TW201302234A - Conditioner - Google Patents

Abstract

An objective of this invention is to provide a conditioner composition which has excellent inhibition effect on discoloration and touching feeling in use. The present invention provides a conditioner composition as claim 1, which is characteristic by containing: (i) a cationic surfactant, (ii) a higher aliphatic alcohol, (iii) 0.01 to 1 weight % of a quaternary ammonium group-containing silyl-urethane type polymer, and the (i) cationic surfactant contains (a) an imidazoline-type quaternary ammonium salt which has a specific structure or a di-long-chain-alkyl type quaternary ammonium salt which has a specific structure, and (b) a mono-long-chain-alkyl type quaternary ammonium salt which has a specific structure.

Description

Conditioning milk [Related application]

The present application claims priority from Japanese Patent Application No. 2011-116993, filed on May 25, 2011.

The present invention relates to moisturizing milk, and more particularly to the effect of inhibiting color fading and the improvement of use feeling.

In recent years, edgy dyeing using oxidative dyes has been widely used. As a major distress of people who are interested in dyeing, it can be mentioned that the color retention is not good, and after fading, the fading is usually apparent in about one month, and if the dyeing is repeated infrequently, the beautiful ochre cannot be maintained. The fading of the oxidative dye is known to cause water to permeate into the inside of the burr during washing or the like, and to wash out the dye which is deep inside the burr. Therefore, it is desirable to have a washing essence or a moisturizing milk which has an effect of suppressing fading.

As described in Patent Document 1, it is a shampoo which has a synergistic composition of a silylated peptide-silane compound and has a color fading suppressing effect. Further, as described in Patent Document 2, it is a treatment containing a lipophilic cationic surfactant and a sterol, and having an effect of suppressing fading. However, these effects are not sufficient, and there is no good feeling of maintaining good twilight.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-315369 Patent Document 2: Japanese Laid-Open Patent Publication No. 2003-176214

In addition, in the case of dyeing with an oxidative dye, it is more or less damaged by the bristles associated with discoloration, resulting in roughness or hardness after dyeing. Therefore, in the case of the edgy after dyeing, the difference in the flexibility of the dried edema after the moisturizing milk tends to be stronger than that of the general edgy. Therefore, in the case of the moisturizing lotion used for the hair dyed hair, it is desirable to not only blend the component having a high fading-suppressing effect, but also to promote the effect of the component, and it has the aforementioned more than the blender in the general moisturizing milk. The use of a specific effect (flexibility after drying) is excellent.

However, it has not been possible to obtain a composition which can enhance the effect of the component having a color fading-reducing effect, and a moisturizing milk component which is remarkably excellent in feeling.

The present invention has been made in view of the above problems, and an object thereof is to provide a moisturizing milk composition which is excellent in suppressing a fading effect and using a feeling.

In order to solve the above problems, the inventors of the present invention have intensively studied and found that the ruthenium amide ester-containing polymer containing a quaternary ammonium group can greatly suppress the fading fading after the use of the moisturizing milk, and further, by using The specific cationic surfactant of the component and the higher aliphatic alcohol further improve the coloring suppressing effect and maintain the excellent feeling of use of the hairy after the dyeing, and the present invention has been completed. That is, the moisturizing milk composition of the present invention is characterized by comprising: (i) a cationic surfactant, (ii) a higher aliphatic alcohol, (iii) a quaternary ammonium ester-based polymer containing a quaternary ammonium group 0.01 to 1% by mass, and (i) the cationic surfactant contains (a) an imidazoline type quaternary ammonium salt represented by the following formula (I) or a di-long chain alkyl group represented by the following formula (II) a quaternary ammonium salt, and (b) a single long chain alkyl type quaternary ammonium salt represented by the following formula (III); (In the above formula, R ¹ and R ² may be the same or different from each other, and represent an alkyl group or an alkenyl group having 12 to 22 carbon atoms, and Z represents a halogen atom selected from a methyl sulfate group and an ethyl sulfate group. Anionic group)

(In the above formula, either of R ³ to R ⁶ represents a straight-chain or branched alkyl group having a hydroxyl group which may be substituted with a carbon number of 8 to 36, or R ⁷ -(Z1) _q -(Y1) _{p -} R ⁷ represents a straight-chain or branched alkyl group having 8 to 36 carbon atoms which may be substituted by a hydroxyl group, and Y1 represents a group selected from -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ a binding group of O-, -CH(OH)CH ₂ O-, and Z1 represents a bonding group selected from the group consisting of a guanamine bond (-CONH-), an ether bond (-O-), and an ester bond (-COO-). q respectively represents an integer of 0 or 1. Meanwhile, the remaining two of R ³ to R ⁶ may be the same or different, and each represents a hydroxyl group-substituted carbon number of 1 to 3 alkyl group or benzyl group. X represents a halogen atom. An alkylsulfate group having 1 or 2 carbon atoms, or an anion capable of forming a salt with a quaternary ammonium such as a residue after removing a hydrogen atom of an organic acid)

(In the above formula, R ⁸ represents a hydroxy group-substituted linear or branched alkyl group having 8 to 36 carbon atoms, or R ¹² -(Z1) _q -(Y1) _{p -.} R ¹² represents a hydroxy-substituted carbon. a linear or branched alkyl group of 8 to 36, and Y1 represents a group selected from -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ O-, -CH(OH)CH ₂ O a binding group, Z1 represents a bonding group selected from the group consisting of a guanamine bond (-CONH-), an ether bond (-O-), and an ester bond (-COO-). p and q each represent an integer of 0 or 1. Further, R ⁹ , R ¹⁰ and R ¹¹ may be the same or different and represent a hydroxy group which may be substituted with a C 1 to 3 alkyl group or a benzyl group. X represents a halogen atom, an alkyl 1 or 2 alkyl sulfate group, or An anion which forms a salt with a quaternary ammonium such as a residue obtained by removing a hydrogen atom of an organic acid).

Further, in the above-mentioned moisturizing milk composition, the component (a) of the (i) cationic surfactant is preferably 0.05 to 2% by mass of the imidazoline type quaternary ammonium salt represented by the above formula (I), or 0.01 to 3% by mass of the di-long-chain alkyl type quaternary ammonium salt represented by the above formula (II).

Further, in the above-mentioned moisturizing milk composition, the component (a) of the (i) cationic surfactant is preferably selected from the group consisting of diammonium imidazoline methyl sulfate. One or more selected from the group consisting of dibehenyl imidazolinium methosulfate, distearylethylammonium chloride, and dicocoylethylmethyl hydroxyethylmonium methosulfate.

According to the present invention, it is possible to obtain a moisturizing milk composition which has an effect of suppressing the fading effect on the dyed hair lice and which is excellent in the use of the so-called flexibility of the dried edema after moisturizing.

Hereinafter, preferred embodiments of the present invention will be described in detail.

The moisturizing milk composition of the present invention comprises: (i) a cationic surfactant, (ii) a higher aliphatic alcohol, and (iii) a halogenated amine ester polymer containing a quaternary ammonium group. First, each component will be explained.

(i) cationic surfactant

In the cationic surfactant used in the present invention, a good feeling of use after use of the composition (toughness of the head after drying) is imparted, and the suppression of discoloration of the ruthenium amide polymer containing a quaternary ammonium group is enhanced. In view of the effect, in particular, those comprising the following (a) and (b): (a) an imidazoline type quaternary ammonium salt (a1) represented by the following formula (I) or the following formula (II) can be used. A long-chain alkyl type quaternary ammonium salt (a2) (b) represented by the following formula (III): a single long-chain alkyl type quaternary ammonium salt represented by the following formula (III).

(a1) imidazoline type quaternary ammonium salt

The imidazoline type quaternary ammonium salt used in the present invention is a compound represented by the following formula (I).

In the above formula (I), R ¹ and R ² may be the same or different from each other, and represent an alkyl group or an alkenyl group having 12 to 22 carbon atoms, and Z represents a halogen atom selected from a methyl sulfate group and ethyl sulfuric acid. An anionic group of an ester group.

As the alkyl group having 12 to 22 carbon atoms in R ¹ and R ² , for example, a dodecyl group, a thirteen group, a tetradecyl group, a fifteen group, a hexadecyl group, a heptadecyl group, an octadecyl group, and a tenth Nine, twenty, twenty-one, twenty-two (behenyl), etc. Further, examples of the alkenyl group having 12 to 22 carbon atoms include, for example, dodecenyl, tridecenyl, pentadecyl, hexadecenyl, heptadecenyl, octadecyl, and decylene. , behenyl, behenyl, eicosadienyl and the like. When the carbon number of R ¹ or R ² exceeds 22, the solubility in water tends to be remarkably lowered.

Further, examples of the halogen atom of Z include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom, and a chlorine atom is particularly preferable. Further, it is particularly preferable to use a methyl sulfate group as the Z system.

The imidazoline type quaternary ammonium salt may, for example, be dioleyl imidazoline methyl sulfate, distearyl imidazoline methyl sulfate, or diammonium imidazole. As the dialkyl or dienyl imidazoline salt such as methyl sulfonate (quaternium-91), it is particularly preferred to use diammonium imidazoline methyl sulfate.

(a2) Di-long chain alkyl type quaternary ammonium salt

The di-long-chain alkyl type quaternary ammonium salt used in the present invention is a compound represented by the following formula (II).

In the above formula (II), either of R ³ to R ⁶ represents a hydroxy-substituted linear or branched alkyl group having 8 to 36 carbon atoms, or R ⁷ -(Z1) _q - (Y1) ) _p -.

R ⁷ represents a hydroxy-substituted linear or branched alkyl group having 8 to 36 carbon atoms, and Y1 represents a group selected from -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ O-, a binding group of -CH(OH)CH ₂ O-, and Z1 represents a bonding group selected from the group consisting of a guanamine bond (-CONH-), an ether bond (-O-), and an ester bond (-COO-). p and q represent an integer of 0 or 1, respectively.

