has been completed. The present invention provides a compound represented by the following chemical formula 1:

[0005]

Embedded image And a repeating unit (1) represented by the following formula:

[0006]

Embedded image A polymer comprising a repeating unit (2) represented by the formula:
The molar ratio of the repeating unit (1) is 0.5 or more and 0.99 or less, the molar ratio of the repeating unit (2) is 0.01 or more and 0.5 or less, and the weight average molecular weight measured by GPC is 10 or more. New hair cosmetic moisturizers in the range of 2,000 to 1,000,000.

However, A is HO-A-OH having a hydroxyl group at least at both ends and having a number average molecular weight of 400 to 10
A divalent group which is a 000 water-soluble polyalkylene polyol (compound A), and B is a polyisocyanate in which OCN-B-NCO is selected from the group consisting of polyisocyanates having 3 to 18 carbon atoms in total. A divalent group which is a nate compound (compound B), wherein D is HO-D-OH represented by the chemical formula 3

[0008]

Embedded image(However, R¹Is a hydrocarbon group having 1 to 20 carbon atoms.
You. Also R^TwoAnd R^ThreeIs a hydrocarbon group having 4 to 21 carbon atoms
It is. The hydrocarbon group R¹, R^TwoAnd R^ThreeHydrogen in
Part or all of it with fluorine, chlorine, bromine or iodine
May be replaced by R^TwoAnd R^ThreeAre the same but different
Is also good. Y and Y 'are hydrogen, methyl or CH
_TwoCl and Y and Y 'may be the same or different
No. Z and Z 'are oxygen, sulfur or CH_TwoIn the base
Z and Z 'may be the same or different. And n is
When Z is oxygen, it is an integer of 0 to 15, and Z is not sulfur
CH _TwoIn the case of a group, it is 0. N 'is Z' of oxygen
Is an integer of 0 to 15, wherein Z 'is sulfur or CH_Two
0 in the case of a group, and n and n 'are the same or different
Or chemical formula 4

[0009]

Embedded image (However, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms. R ⁵ and R ⁶ are a hydrocarbon group having 4 to 21 carbon atoms. The hydrocarbon groups R ⁴ , R ⁵ and A part or all of hydrogen in R ⁶ may be substituted by fluorine, chlorine, bromine or iodine, and R ⁵ and R ⁶ may be the same or different, and Y, Y ′ and Y ″ are hydrogen. , A methyl group or a CH ₂ Cl group, Y and Y ′ may be the same or different, and Z and Z ′ represent oxygen, sulfur or CH ₂
Z and Z ′ may be the same or different. R ⁷ is an alkylene group having 2 to 4 carbon atoms, and k is 0.
It is an integer of １５15. N is 0 to 1 when Z is oxygen.
It is an integer of 5 and is 0 when Z is a sulfur or CH ₂ group. N ′ is an integer of 0 to 15 when Z ′ is oxygen; 0 when Z ′ is sulfur or a CH ₂ group;
And n ′ may be the same or different.)
(Formula 10)

[0010]

Embedded image(However, R⁸And R⁹Is R⁸And R⁹Has a total carbon number of 2
To 20 hydrocarbon groups. Also R^TenAnd R¹¹Is carbon
It is a hydrocarbon group having a number of 4 to 21. The hydrocarbon group R
⁸, R⁹, R^TenAnd R¹¹Some or all of the hydrogen
It may be substituted by nitrogen, chlorine, bromine or iodine. R
⁸And R⁹May be the same or different. R ^TenAnd R¹¹Is the same
It may be the same or different. Also R¹²Has 2 to 7 carbon atoms
Is an alkylene group. Y and Y 'are hydrogen, methyl
Group or CH_TwoCl and Y and Y 'are the same but different
It may be. Z and Z 'have no oxygen or sulfur
CH_TwoZ and Z 'are the same or different
Good. N is an integer of 0 to 15 when Z is oxygen.
Z is sulfur or CH_TwoIn the case of a group, it is 0. Also
n ′ is an integer of 0 to 15 when Z ′ is oxygen;
Is sulfur or CH_TwoGroup is 0, and n and n 'are the same
(Which may be the same or different)
All (compound D) is a divalent group.

In the present invention, the compound A has a number average molecular weight of 4
00-20,000 polyethylene glycol,
The humectant for hair cosmetics, wherein the compound B is a chain aliphatic diisocyanate or a cycloaliphatic diisocyanate. Further, the present invention is the humectant for hair cosmetics, wherein the compound B is hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate or norbornene diisocyanate.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer used in the present invention is a polyurethane having a comb-shaped hydrophobic group obtained by connecting a water-soluble polyalkylene polyol and a comb-shaped hydrophobic diol with a polyisocyanate. The water-soluble polyalkylene polyol (Compound A) used in the present invention is an alkylene oxide polymer having hydroxyl groups at least at both ends of a polymer chain. However, when a polyalkylene polyol having three or more hydroxyl groups is used, the solubility of the product in water tends to decrease. Therefore, it is more preferable to use a polyalkylene glycol having primary hydroxyl groups at both ends of the polymer chain. Examples of the monomer alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and epichlorohydrin. In order to increase the solubility in water and polar solvents, the content of ethylene oxide is 40% by weight or more. Is more preferable. More preferably, a polymer of ethylene oxide (polyethylene glycol; hereinafter abbreviated as PEG) is used.

The compound A has a number average molecular weight of 40.
Those having 0 to 100,000 are preferred. More preferably, it is 1,000 to 20,000. When the molecular weight is less than 400, a product having low water retention is easily obtained, which is not suitable for use as a hairdressing agent. When the molecular weight is larger than 100,000, a product having low solubility is easily obtained. If the molecular weight is 1,
In the range of 000 to 20,000, a product showing sufficient moisture retention and solubility is most easily obtained.

