JPWO2012161215A1 - Conditioner composition - Google Patents

Abstract

The present invention provides a conditioner composition excellent in fading suppression effect and use feeling. (Ii) a cationic surfactant, (ii) a higher aliphatic alcohol, and (iii) 0.01 to 1% by mass of a quaternary ammonium group-containing silylated urethane polymer, and (I) the cationic surfactant has (a) an imidazoline type quaternary ammonium salt having a specific structure, or a dilong chain alkyl type quaternary ammonium salt having a specific structure, and (b) a specific structure. The conditioner composition according to claim 1, comprising a mono long-chain alkyl type quaternary ammonium salt. [Selection figure] None

Description

Related applications

  This application claims the priority of the Japan patent application 2011-116993 of an application on May 25, 2011, and is integrated here.

  The present invention relates to a conditioner composition, and more particularly to its hair color fading-inhibiting effect and improvement in use feeling.

  In recent years, coloring of hair using an oxidation dye has been widely performed. The main problem for people who enjoy hair coloring is that they have poor color, and after discoloration, the discoloration usually becomes noticeable in about one month. If the dyeing is not repeated frequently, it maintains a beautiful hair color. It cannot be mentioned. Oxidative dye fading is known to be caused by water penetrating into the hair during hair washing, etc., and washing off the dye incorporated into the hair, and has an effect of suppressing fading of the hair color. There is a need for shampoos and conditioners.

  Patent Document 1 describes a shampoo having a discoloration suppressing effect, in which a silylated peptide-silane compound copolymer composition is blended. Patent Document 2 describes a treatment having an anti-fading effect containing a lipophilic cationic surfactant and sterols. However, none of these effects were sufficient, and it was impossible to realize the goodness of the hair color.

JP 2004-315369 A JP 2003-176214 A

Further, in the case of hair color with an oxidative dye, some squeaks and wrinkles may occur after dyeing due to hair damage accompanying decolorization. Therefore, in the case of dyed hair, the difference in the suppleness of hair dried after using the conditioner tends to be felt stronger than normal hair. Therefore, in conditioners used for hair that has been colored, not only the combination of ingredients having a high fading-inhibiting effect, but also the effects of the ingredients are promoted, and the above-mentioned specification is more specific than those incorporated in ordinary conditioners. It has been demanded to have a component having an excellent use feeling such as an effect (flexibility after drying).
However, a composition of a conditioner component that can enhance the effect of the blended component having an anti-fading effect and that is remarkably excellent in use feeling has not been obtained at present.

  This invention is made | formed in view of the said subject, and it aims at providing the conditioner composition excellent in the fading suppression effect and the usability | use_condition.

  As a result of intensive studies by the present inventors in order to solve the above problems, the quaternary ammonium group-containing silylated urethane-based polymer greatly suppresses the discoloration of the hair color after using the conditioner. The present invention is completed by finding that the combination of a specific cationic surfactant and a higher aliphatic alcohol results in further improvement of the fading-inhibiting effect and an excellent feeling in use in the hair after dyeing. It came to.

（上記式中、Ｒ^１及びＲ^２は互いに同一でも異なってもよく、炭素数が１２〜２２のアルキル基又はアルケニル基を表し、Ｚはハロゲン原子、メチルサルフェート基及びエチルサルフェート基から選ばれるアニオン性基を表す。）

（上記式中、Ｒ^３〜Ｒ^６のうちいずれか２つはそれぞれ、ヒドロキシル基が置換していてもよい炭素数８〜３６の直鎖または分岐のアルキル基、またはＲ^７−（Ｚ１）_ｑ−（Ｙ１）_ｐ−を表す。Ｒ^７はヒドロキシル基が置換していてもよい炭素数８〜３６の直鎖または分岐のアルキル基を表し、Ｙ１は−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２Ｏ−、−ＣＨ（ＯＨ）ＣＨ_２Ｏ−から選択される結合基を示し、Ｚ１はアミド結合（−ＣＯＮＨ−）、エーテル結合（−Ｏ−）、エステル結合（−ＣＯＯ−）から選択される結合基を示す。ｐ及びｑはそれぞれ０または１の整数を表す。また、Ｒ^３〜Ｒ^６の残りの２つはそれぞれ、ヒドロキシル基が置換していてもよい炭素数１〜３のアルキル基またはベンジル基を表し、同一であってもそれぞれ異なっていてもよい。Ｘはハロゲン原子、炭素数１又は２のアルキル硫酸基、または有機酸の水素原子を除いた残基等の第４級アンモニウムと塩を形成し得るアニオンを示す。）

（上記式中、Ｒ^８はヒドロキシル基が置換していてもよい炭素数８〜３６の直鎖または分岐のアルキル基、またはＲ^１２−（Ｚ１）_ｑ−（Ｙ１）_ｐ−を表す。Ｒ^１２はヒドロキシル基が置換していてもよい炭素数８〜３６の直鎖または分岐のアルキル基を表し、Ｙ１は−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２Ｏ−、−ＣＨ（ＯＨ）ＣＨ_２Ｏ−から選択される結合基を示し、Ｚ１はアミド結合（−ＣＯＮＨ−）、エーテル結合（−Ｏ−）、エステル結合（−ＣＯＯ−）から選択される結合基を示す。ｐ及びｑはそれぞれ０または１の整数を表す。また、Ｒ^９、Ｒ^１０及びＲ^１１は、ヒドロキシル基が置換していてもよい炭素数１〜３のアルキル基またはベンジル基を表し、同一であってもそれぞれ異なっていてもよい。Ｘはハロゲン原子、炭素数１又は２のアルキル硫酸基、または有機酸の水素原子を除いた残基等の第４級アンモニウムと塩を形成し得るアニオンを示す。）That is, the conditioner composition according to the present invention comprises (i) a cationic surfactant,
(Ii) a higher aliphatic alcohol, and (iii) 0.01 to 1% by mass of a quaternary ammonium group-containing silylated urethane polymer, and (i) a cationic surfactant, (a) An imidazoline-type quaternary ammonium salt represented by the following general formula (I), or a di-long-chain alkyl-type quaternary ammonium salt represented by the following general formula (II); and (b) the following general formula (III) And a mono long-chain alkyl type quaternary ammonium salt represented by the formula:

(In the above formula, R ¹ and R ² may be the same or different and each represents an alkyl group or an alkenyl group having 12 to 22 carbon atoms, and Z is an anion selected from a halogen atom, a methyl sulfate group and an ethyl sulfate group. Represents a sex group.)

(In the ^formula, R 3 respectively any two of to R ^6, straight-chain or branched alkyl group which may 8 to 36 carbon atoms which can hydroxyl group substituted or ^R 7, - _{(Z1) q} - _{(Y1) p} - are expressed .R ⁷ represents a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group, Y1 is _{-CH 2 CH 2 -, - CH} 2 CH ₂ represents a bonding group selected from CH ₂ —, —CH ₂ CH ₂ O—, —CH (OH) CH ₂ O—, and Z 1 represents an amide bond (—CONH—), an ether bond (—O—), an ester Represents a linking group selected from a bond (—COO—), p and q each represent an integer of 0 or 1. Further, the remaining two of R ^{3 to} R ⁶ are each substituted with a hydroxyl group. A C1-C3 alkyl group or ben X may be the same or different, and X is a quaternary ammonium such as a halogen atom, an alkyl sulfate group having 1 or 2 carbon atoms, or a residue excluding a hydrogen atom of an organic acid. An anion that can form a salt.)

(In the formula, ^{R 8} is a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group or _{^{R 12, - (Z1) q}} - (Y1) p - represents a ^{.R 12} Represents a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group, and Y1 represents —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O. — Represents a bonding group selected from —CH (OH) CH ₂ O—, and Z 1 represents a bond selected from an amide 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 represent an alkyl group having 1 to 3 carbon atoms or a benzyl group which may be substituted with a hydroxyl group. Even if they are the same X represents an anion capable of forming a salt with a quaternary ammonium such as a halogen atom, an alkyl sulfate group having 1 or 2 carbon atoms, or a residue excluding a hydrogen atom of an organic acid.)

Further, in the conditioner composition, (i) the component (a) of the cationic surfactant is 0.05 to 2% by mass of an imidazoline type quaternary ammonium salt represented by the above general formula (I), Or it is suitable that they are 0.01-3 mass% of di long chain alkyl type | mold quaternary ammonium salt represented by the said general formula (II).
Further, in the conditioner composition, the component (a) of the (i) cationic surfactant is selected from the group consisting of dibehenylimidazolinium methosulfate, distearyldimethylammonium chloride, and dicocoylhydroxyethylmethylmonium methosulfate. It is suitable that it is one or more selected.

