JP4522809B2 - Silicone emulsion and hair cosmetic composition - Google Patents

Description

  The present invention relates to a silicone emulsion and a hair cosmetic composition. More specifically, the present invention includes a silicone emulsion having excellent stability and such a silicone emulsion, and can impart a squeaky feeling to hair during washing and rinsing. The present invention relates to a hair cosmetic composition having excellent combability after drying.

  Conventionally, silicones such as silicone oil are blended in hair cosmetics for the purpose of giving the hair gloss and smoothness. That is, by adding silicones, the function as a conditioning shampoo is given, or the use feeling of a hair treatment agent such as a hair rinse agent used after washing is improved.

  As a hair cosmetic containing such silicones, a detergent composition using a silicone emulsion having a high polymerization degree obtained by emulsion polymerization has been proposed. (For example, see Patent Document 1)

  In this composition, when an anionic emulsifier is used in emulsion polymerization, dodecylbenzene sulfonate is used because of its availability. However, according to PRTR (Pollutant Release and Transfer Register), dodecylbenzene sulfonic acid and its salts are certified as designated chemical substances that are required to be notified of emissions, etc., and their use is restricted. There is a need to select surfactants. In addition, sodium salts such as sodium alkyl sulfate and sodium alkyl ether sulfate have the disadvantage that they are not preferable because they reduce the feeling of use of cosmetics.

  In Patent Document 1, a cyclic siloxane oligomer such as octamethylcyclotetrasiloxane is used as a low molecular weight siloxane to be subjected to emulsion polymerization because it is easily available and can be easily emulsified and ring-opened. .

  However, the ring-opening polymerization of the cyclic siloxane oligomer is an equilibration reaction, and the emulsion after the emulsion polymerization contains the cyclic siloxane oligomer in a proportion of 8 to 15% by weight (typically about 10% by weight). Such a cyclic oligomer may volatilize and may impair the physical stability of the emulsion system.

  In addition, when such an emulsion is used in a large amount as a hair cosmetic, for example, at a beauty salon, and accompanied by a heat blow treatment, the volatilized oligomer contaminates the surrounding environment, particularly the surrounding ventilation fan system. Or contact failure of various electric devices such as fan heaters.

  Furthermore, when used in skin cosmetics, the feel of use may be impaired due to the volatility of the cyclic siloxane oligomer contained in the emulsion. Therefore, when used in such applications, it is required to suppress the amount of cyclic siloxane oligomer in the emulsion, but removing the cyclic siloxane without destroying the emulsion after emulsion polymerization, The current situation was difficult.

  In order to solve such a problem, high molecular weight is obtained by using unsaturated aliphatic sodium sulfonate and / or sodium hydroxide aliphatic sulfonate as a surfactant, or using alkylbenzene sulfonic acid and alkyl sulfuric acid. A method for producing an emulsion containing a polyorganosiloxane has been proposed. (For example, see Patent Document 2 and Patent Document 3) Also, a method for producing an emulsion containing a high molecular weight polyorganosiloxane by using alkylbenzene sulfonic acid or unsaturated aliphatic sulfonic acid as a surfactant has been proposed. ing. (For example, see Patent Document 4)

  However, the polyorganosiloxane emulsions obtained by these methods have not yet been sufficiently satisfactory in the effects of imparting the original functions of hair cosmetics, such as the feel during rinsing and the fingering property during drying.

  Furthermore, a cationized emulsion polymerization composition using a nonionic emulsifier as a compatibilizing surfactant has been proposed for the purpose of improving combability. (For example, see Patent Document 5 and Patent Document 6)

However, in these compositions, the emulsion is relatively stabilized by the combined use of the nonionic emulsifier, but there is a problem that the viscosity of the emulsion becomes high and handling properties are impaired. Moreover, although the combing property at the time of drying is improved, it is not yet sufficient, and there is a problem that the squeaky feeling to the hair at the time of rinsing is not improved.
JP-A-7-138136 Japanese Patent Application Laid-Open No. 11-071522 JP-A-11-222554 JP 2000-53769 A Japanese Patent Laid-Open No. 9-137062 Japanese National Patent Publication No. 11-500459

  The present invention has been made to solve these problems, and can impart a smooth feel to the hair and combability after drying, eliminating the squeaky feeling particularly during rinsing and further to the environment. An object of the present invention is to provide a hair cosmetic composition that is less affected by hair.

  As a result of intensive investigations to achieve the above object, the present inventor has found that using a specific anionic surfactant and further using a polyethylene glycol derivative and a cationic surfactant in combination squeaks when rinsing hair. The present invention has been completed by finding that it is extremely effective in improving the fingering property during drying.