Further, in the above formula (II), the remaining two of R ³ to R ⁶ may be the same or different, and each represents a hydroxyl group-substituted carbon number of 1 to 3 alkyl group or benzyl group. X represents a halogen atom, an alkylsulfate group having 1 or 2 carbon atoms, or an anion capable of forming a salt with a quaternary ammonium such as a residue obtained by removing a hydrogen atom of an organic acid.

The di-long-chain alkyl type quaternary ammonium salt represented by the above formula (II) may, for example, be dinonyldimethylammonium chloride, dicocoyldimethylammonium chloride or brominated dicocohol. Dimethylammonium chloride, dilauryldimethylammonium chloride, chlorinated Myristyl dimethyl ammonium, dicetyl dimethyl ammonium chloride, dipalmityl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, distearyl dimethyl ammonium bromide , dioleyl dimethyl ammonium chloride, dicocoyl ethyl hydroxyethyl ammonium methyl sulfate, dipalmityl ethyl hydroxyethyl ammonium methyl sulfate, dicocoyl hydroxyethyl methyl ammonium sulfate Methyl ester, distearylethyl hydroxyethyl ammonium chloride, and the like. In the present invention, distearyldimethylammonium chloride or dicocoylhydroxyethylmethylammonium sulfate is preferred.

(b) Single long chain alkyl type quaternary ammonium salt

The single long-chain alkyl type quaternary ammonium salt used in the present invention is a compound represented by the following formula (III).

In the above formula (III), R ⁸ represents a hydroxy group-substituted linear or branched alkyl group having 8 to 36 carbon atoms, or R ¹² -(Z1) _q -(Y1) _p -.

R ¹² represents a hydroxy group-substituted linear or branched alkyl group having 8 to 36 carbon atoms, and Y1 represents a group selected from -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ O-, a binding group of -CH(OH)CH ₂ O-, and Z1 represents a bonding group selected from the group consisting of a guanamine bond (-CONH-), an ether bond (-O-), and an ester bond (-COO-). p and q represent an integer of 0 or 1, respectively.

Further, R ⁹ , R ¹⁰ and R ¹¹ in the above formula (III) may be the same or different and each represents an alkyl group or a benzyl group having 1 to 3 carbon atoms which may be substituted with a hydroxyl group. X represents a halogen atom, an alkylsulfate group having 1 or 2 carbon atoms, or an anion capable of forming a salt with a quaternary ammonium such as a residue obtained by removing a hydrogen atom of an organic acid.

The mono-long-chain alkyl type quaternary ammonium salt represented by the above formula (III) may, for example, be lauryl trimethyl ammonium chloride, lauryl trimethyl ammonium bromide or myristyl trimethyl chloride. Ammonium, brominated myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium chloride, stearyltrimethylammonium bromide Ammonium, benzalkonium trimethylammonium chloride, benzalkonium trimethylammonium bromide, cetyltrimethylammonium methanesulfonate, stearyltrimethylammonium sulfate, chlorinated myristyl Dimethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, stearyl dimethylbenzylammonium chloride, octyldihydroxyethylmethylammonium chloride, chlorinated 2- Mercaptotetradecyltrimethylammonium chloride, 2-dodecylhexadecyltrimethylamine chloride, stearyloxypropyltrimethylammonium chloride, brominated stearyl PG trimethylamine, and the like. In the present invention, chlorostearyltrimethylammonium chloride is particularly preferred.

Further, in the present invention, as a component of the quaternary ammonium salt of the monolong-chain alkyl group of the above formula (III), a mono-long-chain alkyl type amine represented by the following formula (IV) and an organic compound can be used. After acid combination, mix.

In the above formula (IV), R ¹³ and R ¹⁴ may be the same or different and each represents a C 1 -3 alkyl group or a benzyl group which may be substituted with a hydroxyl group. R ¹⁵ represents a straight-chain or branched alkyl group having a carbon number of 8 to 36 which may be substituted by a hydroxyl group.

Further, Y2 represents a bonding group selected from the group consisting of -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ O-, -CH(OH)CH ₂ O-, and Z2 represents a guanamine bond selected from A binding group of (-CONH-), an ether bond (-O-), or an ester bond (-COO-). s and t represent an integer of 0 or 1, respectively.

As a combination of the monolong-chain alkyl type amine and the organic acid represented by the above formula (IV) of the present invention, for example, dimethylaminopropylstearamide-dimethyl glutamate- glutamic acid- Glutamic acid), diethylaminopropyl decylamine-lactic acid, stearyloxypropyl dimethyl decylamine-malic acid, stearyl PG dimethylamine-glutamic acid, hawthorn Aminopropyldimethylamine-succinic acid, stearylamine propyldimethanolamine-tartaric acid, and the like.

In the present invention, as the (i) cationic surfactant, it is preferred to formulate the following components: (a1) is preferably 0.05 to 2% by mass of the imidazoline type quaternary ammonium salt with respect to the composition of the present invention, and is 0.05. More preferably, it is 1% by mass or more, or (a2) is preferably from 0.01 to 3% by mass, based on the composition of the present invention, of a di-long-chain alkyl type quaternary ammonium salt, and more preferably from 1 to 3% by mass. b) It is preferably 0.1 to 5% by mass of the single long-chain alkyl type quaternary ammonium salt with respect to the composition of the present invention, and more preferably 0.5 to 3% by mass.

When the blending amount of the component (a1) or (a2) is outside the range of the above-mentioned blending amount, the flexibility of the dried buttercup after the moisturizing lotion is insufficient.

Further, when the compound of (a2) is a combination of a single long-chain alkyl type amine and an organic acid, the amount of the single long-chain alkyl type amine and the organic acid can be adjusted to form a single amount in the above-mentioned compounding amount range. Long chain alkyl type quaternary ammonium salt.

(ii) higher aliphatic alcohols

The moisturizing milk composition of the present invention contains a higher aliphatic alcohol. The case The higher aliphatic alcohol means a linear aliphatic alcohol or a branched chain aliphatic alcohol having a carbon number of 12 to 36 which is usually used in cosmetics or pharmaceuticals.

Examples of such linear aliphatic alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, and arachidyl alcohol. Jojoba alcohol, hardened rapeseed oil, tetradecanol, cetyl alcohol, stearyl alcohol, and the like.

Further, examples of the branched chain aliphatic alcohol include, for example, shark liver alcohol, ricinol, 2-mercaptotetradecyl alcohol, lanolin alcohol, cholesterol, phytol, hexyldodecanol, isostearyl alcohol, Octyldodecanol, decyltetradecyl alcohol, hexyl decyl alcohol, dodecyl hexadecanol, tetradecyl octadecyl alcohol, hexadecyl eicosol, and the like.

In the present invention, it is preferable that the higher aliphatic alcohol has a molar ratio of a higher aliphatic alcohol to the above-mentioned cationic surfactant (component (a) + component (b)) of 1:0.5 to 1:10. It is better to mix and match in a way that is 1:1 to 1:6. When the blending is outside the range of the aforementioned molar ratio, the flexibility of the dried ranunculus after using the moisturizing milk may become insufficient. (iii) a hydrazine ester polymer containing a quaternary ammonium group

The ruthenium amide ester polymer containing a quaternary ammonium group may be any compound having at least one quaternary ammonium group and at least one reactive thiol group on the amine ester polymer. The reactive thiol group may, for example, be a hydrolyzable thiol group or a decyl alcohol group.

In the present invention, a quaternary ammonium-based oxime-based ester-based polymer containing a constituent unit relative to the following component (A), component (B), and component (C), and the component (C) The tertiary amine moiety is at the isocyanate end of the quaternary ammonium ionized amine ester polymer and has a bonding component (D) to form a urine. A compound having a structure of a urea bond is preferred.

Component (A): Polyisocyanate Compound Component (B): Polyol Compound Component (C): A tertiary amine compound component (D) having two or more hydroxyl groups: containing the following formula (d1), (d2) or (d3) Ester-modified amine alkoxy decane

(In the above formula, R ¹ and R ² are the same or different and each represents an alkyl group, and R ³ and R ⁴ are the same or different, and represent an alkylene group which may have a substituent or an extended aryl group which may have a substituent. R ⁵ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, R ⁶ represents a hydrogen atom or -COOR ^6' , and R ^6' represents an alkyl group. Further, m is an integer of 1 to 3. If m is 1 In the case of an integer, two R ^{2 's} may be the same or different. When m is an integer of 2 or more, two or more R ¹ O- groups may be the same or different.

The quaternary ammonium ester-based polymer containing a quaternary ammonium group can be synthesized by at least the following steps (1), (2), and (3).

Step (1): a step of reacting the above component (A), component (B) and component (C) to synthesize an amine ester polymer

Step (2): a step of subjecting the tertiary amine moiety of the component (C) to quaternary ammonium ionization

Step (3): a step of reacting the above component (D) at the acid ester terminal of the amine ester polymer

[ingredient (A): polyisocyanate compound]

The component (A) may be a compound having at least two isocyanate groups in the molecule, and examples thereof include an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and an aromatic aliphatic polyisocyanate.

Examples of the aliphatic polyisocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, and 1,5-pentamethylene group. Diisocyanate, 1,6-hexamethylene diisocyanate, 1,2-propyl diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-die Diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6- An aliphatic diisocyanate such as hexamethylene diisocyanate, 2,6-diisocyanate methyl hexanoate or lysine diisocyanate.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and 4,4'-methylene double. (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, 1,4- An alicyclic diisocyanate such as bis(isocyanatemethyl)cyclohexane, isophorone diisocyanate (IPDI) or norbornane diisocyanate.

Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylenediisocyanate, and 2,6-methyl extension. Phenyl diisocyanate, stilbene-1,4-diisocyanate, naphthyl-1,5-diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4 An aromatic diisocyanate such as '-diisocyanate, 4,4'-diphenylpropane diisocyanate or 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

Examples of the aromatic aliphatic polyisocyanate include 1,3-xylylenediisocyanate, 1,4-xylylene diisocyanate, and ω,ω'-diisocyanate. 1,4-Diethylbenzene, 1,3-bis(1-isocyanate-1-methylethyl)benzene, 1,4-bis(1-isocyanate-1-methylethyl)benzene, 1,3 An aromatic aliphatic diisocyanate such as bis(α,α-diisocyanatemethyl)benzene or the like.

Further, for example, from the above aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, aromatic aliphatic polyiso Dimer or trimer, reactive product or polymer of cyanate ester (for example, dimer or trimer of diphenylmethane diisocyanate, trimethylolpropane and methylphenyl diisocyanate) The reactive product, a reactive product of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate, polyester polyisocyanate, etc.).

As the component (A) in the present invention, among them, 1,6-hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,3-bis(isocyanate A) are applicable. Base) cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, isophorone diisocyanate (IPDI), 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate , 4,4'-diphenylmethane diisocyanate, 1,3-terephthalic diisocyanate, 1,4-phenylene diisocyanate, norbornane diisocyanate, 1,3-double (α , α-dimethyl isocyanate methyl) benzene, and the like. These systems may be used singly or in combination of two or more. Further, when an aliphatic polyisocyanate is used, a resin having less discoloration can be obtained.

[ingredient (B): polyol compound]

The component (B) is not particularly limited as long as it is a compound having two or more hydroxyl groups, and examples thereof include a polyol, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, and a polyacrylic acid polyol. An alcohol, a polyalkylene oxide adduct of a trivalent or higher polyhydric alcohol or a derivative in which a hydroxyl group at the terminal is sealed, castor oil or the like. In the component (B) of the present invention, since it is easier to handle at the time of production, it is preferably a polyalkylene oxide selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, and trivalent or higher polyols. Derivatization of an adduct or a hydroxyl group at its end a compound of matter.

Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol (PTMG); and a plurality of extensions including an ethylene oxide-propylene oxide copolymer. a copolymer of an alkoxide (alkylene oxide - other alkylene oxide), and the like. In the present invention, a commercially available product such as the trade name "PTMG2000" (manufactured by Mitsubishi Chemical Corporation) can also be used.

As the polyester polyol, for example, a polycondensate of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); and three components of a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester can be used. The resulting reactants and the like. These systems may be used singly or in combination of two or more.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butylene glycol, and 2-methyl group. -1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1 , 5-pentanediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediol (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar Alcohols (xylitol, sorbitol, etc.) and the like. Examples of the polyvalent carboxylic acid include malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, and sebacic acid. An aliphatic dicarboxylic acid such as dodecanedioic acid; an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2 An aromatic dicarboxylic acid such as 6-naphthalenedicarboxylic acid, p-benzene dicarboxylic acid or trimellitic acid. Further, examples of the cyclic ester include propiolactone, β-methyl-δ-valerol, and ε-caprolactone.

Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene, a ring-opening polymer of a cyclic carbonate, and the like. These systems may be used singly or in combination of two or more. The polyol used for the reaction of the polyol and phosgene is exemplified by the same examples as the above polyol. In addition, examples of the cyclic carbonate include a carbonic acid alkyl ester such as ethyl carbonate, methyl trimethylene carbonate, tetramethylene carbonate or hexamethylene carbonate. Further, the polycarbonate polyol in the present invention may be a compound having a carbonate bond in the molecule and a hydroxyl group at the terminal, and may have both a carbonate bond and an ester bond.

The polyalkylene oxide adduct of the trivalent or higher polyhydric alcohol or the derivative in which the terminal hydroxyl group is sealed may, for example, be a hydroxyl group of a trivalent or higher polyhydric alcohol, and a polyalkylene adduct. a compound obtained by an oxide; or a derivative in which a terminal hydroxyl group of the adduct is blocked with an alkyl group such as a methyl group or an ethyl group or a mercapto group such as an ethenyl group or a benzamidine group.

Examples of the trivalent or higher polyhydric alcohol include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, xylitol, and sorbitol. These polyols may be used singly or in combination of two or more. In the present invention, trimethylolpropane and trimethylolethane are preferred.

Further, examples of the polyalkylene oxide include an alkylene oxide derivative containing a single alkylene oxide, and a plurality of alkylene oxides (alkylene oxide-other alkylene oxide). Copolymer. Further, examples of the polyalkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, and 1- 1-butene oxide, 2-butylene oxide, trimethyloxirane, tetramethylene oxide, tetramethyloxirane, butadiene monooxide, octylene oxide Other than the alkylene oxide having 2 to 8 carbon atoms, such as an octylene oxide, an aliphatic epoxide such as dipentane ethylene oxide or dihexane ethylene oxide; An alicyclic epoxide such as methylene oxide, tetrahydrofuran, tetrahydropyran or octylene oxide; an aromatic epoxide such as styrene oxide or 1,1-diphenylethylene oxide. Among the polyalkylene oxides of the present invention, in terms of water dispersion stability, it is preferred to contain an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide or propylene oxide, and contain epoxy B. The alkane is especially good.

The polyalkylene oxide adduct of the trivalent or higher polyhydric alcohol or the derivative of the terminal hydroxyl group in the present invention may, for example, be trimethylolpropane mono(polyethylene oxide methyl ether). Trimethylolpropane mono(polyalkylene oxide alkyl ether) such as trimethylolpropane mono(polyethylene oxide ether); polyoxyethylene ethyl sorbitan monolaurate, polyoxyethyl ether Polyoxyalkylene sorbitan mono-fatty acid ester such as sorbitan monostearate; polyoxyethyl glycerol monolaurate, polyoxyethyl glyceryl monostearate, etc. Mono-fatty acid ester; trimethylolpropane mono (polyalkylene oxide alkyl ether) such as trimethylolpropane mono(polyethylene oxide methyl ether).

In the present invention, a trimethylolpropane mono(polyalkylene oxide alkyl ether) is preferred, and a compound represented by the following formula (b) is particularly preferred. In the present invention, a commercially available product such as the trade name "YmerN120" (manufactured by Perstorp Co., Ltd.) may be used; (In the above formula, n1 represents an integer of 10 to 40).

The number average molecular weight of the component (B) of the present invention is, for example, preferably about 500 to 5,000, and more preferably about 800 to 3,000. If the number average molecular weight is less than 500, the effect of suppressing fading tends to be lowered. On the other hand, if the number average molecular weight is higher than 5,000, the water dispersion stability tends to decrease.

The component (B) of the present invention preferably contains a polyalkylene oxide adduct selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, and trivalent or higher polyhydric alcohols or has been sealed at its terminal hydrogen. In one or more compounds of the oxy derivative, in particular, by introducing a pendant nonionic side chain (hydrophilic group) into the amine ester polymer, the adsorption property on the surface of the edulis is further improved, and the fading is further enhanced. From the viewpoint of the effect, it is preferably a polyalkylene oxide adduct containing at least a trivalent or higher polyhydric alcohol or a derivative having a terminal hydroxyl group (particularly the compound represented by the above (b)).

The ratio of the alkylene oxide adduct of the trivalent or higher polyhydric alcohol in the component (B) or the derivative of the terminal hydroxyl group which has sealed the adduct is, for example, 5 to 100% by mass, which is 10 It is preferably 50% by mass, and particularly preferably 20 to 40% by mass.

[Component (C): a tertiary amine compound having two or more hydroxyl groups]

The component (C) may be a tertiary amine having two or more hydroxyl groups obtained by cationization, and examples thereof include triethanolamine and tri-n-propanol. A trialkanolamine such as an amine or a tri-isopropanolamine; an N-hydrocarbyl-substituted-dialkylolamine such as N-methyldiethanolamine or N-phenyldiethanolamine.

As the component (C) of the present invention, it is preferred to substitute N-hydrocarbyl-N,N-diethanolamine, and N-methyl-N,N-diethanolamine, N-ethyl-N,N-di Ethanolamine, N-methyl-N,N-dipropanolamine is especially preferred.

[ingredient (D): alkoxydecane containing an ester-modified amine group]

The component (D) of the present invention is represented by the above formula (d1), (d2) or (d3). In the formula, R ¹ and R ² are the same or different and each represents an alkyl group, and R ³ and R ⁴ are the same or different, and represent an alkylene group which may have a substituent or an extended aryl group which may have a substituent. R ⁵ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, R ⁶ represents a hydrogen atom or -COOR ^6' , and R ^6' represents an alkyl group. Also, m is an integer of 1 to 3. When m is 1, two R ^{2 's} may be the same or different. When m is an integer of 2 or more, two or more R ^{1 's} may be the same or different.

R ¹ and R ² in the above (d1), (d2), and (d3) are the same or different and each represents an alkyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group, an isopentyl group or a second pentyl group. , third amyl, hexyl, isohexyl, second hexyl, third hexyl, heptyl, octyl, decyl, decyl, eleven, twelve, thirteen, fourteen, fifteen , sixteen base, seventeen base, eighteen base, nineteen base, twenty base, and so on. The alkyl group of R ¹ and R ² of the present invention is preferably an alkyl group having about 1 to 6 carbon atoms (particularly, in terms of safety, it is preferably an ethyl group).

R ³ and R ⁴ in the above (d1), (d2), and (d3) are the same or different and each represents an alkylene group which may have a substituent or an extended aryl group which may have a substituent. Examples of the alkylene group include a methylene group, an ethylidene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a decamethylene group, and a tetramethylene group. The alkylene group of R ³ and R ⁴ of the present invention is preferably an alkylene group having 1 to 10 carbon atoms. Examples of the above-mentioned extended aryl group include a stretching phenyl group, a stretching naphthyl group, an anthrylene group, and the like. The aryl group of R ³ and R ⁴ of the present invention is preferably a aryl group having 6 to 10 carbon atoms.