The polyisocyanate compound (compound B) used in the present invention has a total carbon number selected from the group consisting of linear aliphatic polyisocyanates, cycloaliphatic polyisocyanates, and aromatic polyisocyanates. Is (N
3-18 polyisocyanate compounds (including the carbon of the CO group). Polyisocyanates having a total carbon number of 18
If it is larger, the solubility of the polyurethane tends to decrease. However, when a polyisocyanate having three or more NCO groups in the molecule is used, the solubility of the product in water tends to decrease. Therefore, it is more preferable to use diisocyanates having two NCO groups in the molecule.

The diisocyanates include aromatic diisocyanates, chain aliphatic diisocyanates, cycloaliphatic diisocyanates, and the like. Among them, chain aliphatic diisocyanates and cycloaliphatic diisocyanates. The natos are mildly reactive compared to the aromatic diisocyanates, are relatively low in irritation, and are easy to use. Accordingly, it is more preferable to use chain and cyclic aliphatic diisocyanates having 3 to 18 carbon atoms. More preferably, hexamethylene diisocyanate (commonly referred to as HDI), isophorone diisocyanate (commonly known as IPDI), hydrogenated tolylene diisocyanate (commonly known as HTDI), hydrogenated xylylene diisocyanate (commonly known as HXDI), or norbornene diisocyanate (commonly known) NBDI). Particularly preferably, HDI is used.

The chain aliphatic diisocyanates are NCO
A diisocyanate compound having a structure in which groups are connected by a linear or branched alkylene group, and specific examples include methylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, and 1-methylethylene. Diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, 2,2′-dimethylpentane -1,5-diisocyanate, lysine diisocyanate methyl ester (LD
I), octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4
-Trimethylpentane-1,5-diisocyanate, nonamethyldiisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate, decamethylenediisocyanate, undecamethylenediisocyanate, dodecamethylenedi Isocyanate, tridecamethylene diisocyanate, tetradecamethylene diisocyanate,
Pentadecamethylene diisocyanate, hexadecamethylene diisocyanate, trimethylhexamethylene diisocyanate and the like can be mentioned.

Cycloaliphatic diisocyanates are NCO
A diisocyanate compound in which an alkylene group connecting the groups has a cyclic structure, and specific examples thereof include cyclohexane-1,2-diisocyanate and cyclohexane-1,3.
-Diisocyanate, cyclohexane-1,4-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1-methylcyclohexane-2,6-diisocyanate, 1-ethylcyclohexane-2,4-
Diisocyanate, 4,5-dimethylcyclohexane-
1,3-diisocyanate, 1,2-dimethylcyclohexane-ω, ω′-diisocyanate, 1,4-dimethylcyclohexane-ω, ω′-diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane -4,4'-diisocyanate, dicyclohexylmethylmethane-4,4'-diisocyanate, dicyclohexyldimethylmethane-4,4'-diisocyanate, 2,2'-dimethyldicyclohexylmethane
4,4′-diisocyanate, 3,3′-dimethyldicyclohexylmethane-4,4′-diisocyanate,
4,4′-methylene-bis (isocyanatocyclohexane), isopropylidenebis (4-cyclohexyl isocyanate) (IPCI), 1,3-bis (isocyanatomethyl) cyclohexane, hydrogenated tolylene diisocyanate (HTDI), Hydrogenated 4,4'-diphenylmethane diisocyanate (HMDI), hydrogenated xylylene diisocyanate (HXDI), norbornene diisocyanate (NBDI) and the like can be mentioned.

Aromatic diisocyanates are diisocyanate compounds in which NCO groups are linked by an aromatic group such as a phenylene group, an alkyl-substituted phenylene group and an aralkylene group or a hydrocarbon group containing an aromatic group. Specific examples thereof include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate (2,4-TDI), and 1-methyl-2,6-
Phenylene isocyanate (2,6-TDI), 1-
Methyl-2,5-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3
-Dimethyl-2,4-phenylene diisocyanate,
1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, m-xylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1- Methyl-3,5-diethylbenzene-
2,4-diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5
-Triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-
1,5-diisocyanate, 1-methylnaphthalene-
1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'- Diisocyanate, biphenyl-4,4'-diisocyanate, 1,3-bis (1
-Isocyanato-1-methylethyl) benzene, 3,
3'-dimethylbiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4'-diisocyanate And xylylene diisocyanate (XDI).

Other polyisocyanates include 1,
6,11-undecatriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane,
1,3,6-hexamethylene triisocyanate and the like.

The comb-shaped hydrophobic diol (compound D) used in the present invention has two secondary hydroxyl groups in the molecule represented by the chemical formulas 3, 4 and 5, and has a hydrophobic chain in the molecule. Are three or more hydrophobic diols. The hydrophobic diols can be obtained by adding various oxirane compounds (compounds having an oxirane ring) to primary amines. The addition reaction between the amino group of the amines and the oxirane compound has a high activity, and the reaction proceeds sufficiently without a catalyst.

More specifically, the primary amines include primary linear or cyclic alkylamines, primary linear or cyclic alkenylamines, primary aralkylamines, and primary dialkylamino. Alkylamines,
Primary N-benzylaminopyrrolidines, primary N-aminoalkylmorpholines, primary arylamines,
Primary aminopyridines, primary aminoalkylpyridines, primary alkyloxyalkylamines, primary alkenyloxyalkylamines, primary aryloxyalkylamines, primary aralkyloxyalkylamines And the like.