  ADVANTAGE OF THE INVENTION According to this invention, the conditioner composition excellent in the use feeling, such as the fading suppression effect with respect to the hair after dyeing | staining, and the softness of the hair dried after using a conditioner, can be obtained.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The conditioner composition according to the present invention contains (i) a cationic surfactant, (ii) a higher aliphatic alcohol, and (iii) a quaternary ammonium group-containing silylated urethane-based polymer. First, each component will be described.

(I) Cationic surfactant The cationic surfactant used in the present invention imparts a good feeling after use (the suppleness of hair after drying) to the composition, and is also a quaternary ammonium. From the point of improving the anti-fading effect of the group-containing silylated urethane polymer,
(A) an imidazoline type quaternary ammonium salt (a1) represented by the following general formula (I), or a dilong chain alkyl type quaternary ammonium salt (a2) represented by the following general formula (II):
(B) a mono long-chain alkyl-type quaternary ammonium salt represented by the following general formula (III):
Is used.

(A1) Imidazoline-type quaternary ammonium salt The imidazoline-type quaternary ammonium salt used in the present invention is a compound represented by the following general formula (I).

In the above general formula (I), R ¹ and R ² may be the same or different and each represents an alkyl group or an alkenyl group having 12 to 22 carbon atoms, and Z represents a halogen atom, a methyl sulfate group or an ethyl sulfate group. Represents a selected anionic group.
In R ¹ and R ² , examples of the alkyl group having 12 to 22 carbon atoms include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heneicosyl group, A docosyl (behenyl) group etc. can be illustrated. Examples of the alkenyl group having 12 to 22 carbon atoms include dodecenyl group, tridecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icosadecenyl group, helicosadecenyl group, docosadecenyl group and the like. It can be illustrated. 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 that Z can take include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom, and a chlorine atom is particularly preferable. Z is particularly preferably a methyl sulfate group.

  Examples of the imidazoline type quaternary ammonium salt include dialkyl or dialkenyl imidazolinium such as dioleoyl imidazolinium methosulfate, distearyl imidazolinium methosulfate, dibehenyl imidazolinium methosulfate (quaternium-91). And the use of dibehenylimidazolinium methosulfate is particularly suitable.

(A2) Dilong 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 general formula (II).

In the general formula ^(II), R 3 respectively any two of to R ^6, straight-chain or branched alkyl group which may 8 to 36 carbon atoms which can hydroxyl group substituted or ^R 7, - ( Z1) represents _q- (Y1) _p- .
R ⁷ represents a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group, and Y 1 represents —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH. ₂ O— represents a linking group selected from —CH (OH) CH ₂ O—, and Z 1 is selected from an amide bond (—CONH—), an ether bond (—O—), and an ester bond (—COO—). Represents a bonding group. p and q each represents an integer of 0 or 1.
In the above formula (II), the remaining two of R ^{3 to} R ⁶ each represent an alkyl group having 1 to 3 carbon atoms or a benzyl group which may be substituted with a hydroxyl group, and may be the same. Each may be different. X represents an anion capable of forming a salt with a quaternary ammonium such as a halogen atom, an alkyl sulfate group having 1 or 2 carbon atoms, or a residue excluding a hydrogen atom of an organic acid.

  Examples of the dilong chain alkyl quaternary ammonium salt represented by the general formula (II) include didecyldimethylammonium chloride, dicocoyldimethylammonium chloride, dicocoyldimethylammonium bromide, dilauryldimethylammonium chloride, Dimyristyldimethylammonium chloride, dicetyldimethylammonium chloride, dipalmityldimethylammonium chloride, distearyldimethylammonium chloride, distearyldimethylammonium bromide, dioleyldimethylammonium chloride, dicocoylethylhydroxyethylmonium methosulfate, dipalmitoylethyl Hydroxyethylmonium methosulfate, dicocoyl hydroxyethylmethylmonium methosulfate, distearylethylhydroxyethylmonium Roraido, and the like. Particularly preferred in the present invention are distearyldimethylammonium chloride and dicocoylhydroxyethylmethylmonium methosulfate.

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

In the general formula (III), ^{R 8} represents a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group or ^R 12, - represents the _{- (Z1) q - (Y1} ) p .
R ¹² represents a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group, and Y 1 represents —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH. ₂ O— represents a linking group selected from —CH (OH) CH ₂ O—, and Z 1 is selected from an amide bond (—CONH—), an ether bond (—O—), and an ester bond (—COO—). Represents a bonding group. p and q each represents an integer of 0 or 1.
Moreover, R <^9> , R < ¹⁰ > and R < ¹¹ > in the said formula (III) represent the C1-C3 alkyl group or benzyl group which the hydroxyl group may substitute, and it is respectively different even if it is the same. May be. X represents an anion capable of forming a salt with a quaternary ammonium such as a halogen atom, an alkyl sulfate group having 1 or 2 carbon atoms, or a residue excluding a hydrogen atom of an organic acid.

  Examples of the mono long chain alkyl type quaternary ammonium salt represented by the general formula (III) include lauryl trimethyl ammonium chloride, lauryl trimethyl ammonium bromide, myristyl trimethyl ammonium chloride, myristyl trimethyl ammonium bromide, cetyl trimethyl chloride. Ammonium, cetyltrimethylammonium bromide, stearyltrimethylammonium chloride, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, behenyltrimethylammonium bromide, cetyltrimethylammonium methanesulfonate, stearyltrimethylammonium methosulfate, myristyldimethylbenzylammonium chloride, cetyl chloride Dimethylbenzylammonium, stearyl dimethylbenzylamine chloride Chloride, octyl dihydroxyethyl methyl ammonium chloride, 2-decyl tetradecyl trimethyl ammonium chloride, 2-dodecyl hexadecyl trimethyl ammonium chloride, steer chloride b propyl trimethyl ammonium, it may be mentioned stearyl bromide PG trimethylamine. Particularly preferred in the present invention is stearyltrimethylammonium chloride.

  In the present invention, the mono long-chain alkyl amine represented by the following general formula (IV) and the organic acid are used as components for producing the mono long-chain alkyl quaternary ammonium salt of the general formula (III). Can be combined.

In the general formula (IV), R ¹³ and R ¹⁴ each represent an alkyl group having 1 to 3 carbon atoms or a benzyl group which may be substituted with a hydroxyl group, and may be the same or different. R ¹⁵ represents a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group.
Also, Y2 is _{-CH 2 CH 2 -, - CH} 2 CH 2 CH 2 -, - CH 2 CH 2 O -, - CH (OH) represents a bonding group selected _CH 2 from O-, Z2 is an amide bond A linking group selected from (—CONH—), an ether bond (—O—), and an ester bond (—COO—) is shown. s and t each represents an integer of 0 or 1.

  Examples of the combination of a mono long-chain alkyl amine represented by the above formula (IV) suitable for blending with the present invention and an organic acid include, for example, stearic acid dimethylamidopropylamide-glutamic acid, stearic acid diethylamidopropylamide-lactic acid, Examples include stearoxypropyldimethylamide-malic acid, stearyl PGdimethylamine-glutamic acid, behenamidopropyldimethylamine-succinic acid, stearamidepropyldimethanolamine-tartaric acid, and the like.

In the present invention, (i) as a cationic surfactant,
(A1) The imidazole-type quaternary ammonium salt, preferably 0.05 to 2% by mass, more preferably 0.05 to 1% by mass, based on the composition of the present invention, or
(A2) To the composition of the present invention, preferably 0.01 to 3% by mass, more preferably 1 to 3% by mass of a dilong chain alkyl type quaternary ammonium salt;
(B) It is preferable that 0.1 to 5% by mass, more preferably 0.5 to 3% by mass of a mono long chain alkyl type quaternary ammonium salt is blended with the composition of the present invention. It is.
When the blending amount of the component (a1) or (a2) is outside the blending amount range, the suppleness of the hair dried after using the conditioner may be insufficient.
In addition, as a compound of (a2), when a mono long-chain alkyl amine and an organic acid are combined, the mono long-chain alkyl quaternary ammonium salt is produced so that the mono long-chain alkyl quaternary ammonium salt is generated in the above blending amount range. The compounding quantity of an alkyl type amine and organic acid is adjusted.

(Ii) Higher aliphatic alcohol The conditioner composition according to the present invention contains a higher aliphatic alcohol. The higher aliphatic alcohol in the present application represents a linear aliphatic alcohol or a branched aliphatic alcohol having 12 to 36 carbon atoms, which is usually used in cosmetics and pharmaceuticals.
Examples of such linear aliphatic alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, aralkyl alcohol, jojoba alcohol, hardened rapeseed oil alcohol, tetradecyl alcohol, Examples include hexadecyl alcohol and octadecyl alcohol.