In addition, examples of the substituent which R ³ and R ⁴ may have include an aryl group such as a phenyl group; an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a cycloalkyl group such as a cyclohexyl group; and the like. Further, the substituent may have other substituents (for example, an alkoxy group, an aryloxy group, a cycloalkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cycloalkoxycarbonyl group, a decyl group, an amine group, etc.).

R ⁵ in the above (d1), (d2), and (d3) represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. The alkyl group may be the same as the above-mentioned examples of the alkyl group of R ¹ and R ² . The alkyl group of R ⁵ of the present invention is preferably an alkyl group having 1 to 20 carbon atoms. Examples of the cycloalkyl group include a monocyclic, polycyclic or condensed cyclic cycloalkyl group having a carbon number of 3 to 20 such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group. The aryl group may, for example, be an aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group, an anthracenyl group, a phenanthryl group or a biphenyl group. The above-mentioned aralkyl group may, for example, be the aforementioned alkyl group substituted with the above aryl group.

R ⁶ in the above formulas (d1), (d2), and (d3) represents a hydrogen atom or -COOR ^6' , and R ^6' represents an alkyl group. Examples of the alkyl group of R ^{6 '} include the same examples as the alkyl group of the above R ¹ and R ² .

The alkoxy oxane containing an ester-modified amine group represented by the above formulas (d1), (d2), and (d3), for example, an alkoxy group having a primary and secondary amine group represented by the following formula (d1, 2-1) a decane compound or a nitrogen atom of a primary or secondary amine group in a primary amino group-containing alkoxysilane compound represented by the following formula (d3, 1), which is an unsaturated carboxylic acid ester represented by the following formula (1) The unsaturated bond (carbon-carbon double bond) is synthesized by a Michael addition reaction. The aforementioned Michael addition reaction can be carried out in the presence or absence of a solvent. In addition, heating or pressurization may be performed during the reaction;

(In the above formula, R ¹ , R ² , R ³ , R ⁴ and m are the same as the above formulas (d1) to (d3))

(In the above formula, R ¹ , R ² , R ³ and m are the same as in the above formulas (d1) to (d3))

(In the above formula, R ⁵ and R ⁶ are the same as in the above formulae (d1) to (d3)).

The alkoxydecane compound containing a primary and secondary amine group represented by the formula (d1, 2-1) may, for example, be N-β(aminoethyl)-γ-aminopropyltrimethoxydecane, N. N-(aminoalkyl)-aminoalkyltrialkoxydecane such as β-(amino)-γ-aminopropyltriethoxydecane; N-β(aminoethyl)-γ N-(aminoalkyl)aminoalkylane such as aminopropylmethyldimethoxydecane or N-β(aminoethyl)-γ-aminopropylmethyldiethoxydecane Alkoxy alkane and the like. In the present invention, commercially available products such as "KBE602", "KBM602", "KBE603", and "KBM603" (above, Shin-Etsu Chemical Co., Ltd.) can be used.

Examples of the alkoxydecane compound having a primary amino group represented by the formula (d3-1) include, for example, aminomethyltrimethoxydecane, aminomethyltriethoxydecane, and 2-aminoethyltrimethyl. Oxydecane, 2-aminoethyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropyltripropoxydecane , aminoalkyl trialkoxysilane such as 3-aminopropyltriisopropoxydecane or 3-aminopropyltributoxydecane; 2-aminoethylmethyldimethoxydecane, 2 - (aminoalkyl) alkoxydecane, etc., such as aminoethylmethyldiethoxydecane, 3-aminopropylmethyldipropoxydecane. In the present invention, commercially available products such as "KBE902", "KBM902", "KBE903", and "KBM903" (above, Shin-Etsu Chemical Co., Ltd.) can be used.

Examples of the unsaturated carboxylic acid ester represented by the above formula (1) include n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, and 3-butylcyclohexyl acrylate. Lauryl acrylate, cetyl acrylate, stearyl acrylate, behenyl acrylate, glycidyl acrylate, and the like. The unsaturated carboxylic acid ester represented by the formula (1) of the present invention is preferably n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate or the like.

[Step (1): Synthesis of Amine Ester Polymer]

The amine ester-based polymer can be synthesized by reacting the above components (A), (B), and (C) in accordance with a conventional or conventional method of preparing an amine ester polymer from a polyhydric alcohol compound and a polyisocyanate compound. Amine ester polymer synthesis A polymerization catalyst can also be used to promote the reaction.

As the polymerization catalyst, a known or conventional polymerization catalyst (curing catalyst) used for the reaction between the polyol compound and the polyisocyanate compound can be used, and examples thereof include a basic compound such as an amine compound. The basic compound of the amine compound may, for example, be an amino decane such as γ-aminopropyltrimethoxydecane or γ-aminopropyltriethoxydecane; tetramethylammonium chloride or benzene chloride; Tetra-ammonium salts such as benzalkonium chloride; trade name "DABCO" or "DABCO BL" series manufactured by Sankyo Air Products, 1,8-dioxinbicyclo[5.4.0]undec-7-ene (1,8-diazabicyclo[5.4.0]-undec-7-ene; DBU), etc., a linear or cyclic tertiary amine or a quaternary ammonium salt containing a plurality of nitrogen atoms.

Further, the reaction can be carried out in a solvent. The solvent may, for example, be acetone, methyl ethyl ketone, methyl isobutyl ketone, N-methyl pyrrolidone, tetrahydrofuran or ethyl acetate. The surrounding environment at the time of the reaction is not particularly limited, and is selected from the environment around the air, the environment around the nitrogen, and the environment around the argon. The reaction temperature is appropriately selected depending on the type of the reaction component, etc., and is, for example, 20 to 150 ° C, preferably about 20 to 100 ° C. The reaction can be carried out under normal pressure or under reduced pressure or under pressure. The reaction time is appropriately selected depending on the reactivity of the component, and is, for example, 2 to 20 hours, preferably about 3 to 10 hours.

The amount of the component (A), the component (B), and the component (C) to be used is not particularly limited, and may be appropriately adjusted depending on the desired physical properties. For example, the isocyanate group/component (B) and the component of the component (A) are appropriately adjusted. The hydroxyl group (NCO/OH group) (equivalent ratio) of (C) is more than 1, 1.5 or less (preferably more than 1, 1.3 or less, And it is more than 1 and 1.2 or less. When the ratio of the NCO/OH group is too large (for example, when it exceeds 1.5 (equivalent ratio)), the dispersibility tends to decrease. On the other hand, when the ratio of the NCO/OH group is too small (for example, 1 or less (equivalent ratio)), the sulfhydryl group may not be sufficiently introduced, and the fading effect may be suppressed from being lowered.

In addition, the content of the component (C) is preferably such that the content of the tertiary amine obtained by cationization in the amine ester polymer is 2 to 90% by mass (preferably 2 to 50% by mass, and 5 to 20%) Better quality %). If the content of the tertiary amine obtained by the cationization is higher than the above range, the viscosity becomes too high and there is a tendency to be difficult to use. On the other hand, when the content of the tertiary amine obtained by the cationization is less than the above range, the water stability tends to be lowered.

The content of the terminal isocyanate group as the amine ester polymer is, for example, preferably about 0.3 to 7.0% by weight. When the content of the terminal isocyanate group is more than 7.0% by weight, water dispersion tends to be difficult. On the other hand, when the content of the terminal isocyanate group is less than 0.3% by weight, the viscosity at the time of the synthesis becomes too high, and the synthesis tends to be difficult.

[Step (2): Tetra-ammonium ionization of the tertiary amine moiety]

By carrying out quaternary ammonium ionization (cationization) of the tertiary amine moiety derived from the component (C) in the amine ester polymer obtained in the above step (1), an amine ester polymerization containing a quaternary ammonium group can be synthesized. Things. The method of cationizing the nitrogen atom of the tertiary amine includes, for example, reacting an alkylating agent (quaternary agent) with the amine ester polymer obtained in the above step (1), and is derived from the component (C). The tertiary amine moiety introduces a carbon number of methyl, ethyl, propyl, butyl, etc. Alkyl group to 20; vinyl, isopropenyl, allyl, methallyl, 3-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butyl Alkene having 2 to 20 carbon atoms such as an alkenyl group, a 2-methyl-3-butenyl group or a 3-methyl-3-butenyl group; a carbon number of 7 to 11 such as a benzyl group or a 2-phenylethyl group; A method such as an aralkyl group or the like.

Examples of the alkylating agent (four-stage forming agent) include a sulfate such as dimethyl sulfate or diethyl sulfate; and a halogenated product such as methyl chloride, methyl bromide, methyl iodide, benzyl chloride or benzyl bromide. Things and so on.

The amount of the alkylating agent to be used is appropriately adjusted, and is, for example, 30 mol% or more (preferably 50 to 30 mol%) based on the tertiary amine moiety (tribasic amine group) in the amine ester polymer. 120% by mole, and more preferably 80 to 100% by mole. When the amount of the alkylating agent used is more than the above range, the heat rise during the reaction is intense and the workability tends to be lowered. On the other hand, when the amount of the alkylating agent used is less than the above range, the effect of suppressing fading tends to be lowered.

Further, the above cationization reaction can be carried out in a solvent. The solvent may, for example, be acetone, methyl ethyl ketone, methyl isobutyl ketone, N-methyl pyrrolidone, tetrahydrofuran or ethyl acetate. The surrounding environment at the time of the reaction is not particularly limited, and is selected from the environment around the air, the environment around the nitrogen, and the environment around the argon. The reaction temperature is appropriately selected depending on the kind of the reaction component, etc., and is, for example, 0 to 100 ° C, and preferably about 20 to 80 ° C. The reaction can be carried out under normal pressure or under reduced pressure or under pressure. The reaction time is appropriately selected depending on the reaction rate, for example, from 10 minutes to 5 hours, preferably from about 30 minutes to about 3 hours.