Examples of primary chain alkylamines include:
Methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, ter-butylamine, sec-butylamine, n-pentylamine,
n-hexylamine, n-heptylamine, 2-aminoheptane, n-octylamine, isooctylamine,
2-aminooctane, 2-ethylhexylamine, 2-
Amino-6-methylheptane, nonylamine, isononylamine, 1,4-dimethylheptylamine, 3-aminononane, 2-amino-6-ethylheptane, n-decylamine, n-undecylamine, 2-aminoundecane, 6 -Aminoundecane, n-dodecylamine, n-
Tridecylamine, 2-aminotridecane, n-tetradecylamine, 2-aminotetradecane, n-pentadecylamine, 8-aminopentadecane, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n And linear alkylamines such as -nonadecylamine and 2-aminononadecane.

Examples of primary chain alkenylamines include allylamine and oleylamine. Examples of primary cyclic alkylamines include cyclohexylamine, cycloheptylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, aminomethylcyclohexane, cyclooctylamine, 2,3-dimethylcyclohexyl Amine, 3,3,5-trimethylcyclohexylamine, 4-ter-butylcyclohexylamine, 1-
Cyclopentyl-2-aminopropane, 1-aminoindan, cyclododecylamine, o-aminobicyclohexyl, 3-aminospiro [5,5] undecane, bornylamine, 1-adamantanamine, 2-aminonorbornane, 1-adamantanmethylamine and the like Is mentioned.

Examples of the primary cyclic alkenylamines include dihydroabiethylamine, 2- (1-cyclohexenyl) ethylamine and the like. Examples of primary aralkylamines include benzylamine, phenethylamine, p-methoxyphenethylamine, α-phenylethylamine, 1-methoxy-3-phenylpropylamine, N-aminopropylaniline and the like.

Examples of primary dialkylaminoalkylamines include N, N-dimethylethylenediamine, N, N
N-diethylethylenediamine, N, N-diisopropylethylenediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, diethylaminopropylamine, dibutylaminopropylamine, 1-dimethyl Amino-2-propylamine, N2, N2-dimethyl-1,2-propanediamine, 4-dimethylaminobutylamine, 1-dimethylaminoethyl-2-aminopropane, N, N-dimethylneopentanediamine, 1-diethylamino- 2-propylamine, 6-dimethylaminohexylamine, 2-
Di-n-propylaminoethylamine, N-ethyl-N
-Butylethylenediamine, 7-diethylaminoheptylamine, N1, N1-di-n-propyl-1,2-propanediamine, N ', N'-di-n-propanediamine, 5-diethylaminopentylamine, 2- Amino-
5-diethylaminopentane, N, N-di-n-butylethylenediamine, N, N-di-tert-butylethylenediamine, 2-diisobutylaminoethylamine,
4-diisopropylaminobutylamine, 7-diethylaminoheptylamine, 3- (di-n-butylamino)
Propylamine, N, N-diisobutyl-1,6-hexanediamine, 3-dioctylaminopropylamine,
3-didecylaminopropylamine, 1- (2-aminoethyl) piperidine, 3-piperidinopropylamine,
4-pyrrolidinobutylamine, N-aminoethyl-4-
Pipecoline, 3-aminotropane, 5-pyrrolidinoamylamine, N-aminopropyl-4-pipecholine, 1-
(3-aminopropyl) -2-pipecholine, 1-aza-
Bicyclo [2.2.2] oct-3-ylamine, 1-
Benzyl-3-aminopyrrolidine, N1-ethyl-N1
-Phenylpropane-1,3-diamine and the like.

Examples of primary N-benzylaminopyrrolidines include N-benzyl-3-aminopyrrolidine and N-benzylaminopyrrolidine.
-Benzyl-2-methyl-3-aminopyrrolidine and the like. Examples of primary N-aminoalkylmorpholines include N-aminoethylmorpholine, N-aminopropylmorpholine and the like.

Examples of primary arylamines include aniline, 2-chloroaniline, 2,3-dichloroaniline, 2,4-dibromoaniline, 2,4,6-tribromoaniline, o-toluidine, -Chloro-4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2-ethylaniline, 2-isopropylaniline, 4-tert-butylaniline, p-decylaniline , P-dodecylaniline, p-tetradecylaniline, 4-cyclohexylaniline, 2-aminobiphenyl, 1-naphthylamine, 5-aminoindane, 1-aminonaphthacene, 6-
Aminochrysene, 1-aminopyrene and the like can be mentioned.

Examples of primary aminopyridines include 2
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-propylpyridine, 2-amino-4, 6-dimethylpyridine, 2
-Amino-3-nitropyridine and the like. Examples of primary aminoalkylpyridines include 2-aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 3-aminomethyl-6-chloropyridine, and the like.

The primary alkyloxyalkylamines include 2-alkoxyethylamines, 3-alkoxypropylamines, 4-alkoxybutylamines, alkenyloxyalkylamines, aralkyloxyalkylamines, and aryloxyalkylamines. Phenols, aminoalkyl ethers of alcohol-alkylene oxide adducts, and aminoalkyl ethers of phenol / alkyl-substituted phenol-alkylene oxide adducts.

The 2-alkoxyethylamines include
2-methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine, 2-isopropoxyethylamine, 2-butoxyethylamine, 2- (isobutoxy) ethylamine, 2- (tert-butoxy) ethylamine, 2-pentyloxyethylamine, 2- Hexyloxyethylamine, 2-heptyloxyethylamine, 2-octyloxyethylamine, 2- (2-
Ethylhexyloxy) ethylamine, 2- (α-butyloctyloxy) ethylamine, 2-decyloxyethylamine, 2-dodecyloxyethylamine, 2-tetradecyloxyethylamine, 2-pentadecyloxyethylamine, 2-hexadecyloxyethylamine, -Heptadecyloxyethylamine, 2-octadecyloxyethylamine, 2-nonadecylethylamine, 2-eicosylethylamine and the like.