The first invention of the present invention are silicone emulsion, (a) the general _{^{formula: HO [(R 1) 2}} SiO] m H ......... (I) ( wherein, or different ^{R 1} are identical to each other even if rather good, (1) an alkyl group having 1 to 30 carbon atoms, (2) a cycloalkyl group having 4 to 7 carbon atoms, (3) an alkenyl group having 2 to 8 carbon atoms, (4) aryl moiety is a phenyl Or an alkyl moiety substituted with an aralkyl group having up to 4 carbon atoms, (5) a phenyl group or an alkyl-substituted phenyl group having up to 4 carbon atoms, and (6) a halogen. It represents a monovalent hydrocarbon group selected from the alkyl group of (1) , and m is a value that makes the viscosity of component (a) at 25 ° C. 0.01 to 3.0 Pa · s. Silanol group-terminated polydiorgano Siloxane and (b) General formula: R ² O (CH ₂ CH ₂ O) _n SO ₃ M (wherein R ² represents a saturated or unsaturated hydrocarbon group having 8 to 20 carbon atoms, and M is An anionic surfactant represented by alkali metal, alkaline earth metal, ammonium or organic amine, n represents a number of 0 to 5), and (c) a polymer obtained by emulsion polymerization from water. An organosiloxane emulsion; (d) one or more polyethylene glycols or derivatives thereof selected from polyethylene glycol having a molecular weight of 200 to 3,000 or polyethylene glycol glyceryl ether; and (e) a cationic surfactant. It is characterized by containing.

The second invention of the present invention comprises (A) 0.01 to 20% by weight of a silicone emulsion, (B) 0.1 to 15% by weight of a high melting point aliphatic compound having a melting point of 25 ° C. or higher, and (C1) a cation. A hair cosmetic composition containing 0.1 to 10% by weight of a conditioning agent and (D) water, respectively, wherein (A) the silicone emulsion comprises (a) a general formula: HO [(R ¹ ) ₂ SiO] _m H ......... (I) (in the formula, ^{R 1} rather good even though it or different mutually identical, (1) an alkyl group having 1 to 30 carbon atoms, (2) cycloalkyl having a carbon number of 4 to 7 An alkyl group, (3) an alkenyl group having 2 to 8 carbon atoms, (4) an aryl moiety is a phenyl group or a lower alkyl-substituted phenyl group having up to 4 carbon atoms, and an alkyl moiety is an aralkyl group having up to 4 carbon atoms, (5) Phenyl group or up to 4 carbon atoms Represents an alkyl group monovalent hydrocarbon group, selected from alkyl-substituted phenyl group, and that (6) the halogen-substituted (1), m is 0.01 viscosity at 25 ° C. of the component (a) And (b) general formula: R ² O (CH ₂ CH ₂ O) _n SO ₃ M (wherein R ² is a value of 3.0 Pa · s). C represents a saturated or unsaturated hydrocarbon group having 8 to 20 carbon atoms, M represents an alkali metal, an alkaline earth metal, ammonium or an organic amine, and n represents a number of 0 to 5. (C) a polyorganosiloxane emulsion obtained by emulsion polymerization from water, and (d) a polyethylene glycol or polyethylene glycol having a molecular weight of 200 to 3,000. One or the two or more polyethylene glycols or derivatives thereof selected from glyceryl ether, characterized in that each containing (e) a cationic surfactant.

According to a third aspect of the present invention, (A) 0.01 to 20% by weight of a silicone emulsion, (E) 5 to 50% by weight of a detersive surfactant, and (C2) 0.1 to 20% by weight of a conditioning agent. And (D) a hair cosmetic composition each containing water, wherein the (A) silicone emulsion comprises (a) a general formula: HO [(R ¹ ) ₂ SiO] _m H (I) ( in the formula, ^{R 1} rather good even or different and are identical to each other, (1) an alkyl group having 1 to 30 carbon atoms, (2) a cycloalkyl group having 4 to 7 carbon atoms, (3) 2 carbon atoms -8 alkenyl groups, (4) an aryl moiety is a phenyl group or a lower alkyl-substituted phenyl group having up to 4 carbon atoms, and an alkyl moiety is an aralkyl group having up to 4 carbon atoms, (5) a phenyl group or an alkyl having up to 4 carbon atoms A substituted phenyl group, and 6) represents an alkyl group monovalent hydrocarbon group, selected from the halogen-substituted (1), m is the viscosity at 25 ° C. of the component (a) to 0.01~3.0Pa · s And (b) general formula: R ² O (CH ₂ CH ₂ O) _n SO ₃ M (wherein R ² has 8 to 20 carbon atoms). An anionic surfactant represented by a saturated or unsaturated hydrocarbon group, wherein M represents an alkali metal, an alkaline earth metal, ammonium or an organic amine, and n represents a number of 0 to 5. And (c) a polyorganosiloxane emulsion obtained by emulsion polymerization from water, and (d) polyethylene glycol or polyethylene glycol glyceryl ether having a molecular weight of 200 to 3,000. And one or more polyethylene glycols or derivatives thereof, characterized in that each containing (e) a cationic surfactant.

In the silicone emulsion of the present invention, (b) an anionic surfactant represented by the general formula: R ² O (CH ₂ CH ₂ O) _n SO ₃ M is used, and (d) polyethylene glycol or a derivative (E) By using a cationic surfactant in combination, a silicone emulsion in which an emulsion polymerized silicone polymer (polyorganosiloxane) is stably dispersed can be obtained. And since such a silicone emulsion is contained, according to the hair cosmetic composition of the present invention, it is possible to impart a smooth and moist feel to the hair, especially during washing and rinsing. A feeling of squeaking can be eliminated and good combing property after drying can be imparted.