Examples of branched aliphatic alcohols include batyl alcohol, chimyl alcohol, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, decyltetradecanol, Examples include hexyl decanol, dodecyl hexadecanol, tetradecyl octadecanol, hexadecyl eicosanol and the like.
Among the above higher aliphatic alcohols, cetyl alcohol is particularly preferable.

  In the present invention, the higher aliphatic alcohol has a molar ratio of the higher aliphatic alcohol to the cationic surfactant (component (a) + component (b)), preferably 1: 0.5 to 1:10. More preferably, it is blended so as to be 1: 1 to 1: 6. When blended outside the range of the molar ratio, the flexibility of the hair dried after using the conditioner may be insufficient.

(Iii) Quaternary ammonium group-containing silylated urethane polymer The quaternary ammonium group-containing silylated urethane polymer includes at least one quaternary ammonium group and at least one reactive silyl group in the urethane polymer. Any compound having any of the above may be used. Examples of reactive silyl groups include hydrolyzable silyl groups and silanol groups.

（上記式中、Ｒ^１、Ｒ^２は、同一又は異なって、アルキル基を示し、Ｒ^３、Ｒ^４は、同一又は異なって、置換基を有していてもよいアルキレン基又は置換基を有していてもよいアリーレン基を示す。Ｒ^５はアルキル基、シクロアルキル基、アリール基又はアラルキル基を示し、Ｒ^６は水素原子又は−ＣＯＯＲ^６’を示し、Ｒ^６’はアルキル基を示す。また、ｍは１〜３の整数である。ｍが１である場合、２個のＲ^２は同一であってもよく、異なっていてもよい。ｍが２以上の整数である場合、２個以上のＲ^１Ｏ−基は同一であってもよく、異なっていてもよい）The quaternary ammonium-containing silylated urethane-based polymer in the present invention includes, among others, constituent units for the following component (A), component (B), and component (C), and is derived from the component (C). A compound having a structure in which the following component (D) is bonded to an isocyanate terminal of a urethane polymer in which a quaternary amine moiety is quaternary ammonium ionized to form a urea bond is preferable.
Component (A): Polyisocyanate compound Component (B): Polyol compound Component (C): Tertiary amine compound having two or more hydroxyl groups Component (D): Formula (d1), (d2) or (d3) below Ester-modified amino group-containing alkoxysilane represented by

(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 each has an optionally substituted alkylene group or 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. M is an integer of 1 to 3. When m is 1, two R ² may be the same or different, and when m is an integer of 2 or more, 2 The above R ¹ O— groups may be the same or different)

The quaternary ammonium group-containing silylated urethane polymer can be synthesized through at least the following steps (1), (2), and (3).
Step (1): A step of synthesizing a urethane polymer by reacting the component (A), the component (B), and the component (C) Step (2): A tertiary amine site derived from the component (C) Step of quaternary ammonium ionization Step (3): Step of reacting the component (D) with the isocyanate terminal of the urethane polymer

[Component (A): Polyisocyanate compound]
The component (A) may be a compound having at least two isocyanate groups in the molecule, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. it can.

  Examples of the aliphatic polyisocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, , 2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylene diisocyanate 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, lysine diiso Aliphatic diisocyanates such as Aneto like.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), and methyl-2,4-cyclohexane. Examples include alicyclic diisocyanates such as diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate (IPDI), norbornane diisocyanate, and the like. be able to.

  Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthylene-1,4-diisocyanate, and naphthylene-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′-dimethyl Examples thereof include aromatic diisocyanates such as diphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropane diisocyanate, and 3,3′-dimethoxydiphenyl-4,4′-diisocyanate.

  Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis (1-isocyanate-1 Examples include aromatic aliphatic diisocyanates such as -methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, and 1,3-bis (α, α-dimethylisocyanatomethyl) benzene. .

  In addition, dimers and trimers, reactive organisms or polymers (for example, diphenylmethane diisocyanate dimers and trimers of diphenylmethane diisocyanate) based on the aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate. , Reactive products of trimethylolpropane and tolylene diisocyanate, reactive products of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenol isocyanate, polyether polyisocyanate, polyester polyisocyanate, etc.) it can.

  The component (A) in the present invention includes, among others, 1,6-hexamethylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanate). Methyl) cyclohexane, isophorone diisocyanate (IPDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, Norbornane diisocyanate, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene and the like can be suitably used. These can be used alone or in admixture of two or more. Moreover, when aliphatic polyisocyanate is used, a resin with little discoloration can be obtained.

[Component (B): Polyol compound]
As the component (B), any compound having two or more hydroxyl groups may be used. For example, a polyhydric alcohol, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, a polyacryl polyol, a trihydric or higher polyhydric alcohol. And polyalkylene oxide adducts thereof, derivatives having their terminal hydroxyl groups sealed, castor oil, and the like. The component (B) in the present invention is, among others, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyalkylene oxide adduct of a trihydric or higher polyhydric alcohol, or its A compound selected from derivatives having a terminal hydroxyl group sealed is preferred.

  Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol (PTMG); and a plurality of alkylene oxides such as ethylene oxide-propylene oxide copolymers (alkylene oxide-others). An alkylene oxide) copolymer etc. can be mentioned. In the present invention, a commercial product such as a trade name “PTMG2000” (manufactured by Mitsubishi Chemical Corporation) may be used.

  Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. A reactant or the like can be used. These can be used alone or in admixture of two or more.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl. Methylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol). Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexanedicarboxylic acid And alicyclic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, trimellitic acid and the like. Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

  Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymerization product of a cyclic carbonate. These can be used alone or in admixture of two or more. Examples of the polyhydric alcohol used for the reaction between the polyhydric alcohol and phosgene include the same examples as those of the polyhydric alcohol. Examples of the cyclic carbonate include alkylene carbonates such as ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. In the present invention, the polycarbonate polyol may be a compound having a carbonate bond in the molecule and having a hydroxyl group at the end, and may have an ester bond together with the carbonate bond.

  As the polyalkylene oxide adduct of a trihydric or higher polyhydric alcohol or a derivative in which a terminal hydroxyl group is capped, polyalkylene oxide is added to one of the hydroxyl groups of the trihydric or higher polyhydric alcohol. Examples thereof include derivatives in which the terminal hydroxyl group of the resulting compound or the adduct is blocked with an alkyl group such as methyl or ethyl group or an acyl group such as acetyl or benzoyl group.

  Examples of the trihydric or higher polyhydric alcohol include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, xylitol, sorbitol and the like. These can be used alone or in admixture of two or more. In the present invention, trimethylolpropane and trimethylolethane are particularly preferable.

  Examples of the polyalkylene oxide include an alkylene oxide derivative containing a single alkylene oxide and a copolymer (alkylene oxide-other alkylene oxide) containing a plurality of alkylene oxides. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, and octylene oxide. In addition to alkylene oxides having 2 to 8 carbon atoms, aliphatic epoxides such as dipentane ethylene oxide and dihexane ethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran, and octylene oxide; styrene oxide, Examples include aromatic epoxides such as 1,1-diphenylethylene oxide. In particular, the polyalkylene oxide in the present invention preferably contains an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, and particularly preferably contains ethylene oxide, from the viewpoint of excellent water dispersion stability.

  Examples of the polyalkylene oxide adduct of a trihydric or higher polyhydric alcohol in the present invention or a derivative in which a terminal hydroxyl group is blocked include, for example, trimethylolpropane mono (polyethylene oxide methyl ether), trimethylolpropane mono (polyethylene oxide ethyl). Ether) trimethylolpropane mono (polyalkylene oxide alkyl ether); polyoxyethylene sorbitan monolaurate, polyoxyalkylene sorbitan monofatty acid ester such as polyoxyethylene sorbitan monostearate; polyoxyethylene glyceryl monolaurate, poly Polyoxyethylene glyceryl mono fatty acid esters such as oxyethylene glyceryl monostearate; trimethylolpropane mono (polyethylene oxide methyl ether) It can be exemplified Le) trimethylolpropane and mono- (polyalkylene oxide alkyl ether) and the like.

（上記式中、ｎ１は１０〜４０の整数を示す）
で表される化合物が好ましい。本発明においては、商品名「ＹｍｅｒＮ１２０」（Ｐｅｒｓｔｏｒｐ社製）等の市販品を使用してもよい。In the present invention, trimethylolpropane mono (polyalkylene oxide alkyl ether) is particularly preferable, and in particular, the following formula (b)

(In the above formula, n1 represents an integer of 10 to 40)
The compound represented by these is preferable. In the present invention, a commercial product such as a trade name “YmerN120” (manufactured by Perstorp) may be used.

