JP5160921B2 - Organopolysiloxane compounds having urethane bond-containing groups - Google Patents

Description

  The present invention relates to a novel organopolysiloxane compound, more specifically, an organopolysiloxane compound having a urethane bond-containing group, a production method thereof, and a cosmetic containing the same.

Conventionally, a silicone compound has been used as a base material for imparting water repellency and lubricity to the surface of fibers, hair, skin and the like and protecting the surface. Among these, amino-modified silicones are known to have an amino group in the molecule and thus have good adsorptivity to various surfaces, and in particular, have excellent flexibility imparting effects on hair (Patent Documents 1 and 2). etc).
JP 09-110653 A Japanese Patent Laid-Open No. 01-190619

  The amino-modified silicone has a problem that not only the conditioning effect is insufficient, but also it is easily washed away by shampoo treatment, and the durability of the effect is inferior. In addition, the texture of amino-modified silicone is becoming less favored, and in recent years, with the development of technology, there has been a strong demand for the development of a base material that is superior in adsorption power and sustainability and gives a smooth feel to hair. Yes.

  An object of the present invention is to provide an organopolysiloxane compound capable of imparting a conditioning effect such as sufficient moist feeling and smoothness to hair and the like, and further improving the sustainability of the effect, and a cosmetic containing the same. is there.

  In the present invention, a urethane bond-containing group represented by the following general formula (1) (hereinafter referred to as urethane bond-containing group (1)) is bonded to at least one silicon atom of the organopolysiloxane segment constituting the main chain. An organopolysiloxane compound, a process for producing the organopolysiloxane compound, and a cosmetic containing the organopolysiloxane compound are provided.

[Wherein, X and Y are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, d is a number having 0 to 10 and G is the following general formula (2-1) or (2-2). The group represented is shown.

However, R < ² > shows a hydrogen atom or a C1-C3 monovalent hydrocarbon group, and several R < ² > may be same or different. ]

  According to the present invention, it is possible to provide a novel organopolysiloxane compound that imparts conditioning effects such as moist feeling and smoothness to hair and the like, and is excellent in the sustainability of the effect, and is also sufficiently moist and smooth to hair and the like. It is possible to provide a cosmetic that imparts a conditioning effect such as a thickness and further improves the sustainability of the effect. Moreover, according to the production method of the present invention, a novel organopolysiloxane compound can be easily synthesized in a high yield without requiring a reaction catalyst or purification and without any by-products.

[Organopolysiloxane compound]
The organopolysiloxane compound of the present invention is obtained by bonding the urethane bond-containing group (1) to at least one silicon atom of the organopolysiloxane segment constituting the main chain.

  The organopolysiloxane segment constituting the main chain is not particularly limited and may be linear or branched, but is preferably linear.

In the urethane bond-containing group (1), the divalent hydrocarbon group having 1 to 10 carbon atoms represented by X and Y is a linear or branched divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or A divalent aromatic hydrocarbon group having 5 to 10 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms, and further an alkylene group or phenylene group having 2 to 6 carbon atoms is more preferable, ethylene group, trimethylene group, propylene group, butylene group, hexamethylene. More preferably a group or a phenylene group. Although d shows the number of 0-10, the number of 0-3 is preferable. G represents a group represented by the general formula (2-1) or (2-2), and R ² in the general formulas (2-1) and (2-2) represents a hydrogen atom or 1 to 3 carbon atoms. The monovalent hydrocarbon group having 1 to 3 carbon atoms is a straight or branched monovalent group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group. An aliphatic hydrocarbon group is mentioned. R ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group, and even more preferably a hydrogen atom.

  The urethane bond-containing group (1) is bonded to at least one silicon atom of the organopolysiloxane segment, but may be bonded to any position on the terminal or inside of the organopolysiloxane segment.

  Examples of the organopolysiloxane compound of the present invention include a compound represented by general formula (3) (hereinafter referred to as compound (3)).

[Wherein R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, M is a urethane bond-containing group (1), Q is an amino group-containing group represented by the following general formula (4) ( (Hereinafter referred to as amino group-containing group (4)), A represents a group selected from R ¹ , M, Q and a hydroxyl group, and a plurality of R ¹ , M, Q and A may be the same or different. a represents a number from 0 to 5000, b represents a number from 0 to 1000, c represents a number from 0 to 1000, and when b is 0, at least one of A represents M.