Examples of 3-alkoxypropylamines include 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3- (isobutoxy) Propylamine, 3- (te
(r-butoxy) propylamine, 3-pentyloxypropylamine, 3-hexyloxypropylamine, 3
-Heptyloxypropylamine, 3-octyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3- (α-butyloctyloxy) propylamine, 3-decyloxypropylamine, 3-dodecyloxypropylamine, 3-, 3-tetradecyloxypropylamine, 3-pentadecyloxypropylamine, 3-hexadecyloxypropylamine, 3
-Heptadecyloxypropylamine, 3-octadecyloxypropylamine, 3-nonadecylpropylamine, 3-eicosylpropylamine and the like.

Examples of 4-alkoxybutylamines include 4-methoxybutylamine, 4-ethoxybutylamine, 4-propoxybutylamine, 4-isopropoxybutylamine, 4-butoxybutylamine, 4- (isobutoxy) butylamine, and 4- (tert-butylamine). -Butoxy)
Butylamine, 4-pentyloxybutylamine, 4-
Hexyloxybutylamine, 4-heptyloxybutylamine, 4-octyloxybutylamine, 4- (2
-Ethylhexyloxy) butylamine, 4- (α-butyloctyloxy) butylamine, 4-decyloxybutylamine, 4-dodecyloxybutylamine, 4-
Tetradecyloxybutylamine, 4-pentadecyloxybutylamine, 4-hexadecyloxybutylamine, 4-heptadecyloxybutylamine, 4-octadecyloxybutylamine, 4-nonadecylbutylamine, 4-eicosylbutylamine, 4- (2,4 -Ji-
ter-amylphenoxy) butylamine and the like.

Examples of alkenyloxyalkylamines include 3-vinylpropylamine, 2-allyloxyethylamine, 3-oleyloxypropylamine and the like. Examples of aralkyloxyalkylamines include 2-benzyloxyethylamine,
Examples include 3-phenethyloxypropylamine. As aryloxyalkylamines,
Examples thereof include 2-phenyloxyethylamine and 3- (p-nonylphenyloxy) propylamine.

Other amines include aminoalkanol ethers of alkylene oxide adducts of alcohols and phenols (ethylene oxide adduct, propylene oxide adduct, epichlorohydrin adduct, etc.). Examples of aminoalkanol ethers of alcohol-ethylene oxide adducts include 2
-[2- (dodecyloxy) ethoxy] ethylamine,
3,6,9-trioxapentadecylamine and the like. Similarly, aminoalkanol ethers of propylene oxide adducts of alcohols and phenols, propylene oxide / ethylene oxide adducts, and epichlorohydrin adducts can also be used. Appropriate number k of addition is about 1-15. Addition number is 1
If it exceeds 5, it tends to be sticky when applied to hair. Other 1
As the secondary amines, 2-aminomethylpyrazine, 2-aminomethylpyrazine
Pyrazines such as aminopyrazine and sulfalene;

As oxirane compounds, various glycidyl ethers, 1,2-epoxyalkanes, 1,2
-Epoxy alkenes, glycidyl sulfides and the like can be used. Examples of glycidyl ethers include alkyl glycidyl ethers, alkenyl glycidyl ethers, aralkyl glycidyl ethers, and aryl glycidyl ethers.

Examples of alkyl glycidyl ethers include n-butyl glycidyl ether, sec-butyl glycidyl ether, ter-butyl glycidyl ether, glycidyl pentyl ether, glycidyl hexyl ether, glycidyl octyl ether, 2-ethylhexyl glycidyl ether, Methyl octyl glycidyl ether, glycidyl nonyl ether, decyl glycidyl ether, dodecyl glycidyl ether, glycidyl lauryl ether, glycidyl tridecyl ether, glycidyl tetradecyl ether, glycidyl pentadecyl ether, glycidyl hexadecyl ether,
Glycidyl stearyl ether, 3- (2- (perfluorohexyl) ethoxy) -1,2-epoxypropane, 3- (3-perfluorooctyl-2-iodopropoxy) -1,2-epoxypropane and the like can be mentioned. .

Examples of alkenyl glycidyl ethers include allyl glycidyl ether and oleyl glycidyl ether. Examples of aralkyl glycidyl ethers include benzyl glycidyl ether and phenethyl glycidyl ether. Examples of aryl glycidyl ethers include phenyl glycidyl ether, 4-ter-butylphenyl glycidyl ether, 2-ethylphenyl glycidyl ether,
-Ethylphenyl glycidyl ether, 2-methylphenyl glycidyl ether, glycidyl-4-nonyl phenyl ether, glycidyl-3- (pentadecadienyl) phenyl ether, 2-bisphenyl glycidyl ether, benzyl glycidyl ether, α-naphthyl glycidyl ether And dibromophenyl glycidyl ether. Other glycidyl ethers include glycidyl ethers of alkylene oxide adducts of alcohols and phenols (such as ethylene oxide adducts, propylene oxide adducts, and epichlorohydrin adducts).

Examples of the glycidyl ether of the ethylene oxide adduct include 2-ethylhexyl alcohol
Examples include glycidyl ether of ethylene oxide adduct, glycidyl ether of lauryl alcohol-ethylene oxide adduct, glycidyl ether of 4-ter-butylphenol-ethylene oxide adduct, and glycidyl ether of nonylphenol-ethylene oxide adduct.

Similarly, glycidyl ethers of propylene oxide adducts of alcohols and phenols, propylene oxide / ethylene oxide adducts, and epichlorohydrin adducts can be used.
The glycidyl ethers of industrial chemicals usually contain glycidyl ethers of epichlorohydrin adduct as by-products, but such low-purity raw materials can also be used. The addition number n is suitably about 1 to 15.
When the number of additions exceeds 15, the aqueous solution viscosity of the polyurethane tends to decrease.