  Embodiments of the present invention will be described below.

The silicone emulsion according to the first embodiment of the present invention has (a) a general formula: HO [(R ¹ ) ₂ SiO] _m H (I) (wherein R ¹ are the same as each other, or It represents a substituted or unsubstituted monovalent hydrocarbon group that may be different, and m is a value that makes the viscosity of component (a) at 25 ° C. 0.01 to 3.0 Pa · s. Silanol group-terminated polydiorganosiloxane and (b) general formula: R ² O (CH ₂ CH ₂ O) _n SO ₃ M (wherein R ² is a saturated or unsaturated hydrocarbon group having 8 to 20 carbon atoms) M represents an alkali metal, an alkaline earth metal, ammonium or an organic amine, n represents a number of 0 to 5, and (c) emulsified from water. Polyorganosiloxane obtained by polymerization And Marujon, (d) a molecular weight contains a polyethylene glycol or derivative thereof 200 to 3,000, (e) a cationic surfactant, respectively.

  The second embodiment of the present invention is a hair cosmetic composition comprising 0.01 to 20% by weight of (A) a silicone emulsion and 0.1 to 15% by weight of (B) a high melting point aliphatic compound (melting point). 25 ° C. or higher), 0.1 to 10% by weight of (C1) cation conditioning agent, and (D) water. As the (A) silicone emulsion, the silicone emulsion of the first embodiment described above is used.

First, (A) the silicone emulsion will be described. (A) The main component constituting the silicone emulsion is (a) a polydiorgano in which the molecular chain end represented by the general formula: HO [(R ¹ ) ₂ SiO] _m H (I) is blocked with a silanol group It is a polyorganosiloxane emulsion obtained from siloxane by emulsion polymerization. Hereinafter, the polydiorganosiloxane represented by the general formula may be referred to as α, ω-dihydroxypolydiorganosiloxane. In addition, since this polydiorganosiloxane is in a monomer relationship with the polyorganosiloxane that is the final polycondensation reaction product, its degree of polymerization is lower than that of the final polycondensation product, and is called an oligodiorganosiloxane. You can also.

  The component (a), the silanol group-terminated polydiorganosiloxane, is the main raw material for emulsion polymerization, and its molecular structure is linear as shown in the general formula (I), but the molecular chain terminal is As long as it is blocked with a silanol group, a part of it may contain a branched structure.

m represents the viscosity of the polydiorganosiloxane at 25 ° C. in the range of 0.01 to 3.0 Pa · s, preferably 0.015 to 1.0 Pa · s, more preferably 0.02 to 0.3 Pa · s. Is the value to be A silanol-terminated polydiorganosiloxane having a viscosity of less than 0.01 Pa · s is difficult to synthesize and purify stably. When the viscosity exceeds 3.0 Pa · s, emulsification becomes difficult. The value of m varies depending on the type of R ¹ bonded to the silicon atom and the mutual ratio. For the most preferred polydimethylsiloxane, the value of m is in the range of 8 to 500.

In the general formula (I), R ¹ bonded to the silicon atom includes (1) an alkyl group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. , An octyl group, a decyl group, etc. (2) a cycloalkyl group having 4 to 7 carbon atoms, preferably 6 cycloalkyl groups such as a cyclohexyl group, and (3) an alkenyl group having 2 to 8 carbon atoms, preferably 2 to 3 carbon atoms such as vinyl. Groups, allyl groups, etc. (4) Aralkyl groups, especially those in which the aryl moiety is a phenyl group or a lower alkyl (up to about C4) substituted phenyl group and the alkyl part is up to about C4, such as 2-phenylethyl group, 2-phenylpropylene (5) aryl groups, particularly phenyl groups or substituted phenyl groups (substituents are, for example, alkyl groups up to about C4), such as tolyl groups, And (6) substituted hydrocarbon groups, particularly those in which the substituent is halogen, such as 3,3,3-trifluoropropyl group.

High molecular weight polyorganosiloxane obtained by emulsion polymerization is well spread when tension is applied is low, elongation, 85 water-repellent and excellent gloss, and because there is no physiological activity, R ¹ in the molecule % Or more is preferably a methyl group, and it is particularly preferable that substantially all are methyl groups. Accordingly, the component (a) is preferably α, ω-dihydroxypoly (dimethylsiloxane), and some of the dimethylsiloxane units are methylethylsiloxane units, methylhexylsiloxane units, methylphenylsiloxane units, diphenylsiloxane units, etc. It is a copolymerized polysiloxane substituted with Of these, α, ω-dihydroxypoly (dimethylsiloxane) is particularly preferred.

  As such a silanol group-terminated polydiorganosiloxane, for example, one synthesized by hydrolysis and polycondensation of dimethyldichlorosilane is used. If desired, it was synthesized by ring-opening polymerization of the corresponding cyclic siloxane oligomer in the presence of an acidic catalyst such as sulfuric acid or an alkaline catalyst such as potassium hydroxide or potassium silanolate with water as the end-stopper. It may be a thing.