(Wherein X, Y and d have the same meaning as described above.)]
In the compound (3) of the present invention, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include a methyl group, ethyl C1-C10 linear or branched monovalent aliphatic hydrocarbon group such as a group, propyl group, butyl group, hexyl group, decyl group, etc., C5-C10 monovalent aromatic carbonization such as a phenyl group Examples thereof include monovalent alicyclic hydrocarbon groups having 3 to 10 carbon atoms such as a hydrogen group and a cyclohexyl group. R ¹ is preferably a methyl group or a phenyl group from the viewpoint of ease of production, and is mainly a methyl group from the viewpoint of effectively exerting the conditioning performance when blended in cosmetics such as hair cosmetics. More preferred.

  M represents a urethane bond-containing group (1). Q represents an amino group-containing group (4), and X, Y and d in the formula (4) are preferably those exemplified as X, Y and d in the urethane bond-containing group (1).

  Preferable examples of the amino group-containing group (4) include the following.

-C ₃ H ₆ -NH _{2,
-C 3 H 6 -NH-C 2} H 4 -NH 2,
_{-C 3 H 6 -NH- (C 2} H 4 -NH) 2 -H,
_{-C 3 H 6 -NH- (C 2} H 4 -NH) 3 -H.

A represents a group selected from R ¹ , M, Q and a hydroxyl group. When b is 0, at least one of A is M.

  a shows the number of 0-5000, the number of 20-4000 is preferable and the number of 50-2000 is more preferable. Although b shows the number of 0-1000, the number of 0-500 is preferable and the number of 0-100 is more preferable. Although c shows the number of 0-1000, the number of 0-500 is preferable and the number of 0-100 is more preferable. Furthermore, it is preferable that a + b + c> 1. The ratio of b / (b + c) is preferably 0.1 to 1, more preferably 0.2 to 1, and still more preferably 0.2 to 0.8.

  The organopolysiloxane compound of the present invention is useful as a cosmetic, in particular, a hair cosmetic conditioning agent, a hair set agent, a hair foam agent, a hair spray agent and the like.

[Method for producing organopolysiloxane compound]
The organopolysiloxane compound of the present invention comprises a compound in which an amino group-containing group (4) is bonded to at least one silicon atom of an organopolysiloxane segment constituting the main chain (hereinafter referred to as amino-modified organopolysiloxane) and It can be produced by reacting a compound represented by general formula (5) (hereinafter referred to as compound (5)).

(Wherein R ² represents the same meaning as described above, and a plurality of R ² may be the same or different.)
Examples of the amino-modified organopolysiloxane include a compound represented by the following general formula (6) (hereinafter referred to as compound (6)).

(Wherein R ¹ , Q and a represent the same meaning as described above, B represents a group selected from R ¹ , Q and a hydroxyl group, and a plurality of R ¹ , Q and B may be the same or different. E is a number from 0 to 2000, preferably a number from 0 to 1000, more preferably a number from 0 to 200, and when e is 0, at least one of B represents Q.)
Specific examples of the compound (6) include amino-modified silicones KF-8003, KF-8008, KF-864 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BY-16, which are readily available as commercially available products. -203, BY-16-850, BY-16-213 (all manufactured by Toray Dow Corning Co., Ltd.).

As the compound (5), a compound represented by the following formula (5-1) is preferable, and glycerin carbonate in which all R ² are hydrogen atoms is more preferable.

  Since the reaction between the amino-modified organopolysiloxane and the compound (5) proceeds rapidly and quantitatively even without a catalyst, the compound (5) is excessively added to the amino group of the amino-modified organopolysiloxane. There is no need. Therefore, a purification step after the reaction is not necessary. When the amount of the compound (5) is insufficient relative to the amino group of the amino-modified organopolysiloxane, a part of the amino group in the amino-modified organopolysiloxane remains unreacted, but the amino group Since it is a functional group that imparts good adsorptivity and flexibility to hair and the like, the charge amount is adjusted according to the required conditioning performance, and the amino group-containing group (4 ) May be left selectively.

  It is desirable to use a solvent during the reaction between the amino-modified organopolysiloxane and the compound (5). The solvent is not particularly limited as long as it is compatible with both the amino-modified organopolysiloxane and the compound (5) and does not react with the amino-modified organopolysiloxane and the compound (5). Among such solvents, alcohols such as ethanol and isopropanol, methyl ethyl ketone, ethyl acetate, toluene and the like are particularly preferable examples.

  In the reaction of the amino-modified organopolysiloxane with the compound (5), a catalyst is not particularly required, and the reaction temperature is 60 to 100 from the viewpoint of accelerating the reaction and suppressing the decomposition of the amino-modified organopolysiloxane. ° C is preferred. Under these conditions, it is possible to complete the reaction sufficiently in 5 to 8 hours. After the reaction, the target product can be taken out by distilling off the solvent, but it may be used as it is or after further dilution with a solvent.