In addition, 1,2-epoxyalkanes and 1,2
Examples of epoxy alkenes include 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, and 1,2-epoxidedodecane. , 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,
Examples thereof include 2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxy-7-octene, and 1,2-epoxy-9-decene.

Other oxirane compounds include alkyl glycidyl thioethers (alkyl glycidyl sulfides) such as 2-ethylhexyl glycidyl sulfide and decyl glycidyl sulfide, and aryl glycidyl thioethers (aryl glycidyl sulfide) such as p-nonylphenyl glycidyl sulfide. Can be

The above amines and oxirane compounds are
Compound D can be obtained by reacting one molecule of the amine with two molecules of the oxirane compound. Chemical formula 6
Represents a reaction formula (Chem. 11).

[0043]

Embedded image (However, R ^a , R ^b , and R ^c are substituents corresponding to each of the comb-shaped hydrophobic diols represented by the chemical formulas 3, 4 and 5.) The reaction was performed using 1,2-epoxyalkanes as oxirane compounds, It is easier to use glycidyl ethers than to use 1,2-epoxyalkenes and glycidyl sulfides. This is probably because the reactivity of glycidyl ethers with amines is high.

Compound D has 3 to 4 hydrophobic chains (R ¹ , R ² and R ^{3 in} Formula ³ or R ⁴ , R ⁵ and R ^{6 in} Formula 4 or R ^{8 in} Formula 5; R ⁹ , R
¹⁰ and R ¹¹ ), but having these hydrophobic chains close to each other has an effect of imparting appropriate hydrophobicity to the polyurethane. It is presumed that it is this moderate hydrophobicity that gives the hair a crisp feel when used in hair styling agents and the like. The number of carbon atoms in each hydrophobic chain needs to be long enough to impart appropriate hydrophobicity to the polyurethane.

The number of carbon atoms in the hydrophobic chain of the amines is preferably 1 or more and 20 or less. When amines having more than 20 carbon atoms in the substituents R ¹ to R ⁴ are used, the solubility of the polyurethane may be reduced. Similarly, when an amine having a total of carbon atoms of the substituents R ⁸ and R ⁹ exceeding 20 is used, the solubility of the polyurethane may be reduced.

The hydrophobic chains of glycidyl ethers (formula 3
The carbon number of R ² and R ^{3 in the} formula, R ⁵ and R ⁶ in the chemical formula 4, or R ¹⁰ and R ¹¹ ) in the chemical formula 5 is preferably from 4 to 21. If a glycidyl ether having less than 4 carbon atoms is used, the hydrophobicity of the polyurethane may not be sufficiently high. When a glycidyl ether having more than 21 carbon atoms is used, the solubility of the polyurethane may decrease. More preferably, alkyl glycidyl ethers having a linear or branched alkyl group having 4 to 18 carbon atoms as a hydrophobic group, or an aromatic group having 6 to 18 carbon atoms or an alkyl-substituted aromatic group as a hydrophobic group. Aryl glycidyl ethers. For the same reason, the number of carbon atoms of the hydrophobic group of 1,2-epoxyalkane, 1,2-epoxyalkene, alkyl glycidyl thioether and aryl glycidyl thioether is preferably 4 or more and 21 or less.

The method for producing the comb-shaped hydrophobic diol will be described below, but the method for synthesizing the comb-shaped hydrophobic diol used in the present invention is not limited to this example. Raw materials amines and oxirane compounds are charged into a reaction vessel having a stirrer, a raw material introduction mechanism, and a temperature control mechanism, and reacted while stirring at a predetermined reaction temperature. The reaction can be performed without a solvent, but a general solvent such as DMF may be used. For the introduction of the raw materials, the amines and the oxirane compounds may be charged all at once, or one of them may be charged into a reaction vessel, and the other may be introduced continuously or stepwise.
The reaction temperature is from room temperature to about 160 ° C., more preferably 60 ° C.
A temperature of about -120 ° C is appropriate. The reaction time is about 0.5 to 10 hours, depending on the reaction temperature and the like. The degree of dispersion of the diol after completion of the reaction can be determined by GPC. Further, the OH value can be determined by a conventional method. Soluble polyurethane having a comb-shaped hydrophobic group is represented by the following chemical formula (7).
2)

[0048]

Embedded image As shown in the above, polyalkylene glycol (compound A)
And two hydroxyl groups of a comb-like hydrophobic diol (compound D) and two NCOs of a diisocyanate compound (compound B)
It is synthesized by the reaction of groups. The soluble polyurethane in which the molar ratio of the repeating unit (1) is (1-x) and the molar ratio of the repeating unit (2) is x is a compound A and a compound D
Are obtained by reacting at a molar ratio of (1-x): x.

Hereinafter, a method for producing a soluble polyurethane will be described with reference to examples, but the present invention is, of course, not limited to the following method. The inside of a reaction vessel having a stirring device, a raw material introduction mechanism, and a temperature control mechanism is replaced with an inert gas.
A polyalkylene glycol is charged into a reaction vessel. In some cases, a solvent is charged. The catalyst is added while controlling the reaction vessel at the set reaction temperature. While stirring the inside of the vessel, the diisocyanate compound and the comb-shaped hydrophobic diol are introduced into the reaction vessel. The method of introduction is not particularly limited. It may be introduced continuously or intermittently. Also, the diisocyanate compound and the comb-shaped hydrophobic diol may be introduced simultaneously, or even if the comb-shaped hydrophobic diol is introduced after the introduction of the diisocyanate compound, the diisocyanate compound may be introduced after the introduction of the comb-shaped hydrophobic diol. Is also good.