[Step (3): Suihua]

By melting the component (D) by the isocyanate group terminal of the quaternary ammonium group-containing amine ester polymer obtained in the above step (2), a quaternized ammonium ester-based polymer containing a quaternary ammonium group can be synthesized. (Sputum reaction). Moreover, the processing of the step (3) can also be carried out before the above step (2) is carried out. In this case, the above-mentioned component (D) can be synthesized by adding the above component (D) to the isocyanate terminal of the amine ester polymer obtained in the above step (1), and then, by the above step (2) A quaternary ammonium ester-based polymer containing a quaternary ammonium group can be synthesized by subjecting a nitrogen atom of a tertiary amine moiety to quaternary ammonium ionization. Hereinafter, the method relating to the steps (2) to (3) is the same, but the case of the steps (3) to (2) is also the same.

The above-described deuteration reaction can be carried out by mixing the quaternary ammonium group-containing amine ester-based polymer obtained in the above step (2) with the component (D), and heating as required. By carrying out the deuteration reaction, the isocyanate-based ester-containing ester at the terminal of the amine ester-based polymer containing the quaternary ammonium group can be modified to form a deuterated amine ester-based polymer containing a quaternary ammonium group. At the time of the deuteration reaction, a polymerization catalyst may also be used as needed. Further, the reaction can be carried out in the presence or absence of a solvent.

In the component (D), the content of the ruthenium atom in the ruthenium amide ester polymer containing a quaternary ammonium group is preferably 0.05 to 10% by mass (preferably 0.05 to 5% by mass, and more preferably 0.05 to 2% by mass). The ratio of the ratio is added. When the content of the cerium is more than the above range, the storage stability tends to be lowered. On the other hand, when the cerium content is less than the above range, the fading effect tends to be lowered.

The surrounding environment during the deuteration reaction is not particularly limited and is selected from the environment around the air, the environment around the nitrogen, and the environment surrounding the argon. The reaction temperature is appropriately selected depending on the type of the reaction component, etc., and is, for example, 20 to 100 ° C, preferably about 40 to 80 ° C. The reaction can be carried out under normal pressure or under reduced pressure or under pressure. The reaction time can be suitably selected, for example, from 10 minutes to 3 hours, preferably from about 20 minutes to about 2 hours.

[Step (4): Addition of a silicone chain]

In the quaternary ammonium ester-based polymer containing a quaternary ammonium group obtained by the above steps (1) to (3), a compound having a group having a hydrolyzable ruthenium atom may be added to the compound (D) derived from the above component (D). The terminal alkoxyfluorenyl group is further reacted, and the above-mentioned quaternary ammonium group-containing deuterated amine ester-based polymer is subjected to a polyoxygen chain addition step (step (4)). By adding a polyfluorene chain to the ruthenium amide ester polymer containing a quaternary ammonium group, the adsorption to the surface of the edulis can be further enhanced, and the effect of suppressing fading can be further enhanced.

The compound having a group having a hydrolyzable ruthenium atom is not particularly limited as long as it is a compound having at least one group containing a hydrolyzable ruthenium atom in the molecule. Examples of the hydrolyzable ruthenium atom-containing group include an alkoxyfluorenyl group, a hydrosilyl group, and a halogenated fluorenyl group (for example, a ruthenium chloride group, a ruthenium bromide group, a ruthenium iodide group, and a ruthenium fluoride group). Hydrolyzable thiol and the like. Further, in the hydrolyzable thiol group, in the case of a group or an atom (alkoxy group, hydrogen atom, halogen atom, etc.) bonded to a ruthenium atom, usually 1 to 3 bonds are bonded to one ruthenium atom (suitable 2 or 3) may be bonded to the same group (especially an alkoxy group) or an atom, or two or more different groups or atoms may be combined and bonded.

The hydrolyzable thiol group of the present invention is preferably an alkoxy fluorenyl group or an anthracenyl hydrogen group, and is preferably an alkoxy fluorenyl group. As the compound having at least one alkoxyfluorenyl group in the molecule, a compound (E) represented by the following formula (e1) or (e2) is particularly preferably used;

In the formula (e1), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or an alkyl group. m' is 1 or 2. N2 is an integer of 1 or more. Further, in the formula (e2), R ¹¹ represents (OR ⁷ ) or R ⁸ , and R ¹² represents an organic group. N3 is an integer of 1 or more. R ⁷ , R ⁸ , m' are the same as described above.

Examples of the alkyl group of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include the same examples as the alkyl group of R ¹ and R ² described above, and an alkyl group having 1 to 10 carbon atoms is preferred (1). Better to 6 to 1 to 4).

Further, the alkyl group of R ⁷ or R ⁸ may have a substituent. Further, the alkyl group of R ⁷ or R ⁸ may be bonded to another alkyl group (for example, an alkyl group bonded to R ⁷ or R ⁸ of another deuterium atom) through the substituent or the like to form a ring ( Aromatic ring or non-aromatic ring). And further, R ⁷ and R ⁸ may be bonded with each R is the same or different in the silicon atoms ⁷ and R ⁸ are bonded.

m' is 1 or 2 and is preferably 2. Further, when m' is 2, it means that R ⁸ does not exist, and the ruthenium atom in the formula (e1) is bonded to two (OR ⁷ ) groups. N2 is an integer of 1 or more. When n2 is 2, it means that the compound represented by the above formula (e1) is a monomer; and when n2 is an integer of 2 or more, it means that it is a polymer such as an oligomer or a polymer.

Examples of the compound represented by the above formula (e1) include tetraalkoxydecane such as tetramethoxynonane, tetraethoxysilane, tetrapropoxydecane, tetraisopropoxydecane or tetrabutoxydecane. a compound such as alkoxytrialkyloxydecane such as methoxytriethoxydecane or a dialkoxydialkoxydecane such as dimethoxydiethoxydecane; polytetramethoxydecane; , polytetraalkoxy decane such as polytetraethoxy decane, polytetrapropoxy decane, polytetraisopropoxy decane, polytetrabutoxy decane, poly(methoxy ethoxy decane), etc. Alkoxyalkoxydecane; poly(methoxy decane), poly(butoxydecane), etc. poly(alkoxydecane); poly(methoxymethyldecane), poly(methoxyethyl) A compound of a polymer such as poly(alkoxyalkylnonane) such as decane or poly(ethoxymethyldecane).

In the formula (e2), R ¹¹ is OR ⁷ or ^{R 8, R 7, R 8} , m ' is R in the formula (e1) of the ^7, R ^8, m' the same. Further, a plurality of OR ⁷ or R ⁸ bonded to the same argon atom may be the same or different.

In addition, examples of the organic group of R ¹² include an alkyl group which may have a substituent, or a hetero atom having an atom other than a carbon atom (oxygen atom, nitrogen atom, sulfur atom, etc.) in the main chain of the alkyl group. The radical or the like of the atom; the alkyl group or the hetero atom-containing group which may have a substituent, and may have any one of monovalent or polyvalent. Examples of the organic group of R ¹² include, for example, a vinyl group and a fluorenyl group: a vinyl-alkyl group, a vinyl-(alkyl)-aryl group, a vinyl-(alkyl)-cycloalkyl group, or a (meth) group. Propylene fluorenyl, (meth) propylene decyl oxyalkyl (vinyl-carbonyl oxyalkyl), (meth) propylene fluorenyl aryl aryl, fluorenyl-alkyl, fluorenyl-(alkyl)-aryl, Mercapto-(alkyl)-cycloalkyl and the like.

N3 is an integer of 1 or more, and is preferably an integer of 1 to 4 (more preferably 1 or 2, more preferably 1). Further, when n3 is an integer of 2 or more, it means a group containing two or more hydrolyzable ruthenium atoms bonded to the organic group of R ¹² .

The compound represented by the above formula (e2) wherein R ¹² is an alkyl group, in addition to, for example, an alkyltrialkoxy group such as methyltrimethoxydecane, ethyltrimethoxydecane or methyltriethoxydecane. Decane, or dimethyldimethoxydecane, dimethyldiethoxydecane, diethyldiethoxydecane, diisopropyldimethoxydecane, isopropyldimethoxymethylnonane Examples of the dialkyldialkoxydecane such as isopropyldiethoxymethyldecane include a trialkyl alkoxydecane corresponding to the compounds.

Further, the compound having a substituent (e.g., glycidoxy (Glycidoxy), isocyanate, amine and the like) of the alkyl group having as R ¹² include, for example: as the corresponding R ¹² is an alkyl group of exemplified compounds Compounds and the like.

Examples of the compound represented by the above formula (e2) wherein R ¹² is a vinyl group include, for example, an ethylene trialkoxy decane such as ethylene trimethoxy decane or ethylene triethoxy decane; and ethylene methyl dimethoxy group. (Vinyl)alkyldialkoxydecane such as decane or ethylene methyldiethoxydecane, or (vinyl)dialkyl(mono)alkoxydecane or the like corresponding to the compounds.

The compound represented by the above formula (e2) wherein R ¹² is a (meth) propylene fluorenyloxyalkyl group, for example, 3-(meth)acryloxypropyl-trimethoxydecane, 3 -(Meth)acryloxypropyl-triethoxydecane, etc. (meth) propylene oxyalkyl-trialkoxy decane; 3-(methyl) propylene methoxy propyl-methyl (meth) propylene oxyalkyl-alkyl dialkoxy decane such as dimethoxy decane, 3-(methyl) propylene methoxy propyl-methyl diethoxy decane, or the like (meth) propylene decyloxyalkyl-dialkyl (mono) alkoxy decane, etc. of the compound.