[Cosmetics]
The cosmetic of the present invention contains the organopolysiloxane compound of the present invention and may contain the organopolysiloxane compound produced by the production method as it is.

  As the cosmetic of the present invention, a hair cosmetic is preferable. The content of the organopolysiloxane compound of the present invention in the hair cosmetic is preferably from 0.1 to 20% by mass (hereinafter simply expressed as%) from the viewpoint of obtaining a good conditioning effect and its sustainability. -10% is more preferable, and 1-5% is still more preferable.

  The hair cosmetic composition of the present invention may further contain an oil agent, particularly an oil agent having a conditioning action on the hair. Examples of the oil include saturated or unsaturated alcohols having 12 to 30 carbon atoms; ethers of the alcohol and polyhydric alcohols; esters of the alcohol and fatty acids having 1 to 11 carbon atoms; saturated or unsaturated having 12 to 30 carbon atoms. Saturated fatty acids; esters of fatty acids with mono- or polyhydric alcohols; amides of fatty acids with amines; sterols; squalene; phospholipids; glycolipids; animal fats; Examples thereof include one or more silicones selected from polysiloxane, alkyl-modified silicone, methylphenyl polysiloxane, and polyether-modified silicone.

  The blending amount of these oils into the hair cosmetic is preferably 0.01 to 30%, more preferably 1 to 25%, still more preferably 3 to 20%.

  Furthermore, in the hair cosmetic composition of the present invention, a thickener such as hydroxyethyl cellulose, a surfactant, an anionic / amphoteric / cationic / nonionic polymer, if necessary, within a range not impairing the effects of the present invention. You may mix | blend a fragrance | flavor, a pearling agent, a polymer for hair setting, a pigment | dye, a ultraviolet absorber, antioxidant, antiseptic | preservative, etc.

  The surfactant is not particularly limited as long as it is used in normal hair cosmetics, and any of anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants can be used. It can be preferably used.

Specifically, examples of the anionic surfactant include those shown below.
(Bi) Alkyl benzene sulfonate, preferably a linear or branched alkyl benzene sulfonate having an alkyl group having an average carbon number of 10 to 16.
(B-ii) Alkyl ether sulfate or alkenyl ether sulfate, preferably having a linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 20, and an average of 0.5 to 8 mol in one molecule Ethylene oxide, propylene oxide, butylene oxide, ethylene oxide and propylene oxide at a molar ratio of 0.1 / 9.9 to 9.9 / 0.1, or ethylene oxide and butylene oxide at 0.1 / 9.9. Alkyl ether sulfate or alkenyl ether sulfate added at a molar ratio of ˜9.9 / 0.1.
(B-iii) Alkyl sulfate or alkenyl sulfate, preferably alkyl sulfate or alkenyl sulfate having an average alkyl group or alkenyl group having 10 to 20 carbon atoms.
(B-iv) Olefin sulfonates, preferably olefin sulfonates having an average of 10 to 20 carbon atoms in one molecule.
(Bv) Alkane sulfonate, preferably an alkane sulfonate having an average of 10 to 20 carbon atoms in one molecule.
(B-vi) Higher fatty acid salts, preferably saturated or unsaturated fatty acid salts having an average of 10 to 24 carbon atoms in one molecule.
(B-vii) (Amido) ether carboxylic acid type surfactant.
(B-viii) α-sulfo fatty acid salt or ester, preferably α-sulfo fatty acid salt or ester having an alkyl or alkenyl group consisting of an average of 10 to 20 carbon atoms.
(B-ix) N-acyl amino acid type surfactants, preferably N-acyl amino acid type surfactants having an acyl group having 8 to 24 carbon atoms and a free carboxylic acid residue (for example, N-acyl sarcosinate, N -Acyl-β-alanine and the like.
(Bx) Phosphate ester type surfactants, preferably phosphate mono- or diester type surfactants having an alkyl group or alkenyl group having 8 to 24 carbon atoms or an alkylene oxide adduct thereof.
(B-xi) Sulfosuccinic acid ester type surfactants, preferably sulfosuccinic acid esters such as higher alcohols having 8 to 22 carbon atoms or ethoxylates thereof or higher fatty acid amides.
(B-xii) Polyoxyalkylene fatty acid amide ether sulfates, preferably sulfates such as ethoxylates of linear or branched, saturated or unsaturated fatty acid monoethanolamides or diethanolamides having 8 to 24 carbon atoms.
(B-xiii) Monoglyceride sulfate, preferably monoglyceride sulfate having a linear or branched saturated or unsaturated fatty acid group having 8 to 24 carbon atoms.
(B-xiv) An acylated isethionate, preferably an acylated isethionate having a linear or branched saturated or unsaturated fatty acid group having 8 to 24 carbon atoms.
(B-xv) Alkyl glyceryl ether sulfate or alkyl glyceryl ether sulfonate, preferably alkyl glyceryl having 8 to 24 carbon atoms or straight chain or branched chain alkyl group or alkenyl group or alkylene oxide adduct thereof Ether sulfate or alkyl glyceryl ether sulfonate.
(B-xvi) alkyl or alkenyl amide sulfonate, preferably an alkyl or alkenyl amide sulfonate having a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms.
(B-xvii) Alkanolamide sulfosuccinate, preferably an alkanolamide sulfosuccinate having a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms.
(B-xviii) Alkyl sulfoacetate, preferably an alkyl sulfoacetate having a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms.
(B-xix) An acylated taurate, preferably an acyl taurate having a C8-24 linear or branched saturated or unsaturated fatty acid group.
(B-xx) N-acyl-N-carboxyethylglycine salt, preferably N-acyl-N-carboxyethylglycine salt having an acyl group having 6 to 24 carbon atoms.