It is not necessary to add the catalyst to the polyalkylene glycol before the reaction, and the reaction can be started by adding the catalyst after adding the diisocyanate compound or the comb-shaped hydrophobic diol to the polyalkylene glycol. Alternatively, it is also possible to add a catalyst to the diisocyanate compound or the comb-shaped hydrophobic diol in advance, and to react these with the polyalkylene glycol. The catalyst used for the reaction is not particularly limited, and known catalysts generally used for the reaction of isocyanates and polyols, such as organometallic compounds, metal salts, tertiary amines, other base catalysts and acid catalysts, may be used. Can be used. For example, dibutyltin dilaurate (hereinafter referred to as DBTDL)
Abbreviated), dibutyltin di (dodecylthiolate), stannous octanoate, phenylmercuric acetate, zinc octoate, lead octoate, zinc naphthenate, lead naphthenate, triethylamine (TEA), tetramethylbutanediamine (TMBDA), N-ethylmorpholine (NEM), 1,4-diaza [2.2.2] bicyclooctane (DABCO), 1,8-diazabicyclo [5.
4.0] -7-undecene (DBU), N, N'-dimethyl-1,4-diazacyclohexane (DMP) and the like.

The amount of the catalyst used in the reaction varies depending on the reaction temperature and the type of the catalyst, and is not particularly limited.
0.0001 per mole of polyalkylene glycol
0.1 mol, more preferably about 0.001 to 0.1 mol is sufficient. The reaction can be carried out without a solvent, but the reaction can also be carried out using a solvent in order to reduce the melt viscosity of the product. Solvents include halogenated solvents such as carbon tetrachloride, dichloromethane, chloroform and trichlene; aromatic solvents such as xylene, toluene and benzene; and saturated hydrocarbons such as decane, octane, heptane, hexane, cyclohexane and pentane. Solvent or
Dioxane, tetrahydrofuran, diethyl ether,
Solvents without active hydrogen, such as ether solvents such as dimethyl ether and ethylene glycol dimethyl ether, ketone solvents such as diethyl ketone, methyl ethyl ketone and dimethyl ketone, and ester solvents such as ethyl acetate and methyl acetate are effectively used. . However, not using a solvent is advantageous in terms of manufacturing cost because the step of removing the solvent is unnecessary, and is more preferable because there is less risk of environmental pollution.

The amount of the diisocyanate compound used in the reaction is such that the total number of moles of the polyalkylene glycol and the comb-shaped hydrophobic diol is 1 mole, and the number of moles of the diisocyanate compound (NCO / OH) is 0 mole. 0.7 to 1.3 mol, more preferably 0.8 to 1.2 mol. 0.7
If it is less than 1.3 or more than 1.3, the average molecular weight of the product is small and the ability as a hair cosmetic humectant is not sufficient. However, when water is contained in the polyalkylene glycol or the comb-shaped hydrophobic diol, the amount of the above-mentioned diisocyanate compound needs to be used in excess of the amount by which the diisocyanate is decomposed by the water. Therefore, it is more preferable to use a sufficiently dried raw material. If possible, the water content of the raw material is preferably 5,000 ppm or less. More preferably 1,000 ppm or less, further preferably 200p
pm or less.

The amount of the comb-shaped hydrophobic diol used in the reaction is as follows:
Depending on the molecular weight of the polyalkylene glycol and the number of carbon atoms in the hydrophobic group of the comb-shaped hydrophobic diol, the number of moles of the comb-shaped hydrophobic diol is 0.01 to 1 mole per mole of the polyalkylene glycol (x is 0.01 to 0). .5) is appropriate. If the amount is less than 0.01 mol, a sufficient hydrophobic effect may not be exhibited. In addition, it is not preferable to cause the reaction to exceed 1 mol because the solubility may be reduced.
In addition, the numerical value in () represents the value of x in the chemical formula 7.

The reaction temperature varies depending on the type and amount of the catalyst used, but is suitably from 50 to 180 ° C. More preferably 60 to 150 ° C, further preferably 80 to 12 ° C.
It is in the range of 0 ° C. If the reaction temperature is lower than 50 ° C., the reaction rate is low and it is not economical. If the temperature exceeds 180 ° C., the product may be thermally decomposed. The reaction time varies depending on the type and amount of the catalyst used, the reaction temperature and the like, and is not particularly limited, but about 1 minute to 10 hours is sufficient. The reaction pressure is not particularly limited. The reaction can be carried out under normal pressure, reduced pressure or increased pressure. More preferably, the reaction is carried out under normal pressure or weak pressure.

The characteristics of the soluble polyurethane obtained by the present invention are described below. Polymers having a weight average molecular weight measured by GPC in the range of about 10,000 to 1,000,000 are suitable for the present invention. More preferably, the weight average molecular weight is 1
10,000 to 500,000 polyurethanes. GPC used a chloroform solution and calibrated the molecular weight with standard polystyrene. When the weight average molecular weight is less than 10,000, water retention is often insufficient. On the other hand, if the weight average molecular weight exceeds 1,000,000, the stickiness becomes so strong that it may not be suitable as a moisturizer for hair cosmetics. These polyurethanes can be easily dissolved in water or a polar organic solvent such as ethanol. In order to use these soluble polyurethanes as hair cosmetics, a composition to which other common components are added according to the purpose is used. For example, various surfactants, propylene glycol, liquid paraffin, glycerin, silicone oil, ethanol,
Metal ion supplements such as EDTA, fragrances, preservatives, purified water and the like.

[0056]

The present invention will be described below with reference to examples.
Of course, the present invention is not limited to this embodiment.