The compound represented by the above formula (e2) wherein R ¹² is a mercapto-alkyl group may, for example, be a mercaptoalkyl group such as 3-mercaptopropyltrimethoxydecane or 3-mercaptopropyltriethoxydecane. Or alkoxy decane; 3-mercaptopropylmethyldipropoxydecane, 3-mercaptopropylmethyldiisopropoxydecane, etc., or corresponding to such (decylalkyl)alkyldialkoxy decane A (decylalkyl)dialkyl(mono)alkoxydecane of the compound or the like.

Among the compounds having such a dialkoxyfluorenyl group, dimethyldimethoxydecane, dimethyldiethoxydecane, dimethyldipropoxydecane, and diethyldimethoxy can be used. a dialkyldialkoxy group such as decane, diethyldiethoxydecane, diethyldipropoxydecane, isopropyldimethoxymethylnonane or isopropyldiethoxymethyldecane a (vinyl)alkyl dialkoxy decane such as ethylene methyl dimethoxy decane or ethylene methyl diethoxy decane; 3-methyl propylene methoxy propyl methyl dimethoxy decane, (Meth) propylene methoxyalkyl-alkyl dialkoxy decane, etc., such as 3-methacryl methoxy propyl methyl diethoxy decane.

Further, among the compounds having a trialkoxyfluorenyl group, methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, ethyltrimethoxydecane, and ethyltrile may be used. Ethoxy decane, ethyl tripropoxy fluorene An alkyltrialkoxy decane such as an alkyl group, an isopropyltrimethoxy decane or an isopropyltriethoxy decane; a vinyl trialkoxy decane such as a vinyltrimethoxydecane or a vinyltriethoxydecane; (meth)acryloxyalkyl-trioxane such as 3-(methyl)propenyloxypropyl-trimethoxydecane, 3-(methyl)propenyloxypropyl-triethoxydecane Oxydecane, etc.

The amount of the compound (E) to be used is, for example, preferably from 1 to 50 moles per 1 to 50 moles (preferably from 5 to 40 moles, relative to 5 moles of the alkyl group-containing amine ester-based polymer). Use up to 20 moles). When the amount of the compound (E) used is more than the above range, the storage stability tends to be lowered.

The surrounding environment in the polyoxygen chain addition reaction is not particularly limited, and is selected from the environment around the air, the environment around the nitrogen, and the environment around the argon. The reaction temperature is appropriately selected depending on the type of the reaction component, etc., and is, for example, 20 to 100 ° C, preferably about 40 to 80 ° C. The reaction can be carried out under normal pressure or under reduced pressure or under pressure. The reaction time can be suitably selected, for example, from 1 to 20 hours, preferably from about 1 to 5 hours.

In the moisturizing milk composition of the present invention, (iii) the compounding amount of the quaternary ammonium sulfonated amine ester polymer is not particularly limited, but the effect of suppressing fading is considered, and the mass is 0.01 to 1 with respect to the composition. % is preferably, and more preferably 0.05 to 0.6% by mass. When the amount of the compound is less than 0.01% by mass, the effect of suppressing fading is insufficient. When the amount is more than 1% by mass, the bristles after use may be hard, and the feeling of use may be lowered.

In addition to the above-mentioned components, the moisturizing milk composition of the present invention can be formulated in a usual manner by blending other components which can be used for general cosmetics or pharmaceuticals, without impairing the effects of the present invention.

Examples of the other component include an oil component, a cationic surfactant other than the above, a nonionic surfactant, a powder component, a moisturizer, a natural polymer, a synthetic polymer, an ultraviolet absorber, a metal ion chelating agent, and the like. pH adjusters, skin nutrients, vitamins, antioxidants, antioxidants, fragrances, water, etc.

Examples of the oil component include liquid fats and oils, solid fats and oils, hydrocarbon oils, and polyoxygenated oils.

Examples of the liquid fats and oils include avocado oil, Japanese camellia oil, sea turtle oil, Hawaiian soybean oil, corn oil, oyster sauce, olive oil, rapeseed oil, egg butter, sesame oil, almond oil, wheat germ oil, and camellia oil. Castor oil, linseed oil, sunflower oil, cottonseed oil, eucalyptus oil, soybean oil, peanut oil, tea seed oil, hazelnut oil, rice bran oil, Zhinatong oil, Japanese tung oil, jojoba oil, germ oil, triglycerin, etc.

Examples of the solid fats and oils include cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, sheep fat, hardened tallow, palm kernel oil, lard fat, beef bone fat, and wood wax. Kernel oil), hardened oil, beef fat, wood wax, hardened castor oil, etc.

Examples of the hydrocarbon oil include liquid paraffin, ozocerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, and the like.

Examples of the polyoxygenated oil include a chain polyoxyalkylene (for example, dimethyl polyoxyalkylene, methylphenyl polyoxyalkylene, diphenyl polyoxyalkylene, etc.); cyclic polyfluorene Oxyalkane (eg, octamethylcyclotetraoxane, decamethylcyclopentaoxane, dodecamethylcyclohexaoxane, etc.); forming a three-dimensional network structure Polyoxyxylene resin, polyoxyxene rubber, various modified polyoxyalkylene oxides (amine modified polyoxyalkylene oxide, polyether modified polyoxyalkylene oxide, alkyl modified polyoxyalkylene, polyether-alkyl Co-modified polyoxyalkylene, fluorine modified polyoxyalkylene, polyoxyethylene/polyoxypropylene copolymerized modified polyoxyalkylene, linear amino polyether modified polyoxyalkylene, decylamine modified Polyoxymethane, amino diol modified polyoxyalkylene, aminophenyl modified polyoxyalkylene, methanol modified polyoxyalkylene, polyglycerol modified polyoxyalkylene, polyglycerol-alkyl Co-modified polyoxyalkylene, etc.), polymethinol (dimethiconol), acrylic acid polyoxane, and the like. The compounding conditions of the polyoxygenated oil are either soluble in the composition and emulsified in the composition, and the particle size after emulsification is also the same as that of the general detergent composition.

The cationic surfactant may, for example, be an alkylpyridine salt (for example, cetylpyridinium chloride or the like); chlorinated poly(N,N'-dimethyl-3,5-methylene Alkylpyridinium salt; dialkyl morpholinium salt; POE alkylamine; alkylamine salt; polyamine salt fatty acid derivative; pentanol fatty acid derivative; Ammonium methane; benzethonium chloride and the like.

Examples of the nonionic surfactant include fatty acid alkanolamines such as coconut oil fatty acid monoethanol decylamine, coconut oil fatty acid diethanol amide, lauric acid isopropyl decylamine, and oleic acid diethanol decylamine; Sorbitan fatty acid esters such as sorbitan monostearate and sesquioleic acid sorbitan; diethylene glycol laurate, propylene glycol laurate, ethylene glycol monooleate, ethylene glycol distearate, etc. Alkanediol fatty acid esters; hardened castor oil derivatives, glyceryl alkane ethers, POE sorbitan monooleate, monostearate polyoxyethylene sorbitan, and other POE sorbitan fatty acid esters; POE sorbitol monolauric Acid ester and other POE Sorbitol fatty acid esters; POE glycerol fatty acid esters such as POE-glycerol monoisostearate; POE glycerol fatty acid esters such as polyethylene glycol monooleate and POE distearate; POE-octyl twelve POE alkyl ethers such as ether; POE alkyl phenyl ethers such as POE nonylphenyl ether; POE/POP alkyl ethers; triblock copolymer type; POE castor oil; POE hardened castor oil derivatives; A saccharide such as a glycoside or a glycosidamide; an alkylglycoside or the like.

Examples of the powder component include inorganic powders (for example, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, red mica, biotite, vermiculite, magnesium carbonate, calcium carbonate, and strontium). Aluminum acid, barium strontium citrate, calcium citrate, magnesium citrate, barium strontium citrate, metal citrate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorine phosphorus Gray stone, hydroxyapatite, ceramic powder, metal soap (such as zinc myristate, calcium palmitate, aluminum stearate, boron nitride, etc.); organic powder (such as polyamide resin powder (nylon powder), Polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); Inorganic white pigments (such as titanium dioxide, zinc oxide, etc.); inorganic red pigments (such as iron oxide (red iron oxide), iron titanate, etc.); inorganic brown pigments (such as γ-iron oxide, etc.); inorganic yellow pigments ( Such as yellow iron oxide, loess, etc.; Black pigments (for example, black iron oxide, low-order titanium oxide, etc.); inorganic purple pigments (for example, manganese violet, cobalt violet, etc.); inorganic green pigments (such as chromium oxide, chromium hydroxide, cobalt titanate, etc.) Inorganic blue pigments (eg, ultramarine blue, Prussian blue, etc.); pearlescent Pigments (for example, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc.); metal powder pigments (for example, aluminum powder, copper powder, etc.) ); organic pigments such as zirconium, hafnium or aluminum lake (eg red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 405, Organic pigments such as orange 203, orange 204, yellow 205, yellow 401 and blue 404, red 3, red 104, red 106, red 227, red 230, red 401, red 505 No., Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1, etc.); natural pigments (such as chlorophyll, β-carotene, etc.); clay minerals Soil, hectorite, laponite, etc.).

Examples of the humectant include polyethylene glycol, propylene glycol, dipropylene glycol, isopropyl glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, and the like. Hyaluronic acid, mucoitin sulfate, secantonic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, cholate, d1-pyrrolidone Acid salt, short-chain soluble collagen, diglycerin (EO) PO adduct, Rosa roxburghii extract, Achillea millefolium extract, melilot extract, and the like.