  As a number average molecular weight of the component (B) in this invention, about 500-5000 are preferable, for example, About 800-3000 are especially preferable. When the number average molecular weight is less than 500, the fading suppression effect tends to decrease. On the other hand, when the number average molecular weight exceeds 5000, the water dispersion stability tends to decrease.

  As the component (B) in the present invention, one or more selected from polyether polyol, polyester polyol, polycarbonate polyol, polyalkylene oxide adduct of trihydric or higher polyhydric alcohol or a derivative in which a terminal hydroxyl group is capped. It is preferable to contain a compound. In particular, by introducing a pendant nonionic side chain (hydrophilic group) into the urethane-based polymer, the adsorptivity to the hair surface is further improved, and the discoloration suppressing effect can be further improved. In view of this, it is preferable to include a polyalkylene oxide adduct of at least a trihydric or higher polyhydric alcohol or a derivative in which a terminal hydroxyl group is capped (particularly a compound represented by the above formula (b)).

  The proportion of the polyalkylene oxide adduct of a trihydric or higher polyhydric alcohol in the component (B) or the derivative in which the terminal hydroxyl group of the adduct is blocked is, for example, 5 to 100% by mass, preferably 10 to 50% by mass. %, Particularly preferably 20 to 40% by mass.

[Component (C): Tertiary amine compound having two or more hydroxyl groups]
As the component (C), a cationizable tertiary amine and two or more hydroxyl groups may be used, and examples thereof include triethanolamine, tri-n-propanolamine, tri-iso-propanolamine and the like. Trialkanolamines: N-hydrocarbon group-substituted dialkanolamines such as N-methyldiethanolamine and N-phenyldiethanolamine.

  As the component (C) in the present invention, N-hydrocarbon group-substituted N, N-dialkanolamine is preferable, and N-methyl-N, N-diethanolamine, N-ethyl-N, N-diethanolamine are particularly preferable. N-methyl-N, N-dipropanolamine is preferred.

[Component (D): Ester-modified amino group-containing alkoxysilane]
Component (D) in the present invention is represented by the above formula (d1), (d2) or (d3). In formula, R < ¹ >, R < ² > is the same or different and shows an alkyl group, R < ³ >, R < ⁴ > is the same or different, and has the alkylene group or substituent which may have a substituent. The arylene group which may be sufficient is shown. 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. Moreover, m is an integer of 1-3. When m is 1, two R2s 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.

R ¹ and R ² in the above formulas (d1), (d2), and (d3) are the same or different and represent an alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, t-pentyl, hexyl, isohexyl, s-hexyl, t- Examples include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups. As the alkyl group in R ¹ and R ² of the present invention, an alkyl group having about 1 to 6 carbon atoms (in particular, an ethyl group from the viewpoint of safety) is particularly preferable.

R ³ and R ⁴ in the above formulas (d1), (d2) and (d3) are the same or different and may have an alkylene group which may have a substituent or an arylene group which may have a substituent. Indicates. Examples of the alkylene group include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, decamethylene, and tetradecamethylene groups. The alkylene group for R ³ and R ⁴ of the present invention is preferably an alkylene group having 1 to 10 carbon atoms. Examples of the arylene group include phenylene, naphthylene, and anthrylene group. As the arylene group in R ³ and R ⁴ of the present invention, an alkylene group having 6 to 10 carbon atoms is particularly preferable.

Examples of the substituent that R ³ and R ⁴ may have include, for example, an aryl group such as a phenyl group; an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; and a cycloalkyl such as a cyclohexyl group. Groups and the like. In addition, the substituent is a further substituent (for example, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cycloalkyloxycarbonyl group, an acyl group, an amino group, etc.). You may have.

R ⁵ in the above formulas (d1), (d2), and (d3) represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Examples of the alkyl group include the same examples as the alkyl groups in R ¹ and R ² above. The alkyl group of R ⁵ of the present invention, in which preferable is an alkyl group having 1 to 20 carbon atoms. Examples of the cycloalkyl group include monocyclic, polycyclic or condensed cyclic cycloalkyl groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as phenyl, tolyl, xylyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, and biphenyl groups. Examples of the aralkyl group include the alkyl group substituted with the 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 for R ^{6 ′} include the same examples as the examples of the alkyl group for R ¹ and R ² above. Among them, an alkyl group having 1 to 20 carbon atoms is preferable.

（上記式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｍは前記式（ｄ１）〜（ｄ３）に同じ）
で表される第１級及び第２級アミノ基含有アルコキシシラン化合物、又は下記式（ｄ３−１）

（上記式中、Ｒ^１、Ｒ^２、Ｒ^３、ｍは前記式（ｄ１）〜（ｄ３）に同じ）
で表される第１級アミノ基含有アルコキシシラン化合物における第１級又は第２級アミノ基の窒素原子に、下記式（１）

（上記式中、Ｒ^５、Ｒ^６は前記式（ｄ１）〜（ｄ３）に同じ）
で表される不飽和カルボン酸エステルの不飽和結合（炭素−炭素二重結合）をマイケル付加反応することにより合成することができる。前記マイケル付加反応は、溶媒の存在下又は非存在下で行うことができる。また、反応に際し加熱や加圧を行ってもよい。The ester-modified amino group-containing alkoxysilanes represented by the above formulas (d1), (d2), and (d3) are, for example, the following formulas (d1, 2-1)

(In the above formula, R ¹ , R ² , R ³ , R ⁴ , m are the same as the above formulas (d1) to (d3))
A primary and secondary amino group-containing alkoxysilane compound represented by the formula (d3-1):

(In the above formula, R ¹ , R ² , R ³ and m are the same as those in the above formulas (d1) to (d3)).
In the primary amino group-containing alkoxysilane compound represented by the following formula (1):

(In the above formula, R ⁵ and R ⁶ are the same as the above formulas (d1) to (d3)).
It can synthesize | combine by carrying out Michael addition reaction of the unsaturated bond (carbon-carbon double bond) of unsaturated carboxylic acid ester represented by these. The Michael addition reaction can be performed in the presence or absence of a solvent. Moreover, you may heat and pressurize in the case of reaction.

  Examples of the primary and secondary amino group-containing alkoxysilane compounds represented by the formula (d1, 2-1) include N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β ( N- (aminoalkyl) aminoalkyltrialkoxysilanes such as aminoethyl) -γ-aminotopyltriethoxysilane; N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl)- Examples thereof include N- (aminoalkyl) aminoalkylalkyldialkoxysilanes such as γ-aminopropylmethyldiethoxysilane. In the present invention, commercial products such as trade names “KBE602”, “KBM602”, “KBE603”, and “KBM603” (manufactured by Shin-Etsu Chemical Co., Ltd.) may be used.

  Examples of the primary amino group-containing alkoxysilane compound represented by the formula (d3-1) include aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, and 2-aminoethyltriethoxy. Aminoalkyltrialkoxysilanes such as silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropyltributoxysilane; (Aminoalkyl) alkoxysilanes such as 2-aminoethylmethyldimethoxysilane, 2-aminoethylmethyldiethoxysilane, and 3-aminopropylmethyldipropoxysilane can be exemplified. In the present invention, commercially available products such as trade names “KBE902”, “KBM902”, “KBE903”, “KBM903” (manufactured by Shin-Etsu Chemical Co., Ltd.) may 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, 3-butylcyclohexyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, Examples include behenyl acrylate and glycidyl acrylate. As unsaturated carboxylic acid ester represented by Formula (1) in this invention, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, etc. are preferable especially.

[Step (1): Synthesis of urethane polymer]
The urethane polymer can be synthesized by reacting the components (A), (B), and (C) according to a known or conventional method for preparing a urethane polymer from a polyol compound and a polyisocyanate compound. . In the synthesis of the urethane polymer, a polymerization catalyst may be used to accelerate the reaction.

  As said polymerization catalyst, the well-known thru | or usual polymerization catalyst (curing catalyst) used for reaction of a polyol compound and a polyisocyanate compound can be used, For example, basic compounds, such as an amine compound, can be mentioned. Examples of basic compounds such as amine compounds include aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride; Linear products containing a plurality of nitrogen atoms such as trade names “DABCO” series and “DABCO BL” series, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) manufactured by Air Products Examples thereof include cyclic tertiary amines or quaternary ammonium salts.

  The reaction can be performed in a solvent. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate and the like. The atmosphere during the reaction is not particularly limited, and is selected from an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature can be appropriately selected according to the type of reaction components and the like, and is, for example, about 20 to 150 ° C., preferably about 20 to 100 ° C. The reaction may be performed under normal pressure, or may be performed under reduced pressure or under pressure. The reaction time can be appropriately selected according to the reactivity of the components, and is, for example, about 2 to 20 hours, preferably about 3 to 10 hours.