  (B) component used for embodiment of this invention is a component required in order to emulsify (a) component in water, and is an anionic surfactant. In addition to functioning as an emulsifier, the component (b) can also function as a polymerization catalyst for the component (a) as described later. That is, the component (b) acts as a surfactant that disperses and emulsifies the silanol-terminated polydiorganosiloxane that is the component (a) in the component (c), and as a catalyst for the dehydration polycondensation reaction of the silanol group of the component (a). Can function.

  In the embodiment, the anionic surfactant of the component (b) is at least two compounds selected from polyoxyethylene alkyl ether sulfuric acid, alkyl sulfuric acid, and salts thereof.

  In these anionic surfactants, the carbon number of the alkyl group, the average number of added moles of ethylene oxide, and the like are not particularly limited, and any commercially available compound can be used. Specifically, polyoxyethylene alkyl ether sulfuric acid includes polyoxyethylene (2) octyl ether sulfuric acid, polyoxyethylene (8) decyl ether sulfuric acid, polyoxyethylene (3) lauryl ether sulfuric acid, and the like. Examples thereof include sulfuric acid, myristyl sulfuric acid, cetyl sulfuric acid, and the like, and salts thereof, that is, salt-type anionic surfactants are also included. As the types of salts, amine salts such as sodium salt, potassium salt, ammonium salt and triethanolamine are preferable from the viewpoint of emulsifying effect, and among them, triethanolamine and ammonium salt are preferable from the viewpoint of feeling during rinsing. Use is preferred.

  The component (b) as described above may be mixed with the component (a) and the component (c) in the form of an acid and used for emulsification, but after being used as an emulsifier in the form of a water-soluble salt or a neutralized salt. The acid type (b) component can be generated in the reaction system by adding an acid to function as an emulsion polymerization catalyst. In particular, when the emulsification is carried out at a high temperature or when the temperature rises during emulsification, it is preferable that the component (b) is first acted as a surfactant and then acted as a polymerization catalyst. When configured in this manner, the emulsion polymerization conditions are easy to control, the emulsion state is good, the high molecular weight polyorganosiloxane does not float during storage, and the emulsion has excellent stability. can get. Furthermore, the content of the cyclic siloxane oligomer in the obtained emulsion can be further reduced.

  In embodiment of this invention, it is preferable to use together 2 or more types of said (b) anionic surfactant, and, when using 2 types of anionic surfactant together, the compounding ratio is 1: 20- It is in the range of 20: 1, preferably in the range of 1:10 to 10: 1. Outside the range of 1:20 to 20: 1, the stability is deteriorated and sufficient effects cannot be obtained. Moreover, the mixture ratio in the case of using together 3 types is the range of (1-20) :( 1-20) :( 1-20), Preferably (1-10) :( 1-10) :( 1-10).

  The amount of the component (b) used may be any amount as long as the component (b) is used as the surfactant and the polymerization catalyst in consideration of the purpose of the present invention. Can be. A typical example is as follows. That is, the total amount of the anionic surfactant of the acid type or a salt thereof is preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of component (a) in terms of acid. 1 to 50 parts by weight is more preferable, and 2 to 10 parts by weight is particularly preferable. If it is less than 0.5 part by weight, the stability of the emulsion may be deteriorated and separated, and if it exceeds 100 parts by weight, the emulsion may be thickened and fluidity may be deteriorated.

  In the embodiment of the present invention, a polymerization catalyst may be used. The polymerization of component (a) belongs to the category of polymerization involving dehydration of terminal hydroxyl groups, that is, polycondensation. Polymerization catalyst components include inorganic acids and organic acids. Inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, sulfamic acid, and the like. Examples of the organic acid include carboxylic acid (including formic acid), sulfonic acid, and sulfuric monoester. Among organic acids, sulfonic acid and / or sulfuric acid monoester includes those having a large contribution of the organic group, and therefore having surface activity. When an anionic surfactant having a catalytic action is used as the component (b), at least a part of the polymerization catalyst can be omitted.

  As described above, a polymerization catalyst can be obtained by changing the salt type anionic surfactant added as an emulsifier to an acid type anionic surfactant by adding an acid. In this case, the acid added after emulsification has a function of converting at least a part of the salt type anionic surfactant into the acid type and acting as a polymerization catalyst. Examples of such acids include sulfuric acid, hydrochloric acid, phosphoric acid, formic acid and the like. Sulfuric acid and hydrochloric acid are preferred because they themselves function as a catalyst for the dehydration polycondensation reaction of the silanol group of component (a) and a high polymerization rate can be obtained even at low temperatures. Thus, when using an acid together, the usage-amount of the acid is not specifically limited, However, 0.05-10 weight part is preferable with respect to 100 weight part of (a) component, 0.1-5 weight part is More preferred.