Examples of the natural water-soluble polymer include plant-based polymers (for example, gum arabic, tragacanth gum, galactan, guar gum, and carrageen gum). ), 梧 Karaya gum, carrageenan, tamarind gum, locust bean gum, pectin, agar, alfalfa (榅桲), algin (a brown algae) Extract), starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (eg xanthan gum, dextran, amber xylan) (succinoglucan), polytriglucose (pululan), etc.; animal-based polymers (for example, collagen, casein, albumin, gelatin, etc.). Further, such derivatives (POE-POP modification, alkyl modification, cationization, anionization, deuteration) may also be mentioned.

Examples of the semi-synthetic water-soluble polymer include starch-based polymers (for example, carboxymethyl starch and methyl hydroxypropyl starch), and cellulose-based polymers (methylcellulose and ethylcellulose, Methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, dialkyl dimethyl ammonium sulfate cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystallization Cellulose, cellulose powder, and hydrophobic modified compounds of such polymers <for example, a part of stearoxy groups are modified> and cationically modified compounds of such polymers); alginic acid-based polymers (for example, algae) Sodium, propylene glycol alginate, etc.; sodium pectate and the like.

Examples of the water-soluble polymer to be synthesized include an ethylene-based polymer (for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, or a carboxyvinyl polymer); and a polyoxyethylene-based polymer (for example, Polyethylene glycol 20,000, 40,000, 60,000 polyoxyethylene polyoxypropylene copolymer, etc.; poly(halogenated dimethyl diallylammonium) type cationic polymer (for example, Merquat 100 (manufactured by Merck, USA)); Halogenated dimethyl diallyl a copolymer type cationic polymer of ammonium and acrylamide (for example, Merquat 550 (manufactured by Merck, USA); an acrylic polymer (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); Ethyleneimine; cationic polymer; magnesium silicate (Veegum); polyquaternium-39 (polyquaternium-39).

Examples of the ultraviolet absorber include a benzoic acid-based ultraviolet absorber (for example, p-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglyceride, N,N-dipropoxy PABAethyl ester, N,N. -diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, etc.); o-aminobenzoic acid-based ultraviolet absorber (for example, liter a base-N-acetamido-amino benzoate or the like; a salicylic acid-based ultraviolet absorber (for example, amyl salicylate, salicylic acid) Ester, salicylic acid Ester, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.; cinnamic acid ultraviolet absorber (such as octyl cinnamate, ethyl cinnamate) 4-isopropyl ester, cinnamic acid methyl-2,5-diisopropyl ester, cinnamic acid ethyl-2,4-diisopropyl ester, cinnamic acid methyl-2,4-diisopropyl ester, cinnamic acid Propyl-p-methoxy ester, isopropyl-p-methoxy cinnamate, isoamyl-p-methoxy cinnamate, octyl-p-methoxy cinnamate (2-ethylhexyl cinnamate) -p-methoxy ester), 2-ethoxyethyl-p-methoxy cinnamic acid, cyclohexyl-p-methoxy cinnamate, ethyl-α-cyano-β-phenyl cinnamate, 2-ethylhexyl-α-cyano-β-phenyl cinnamic acid, glycerol mono-2-ethylhexyl-di-methoxy ester, etc.; benzophenone ultraviolet absorber (eg 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxydiphenyl Methyl ketone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methyl two Benzophenone, 2-hydroxy-4-methoxybenzophenone- 5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octyloxy Benzophenone, 4-hydroxy-3-carboxybenzophenone, etc.; 3-(4'-methylbenzylidene)-d, 1-camphor, 3-benzylidene-d, 1-camphor ; 2-phenyl-5-methylbenzo Azole; 2,2'-hydroxy-5-methylphenylbenzo Azole; 2-(2'-hydroxy-5'-th-octylphenyl)benzo Azole; 2-(2'-hydroxy-5'-methylphenyl)benzo Azole; di-anisyl methane; 4-methoxy-4'-t-butyldibenylmethane; 5-(3,3-dimethyl-2-arsenyl)-3- Pentane-2-one, etc.); three UV absorber (eg 2-4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl)-4,6-bis(2,4-dimethyl) Phenyl)-1,3,5-three , 2-4-[(2-hydroxy-3-trisyloxypropyl)oxy]-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 , 3,5-three Wait).

Examples of the metal ion chelating agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, and ethylenediaminetetraacetic acid disodium (edetate). Disodium), trisodium edetate, tetrasodium edetate, sodium citrate, sodium polyphosphate, sodium methyl phosphate, gluconic acid, phosphoric acid, citric acid, adipic acid, succinic acid, ethylenediamine Tetraacetic acid, ethylenediamine hydroxyethyl triacetate, and the like.

Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and sodium succinate-succinate.

Examples of the vitamins include vitamin A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, and biotin.

Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, and gallic acid esters.

As other components to be formulated, for example, a preservative (ethylparaben, butyl paraben, 1,2-alkanediol) (carbon chain length 6) To 14) and its derivatives, phenoxyethanol, methylchloroisothiazolinone, etc.; anti-inflammatory agents (such as glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, Japanese hinokitiol, zinc oxide, allantoin, etc.; whitening agents (such as Saxifrage extract, arbutin, etc.); various extracts (such as scutellaria, berberine, purple root, peony, medicine) , Birch, sage, medlar, carrot, aloe, mallow, iris, grape, coix seed, loofah, lily, saffron, chuanxiong, ginger, small forsythia, stalk (Ononis), garlic, pepper, dried tangerine peel, angelica, seaweed, etc.), activators (such as royal jelly, photoreceptors, cholesterol derivatives, etc.); blood circulation promoters (for example, vanillin amide (nonylic) Acid vanillylamide), benzyl nicotinic acid, beta-butoxy nicotinic acid Ester, capsaicin, zingerone, cantharides tincture, ichthammol, tannic acid, alpha-Borneol, nicotinic tocopherol, hexacnic acid Inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetylcholine, verapamil, cephalosporin Cepharanthine, γ-oryzanol, etc.; anti-lipid leakage agent (such as sulfur, thianthol, etc.); anti-inflammatory Agents (for example, tranexamic acid, thiotaurine, hypotaurine, etc.); aromatic alcohols (benzyl alcohol, benzyloxyethanol, etc.) and the like.

When the moisturizing milk composition of the present invention is applied to a ranunculus, the quaternary ammonium ester-based polymer containing a quaternary ammonium group can be rapidly and stably adsorbed on the surface of the edulis, and it is not lost even if it is rinsed with water. Therefore, it is possible to suppress the penetration of moisture into the inside of the burr during washing, and to suppress the dye from flowing out inside the burrs, thereby exhibiting an excellent effect of suppressing fading.

Further, by using a specific cationic surfactant and a higher aliphatic alcohol in combination, it is possible to further promote the above-described effect of suppressing fading, and at the same time, it has a good feeling of use such as the flexibility of the dried edgy after application of the edema after application.

Therefore, if the moisturizing lotion containing the moisturizing lotion composition of the present invention is used for daily washing, the fading of the coloring can be remarkably suppressed, and the beautiful ochre can be maintained. At the same time, it is possible to alleviate the hardness caused by the dyeing, and to obtain a flexible edgy.

Further, in the moisturizing milk composition of the present invention, the effect of suppressing fading and fading can be carried out by using a spectrophotometer for the dyed edgy, and the color of the edgy before and after washing is measured, and the color difference (ΔE) is performed. Evaluation. The closer the color difference (ΔE) is to zero, the higher the effect of suppressing the fading.

When the rinse treatment is carried out using the moisturizing milk composition of the present invention (repeated five times of washing-rinsing-drying treatment), the color difference (ΔEs) before and after the washing treatment is, for example, 3.3 or less, and preferably 2.8 or less. . If the color difference exceeds the above range, the tendency to suppress the fading effect is not easily felt.

(Example)

Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples. In addition, unless otherwise specified, "parts" means "parts by mass", and "%" means "mass%".

First, the evaluation method for suppressing the fading effect and the feeling of use for the following test will be described.

<Evaluation of the effect of suppressing fading>

1. A brown dyeing agent ("DIANISTNB8", manufactured by Shiseido Professional Co., Ltd.) was used, and 100% white hair bundle (manufactured by Beaulax Co., Ltd.) was dyed.

2. The color (C ₁ ) of the dyed hair bundle (dyed hair bundle) was measured using a spectrophotometer (trade name "CM-2500d", manufactured by Konica Minolta Co., Ltd.).

3. The moisturizing milk obtained in the examples and the comparative examples was used for the above-mentioned dyed hair bundle (the number of samples of each moisturizing milk was 10), and the so-called rinse treatment was performed in advance. Then, the dyed hair bundle after the foregoing pretreatment is subjected to a washing treatment (repeated 5 times of washing-rinsing-drying treatment).

4. Using a spectrophotometer, the color of the dyed hair bundle after washing is measured in the same manner as above, and the average value (C ₂ ) thereof is calculated, and the color difference before and after the cleaning treatment is obtained (ΔEs: C ₁ - C ₂ ), compared with the comparative example, and evaluated the effect of suppressing fading according to the following evaluation criteria.

Evaluation basis

(ΔEs in each example) - (ΔEs of the comparative example) has a value of -1 or less: ◎ ◎ (ΔEs of each example) - (ΔEs of the comparative example) has a value exceeding -1, and The value of -0.5 or less: ◎ (ΔEs in each example) - (ΔEs of the comparative example) exceeds -0.5, and is 0 or less: ○ (ΔEs in each example) - (ΔEs of the comparative example) The value exceeds 0: ×

<Evaluation method using feeling>

A functional test was performed on the washed dyed hair bundles by 10 professional reviewers, and the flexibility (dryness after drying) of the dried ranunculus after the moisturizing milk compared with the comparative example was evaluated on the basis of the following criteria. .

Compared with the comparative example, more than 70% of the judges answered “equal” or “good”: ◎ ◎ compared with the comparative example, more than 50% of the judges who did not reach 70% answered “equal” or “good”: ◎ Compared with the comparative example, more than 30% of the judges who did not reach 50% answered “equivalent” or “good”: ○ Less than 30% of the judges answered “equal” or “good” compared with the comparative example: ×

Next, a method for producing the quaternary ammonium group-containing amine ester-based polymer used in the following test will be described.