  As salts of these anionic surfactants, that is, counter ions of anionic residues, alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ions, carbon atoms of 2 or 3 Examples thereof include alkanolamines having 1 to 3 alkanol groups (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine).

  Of these anionic surfactants, alkyl ether sulfates, particularly polyoxyethylene alkyl ether sulfates are preferred.

  Nonionic surfactants include, for example, polyoxyalkylene alkyl ethers or polyalkylenes having a linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 24 and added with ethylene oxide, propylene oxide or butylene oxide. Oxyalkylene alkenyl ether; glycerin ester of fatty acid having 8 to 20 carbon atoms; glycol ester of fatty acid having 8 to 20 carbon atoms; alkylene oxide adduct of monoglyceride of fatty acid having 8 to 20 carbon atoms; fatty acid having 8 to 20 carbon atoms; Sucrose ester; sorbitan ester of fatty acid having 8 to 20 carbon atoms; polyglycerin fatty acid ester having an acyl group having 8 to 20 carbon atoms; monoethanolamide or diethanolamide of fatty acid having 8 to 20 carbon atoms or ethoxylate thereof; Polio Ethylene hydrogenated castor oil; polyoxyalkylene sorbitan fatty acid ester having an acyl group having 8 to 20 carbon atoms; polyoxyethylene sorbite fatty acid ester having an acyl group having 8 to 20 carbon atoms; linear or branched chain having 8 to 18 carbon atoms An alkyl saccharide surfactant having an alkyl group, an alkenyl group or an alkylphenyl group; a linear or branched alkyl group having 8 to 20 carbon atoms, an alkylamine oxide or an alkylamidoamine oxide having an alkenyl group; Polyhydric alcohol ether compounds or ester compounds having 20 linear or branched alkyl groups or alkenyl groups; silicone surfactants such as siloxane derivatives (JP-A-4-108795), polyoxy-modified silicones; polyoxy Alkylene alkyl Aryl ethers, polyoxyalkylene lanolin alcohols, polyoxyalkylene fatty acid ester, Pluronic type block polymer, Tetronic type block polymers, polyoxyalkylene fatty acid amides, polyoxyalkylene alkyl amides, polyethylene imine derivatives.

  The amphoteric surfactant is not particularly limited as long as it is used in normal hair cosmetics. For example, amide amino acid type, carbobetaine type, amide betaine type, sulfobetaine type, amide sulfobetaine type, imidazo Examples include linium betaine type, amino acid type, phosphobetaine type, and phosphate ester type.

  Examples of the cationic surfactant include tertiary amines, quaternary ammonium salts, amidoamines and ester amines. For example, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, N-stearyl-N, N, N-tri (polyoxyethylene) ammonium chloride (ethylene oxide total 3) Mole addition), cetylbenzyldimethylammonium chloride, cetyltriethylammonium bromide, distearyldimethylammonium chloride, 2-decyltetradecyltrimethylammonium chloride, 2-dodecylhexadecyltrimethylammonium chloride, di-2-hexyldecyldimethylammonium Chloride, di-2-octyldodecyl dimethyl Le ammonium chloride, behenyl tertiary amine, stearyl tertiary amines, can be cited stearamidopropyl dimethyl amine and the like.