  The amount of component (A), component (B), and component (C) used is not particularly limited and can be appropriately adjusted according to various physical properties to be obtained. For example, the isocyanate group / component in component (A) The hydroxyl group (NCO / OH group) (equivalent ratio) in the component (B) and the component (C) is greater than 1 and less than or equal to 1.5 (preferably greater than 1 and less than or equal to 1.3, more preferably greater than 1 and 1. 2 or less). When the NCO / OH group ratio is too large (for example, exceeding 1.5 (equivalent ratio)), the dispersibility tends to decrease. On the other hand, if the NCO / OH group ratio is too small (for example, 1 or less (equivalent ratio)), silyl group introduction cannot be performed sufficiently, and the discoloration suppressing effect tends to decrease.

  Furthermore, in the component (C), the cationizable tertiary amine content in the urethane polymer is 2 to 90% by mass (preferably 2 to 50% by mass, more preferably 5 to 20% by mass). It is preferable that it is contained in such a ratio. When the content of the tertiary amine that can be cationized exceeds the above range, the viscosity tends to be too high, making it difficult to use. On the other hand, when the content of the tertiary amine that can be cationized is below the above range, the water dispersion stability tends to decrease.

  The terminal isocyanate group content of the urethane polymer is preferably, for example, about 0.3 to 7.0% by weight. When the content of the terminal isocyanate group exceeds 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 synthesis tends to be too high and the synthesis tends to be difficult.

[Step (2): Quaternary ammonium ionization of tertiary amine moiety]
A quaternary ammonium group-containing urethane polymer is synthesized by ionizing (cationizing) the tertiary amine moiety derived from the component (C) in the urethane polymer obtained through the step (1). can do.

  As a method for cationizing a nitrogen atom of a tertiary amine, for example, an alkylating agent (a quaternizing agent) is allowed to react with the urethane polymer obtained through the above step (1) to obtain a component (C). A tertiary amine moiety derived from an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl and pentyl; vinyl, isopropenyl, allyl, methallyl, 3-butenyl, 2-methyl-1-butenyl, C2-C20 alkenyl groups such as 3-methyl-1-butenyl, 2-methyl-3-butenyl and 3-methyl-3-butenyl groups; C7-C11 such as benzyl and 2-phenylethyl groups Examples thereof include a method for introducing an aralkyl group.

  Examples of the alkylating agent (quaternizing agent) include sulfate esters such as dimethyl sulfate and diethyl sulfate; halides such as methyl chloride, methyl bromide, methyl iodide, benzyl chloride, and benzyl bromide. Can do.

  The amount of the alkylating agent used can be appropriately adjusted, and is, for example, 30 mol% or more (preferably 50 mol) with respect to 1 mol of the tertiary amine moiety (tertiary amino group) in the urethane polymer. ˜120 mol%, more preferably 80 to 100 mol%). When the amount of the alkylating agent used exceeds the above range, the heat rise during the reaction tends to be severe and the workability tends to decrease. On the other hand, when the usage-amount of an alkylating agent is less than the said range, there exists a tendency for the fading suppression effect to fall.

  Moreover, the said cationization reaction can be performed in a solvent. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate and the like. The atmosphere during the reaction is not particularly limited, and is selected from an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature can be appropriately selected according to the type of reaction components, and is, for example, about 0 to 100 ° C., preferably about 20 to 80 ° C. The reaction may be performed under normal pressure, or may be performed under reduced pressure or under pressure. The reaction time can be appropriately selected according to the reaction rate, and is, for example, about 10 minutes to 5 hours, preferably about 30 minutes to 3 hours.

[Step (3): Silylation]
To synthesize a quaternary ammonium group-containing silylated urethane polymer by enriching the component (D) at the isocyanate terminal of the quaternary ammonium group-containing urethane polymer obtained in the step (2). (Silylation reaction). In addition, you may perform the process of a process (3) before performing the process of the said process (2). In that case, a silylated urethane-based polymer is synthesized by adding the component (D) to the isocyanate terminal of the urethane-based polymer obtained in the step (1). A quaternary ammonium group-containing silylated urethane polymer can be synthesized by ionizing the nitrogen atom of the quaternary amine moiety with quaternary ammonium ions. Hereinafter, the method of step (2) -step (3) will be described, but the same applies to the case of step (3) -step (2).

  The silylation reaction can be performed by mixing the quaternary ammonium group-containing urethane polymer obtained in the step (2) and the component (D) and heating as necessary. By performing the silylation reaction, the terminal isocyanate group of the quaternary ammonium group-containing urethane polymer is ester-modified alkoxysilylated to obtain a quaternary ammonium group-containing silylated urethane polymer. In the silylation reaction, a polymerization catalyst may be used as necessary. In addition, this reaction can be performed in the presence or absence of a solvent.

  Component (D) has a content of silicon atoms in the quaternary ammonium group-containing silylated urethane-based polymer of 0.05 to 10% by mass (preferably 0.05 to 5% by mass, more preferably 0.05 to 5% by mass). (2% by mass) is preferably added at such a ratio. When the silicon content exceeds the above range, the storage stability tends to decrease, whereas when the silicon content falls below the above range, the fading suppression effect tends to decrease.

  The atmosphere during the silylation reaction is not particularly limited, and is selected from an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature can be appropriately selected according to the type of reaction components, and is, for example, about 20 to 100 ° C., preferably about 40 to 80 ° C. The reaction may be performed under normal pressure, or may be performed under reduced pressure or under pressure. The reaction time can be appropriately selected and is, for example, about 10 minutes to 3 hours, preferably about 20 minutes to 2 hours.

[Step (4): Silicone chain addition]
The quaternary ammonium group-containing silylated urethane polymer obtained through the steps (1) to (3) further contains a hydrolyzable silicon atom in addition to the terminal alkoxysilyl group derived from the component (D). A step of reacting a compound having a group to add a silicone chain to the quaternary ammonium group-containing silylated urethane polymer may be provided (step (4)). By adding a silicone chain to the quaternary ammonium group-containing silylated urethane-based polymer, the adsorptivity to the hair surface can be further improved, and the fading suppression effect can be further improved.

  The compound having a hydrolyzable silicon atom-containing group is not particularly limited as long as it is a compound having at least one hydrolyzable silicon atom-containing group in the molecule. Examples of hydrolyzable silicon atom-containing groups include hydrolyzed alkoxysilyl groups, hydrosilyl groups, halogenated silyl groups (for example, chlorinated silyl groups, brominated silyl groups, iodinated silyl groups, fluorine or silyl groups, etc.). A decomposable silyl group etc. can be mentioned. In the hydrolyzable silyl group, the group or atom bonded to the silicon atom (alkoxy group, hydrogen atom, halogen atom, etc.) is usually 1 to 3 (preferably 2 or 3) per silicon atom. And the same group (especially alkoxy group) or atoms may be bonded, or two or more different groups or atoms may be combined and bonded.

で表されている化合物（Ｅ）を好適に用いることができる。As the hydrolyzable silyl group in the present invention, an alkoxysilyl group or a hydrosilyl group is preferable, and an alkoxysilyl group is particularly preferable. As the compound having at least one alkoxysilyl group in the molecule, in particular, the following formula (e1) or (e2)

The compound (E) represented by can be used suitably.

In formula (e1), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom or an alkyl group. m ′ is 1 or 2. n2 is an integer of 1 or more. In 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 and m ′ are the same as described above.

Examples of the alkyl group in R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ include the same examples as the alkyl group in R ¹ and R ² above. Among them, the number of carbon atoms is 1 to 10 (more preferably 1 Alkyl groups of -6, especially 1-4) are preferred.

Moreover, the alkyl group of R < ⁷ >, R < ⁸ > may have a substituent. Further, through the substituent such as an alkyl group R ^7, R ⁸ is combined with other alkyl groups (e.g., alkyl groups R ^7, R ⁸ attached to other silicon atoms, etc.) A ring (aromatic ring or non-aromatic ring) may be formed. Furthermore, R ⁷ and R ⁸ may be bonded to R ⁷ and R ⁸ bonded to the same or different silicon atoms, respectively.

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

  Examples of the compound represented by the formula (e1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane; alkoxytrialkoxy such as methoxytriethoxysilane. Silane; monomer compounds such as dialkoxydialkoxysilane such as dimethoxydiethoxysilane; polytetramethoxysilane, polytetraethoxysilane, polytetrapropoxysilane, polytetraisopropoxysilane, polytetrabutoxysilane and other polytetra Poly (alkoxyalkoxysilane) such as poly (methoxyethoxysilane); poly (alkoxysilane) such as poly (methoxysilane) and poly (butoxysilane); poly (methoxymethyl) Silanes), poly (methoxyethyl silane), poly (Compound multimeric poly (alkoxyalkylsilane) etc. ethoxymethyl silane) and the like, and the like.