  The water (c) is a medium in which the component (a) is dispersed and emulsified. The amount of component (c) used is 30 to 1,000 parts by weight with respect to 100 parts by weight of component (a), such that the concentration of component (a) in the emulsion is 10 to 70% by weight. Preferably there is. Since the emulsion of the embodiment has good stability at a high concentration, the amount of the component (c) used is such that the concentration of the component (a) in the emulsion is 40 to 70% by weight. Is particularly preferred. As a medium in which component (a) is dispersed, various solvents such as aliphatic hydrocarbons, aromatic hydrocarbons, and cyclic siloxanes may be included in addition to water as component (c). However, it is desirable not to contain these solvents before emulsion polymerization, that is, to use water containing no solvent.

  The component (d), polyethylene glycol or a derivative thereof, is blended as an admixture of the (b) anionic surfactant and (e) the cationic surfactant. One or more selected from polyethylene glycol having a molecular weight of 200 to 3,000 or polyethylene glycol glyceryl ether is used. A more preferable molecular weight is in the range of 400 to 2,000.

  (D) Although the compounding quantity of a component is not specifically limited, The quantity used as 0.5-100 weight part with respect to 100 weight part of (a) component is preferable, 1-50 weight part is more preferable, 2-10 weight part Is particularly preferred. If the amount is less than 0.5 parts by weight, the emulsion may have poor stability and may be separated. If the amount exceeds 100 parts by weight, the emulsion may be thickened and the fluidity may be deteriorated.

  The cationic surfactant as the component (e) is not particularly limited, but a monoalkyltrimethylammonium halide or dialkyldimethylammonium halide having an alkyl group having 8 to 30 carbon atoms, preferably 12 to 28 carbon atoms. Etc. are preferable. Particularly preferred cationic surfactants include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, polyoxyethylene (15) cocoalkylammonium chloride, distearyldimethylammonium chloride and the like.

  Although the compounding quantity of (e) component is not specifically limited, 0.5-50 weight part is preferable with respect to 100 weight part of (a) component, and 1-10 weight part is more preferable. If the amount is less than 0.5 part by weight, the fingering property at the time of rinsing and drying is not sufficiently improved, and if it exceeds 50 parts by weight, the emulsion may be thickened and the fluidity may be deteriorated.

  Regarding the blending order, both the component (d) and the component (e) were subjected to emulsion polymerization using the component (a), the component (b), and the component (c), and then the polyorgano obtained by emulsion polymerization. It is preferable to add and blend in the siloxane emulsion.

  In the embodiment of the present invention, the (A) silicone emulsion is obtained by polymerizing the component (a) with respect to the emulsion containing the components (a) to (c), and further comprising the components (d) and (e). However, if the emulsion before polymerization contains the components (a) to (c) as essential components, other aids are provided so long as the gist of the present invention is not impaired. The target component may be dissolved or dispersed. Other auxiliary components may be added to the emulsion before or during polymerization, or may be added to the emulsion after polymerization. As long as the polymerization of the component (a) is not inhibited, it is preferable to add these components before or during the polymerization because the dispersibility is improved.

  The (A) silicone emulsion of the embodiment can be produced as follows. That is, first, the polydiorganosiloxane in which the molecular chain terminal as the component (a) is blocked with a silanol group, the anionic surfactant as the component (b), and (c) water are premixed. The order of mixing is arbitrary. For example, the component (b) is mixed and dissolved in the component (c) in a stirring tank, and the component (a) is added to the mixture while stirring. Next, the mixture is passed through an emulsifier such as a homogenizer, a colloid mill, a line mixer, or a sonolator. It is preferable to coarsely emulsify using an emulsifier such as a homomixer, a colloid mill, or a line mixer, and further emulsify through an emulsifier such as a pressure homogenizer or an ultrasonic homogenizer. If necessary, water is further added to uniformly emulsify and disperse. When a salt is used as the component (b) during emulsification, an acid is added and dispersed to produce an alkylsulfuric acid as the component (b). These function as a catalyst for emulsion polymerization, and the polymerization catalyst can be formed “in situ” as described above.

  When the stirring is continued, a high molecular weight polyorganosiloxane is synthesized by a polycondensation reaction of the silanol group at the molecular chain terminal of the component (a), and an emulsion containing this is obtained. In order to obtain a polyorganosiloxane having a higher degree of polymerization and reduce the cracking reaction, the lower the polycondensation reaction temperature, the better. On the other hand, since the stability of the resulting emulsion is impaired when it is excessively cooled, the preferable condensation conditions in total are the emulsion freezing point to 30 ° C., more preferably the emulsion freezing point to 20 ° C., and more preferably the emulsion. It is 2 to 48 hours at a freezing point to 20 ° C. If necessary, the reaction may be performed over a longer time. Particularly preferred condensation conditions are from the emulsion freezing point to less than 5 ° C.