  Surfactant can use 1 type (s) or 2 or more types, It is preferable to mix | blend 0.1-50% in hair cosmetics, Furthermore, if it mix | blends 0.5-40%, especially 1-30%, Since it is excellent in foaming property, it is preferable.

  When the dosage form of the hair cosmetic composition of the present invention is a hair set agent, a hair foam agent, a hair spray agent, or the like, it is preferable to include those exemplified below as a hair set polymer.

(1) Polyvinylpyrrolidone polymer compound / polyvinylpyrrolidone; commercially available products such as Rubiscol K12, K30 (above, manufactured by BASF), PVPK15, K30 (above, made by GAF) and the like.
-Polyvinylpyrrolidone / vinyl acetate copolymer; commercially available products include Rubiscol VA28, VA73 (above, manufactured by BASF), PVP / VA E-735, S-630 (above, manufactured by GAF), and the like.
-Polyvinylpyrrolidone / vinyl acetate / vinyl propionate terpolymer; commercially available products include Rubiscol VAP343 (manufactured by BASF).
-Polyvinylpyrrolidone / alkylaminoacrylate copolymer; commercially available products such as rubiflex (manufactured by BASF), copolymers 845, 937, 958 (manufactured by GAF) and the like.
Polyvinylpyrrolidone / acrylate / (meth) acrylic acid copolymer; commercially available products such as Rubyflex VBM35 (manufactured by BASF) and the like.
-Polyvinylpyrrolidone / alkylamino acrylate / vinyl caprolactam copolymer; as a commercial product, copolymer VC-713 (manufactured by GAF) and the like can be mentioned.

(2) Acidic vinyl ether polymer compound Methyl vinyl ether / alkyl maleic anhydride alkyl half ester copolymer; Gantrez ES-225, ES-425, SP-215 (above, manufactured by GAF) and the like are listed as commercial products.

(3) Acidic polyvinyl acetate polymer compound / vinyl acetate / crotonic acid copolymer; Resin 28-1310 (manufactured by National Starch Co., Ltd.), Ruby Set CA66 (manufactured by BASF Corp.) and the like are listed as commercial products.
-Vinyl acetate / crotonic acid / vinyl neodecanoate copolymer; Resin 28-2930 (manufactured by National Starch Co., Ltd.) and the like are listed as commercial products.
-Vinyl acetate / crotonic acid / vinyl propionate copolymer; Rubyset CAP (manufactured by BASF) and the like are listed as commercial products.
-Vinyl acetate / tert-butyl vinyl benzoate / crotonic acid copolymer; for example, those described in JP-A-6-507646.

(4) Acidic acrylic polymer / (meth) acrylic acid / (meth) acrylic acid ester copolymer; plus size L53P (manufactured by Kyoyo Chemical Co., Ltd.), diamond hold (manufactured by Mitsubishi Chemical Co., Ltd.) -DR-25 (made by Amacor) etc. are mentioned.
-Acrylic acid / acrylic acid alkyl ester / alkyl acrylamide copolymer; Examples of commercially available products include ULTRAHOLD 8 (manufactured by BASF) and Amphomer V-42 (manufactured by National Starch).

(5) Amphoteric acrylic polymer compound / (meth) acrylethylbetaine / (meth) acrylic acid alkyl ester copolymer; for example, N-methacryloyloxyethyl-N, N-dimethylammonium α-N-methylcarboxybetaine ( A copolymer with a meta) acrylic acid alkyl ester, and the like, and Yuka Former M-75, SM (manufactured by Mitsubishi Chemical Corporation) and the like are listed as commercial products.
-Acrylic acid alkyl ester / butylaminoethyl methacrylate / acrylic acid octylamide copolymer; for example, octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer and the like, and commercially available products such as Anformer 28-4910 (National Starch) Manufactured) and the like.

(6) Basic acrylic polymer compound Acrylamide / acrylic ester quaternary copolymer; those described in JP-A-2-180911, JP-A-8-291206, and the like.

(7) Compound having a cellulose skeleton Cationic cellulose derivative; examples of commercially available products include Cellcoat H-100, L-200 (manufactured by National Starch).

(8) Chitin / compound having a chitosan skeleton / hydroxypropyl chitosan; commercially available products include chitofilmer (manufactured by Ichimaru Falcos).
Carboxymethyl chitin, carboxymethyl chitosan, chitosan and monovalent acids such as pyrrolidone carboxylic acid, lactic acid and glycolic acid, or divalent acids such as adipic acid and succinic acid; Acid salt), kaitomer L (lactate) (manufactured by Union Carbide) and the like.