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

Examples of the organic group for R ¹² include an alkyl group which may have a substituent, and atoms other than carbon atoms (oxygen atom, nitrogen atom, sulfur atom, etc.) in the main chain of the alkyl group. The alkyl group and the hetero atom containing group which may have these substituents may have either monovalent or polyvalent form. Examples of the organic group of R ¹² include a vinyl group, a mercapto group, a vinyl-alkyl group, a vinyl- (alkyl) -aryl group, a vinyl- (alkyl) -cycloalkyl group, a (meth) acryloyl group, (meta ) Acryloyloxyalkyl group (vinyl-carbonyloxyalkyl group), (meth) acryloyloxyaryl group, mercapto-alkyl group, mercapto- (alkyl) -aryl group, mercapto- (alkyl) -cycloalkyl group and the like. it can.

n3 is an integer of 1 or more, preferably an integer of 1 to 4 (more preferably 1 or 2, particularly preferably 1). When n3 is an integer of 2 or more, it means that two or more hydrolyzable silicon atom-containing groups are bonded to the organic group of R ¹² .

Among the compounds represented by the formula (e2), examples of the compound in which R ¹² is an alkyl group include alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, and methyltriethoxysilane, and dimethyldimethoxy. In addition to dialkyl dialkoxysilanes such as silane, dimethyldiethoxysilane, diethyldiethoxysilane, diisopropyldimethoxysilane, isopropyldimethoxymethylsilane, isopropyldiethoxymethylsilane, trialkylalkoxysilanes corresponding to these.

Further, R ¹² is a substituent (e.g., a glycidoxy group, an isocyanate group, an amino group, etc.) Examples of the compound is an alkyl radical having, for example, compounds corresponding to those wherein R ¹² is exemplified as a compound is an alkyl group Etc.

Among the compounds represented by the formula (e2), examples of the compound in which R ¹² is a vinyl group include vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; vinylmethyldimethoxysilane, vinylmethyldi (Vinyl) alkyldialkoxysilanes such as ethoxysilane, (vinyl) dialkyl (mono) alkoxysilanes corresponding to these, and the like can be mentioned.

Among the compounds represented by the formula (e2), examples of the compound in which R ¹² is a (meth) acryloyloxyalkyl group include 3- (meth) acryloxypropyl-trimethoxysilane and 3- (meth) acrylic. (Meth) acryloxyalkyl-trialkoxysilane such as loxypropyl-triethoxysilane; (meth) such as 3- (meth) acryloxypropyl-methyldimethoxysilane, 3- (meth) acryloxypropyl-methyldiethoxysilane Examples include acryloxyalkyl-alkyldialkoxysilanes and (meth) acryloxyalkyl-dialkyl (mono) alkoxysilanes corresponding to these.

Among the compounds represented by the formula (e2), examples of the compound in which R ¹² is a mercapto-alkyl group include mercaptoalkyltrialkoxysilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane. And (mercaptoalkyl) alkyl dialkoxysilanes such as 3-mercaptopropylmethyldipropoxysilane and 3-mercaptopropylmethyldiisopropoxysilane, and (mercaptoalkyl) dialkyl (mono) alkoxysilanes corresponding thereto. it can.

  Among such compounds having a dialkoxysilyl group are dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, isopropyldimethoxymethylsilane, isopropyl, among others. Dialkyldialkoxysilanes such as diethoxymethylsilane; (vinyl) alkyldialkoxysilanes such as vinylmethyldimethoxysilane and vinylmethyldiethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and the like (Meth) acryloxyalkyl-alkyldialkoxysilane and the like can be suitably used.

  Examples of the compound having a trialkoxysilyl group include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, isopropyltrimethoxysilane, Alkyltrialkoxysilanes such as isopropyltriethoxysilane; vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 3- (meth) acryloxypropyl-trimethoxysilane, 3- (meth) acryloxypropyl-tri (Meth) acryloxyalkyl-trialkoxysilane such as ethoxysilane can be preferably used.

  The amount of the compound (E) used is, for example, 1 to 50 mol (preferably 5 to 40 mol, more preferably 5 to 20 mol) per 1 mol of silyl group in the quaternary ammonium group-containing silylated urethane polymer. It is preferable to use at a ratio such that When the usage-amount of a compound (E) exceeds the said range, there exists a tendency for storage stability to fall.

  The atmosphere during the silicone chain addition reaction is not particularly limited and is selected from an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature can be appropriately selected according to the type of reaction components and the like, and is, for example, about 20 to 100 ° C., preferably about 40 to 80 ° C. The reaction may be performed under normal pressure, or may be performed under reduced pressure or under pressure. The reaction time can be appropriately selected and is, for example, about 1 to 20 hours, preferably about 1 to 5 hours.

  The amount of (iii) the quaternary ammonium group-containing silylated urethane polymer in the conditioner composition according to the present invention is not particularly limited, but considering its fading inhibiting effect, it is preferably 0.01 to 1 relative to the composition. It is 0.05 mass%, More preferably, it is 0.05-0.6 mass%. If the blending amount is less than 0.01% by mass, the fading-inhibiting effect is insufficient, and if it exceeds 1% by mass, the feel after use may be degraded, for example, the hair after application may be stiff.

In addition to the above components, the conditioner composition according to the present invention can be produced by a conventional method by blending other components usually used in cosmetics and pharmaceuticals within a range not impairing the effects of the present invention.
Other components include, for example, oils, cationic surfactants other than the above, nonionic surfactants, powder components, humectants, natural polymers, synthetic polymers, ultraviolet absorbers, sequestering agents, pH Examples thereof include regulators, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, and water.

Examples of oils include liquid oils, solid oils, hydrocarbon oils, and silicone oils.
Examples of liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.

  Examples of the solid fat include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cattle Leg fats, moles, hydrogenated castor oil and the like.

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

  Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexyl). Silicone resin, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, polyether-alkyl co-modified polysiloxane, Fluorine-modified polysiloxane, polyoxyethylene / polyoxypropylene copolymer-modified polysiloxane, linear amino polyether-modified polysiloxane, amidoalkyl-modified polysiloxane, amino Glycol-modified polysiloxane, aminophenyl modified polysiloxane, carbinol modified polysiloxane, polyglycerin modified polysiloxane, polyglycerin-alkyl co-modified polysiloxane), dimethiconol, and acrylic silicones, or the like. The blending conditions of the silicone oil may be solubilized or emulsified in the composition, and the particle diameter when emulsified is the same as the technique of a normal detergent composition.

  Examples of the cationic surfactant include alkylpyridinium salts (for example, cetylpyridinium chloride); poly (N, N′-dimethyl-3,5-methylenepiperidinium chloride); alkylisoquinolinium salts; Morphonium salts; POE alkylamines; alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

  Examples of nonionic surfactants include fatty acid alkanolamides such as coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, lauric acid isopropanolamide, and oleic acid diethanolamide; sorbitan monostearate, sorbitan sesquioleate, and the like Sorbitan fatty acid esters; alkylene glycol fatty acid esters such as diethylene glycol laurate, propylene glycol laurate, ethylene glycol monooleate, ethylene glycol distearate; hardened castor oil derivatives, glycerin alkyl ether, POE sorbitan monooleate, monostearin POE sorbitan fatty acid esters such as polyoxyethylene sorbitan acid; POE sorby such as POE-sorbite monolaurate Fatty acid esters; POE glycerin fatty acid esters such as POE-glycerin monoisostearate; POE glycerin fatty acid esters such as polyethylene glycol monooleate and POE distearate; POE alkyl ethers such as POE-octyldodecyl ether; POE nonylphenyl POE alkyl phenyl ethers such as ethers; POE / POP alkyl ethers; Pluronic types; POE castor oil; POE hydrogenated castor oil derivatives; sugar esters, sugar ethers, sugar amides, etc .; alkyl glycosides, etc. It is done.

Examples of the powder component include inorganic powders (for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid. Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder , Metal soap (for example, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc .; organic powder (for example, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, poly Styrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); inorganic white pigment (eg, titanium dioxide, zinc oxide, etc.); inorganic red pigment (eg, , Iron oxide (Bengara), iron titanate, etc.); inorganic brown pigment (for example, γ-iron oxide, etc.); inorganic yellow pigment (for example, yellow iron oxide, loess); inorganic black pigment (for example, black) Iron oxide, low-order titanium oxide, etc.); inorganic purple pigments (eg, mango violet, cobalt violet, etc.); inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (eg, For example, ultramarine, bitumen, etc .; pearl pigments (eg, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated tar) , Colored titanium oxide coated mica, bismuth oxychloride, fish scale foil); metal powder pigments (e.g., aluminum powder, copper powder, etc.);
Organic pigments such as zirconium, barium or aluminum lakes (for example, red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 405, orange 203, orange Organic pigments such as No. 204, Yellow No. 205, Yellow No. 401, and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange 205 No. 4, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1); Natural pigments (eg, chlorophyll, β-carotene, etc.); Clay minerals (bentonite, hectorite, laponite) Etc.).