  In the emulsion polymerization of a silicone emulsion, it is known that a higher molecular weight can be obtained by lowering the temperature of the polycondensation reaction. However, in order to increase the polymerization rate and increase the efficiency of the polymerization reaction, heating is performed at the beginning of the reaction, and under such conditions, it is not possible to reduce the amount of low molecular weight siloxane oligomer in the resulting emulsion. It was difficult. In the embodiment of the present invention, the amount of the low molecular weight siloxane oligomer is reduced by performing the reaction from the initial stage to the end of the polycondensation reaction, preferably at a temperature of the emulsion freezing point to 30 ° C. A siloxane emulsion is obtained. Furthermore, by setting the emulsion freezing point to less than 5 ° C., a polyorganosiloxane emulsion having a higher molecular weight and a smaller particle size, for example, an average particle size of 280 nm or less can be obtained.

  When the desired degree of polymerization is reached, an alkaline substance is added to neutralize the acid type anionic surfactant as a catalyst and the added acid to stop the polymerization reaction. Examples of the alkaline substance include inorganic substances such as sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, potassium carbonate, ammonium carbonate and potassium acetate, and amines such as triethanolamine.

  A stable emulsion containing a high-molecular-weight polyorganosiloxane is obtained by adding and blending polyethylene glycol or a derivative thereof as component (d) and a cationic surfactant as component (e) to the emulsion thus obtained. Can be obtained. The polyorganosiloxane obtained by emulsion polymerization has a silanol group at the molecular chain terminal, and the viscosity at 25 ° C. is preferably 10 to 2,000 Pa · s, more preferably 100 to 1,500 Pa · s.

  Depending on the purpose, a polyorganosiloxane having a triorganosilyl group at the molecular chain terminal, for example, a trimethylsilyl group, and a viscosity at 25 ° C. of 10 to 2,000 Pa · s can be efficiently added by adding a terminal terminator described later. Can also be obtained.

  (A) The amount of the cyclic siloxane oligomer contained in the silicone emulsion is largely governed by the content of the cyclic siloxane oligomer in the component (a) used as a starting material, and is 1.0% by weight or less by-produced during emulsion polymerization. The cyclic siloxane oligomer is only added. Therefore, the content of the cyclic siloxane oligomer in the polyorganosiloxane after the emulsion polymerization is preferably 3.5% by weight or less, more preferably 1.0% by suppressing the content in the component (A) as described above. % Or less.

  In the embodiment of the present invention, in order to improve the stability of the (A) silicone emulsion, in addition to the component (b), one or more other anionic and / or nonionic surfactants are added. In addition, it may be blended at any other stage during the first emulsification or after the polycondensation reaction of component (a). As such other anionic surfactants used in combination with the component (b), polyoxyethylene alkyl ether carboxylates, N-acyl amino acid salts, N-acyl taurates and the like are exemplified.

  The amount of the anionic surfactant arbitrarily blended in this way is within a range not impairing the catalytic ability of the component (b) when blended before the emulsion polymerization using the component (b) as a catalyst. Specifically, it is 5 times (by weight) or less of the component (b) or a salt thereof initially blended.

  In addition, to terminate the silanol group at the molecular end of the high molecular weight polyorganosiloxane obtained by emulsion polymerization with a stable triorganosilyl group, or to terminate the average polymerization degree of the polyorganosiloxane to a desired value. As an agent, a small amount of a siloxane oligomer having a triorganosilyl group can be added during emulsification. When the triorganosilyl group is a trimethylsilyl group, examples of the siloxane oligomer to be added include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and the like, and an acidic catalyst in a temperature range from an emulsion freezing point to 30 ° C. Hexamethyldisiloxane is preferred because the reaction rate is excellent and the remaining part can be easily removed by volatilization when added excessively. In addition, a siloxane oligomer having a vinyl group such as 1,3-divinyltetramethyldisiloxane is added, a vinyldimethylsilyl group is introduced as a triorganosilyl group at the molecular end, and the reactivity of the vinyl group is utilized. Or an emulsion of a crosslinkable high molecular weight base polymer.

  In order to form a firm film by using the polyorganosiloxane emulsion obtained by emulsion polymerization for the surface treatment of hair, methyldimethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) in order to give such a reactive silane and good slipperiness and flexibility to the hair surface. Like -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltris (trimethylsiloxy) silane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane Reactive silanes during emulsion polymerization Others may be added in a small amount after the emulsion polymerization. Furthermore, you may add the antiseptic | preservative for preserve | saving an emulsion, an antifungal agent, the rust preventive agent for preventing the corrosion of a metal, etc.

  In the second embodiment of the present invention, the (B) high-melting point aliphatic compound to be blended with the silicone emulsion as the component (A) has a melting point of 25 ° C. or higher. Selected from derivatives, and mixtures thereof.

  (B) Examples of high melting point aliphatic compounds are the International Cosmetic Ingredient Dictionary, 5th edition, 1993, and CTFA (The Cosmetic, Toiletry, and Fragrance Association, Inc.) Cosmetic Ingredient Handbook, Second Edition, 1992, but is not limited thereto.

  Useful fatty alcohols are those having 14 to 30, preferably 16 to 22 carbon atoms. These aliphatic alcohols are saturated and are preferably linear or branched alcohols. Examples of aliphatic alcohols include, but are not limited to, cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof.