(9) Water-dispersible polyester Examples of commercially available products include AQ38S and AQJIS (Eastman Kodak).

(10) Organopolysiloxane linked with poly (N-acylethyleneimine) described in JP-B-9-2716831, JP-A-7-133352, JP-A-5-112423, and JP-A-3-287509 What is being done is mentioned.

  These hair set polymers can be used alone or in combination of two or more. The blending amount of the hair setting polymer in the hair cosmetic is preferably 0.1 to 10%, more preferably 0.5 to 6%, particularly 1 to 4% from the viewpoint of obtaining necessary and sufficient setting power. preferable.

  Examples of hair cosmetics include hair shampoos, hair treatments, hair conditioners used in the bathroom, hair foams, hair sprays, hair creams, hair waxes, hair gels used outside the bathroom, and hair dyes, perms, hair manicures. And agents used for home and beauty salon treatments such as hair bleach and the like, and the organopolysiloxane compound of the present invention can be incorporated into any of these.

  “%” In the following examples means “% by mass” unless otherwise specified. Further, the amine value (mgKOH / g) of the following amino-modified silicone and urethane bond-containing organopolysiloxane is a value obtained by measuring the amino group content by the perchloric acid titration method. The functional group equivalent (g / mol) is a value calculated by 56000 / amine value.

Synthesis example 1
In a 2 L separable flask, amino-modified silicone (KF-8003, manufactured by Shin-Etsu Chemical Co., Ltd., side chain amino-modified type, amine value 29 mgKOH / g, functional group equivalent 1930 g / mol, viscosity-converted molecular weight about 30,000, general formula (6), R ¹ and B are methyl groups, Q is — (CH ₂ ) ₃ —NH ₂ , a is 380, and e is 15) 100 g (51.8 mmol), glycerin carbonate is amino 6.11 g (51.8 mmol), which is an amount corresponding to 1.0 mol equivalent with respect to the amino group of the modified silicone, and 500 g of ethanol were added. A stirrer and a condenser were set in the separable flask, the bath temperature was set at 80 ° C., and the reaction was carried out for 8 hours under ethanol reflux. Thereafter, the solvent was distilled off under reduced pressure to recover the polymer. The recovered polymer (hereinafter referred to as urethane bond-containing organopolysiloxane 1) was recovered after drying under reduced pressure at 60 ° C. The amine value of this urethane bond-containing organopolysiloxane 1 was 1 mgKOH / g or less. Further, a peak derived from a urethane group was confirmed in the vicinity of 1700 cm ⁻¹ from an infrared absorption spectrum (hereinafter referred to as IR). Furthermore, from the ¹ H-NMR spectrum (hereinafter referred to as ¹ H-NMR), a peak derived from a urethane group was confirmed in the vicinity of 3.0 to 4.2 ppm. From the above, it was confirmed that the amino group of the raw material was consumed in an amount corresponding to the charged amount of glycerin carbonate and was substantially substituted with the urethane bond-containing group. IR of this urethane bond-containing organopolysiloxane 1 is shown in FIG. 1, and ¹ H-NMR is shown in FIG.

Synthesis example 2
Except for using 100 g (51.8 mmol) of amino-modified silicone (KF-8003) and 3.05 g (25.9 mmol) of glycerin carbonate in an amount corresponding to 0.5 mol equivalent to the amino group of amino-modified silicone, The same raw materials and the same operations as in Synthesis Example 1 were performed to obtain urethane bond-containing organopolysiloxane 2. The amine value of this urethane bond-containing organopolysiloxane 2 was 12 mgKOH / g. Further, a peak derived from a urethane bond-containing group was confirmed by IR and ¹ H-NMR. From the above, it was confirmed that the amino group of the raw material was consumed in an amount corresponding to the charged amount of glycerin carbonate, and about 0.5 mol of all amino groups were substituted with urethane bond-containing groups. IR of this urethane bond-containing organopolysiloxane 2 is shown in FIG. 3, and ¹ H-NMR is shown in FIG.

Synthesis example 3
Except for using 100 g (51.8 mmol) of amino-modified silicone (KF-8003) and 1.83 g (15.4 mmol) of glycerin carbonate in an amount corresponding to 0.3 mol equivalent to the amino group of amino-modified silicone, The same raw materials as in Synthesis Example 1 and the same operation were performed to obtain urethane bond-containing organopolysiloxane 3. The amine value of this urethane bond-containing organopolysiloxane 3 was 20 mgKOH / g. Further, a peak derived from a urethane bond-containing group was confirmed by IR and ¹ H-NMR. From the above, it was confirmed that the amino group of the raw material was consumed in an amount corresponding to the charged amount of glycerin carbonate, and about 0.3 mol of all amino groups were substituted with urethane bond-containing groups.