  Examples of the humectant include polyethylene glycol, propylene glycol, dipropylene glycol, isoprene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, Cholesteryl-12-hydroxystearate, sodium lactate, bile salt, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, yarrow extract, Merrilot extract, etc. Can be mentioned.

  Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, tamarind gum, locust bean gum, pectin, agar, quince seed (malmello), Arge colloid (gypsum extract), starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial polymer (eg, xanthan gum, dextran, succinoglucan, bull run); animal polymer (eg, collagen, casein) , Albumin, gelatin, etc.). Further, derivatives thereof (POE / POP modification, alkyl modification, cationization, anionization, silylation) are also included.

  Semi-synthetic water-soluble polymers include, for example, starch polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate) , Dialkyldimethylammonium sulfate cellulose, hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder and hydrophobically modified compounds of these polymers <Example: partly stearoxy-modified> and cationically modified compounds of these polymers, etc.) Alginate polymers (for example, sodium alginate, propylene glycol alginate, etc.); sodium pectate, etc. It is below.

  Synthetic water-soluble polymers include, for example, vinyl polymers (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer); polyoxyethylene polymers (eg, polyethylene glycol 20,000, 40). , 000, 60,000 polyoxyethylene polyoxypropylene copolymer, etc.); poly (dimethyldiallylammonium halide) type cationic polymer (for example, Merquat 100 (Merquat 100, manufactured by Merck & Co., USA)); dimethyldiallylammonium halide And acrylamide copolymer-type cationic polymer (for example, Merquat 550 manufactured by Merck & Co., Inc.); acrylic polymer (for example, sodium polyacrylate, polyethylacrylate) Polyethyleneimine; cationic polymer; AlMg silicate (beegum); polyquaternium-39 and the like.

  Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers (for example, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester. N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, etc.); Anthranilic acid-based UV absorber (for example, homomenthyl-N-acetylanthranilate, etc.); Salicylic acid-based UV absorber (for example, amyl) Salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc .; cinnamic acid-based ultraviolet absorbers (for example, octylcinnamate, ethyl- -Isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate , Isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α -Cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, etc.); benzophenone ultraviolet absorbers (for example, 2, 4-di Hydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenyl-benzophenone-2- Carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc.); 3- (4′-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l- Camphor; 2-phenyl-5- 2,2'-hydroxy-5-methylphenylbenzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole; 2- (2'-hydroxy-5'-methyl) Phenylbenzotriazole; dianisoylmethane; 4-methoxy-4′-t-butyldibenzoylmethane; 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, etc.); triazine ultraviolet absorption Agent (eg, 2--4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine , 2-4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl) -4,6-bis ( , 4-dimethylphenyl) -1,3,5-triazine and the like).

  Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.

Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.
Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.

  Other ingredients that can be blended include, for example, preservatives (ethyl paraben, butyl paraben, 1,2-alkanediol (carbon chain length 6 to 14) and derivatives thereof, phenoxyethanol, methylchloroisothiozoline, etc.); (Eg, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); whitening agents (eg, cypress extract, arbutin, etc.); various extracts (eg, buckwheat, auren, shikon, peonies, Assembly, birch, sage, loquat, carrot, aloe, mallow, iris, grape, yokoinin, loofah, lily, saffron, senkyo, ginger, hypericum, onionis, garlic, capsicum, chimpi, cypress, seaweed, etc. For example, low Luzeries, photosensitizers, cholesterol derivatives, etc.); blood circulation promoters (eg, nonyl acid wallenyl amide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ectamol, tannic acid, α-borneol, Tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin, γ-oryzanol, etc.); antiseborrheic agents (eg, sulfur, thianthol, etc.); anti-inflammatory agents (eg, tranexamic acid) , Thiotaurine, hypotaurine, etc.); aromatic alcohols (benzyl alcohol, benzyloxyethanol, etc.) and the like.

When the conditioner composition according to the present invention is applied to hair, the quaternary ammonium group-containing silylated urethane-based polymer is quickly and firmly adsorbed on the hair surface and is not washed away even by rinsing with water. Therefore, the penetration of moisture into the hair can be suppressed during shampooing, the outflow of dye from the inside of the hair can be suppressed, and an excellent fading suppression effect can be exhibited.
Furthermore, by using a specific cationic surfactant and a higher aliphatic alcohol in combination, the fading-inhibiting effect is further promoted, and the dyed hair is good in the suppleness of the hair dried after using the conditioner. It is possible to give a feeling of use.
Therefore, if the conditioner etc. which consist of the conditioner composition concerning this invention are used for daily hair washing use, the fading of a hair color can be suppressed significantly and a beautiful hair color can be maintained. At the same time, it is possible to alleviate wrinkles due to dyeing and to obtain supple hair.

  In addition, the discoloration suppressing effect of the hair color in the conditioner composition according to the present invention is measured using a spectrocolorimeter before and after shampooing the hair that has been subjected to hair coloring, and the color difference thereof. It can be evaluated by (ΔE). The closer the color difference (ΔE) is to zero, the higher the fading suppression effect.

  When the conditioner composition according to the present invention is used to perform a hair washing treatment (treatment in which washing, rinsing and drying are repeated five times), the color difference (ΔEs) of the hair before and after the hair washing treatment is, for example, 3.3 or less, preferably Is 2.8 or less. When the color difference exceeds the above range, it tends to be difficult to realize the fading suppression effect.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples. Hereinafter, unless otherwise specified, “parts” represents “parts by mass” and “%” represents “% by mass”.

First, the fading suppression effect used in the following tests and the evaluation method of the feeling of use will be described.
<Method for evaluating fading suppression effect>
1. A hair bundle of 100% gray hair (manufactured by Beaulux) was dyed using a brown hair color (trade name “Dianist NB8”, manufactured by Shiseido Professional Co., Ltd.).
2. The hair color of the dyed hair bundle (dyed hair bundle) was measured using a spectrocolorimeter (trade name “CM-2500d”, manufactured by Konica Minolta) (C ₁ ).
3. The conditioner obtained in Examples and Comparative Examples (the number of samples was set to 10 for each conditioner) was used for the above-mentioned dyed hair bundle, and a pretreatment of rinsing was performed. Thereafter, the dyed hair bundle after the pretreatment was subjected to a washing treatment (treatment of repeating shampoo-rinse-dry five times).
4). For the dyed hair bundle after washing, the hair color was measured using a spectrocolorimeter in the same manner as described above, the average value (C ₂ ) was calculated, and the color difference before and after the washing treatment (ΔEs: C ₁ − C ₂ ) was obtained and compared with the comparative example, the fading suppression effect was evaluated according to the following evaluation criteria.
Evaluation Criteria (ΔEs of each Example) − (ΔEs of Comparative Example) is −1 or less: ◎◎
The value of (ΔEs of each example) − (ΔEs of the comparative example) exceeds −1 and is −0.5 or less:
The value of (Es of each example)-(ΔEs of the comparative example) exceeds -0.5 and is 0 or less:
The value of (ΔEs in each example) − (ΔEs in the comparative example) exceeds 0: ×

<Method of evaluating the feel of use>
The dyed hair bundle after washing was subjected to a sensory test by 10 professional panelists, and the suppleness (softness after drying) of the hair dried after using the conditioner compared with the comparative example was evaluated according to the following criteria.
More than 70% of panelists replied that they are equivalent or better than the comparative example:
More than 50% and less than 70% of panelists responding that they are equivalent or better than the comparative example:
More than 30% and less than 50% of panelists who answered that they are equivalent or better than the comparative example: ○
Less than 30% of panelists replied that they are equivalent or good compared to the comparative example: ×

Next, the manufacturing method of the quaternary ammonium group containing urethane type polymer used by the following tests is demonstrated.
Preparation Example 1 of Silylated Urethane Polymer Containing Quaternary Ammonium Group
Preparation example of ester-modified amino group-containing alkoxysilane (compound A) γ-aminopropyltriethoxysilane (trade name “KBE903”, manufactured by Shin-Etsu Chemical Co., Ltd.) 221.4 parts, lauryl acrylate 240.4 parts The mixture was reacted at 50 ° C. for 7 days to obtain an ester-modified amino group-containing alkoxysilane (Compound A).