  Fatty acids include those having 10 to 30, preferably 12 to 22, more preferably 16 to 22 carbon atoms. These fatty acids can be saturated and have a linear or branched carbon skeleton. Dibasic acids, tribasic acids and higher polybasic acids are included, and salts of these fatty acids are also included. Examples include, but are not limited to, lauric acid, palmitic acid, stearic acid, behenic acid, sebacic acid, and mixtures thereof.

  Examples of the aliphatic alcohol derivative and the fatty acid derivative include the alkyl ether of the aliphatic alcohol, the alkoxylated aliphatic alcohol, the alkyl ether of the alkoxylated aliphatic alcohol, the ester of the aliphatic alcohol, and the fatty acid of the compound having an esterifiable hydroxy group. Esters, hydroxy substituted fatty acids, and mixtures thereof.

  Specific examples of fatty alcohol derivatives and fatty acid derivatives include methyl stearyl ether and the like; ceteth series such as ceteth-1 to ceteth-45, and ethylene glycol ether of cetyl alcohol in which the numerical designation represents the number of ethylene glycol moieties; Steerless series such as -1 to 10 where the numerical designation represents the number of ethylene glycol moieties; ethylene glycol ethers of steareth alcohol; ceteares 1 to 10, ethylene glycol ethers of cetealess alcohol, ie cetyl alcohol and stearyl alcohol A mixture of aliphatic alcohols mainly containing the number of ethylene glycol moieties; the ceteth, steareth, and ceteares compounds having 1 to 30 carbon atoms. Polyoxyethylene ether of behenyl alcohol; ethyl stearate, cetyl stearate, cetyl palmitate, stearyl stearate, myristyl myristate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether Stearate, ethylene glycol monostearate, polyoxyethylene monostearate, polyoxyethylene distearate, propylene glycol monostearate, propylene glycol distearate, trimethylolpropane distearate, sorbitan stearate, polyglyceryl stearate, Glyceryl monostearate, glyceryl distearate, glyceryl tristearate and it Mixtures of the like.

  High melting point fatty compounds which are single compounds of high purity are preferred, and single compounds of pure fatty alcohols selected from the group consisting of pure cetyl alcohol, stearyl alcohol and behenyl alcohol are particularly preferred.

  In the present specification, the term “pure” means that the compound has a purity of at least 90%, preferably at least 95%. A single compound of high purity exhibits a good rinsing effect during rinsing.

  Commercially available products of such high melting point aliphatic compounds include KONOL series manufactured by Shin Nippon Rika Co., Ltd., NAA series cetyl alcohol, stearyl alcohol, and behenyl alcohol manufactured by Nippon Oil & Fats Co., Ltd., 1- Pure behenyl alcohol from 1-DOCOSANOL, NEO-FAT from Akzo, USA, HYSTRENE from Witco Corp., and Italian baby (Vevy) DERMA (DERMA).

  The (B) high melting point aliphatic compound having a melting point of 25 ° C. or higher is 0.1 to 15% by weight in the hair cosmetic composition, preferably 0.5 to 10% by weight, and more preferably 0.75 to 0.75%. It is contained at a ratio of 5% by weight. And it provides gel and network structure together with the cationic conditioning agent described later, and various conditioning effects such as smooth and smooth feel on wet hair, softness and moisture on dry hair, and suppression of hair splashing. Demonstrate.

  In the second embodiment, the cationic conditioning agent as component (C) is selected from the group consisting of cationic surfactants, cationic polymers, and mixtures thereof. These (C) cationic conditioning agents are contained in the hair cosmetic composition in an amount of 0.1 to 10% by weight, preferably 0.25 to 8% by weight, more preferably 0.5 to 3% by weight. .

As the cationic surfactant, those represented by the following general formula (1) are preferably used.

In the formula, at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is an aliphatic group having 8 to 30 carbon atoms or an aromatic group having 22 or less carbon atoms, an alkoxy group, Selected from a polyoxyalkylene group, an alkylamide group, a hydroxyalkyl group, an aryl group or an alkylaryl group, the rest being independently an aliphatic group having 1 to 22 carbon atoms, or 22 or fewer carbon atoms Selected from an aromatic group, an alkoxy group, a polyoxyalkylene group, an alkylamide group, a hydroxyalkyl group, an aryl group or an alkylaryl group having X is a salt selected from halogen (eg, chloride, bromide), acetate, citric acid, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkylsulfate and alkylsulfonate radicals, etc. Forming anions.

Aliphatic groups can contain other groups such as ether linkages and amino groups in addition to carbon and hydrogen atoms. Furthermore, long-chain aliphatic groups such as those having 12 or more carbon atoms may be saturated or unsaturated. It is preferred that R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from alkyl groups having 1 to 22 carbon atoms.

  Specific examples of useful cationic surfactants include materials having the following CTFA names: quaternium-8, quaternium-14, quaternium-18, quaternium-18 mesosulfate, quaternium-24, and mixtures thereof, It is not limited to these.