Preparation Example 1 of a hydrazine-based amine ester polymer containing a quaternary ammonium group

Preparation example of alkoxydecane (compound A) containing an ester-modified amine group

With respect to 221.4 parts of γ-aminopropyltriethoxydecane (trade name "KBE903", manufactured by Shin-Etsu Chemical Co., Ltd.), lauryl acrylate was mixed at a ratio of 240.4 parts, and reacted at 50 ° C for 7 days. An alkoxydecane (compound A) containing an ester-modified amine group is obtained.

Manufacturing example 1

In a four-necked flask equipped with a nitrogen gas introduction tube, a thermometer, a condenser, and a stirrer, 50 parts of polytetramethylene ether glycol (quantitative average molecular weight: 1944.5, trade name "PTMG2000", manufactured by Mitsubishi Chemical Corporation) was prepared. Trimethylolpropane mono (polyethylene oxide methyl ether) represented by the following formula (2) (quantitative average molecular weight: 1089.3, trade name "Ymer N120", manufactured by Perstorp Co., Ltd.) 25 parts, N-methyl-N, 25 parts of N-diethanolamine (MDA), 60.4 parts of isophorone diisocyanate (IPDI) and 50 parts of methyl ethyl ketone (MEK), 1,8-diguanidine bicyclo [5.4.0] XI as a catalyst 0.1 parts of -7-ene (DBU), and reacting at a temperature of 80 to 85 ° C for 5 hours under a nitrogen atmosphere to obtain a reaction mixture containing a tertiary amine-containing amine ester-based polymer;

150 parts of methyl ethyl ketone (MEK) was added to the reaction mixture containing the amine ester polymer, and cooled to 50 ° C, and 25.2 parts of dimethyl sulfate was added as a quaternizing agent, and 50 at 60 to 60 ° C was carried out. The quaternary ammonium ionization of the tertiary amine moiety in minutes to 1 hour produces an amine ester-based polymer containing a quaternary ammonium group.

After 9.9 parts of the compound A obtained in Preparation Example 1 was mixed and mixed in the reaction mixture of the quaternary ammonium group-containing amine ester polymer, the reaction was carried out at a temperature of 65 to 75 ° C for 1 hour under the atmosphere of nitrogen. A reaction mixture (1) comprising a deuterated amine ester-based polymer containing a quaternary ammonium group is obtained.

Next, after cooling the reaction mixture (1) to 40 ° C, 1,000 parts of deionized water was added under stirring. Then, the solvent was distilled off at 45 to 50 ° C under reduced pressure to give an aqueous dispersion (1).

The above-mentioned evaluation (suppression of fading effect and feeling of use) was carried out for each of the moisturizing milks produced according to the formulations shown in the following Tables 1 and 2. The results are shown in Tables 1 and 2. Further, in comparison with the examples in each evaluation, Comparative Example 1-1 was used as a reference.

(Production method)

After adding a cationic surfactant to the purified water, the mixture is sufficiently stirred and dissolved, and then other components are sequentially added to obtain a moisturizing milk composition.

As shown in Tables 1 and 2, the other examples in which the polymer was blended had an effect of suppressing fading as compared with Comparative Example 1-1 in which the amine ester-based polymer containing a quaternary ammonium group was not formulated.

Further, as a cationic surfactant of a conditioning agent, compared with Comparative Example 1-2 in which only a single long-chain alkyl type quaternary ammonium salt (stearyltrimethylammonium chloride) was formulated, Confirmed that the polymorphism is accompanied by an imidazoline type Examples 1-1 to 1-7 of a quaternary ammonium salt (diammonium imidazoline methyl sulfate), or a di-long-chain alkyl type quaternary ammonium salt (dicocoyl hydroxyethylmethylammonium sulfate) Examples 1-8 to 1-13 of methyl ester or distearyldimethylammonium chloride all improved the flexibility after drying.

The imidazoline type quaternary ammonium salt can sufficiently exhibit the effect of blending 0.01% by mass (Example 1-1), but blending 0.05 to 2% by mass of Examples 1-2 to 1-6 suppresses the fading effect and The flexibility after drying was high, and this tendency was particularly remarkable in Examples 1-2 to 1-5 in which 0.05 to 1% by mass was formulated.

Further, for the di-long-chain alkyl type quaternary ammonium salt, as shown in Examples 1-8 to 1-10 and 1-11 to 1-13, 0.01 to 3% by mass, especially 1 to 3 mass, is formulated. When % is obtained, the effect of suppressing the fading effect and the flexibility after drying can be obtained.

Therefore, in the present invention, it is preferred to formulate a cationic surfactant in addition to the amine ester-based polymer containing a quaternary ammonium group. Further, as the above cationic surfactant, in particular, an imidazoline type quaternary ammonium salt or a dilong chain alkyl type quaternary ammonium salt and a single long chain alkyl type quaternary ammonium salt are preferably used in combination. Further, the amount of the imidazoline type quaternary ammonium salt is preferably from 0.05 to 2% by mass, and more preferably from 0.05 to 1% by mass. The compounding amount of the di-long-chain alkyl type quaternary ammonium salt is preferably from 0.01 to 3% by mass, and more preferably from 1 to 3% by mass.

Further, each of the moisturizing milk compositions manufactured according to the formulations shown in Table 3 below was subjected to the above evaluation (inhibition of fading effect and feeling of use). The results are shown in Table 3. Further, when each evaluation was compared with the example, Comparative Example 2-1 was used as a reference.

(Production method)

After adding a cationic surfactant to the purified water, the mixture is sufficiently stirred and dissolved, and then other components are sequentially added to obtain a moisturizing milk composition.

As shown in Table 3, in comparison with Comparative Example 2-1 in which the amine ester-based polymer containing a quaternary ammonium group was not blended, the example in which 0.01 to 1% by mass of the polymer was blended not only inhibited the effect of fading, but also used Feelings are also improved. In particular, when the amount of the amine ester-based polymer containing a quaternary ammonium group is from 0.05 to 0.6% by mass, the fading effect and the use of the sensory system are remarkably improved.

On the other hand, an amine ester polymer containing a quaternary ammonium group is formulated. In Comparative Example 2-2 of 1.1% by mass, although the effect of suppressing fading was improved, almost no improvement in the feeling of use was observed.

Therefore, the amount of the amine ester-based polymer containing a quaternary ammonium group in the present invention is from 0.01 to 1% by mass, and preferably from 0.05 to 0.6% by mass.

Claims (3)

A moisturizing milk composition characterized by comprising: (i) a cationic surfactant, (ii) a higher aliphatic alcohol, and (iii) a quaternary ammonium ester-based polymer containing a quaternary ammonium group; 0.01 to 1% by mass; And (i) the cationic surfactant contains (a) an imidazoline type quaternary ammonium salt represented by the following formula (I) or a di-long chain alkyl type quaternary ammonium salt represented by the following formula (II) And (b) a single long-chain alkyl type quaternary ammonium salt represented by the following formula (III); (In the above formula, R ¹ and R ² may be the same or different from each other, and represent an alkyl group or an alkenyl group having 12 to 22 carbon atoms, and Z represents a halogen atom selected from a methyl sulfate group and an ethyl sulfate group. Anionic group) (In the above formula, either of R ³ to R ⁶ represents a straight or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group, or R ⁷ -(Z1) _q -(Y1) _p - R ⁷ represents a hydroxy-substituted linear or branched alkyl group having 8 to 36 carbon atoms, and Y1 represents a group selected from -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ O -, -CH(OH)CH ₂ O-, Z1 represents a bond selected from the group consisting of a guanamine bond (-CONH-), an ether bond (-O-), an ester bond (-COO-); p and q Respectively represent an integer of 0 or 1, respectively; the remaining two of R ³ to R ⁶ may be the same or different from each other, respectively representing a hydroxy-substituted carbon number of 1 to 3 alkyl or benzyl; X represents a halogen atom, carbon An alkylsulfate group of 1 or 2, or an anion capable of forming a salt with a quaternary ammonium such as a residue after removing a hydrogen atom of an organic acid) (In the above formula, R ⁸ represents a hydroxy group-substituted linear or branched alkyl group having 8 to 36 carbon atoms, or R ¹² -(Z1) _q -(Y1) _p -; and R ¹² represents a hydroxy-substituted carbon. a linear or branched alkyl group of 8 to 36, and Y1 represents a group selected from -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ O-, -CH(OH)CH ₂ O a binding group, Z1 represents a bonding group selected from the group consisting of a guanamine bond (-CONH-), an ether bond (-O-), and an ester bond (-COO-). p and q each represent an integer of 0 or 1; R ⁹ , R ¹⁰ and R ¹¹ may be the same or respectively different, and represent a hydroxy group which may be substituted with a C 1 to 3 alkyl group or a benzyl group; X represents a halogen atom, an alkylsulfate group having 1 or 2 carbon atoms, or An anion of a salt may be formed with a quaternary ammonium such as a residue after removal of a hydrogen atom of an organic acid. The moisturizing milk composition according to the first aspect of the invention, wherein the component (a) of the (i) cationic surfactant is 0.05 to 2% by mass of the imidazoline represented by the above formula (I) a quaternary ammonium salt of a type, or 0.01 to 3% by mass of a di-long-chain alkyl type quaternary ammonium salt represented by the above formula (II). The moisturizing milk composition according to claim 1 or 2, wherein the component (a) of the (i) cationic surfactant is selected from the group consisting of diamyl imidazoline methyl sulfate, chlorinated. One or more of the group consisting of distearyl dimethyl ammonium and dicocoyl hydroxyethyl methyl ammonium methyl sulfate.