Example of Synthesis of Comb-Shaped Hydrophobic Diol Example 1 A magnetic stirrer was placed in a 500 ml round bottom flask.
A thermometer and a dropping funnel were installed, 64.6 g of 2-ethylhexylamine (Kanto Chemical) was charged, and the atmosphere in the flask was replaced with nitrogen. The flask is heated to 60 ° C. in an oil bath, and while stirring, 2-ethylhexyl glycidyl ether (Nagase Kasei Kogyo, Denacol EX
(−121, epoxy value: 188) 188.0 g was added dropwise over 40 minutes. After dropping, raise the temperature of the oil bath to 80 ° C.
And heated the flask for 10 hours. Subsequently, the temperature of the oil bath was raised to 120 ° C., and a small amount of unreacted substances was distilled off under reduced pressure using a vacuum pump at a degree of vacuum of 3 mmHg. Comb-shaped hydrophobic diol 1 (average molecular weight 49 based on OH value) in which 2-ethylhexylglycidyl ether is added in a ratio of 2 mol per 1 mol of 2-ethylhexylamine.
0) was obtained with a yield of 98%.

Example 2 Comb-shaped hydrophobic diol 2 was synthesized by adding 2 mol of n-butyl glycidyl ether (Tokyo Kasei) to 1 mol of n-butylamine (Tokyo Kasei). Example 3 Comb-shaped hydrophobic diol 3 was synthesized by adding 2-ethylhexyl glycidyl ether at a ratio of 2 mol to 1 mol of n-butylamine. Example 4 Comb-shaped hydrophobic diol 4 was synthesized by adding 2-ethylhexyl glycidyl ether at a ratio of 2 mol to 1 mol of dodecylamine (Kanto Chemical). Example 5 To 1 mole of n-octylamine (Tokyo Kasei), 2 moles of dodecyl glycidyl ether (dodecyl / tetradecyl glycidyl ether manufactured by Aldrich) was added at a ratio of 2 moles, and comb-shaped hydrophobic diol 5 was added. Was synthesized. Example 6 n to 1 mol of n-octadecylamine (Kanto Chemical)
-Octyl glycidyl ether (P & B) was added at a ratio of 2 mol to synthesize a comb-shaped hydrophobic diol 6.

Example 7 Comb-shaped hydrophobic diol 7 was synthesized by adding octadecyl glycidyl ether (Nippon Oil & Fats, Epiol SK) at a ratio of 2 mol to 1 mol of n-butylamine. Example 8 Comb-shaped hydrophobic diol 8 was synthesized by adding 2-ethylhexyl glycidyl ether at a ratio of 2 mol to 1 mol of 3-[(2-ethylhexyl) oxy] -1-propylamine (Kouei Chemical). . Example 9 Comb-shaped hydrophobic diol 9 was synthesized by adding 2-ethylhexyl glycidyl ether at a ratio of 2 mol to 1 mol of dibutylaminopropylamine (Kouei Chemical). Table 1 summarizes the results.

[0060]

[Table 1]

(Synthesis Example of Soluble Polyurethane) A synthesis example of a soluble polyurethane using the hydrophobic diol of Example 1 is shown below, but of course, the present invention is not limited to the following example. Example 10 Commercially available PE was placed in a 500 ml SUS separable flask.
100 g of G # 6000 (Pure Chemical, number average molecular weight 8,700) was charged and melted at 150 ° C. under a nitrogen seal. This was dried under reduced pressure (3 mmHg) for 3 hours while stirring. The residual moisture was 200 ppm. 80
The temperature was lowered to 0 ° C., and while stirring the inside of the flask, 1.00 g of the comb-shaped hydrophobic diol 1 obtained in Example 1 and 2.28 g of hexamethylene diisocyanate (Tokyo Kasei) were charged. When 0.01 g of DBTDL is added as a catalyst,
The viscosity rapidly increased in about 10 minutes. The stirring was stopped and the reaction was continued for another 2 hours. After the reaction was completed, the product was taken out of the flask, cut into small pieces, and allowed to cool. This was cooled with liquid nitrogen and pulverized with an electric mill to a particle size of 1 mm (16 mesh) or less. The weight average molecular weight measured by GPC was 500,000.

Examples 11 to 20 Examples of the synthesis of other polyurethanes using the comb-shaped hydrophobic diols 2 to 9 will be described. The amount of HDI was selected such that the number of moles of HDI was 1.00 times the sum of the number of moles of each of PEG and the comb-shaped hydrophobic diol (NCO / OH = 1.00). The results are summarized in Table 2.

[0063]

[Table 2]

In Table 2, "molecular weight of PEG" is the number average molecular weight of PEG obtained from the OH value (OHV). Further, “hydrophobic diol / PEG” indicates the weight ratio of the hydrophobic diol to PEG in the raw material in percentage. “The coefficient x of the repeating unit” is the coefficient x of the repeating unit represented by the chemical formula 7. The “weight average molecular weight” is a value determined by GPC measurement using monodispersed polystyrene as a standard. As a solvent, chloroform was used. Soluble polyurethane having x in the range of 0.01 to 0.5 and weight average molecular weight in the range of 10,000 to 1,000,000 is obtained.

(Hair Conditioner) As an example of a humectant for hair cosmetics, an example in which the soluble polyurethane of the present invention is mixed with a hair conditioner will be described. As a comparative example, an example using polyethylene glycol (PEG) or hydroxyethyl cellulose (HEC) as a humectant is shown. The composition used for the test is as follows. Stearyltrimethylammonium chloride 1% by weight Propylene glycol 5% by weight Cetyl alcohol 2% by weight Oleyl alcohol EO adduct 0.5% by weight Humectant Predetermined amount in Table 3 Perfume Appropriate Preservative Appropriate Purified water Remaining Total 100% The texture (sitting feeling) of the hair after treating the hair with the object was evaluated. ◎: extremely good sit feeling, ○
Is good and x is bad. Table 3 summarizes the results.