Production Example 1
In a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer, polytetramethylene ether glycol (number average molecular weight: 1944.5, trade name “PTMG2000”, manufactured by Mitsubishi Chemical Corporation), 50 parts, Trimethylolpropane mono (polyethylene oxide methyl ether) represented by the following formula (2) (number average molecular weight: 1089.3, trade name “YmerN120”, manufactured by Perstorp) 25 parts, N-methyl-N, N-diethanolamine (MDA) 25 parts, isophorone diisocyanate (IPDI) 60.4 parts, methyl ethyl ketone (MEK) 50 parts, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) 0.1 part as a catalyst And reacted at a temperature of 80 to 85 ° C. in a nitrogen atmosphere for 5 hours. To obtain a reaction mixture containing a urethane polymer containing.

  Add 150 parts of methyl ethyl ketone (MEK) to the reaction mixture containing this urethane polymer, cool to 50 ° C., add 25.2 parts of dimethyl sulfuric acid as a quaternizing agent, and take 30-60 minutes at 50-60 ° C. Then, quaternary ammonium ionization of the tertiary amine moiety was performed to produce a quaternary ammonium group-containing urethane polymer.

  The reaction mixture of the quaternary ammonium group-containing urethane polymer was mixed with 9.9 parts of the compound A obtained in Preparation Example 1, and then reacted at a temperature of 65 to 75 ° C. for 1 hour in a nitrogen atmosphere. A reaction mixture (1) containing a quaternary ammonium group-containing silylated urethane polymer was obtained.

  Next, after cooling the reaction mixture (1) to 40 ° C., 1000 parts of deionized water was added under restrained stirring. Thereafter, the solvent was distilled off at 45 to 50 ° C. under reduced pressure to obtain an aqueous dispersion (1).

（製造方法）
精製水にカチオン性界面活性剤を加え、十分に撹拌溶解させた後、残りの成分を順次添加しコンディショナー組成物を得た。The above-mentioned evaluation (fading suppression effect and feeling of use) was performed for each conditioner composition produced according to the formulations shown in Tables 1 and 2 below. The results are shown in Tables 1 and 2. In addition, the comparison with the Example in each evaluation used the comparative example 1-1 as a reference | standard.

(Production method)
A cationic surfactant was added to purified water and sufficiently dissolved by stirring, and then the remaining components were sequentially added to obtain a conditioner composition.

As shown in Tables 1 and 2, compared with Comparative Example 1-1 in which the quaternary ammonium group-containing urethane-based polymer was not blended, the other examples in which the polymer was blended improved the fading-inhibiting effect.
Further, as a cationic surfactant that is a conditioning agent, compared to Comparative Example 1-2 in which only a mono long chain alkyl type quaternary ammonium salt (stearyltrimethylammonium chloride) was blended, an imidazoline type quaternary ammonium salt ( Dibehenylimidazolinium methosulfate) Examples 1-1 to 1-7, or di-long chain alkyl type quaternary ammonium salts (dicocoyl hydroxyethylmethylammonium methosulfate or distearyldimethylammonium chloride) In each of the blended Examples 1-8 to 1-13, improvement was observed in the flexibility after drying.

The imidazoline-type quaternary ammonium salt exhibited a sufficient effect with the blending of 0.01% by mass (Example 1-1), but Examples 1-2 to 1-6 blended with 0.05 to 2% by mass. Then, both the fading suppression effect and the flexibility after drying were high, and this tendency was particularly remarkable in Examples 1-2 to 1-5 in which 0.05 to 1% by mass was blended.
Moreover, about the di long chain alkyl type | mold quaternary ammonium salt, as shown in Examples 1-8 to 1-10 and 1-11 to 1-13, 0.01-3 mass%, Especially 1-3 mass% In the blending with, good results were obtained for both the fading suppression effect and the flexibility after drying.
Therefore, in the present invention, it is preferable to add a cationic surfactant in addition to the quaternary ammonium group-containing urethane polymer. Further, as the cationic surfactant, it is particularly preferable to use an imidazoline type quaternary ammonium salt or a di-long chain alkyl type quaternary ammonium salt in combination with a mono long chain alkyl type quaternary ammonium salt, The amount of the imidazoline type quaternary ammonium salt is preferably 0.05 to 2% by mass, more preferably 0.05 to 1% by mass. The blending amount of the di-long-chain alkyl type quaternary ammonium salt is preferably 0.01 to 3% by mass, more preferably 1 to 3% by mass.

（製造方法）
精製水にカチオン性界面活性剤を加え、十分に撹拌溶解させた後、残りの成分を順次添加しコンディショナー組成物を得た。Moreover, the said evaluation (fading suppression effect and use feeling) was performed about each conditioner composition manufactured by the prescription shown in following Table 3. The results are shown in Table 3. In addition, the comparison with the Example in each evaluation was used on the basis of Comparative Example 2-1.

(Production method)
A cationic surfactant was added to purified water and sufficiently dissolved by stirring, and then the remaining components were sequentially added to obtain a conditioner composition.

As shown in Table 3, compared to Comparative Example 2-1 containing no quaternary ammonium group-containing urethane-based polymer, in Examples in which the polymer was blended in an amount of 0.01 to 1% by mass, not only the fading suppression effect but also the use The touch is also improved. In particular, when the blending amount of the quaternary ammonium group-containing urethane polymer was 0.05 to 0.6% by mass, both the fading suppression effect and the feeling of use were significantly increased.
On the other hand, in Comparative Example 2-2 in which 1.1% by mass of the quaternary ammonium group-containing urethane-based polymer was blended, the discoloration suppressing effect was improved, but almost no improvement in use feeling was observed.
Therefore, the compounding quantity of the quaternary ammonium group containing urethane type polymer in this invention is 0.01-1 mass%, Preferably it is 0.05-0.6 mass%.

Claims (3)

(I) a cationic surfactant;
(Ii) a higher aliphatic alcohol;
(Iii) 0.01 to 1% by mass of a quaternary ammonium group-containing silylated urethane polymer,
And (i) a cationic surfactant,
(A) an imidazoline type quaternary ammonium salt represented by the following general formula (I), or a dilong chain alkyl type quaternary ammonium salt represented by the following general formula (II):
(B) a mono long-chain alkyl-type quaternary ammonium salt represented by the following general formula (III):
The conditioner composition according to claim 1, comprising:

(In the above formula, R ¹ and R ² may be the same or different and each represents an alkyl group or an alkenyl group having 12 to 22 carbon atoms, and Z is an anion selected from a halogen atom, a methyl sulfate group and an ethyl sulfate group. Represents a sex group.)

(In the ^formula, R 3 respectively any two of to R ^6, straight-chain or branched alkyl group which may 8 to 36 carbon atoms which can hydroxyl group substituted or ^R 7, - _{(Z1) q} - _{(Y1) p} - are expressed .R ⁷ represents a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group, Y1 is _{-CH 2 CH 2 -, - CH} 2 CH ₂ represents a bonding group selected from CH ₂ —, —CH ₂ CH ₂ O—, —CH (OH) CH ₂ O—, and Z 1 represents an amide bond (—CONH—), an ether bond (—O—), an ester Represents a linking group selected from a bond (—COO—), p and q each represent an integer of 0 or 1. Further, the remaining two of R ^{3 to} R ⁶ are each substituted with a hydroxyl group. A C1-C3 alkyl group or ben X may be the same or different, and X is a quaternary ammonium such as a halogen atom, an alkyl sulfate group having 1 or 2 carbon atoms, or a residue excluding a hydrogen atom of an organic acid. An anion that can form a salt.)

(In the formula, ^{R 8} is a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group or _{^{R 12, - (Z1) q}} - (Y1) p - represents a ^{.R 12} Represents a linear or branched alkyl group having 8 to 36 carbon atoms which may be substituted with a hydroxyl group, and Y1 represents —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O. — Represents a bonding group selected from —CH (OH) CH ₂ O—, and Z 1 represents a bond selected from an amide 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 represent an alkyl group having 1 to 3 carbon atoms or a benzyl group which may be substituted with a hydroxyl group. Even if they are the same X represents an anion capable of forming a salt with a quaternary ammonium such as a halogen atom, an alkyl sulfate group having 1 or 2 carbon atoms, or a residue excluding a hydrogen atom of an organic acid.) The component (a) of the (i) cationic surfactant is
0.05 to 2% by mass of an imidazoline type quaternary ammonium salt represented by the above general formula (I), or 0.01 to 3% by mass of a dilong chain alkyl type represented by the above general formula (II) Quaternary ammonium salts,
The conditioner composition according to claim 1, wherein   The component (a) of the (i) cationic surfactant is at least one selected from the group consisting of dibehenylimidazolinium methosulfate, distearyldimethylammonium chloride, dicocoylhydroxyethylmethylmonium methosulfate. The conditioner composition according to claim 1 or 2, characterized by the above.