Synthesis example 4
Aside from using 100 g (51.8 mmol) of amino-modified silicone (KF-8003) and 0.918 g (7.77 mmol) of glycerin carbonate in an amount corresponding to 0.15 mol equivalent to the amino group of amino-modified silicone, The same raw materials as in Synthesis Example 1 and the same operation were performed to obtain urethane bond-containing organopolysiloxane 4. The amine value of this urethane bond-containing organopolysiloxane 4 was 24 mgKOH / g. Further, a peak derived from a urethane bond-containing group was confirmed by IR and ¹ H-NMR. From the above, it was confirmed that the amino group of the raw material was consumed in an amount corresponding to the charged amount of glycerin carbonate, and about 0.15 mol of all amino groups were substituted with urethane bond-containing groups.

Synthesis example 5
In a 2 L separable flask, amino-modified silicone (KF-864, manufactured by Shin-Etsu Chemical Co., Ltd., side chain modified type, amine value 14 mgKOH / g, functional group equivalent 4000 g / mol, viscosity converted molecular weight about 30,000, general formula ( 6), R ¹ and B are methyl groups, Q is — (CH ₂ ) ₃ —NH ₂ , a is 390, and e is 8)) (100 g, 25.0 mmol), glycerin carbonate is amino-modified 2.95 g (25.0 mmol), which is an amount corresponding to 1.0 mol equivalent to the amino group of silicone, and 500 g of ethanol were added. A stirrer and a condenser were set in the separable flask, the bath temperature was set at 80 ° C., and the reaction was carried out for 8 hours under ethanol reflux. Thereafter, the solvent was distilled off under reduced pressure to recover the polymer. The recovered polymer (hereinafter referred to as urethane bond-containing organopolysiloxane 5) was recovered after drying under reduced pressure at 60 ° C. The amine value of this urethane bond-containing organopolysiloxane 5 was 1 mgKOH / g or less. Further, a peak derived from a urethane group was confirmed by IR and ¹ H-NMR. From the above, it was confirmed that the amino group of the raw material was consumed in an amount corresponding to the charged amount of glycerin carbonate and was substantially substituted with the urethane bond-containing group.

Synthesis Example 6
Except for using 100 g (25.0 mmol) of amino-modified silicone (KF-864) and 1.48 g (12.5 mmol) of glycerin carbonate in an amount corresponding to 0.5 mol equivalent to the amino group of amino-modified silicone, The same raw materials and the same operation as in Synthesis Example 5 were performed to obtain urethane bond-containing organopolysiloxane 6. The amine value of this urethane bond-containing organopolysiloxane 6 was 7 mgKOH / g. Further, a peak derived from a urethane bond-containing group was confirmed by IR and ¹ H-NMR. From the above, it was confirmed that the amino group of the raw material was consumed in an amount corresponding to the charged amount of glycerin carbonate, and about 0.5 mol of all amino groups were substituted with urethane bond-containing groups.

Synthesis example 7
In a 2 L separable flask, amino-modified silicone (KF-8008, manufactured by Shin-Etsu Chemical Co., Ltd., both-end modified type, amine value 10 mgKOH / g, functional group equivalent 5600 g / mol, molecular weight 11200, represented by general formula (6) R ¹ is a methyl group, 2 B are both — (CH ₂ ) ₃ —NH ₂ , a compound in which a is 150, and e is 0) 100 g (17.9 mmol), and glycerin carbonate is amino-modified silicone amino 2.11 g (17.9 mmol) corresponding to 1.0 mol equivalent to the group and 500 g of ethanol were added. A stirrer and a condenser were set in the separable flask, the bath temperature was set at 80 ° C., and the reaction was carried out for 8 hours under ethanol reflux. Thereafter, the solvent was distilled off under reduced pressure to recover the polymer. The recovered polymer (hereinafter referred to as urethane bond-containing organopolysiloxane 7) was recovered after drying under reduced pressure at 60 ° C. The amine value of this urethane bond-containing organopolysiloxane 7 was 1 mgKOH / g or less. Further, a peak derived from a urethane bond-containing group was confirmed by IR and ¹ H-NMR. From the above, it was confirmed that the amino group of the raw material was consumed in an amount corresponding to the charged amount of glycerin carbonate and was substantially substituted with the urethane bond-containing group.