[0066]

[Table 3] The conventional humectant had an inadequate sittability, and had a sticky feeling and a dry feeling. On the other hand, the humectant of the present invention had a good texture and did not have a sticky feeling or a puffy feeling.

[0067]

Industrial Applicability According to the present invention, a moisturizing agent for hair cosmetics which has a sufficient moisturizing property and has a high crispness can be used.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C083 AC072 AC182 AC692 AD071 AD072 CC33 EE06 EE28 4J034 BA07 BA08 CA04 CA05 CB03 CB04 CB07 CC05 CC12 CC23 CC24 CC26 CC28 CC29 CC33 CC34 CC37 CC44 CC45 CC46 CC52 CC53 CC54 CC55 CC62 CC65 CD01 CD04 CD08 CD12 CD13 CD14 DA01 DB04 DB07 DD07 DD08 DD09 DG02 DG03 DG04 DG05 DG08 DG09 DG14 DG15 DG16 DG22 DG25 DG29 DG30 FA01 FB01 FC03 FD01 FE01 HA01 HA07 HA08 HA18 HB12 HC03 HC01 HC09 HC12 HC01 HC01 HC09 JA02 KA01 KB02 KC08 KC17 KC18 KD02 KD12 KE02 QA05 RA02

Claims (3)

[Claims] [Claim 1] Chemical formula 1And a repeating unit (1) represented by the following formula:A polymer comprising a repeating unit (2) represented by the formula:
The molar ratio of the repeating unit (1) is 0.5 or more and 0.99 or less
The molar ratio of the repeating unit (2) is 0.01 or less
0.5 or less and the weight average measured by GPC
Molecular weight in the range of 10,000 to 1,000,000
A new moisturizer for hair cosmetics. However, A is HO-A
-OH has a hydroxyl group at least at both ends and has a number average
Water-soluble polyalkylene having a molecular weight of 400 to 100,000
The polyol (compound A) is a divalent group, and B is OC
NB-NCO having a total carbon number of 3 to 18 isocyanate
Polyisocyanate compound selected from the group consisting of
A compound (compound B), D is HO-DO
H is a chemical formula 3 (Chemical Formula 3)(However, R¹Is a hydrocarbon group having 1 to 20 carbon atoms.
You. Also R^TwoAnd R^ThreeIs a hydrocarbon group having 4 to 21 carbon atoms
It is. The hydrocarbon group R¹, R^TwoAnd R^ThreeHydrogen in
Part or all of it with fluorine, chlorine, bromine or iodine
May be replaced by R^TwoAnd R^ThreeAre the same but different
Is also good. Y and Y 'are hydrogen, methyl or CH
_TwoCl and Y and Y 'may be the same or different
No. Z and Z 'are oxygen, sulfur or CH_TwoIn the base
Z and Z 'may be the same or different. And n is
When Z is oxygen, it is an integer of 0 to 15, and Z is not sulfur
CH _TwoIn the case of a group, it is 0. N 'is Z' of oxygen
Is an integer of 0 to 15, wherein Z 'is sulfur or CH_Two
0 in the case of a group, and n and n 'are the same or different
Or chemical formula 4 (Chemical Formula 4)(However, R^FourIs a hydrocarbon group having 1 to 20 carbon atoms.
You. Also R^FiveAnd R⁶Is a hydrocarbon group having 4 to 21 carbon atoms
It is. The hydrocarbon group R^Four, R^FiveAnd R⁶Hydrogen in
Part or all of it with fluorine, chlorine, bromine or iodine
May be replaced by R^FiveAnd R⁶Are the same but different
Is also good. Y, Y 'and Y "have no hydrogen or methyl group
CH_TwoCl and Y and Y 'are the same or different
You may. Z and Z 'are oxygen, sulfur or CH_Two
Z and Z 'may be the same or different. Ma
R⁷Is an alkylene group having 2 to 4 carbon atoms, and k is 0
It is an integer of １５15. N is 0 to 1 when Z is oxygen.
5, Z is sulfur or CH_Two0 for the group
is there. N ′ is an integer of 0 to 15 when Z ′ is oxygen.
Yes, Z 'is sulfur or CH_Two0 for a group and n
And n 'may be the same or different.)
(Formula 5)(However, R⁸And R⁹Is R⁸And R⁹Has a total carbon number of 2
To 20 hydrocarbon groups. Also R^TenAnd R¹¹Is carbon
It is a hydrocarbon group having a number of 4 to 21. The hydrocarbon group R
⁸, R⁹, R^TenAnd R¹¹Some or all of the hydrogen
It may be substituted by nitrogen, chlorine, bromine or iodine. R
⁸And R⁹May be the same or different. R ^TenAnd R¹¹Is the same
It may be the same or different. Also R¹²Has 2 to 7 carbon atoms
Is an alkylene group. Y and Y 'are hydrogen, methyl
Group or CH_TwoCl and Y and Y 'are the same but different
It may be. Z and Z 'have no oxygen or sulfur
CH_TwoZ and Z 'are the same or different
Good. N is an integer of 0 to 15 when Z is oxygen.
Z is sulfur or CH_TwoIn the case of a group, it is 0. Also
n ′ is an integer of 0 to 15 when Z ′ is oxygen;
Is sulfur or CH_TwoGroup is 0, and n and n 'are the same
(Which may be the same or different)
All (compound D) is a divalent group. 2. Compound A has a number average molecular weight of 400 to 20,
The moisturizer for hair cosmetics according to claim 1, wherein the humectant for hair cosmetics is polyethylene glycol, and the compound B is a linear aliphatic diisocyanate or a cycloaliphatic diisocyanate. 3. The hair cosmetic according to claim 1, wherein the compound B is hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate or norbornene diisocyanate. Moisturizer.