  The urethane bond-containing organopolysiloxanes 1 to 7 obtained in Synthesis Examples 1 to 7 are collectively shown in Table 1.

Examples 1-4 and Comparative Examples 1-3
As the component (a), the urethane bond-containing organopolysiloxanes 2, 3, 4, and 6 obtained in Synthesis Examples 2, 3, 4, and 6 were used, and the components (b) to (d) shown in Table 2 and others were used. The hair conditioner of the present invention having the composition shown in Table 2 was prepared by a conventional method using the above components. Moreover, the comparative hair conditioner of the composition shown in Table 2 was prepared similarly except not containing (a) component or using the comparative silicone compound instead of (a) component.

  About the obtained hair conditioner, sensory evaluation was performed by the following method. The results are shown in Table 2.

<Sensory evaluation method>
The hair bundle (20 g, 20 cm) of a Japanese woman that was bleached with a commercially available bleaching agent was subjected to sensory evaluation while 5 panelists treated the hair bundle in the following manner.

  Apply 2g of the hair conditioner shown in Table 2 to the hair bundle washed with 3g of standard shampoo with the following composition, and after fully acclimating the entire hair, rinse it under running water of about 40 ° C for about 30 seconds. Was evaluated. Next, towel drying was performed, and after drying with a dryer, evaluation after drying was performed. Sensory evaluation was performed on the smoothness, softness, no creaking, and the smoothness, softness and moisturizing effect of the hair after rinsing, and the following criteria were used.

・ Standard shampoo formulation (pH 7.0)
25% polyoxyethylene (2.5) lauryl ether sulfate sodium salt 62.0%
Lauric acid diethanolamide 2.3%
Edetate disodium 0.15%
Sodium benzoate 0.5%
Sodium chloride 0.8%
75% phosphoric acid appropriate amount Fragrance, methyl paraben appropriate amount Purified water remaining.

・ Evaluation criteria ◎: 4 to 5 people responded effective ○: 3 people answered effective △: 2 people answered effective ×: 1 or 0 responded effective

* 1: KHS-3 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 2: KF-8003 (Shin-Etsu Chemical Co., Ltd.)
* 3: pH indicates a value at 25 ° C. when diluted 20 times by mass with water.

2 is an infrared absorption spectrum of urethane bond-containing organopolysiloxane 1 obtained in Synthesis Example 1. 2 is a ¹ H-NMR spectrum of urethane bond-containing organopolysiloxane 1 obtained in Synthesis Example 1. FIG. 3 is an infrared absorption spectrum of urethane bond-containing organopolysiloxane 2 obtained in Synthesis Example 2. 2 is a ¹ H-NMR spectrum of a urethane bond-containing organopolysiloxane 2 obtained in Synthesis Example 2. FIG.

Claims (5)

Following general formula (3) compound der represented by Ru organopolysiloxane compound.

Table Under wherein, R ¹ represents a monovalent hydrocarbon group hydrogen atom or a C1-10, M is a urethane bond-containing group represented by the following general formula (1), Q the following general formula (4) The amino group-containing group, A represents a group selected from R ¹ , M, Q and a hydroxyl group, and a plurality of R ¹ , M, Q and A may be the same or different. a represents a number of 0 to 5000, b represents a number of 0 to 1000, c represents a number of 0 to 1000, and b / (b + c) = 0.1 to 0.3 .

(In the formula, X and Y are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, d is a number of 0 to 10, and G is the following general formula (2-1) or (2-2). Represents the group represented.)

(In the formula, R ² represents a hydrogen atom.)

(In the formula, X, Y and d have the same meaning as described above .)] A compound in which the amino group-containing group represented by the general formula (4) according to claim 1 is bonded to at least one silicon atom of the organopolysiloxane segment constituting the main chain (hereinafter referred to as amino-modified organopolysiloxane). ) is reacted with a compound represented by the following general formula (5) the method according to claim 1 organopolysiloxane compound as claimed.

(Wherein, R ² indicates to a hydrogen atom.) The production method according to claim 2 , wherein the amino-modified organopolysiloxane is a compound represented by the following general formula (6).

(Wherein R ¹ , Q and a represent the same meaning as in claim 1 , B represents a group selected from R ¹ , Q and a hydroxyl group, and a plurality of R ¹ , Q and B are the same or different. E represents a number from 0 to 2000, and when e is 0, at least one of B represents Q.) Containing claim 1 organopolysiloxane compound according or organopolysiloxane compound produced by the production method according to claim 2 or 3, cosmetics. The cosmetic according to claim 4 , which is a hair cosmetic.

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