  Among the cationic surfactants represented by the general formula (1), those containing at least one alkyl chain having at least 16 carbon atoms in the molecule are preferable. Examples of such cationic surfactants are: for example, trade name INCROQUAT TMC-80 manufactured by Croda, or behenyltrimethylammonium chloride available as ECONOL TM22 from Sanyo Kasei. Cetyltrimethylammonium chloride available under the trade name CA-2350 from Nikko Chemicals; hydrogenated tallow alkyltrimethylammonium chloride, dialkyl (14-18) dimethylammonium chloride, ditallowalkyldimethylammonium chloride, two Hydrogenated tallow alkyldimethylammonium chloride, distearyldimethylammonium chloride, dicetyldimethylammonium chloride, di (behenyl / arachidyl) dimethylammonium Lorido, dibehenyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, stearylpropylene glycol phosphate dimethylammonium chloride, stearoylamidopropyldimethylbenzylammonium chloride, stearoylamidopropyldimethyl (myristyl acetate) ammonium chloride, and N- (stearoylcholaminoformylmethyl) ) Pyridinium chloride and the like, but not limited thereto.

Preferred cationic surfactants contain one or more aromatic, ether, ester, amide, or amino moieties in which at least one of the substituents is present as a substituent or bond in the radical chain, and R ^At least one of the ^{3 to} R ⁶ groups is an alkoxy group (preferably an alkoxy group having 1 to 3 carbon atoms), a polyoxyalkylene group (preferably a polyoxyalkylene group having 1 to 3 carbon atoms), an alkylamide group, or a hydroxyalkyl group. , Alkyl ester groups, and hydrophilically substituted cationic surfactants containing one or more hydrophilic moieties selected from combinations thereof. The hydrophilically substituted cationic surfactant preferably contains 2 to 10 non-ionic hydrophilic moieties located within the above range. Preferred cationic surfactants that are hydrophilically substituted include those represented by the following formulas (2) to (8):

式中、ｐは８〜２８、ｘ＋ｙは２〜４０の数を表し、Ｚ¹は短鎖アルキル基、好ましくは炭素数１〜３のアルキル基、より好ましくはメチル基、あるいは（ＣＨ_２ＣＨ_２Ｏ）_ｚＨである。ｘ＋ｙ＋ｚは６０以下、Ｘは前記塩形成アニオンである。

In the formula, p represents 8 to 28, x + y represents a number of 2 to 40, Z ¹ represents a short-chain alkyl group, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, or (CH ₂ CH ₂ O) _zH . x + y + z is 60 or less, and X is the salt-forming anion.

式中、ｑは１〜５の数、Ｒ^７、Ｒ^８およびＲ^９のうち１つ以上は、それぞれ独立して炭素数１〜３０のアルキル基であり、その他はＣＨ_２ＣＨ_２ＯＨであり、Ｒ^１０、Ｒ^１１およびＲ^１２のうち１つまたは２つはそれぞれ炭素数１〜３０のアルキル基であり、その他はＣＨ_２ＣＨ_２ＯＨである。Ｘは前記塩形成アニオンである。

In the formula, q is a number of 1 to 5, one or more of R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 30 carbon atoms, and the others are CH ₂ CH ₂ OH. , R ¹⁰ , R ¹¹ and R ¹² are each an alkyl group having 1 to 30 carbon atoms, and the other is CH ₂ CH ₂ OH. X is the salt-forming anion.

In each of the formulas (4) and (5), Z ² is an alkyl group, preferably a methyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and Z ³ is a short-chain hydroxyalkyl group, preferably a hydroxymethyl group or A hydroxyethyl group, and r and s are each an integer of 2 to 4, preferably 2 to 3, more preferably 2. R ¹³ and R ¹⁴ are each a substituted or unsubstituted hydrocarbon, preferably an alkyl or alkenyl group having 12 to 20 carbon atoms, and X is the salt-forming anion.

式中、Ｒ^１５はヒドロカルビル基、好ましくは炭素数１〜３のアルキル基より好ましくはメチル基であり、Ｚ^４およびＺ^５はそれぞれ短鎖ヒドロカルビル基、好ましくは炭素数２〜４のアルキル基またはアルケニル基より好ましくはエチル基であり、ａは２〜４０好ましくは７〜３０の数、Ｘは前記の塩形成アニオンである。

In the formula, R ¹⁵ is a hydrocarbyl group, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and Z ⁴ and Z ⁵ are each a short-chain hydrocarbyl group, preferably an alkyl group having 2 to 4 carbon atoms, or An alkenyl group is more preferably an ethyl group, a is a number of 2 to 40, preferably 7 to 30, and X is a salt-forming anion.

式中、Ｒ^１６およびＲ^１７は、それぞれ炭素数１〜３のアルキル基より好ましくはメチル基、Ｚ^６は炭素数１２〜２２のヒドロカルビル基、アルキルカルボキシ基またはアルキルアミド基である。Ａはたんぱく質、好ましくはコラーゲン、ケラチン、乳たんぱく質、シルク、大豆たんぱく質、小麦たんぱく質、またはそれらの加水分解型であり、Ｘは前記塩形成アニオンである。

In the formula, each of R ¹⁶ and R ¹⁷ is more preferably a methyl group than an alkyl group having 1 to 3 carbon atoms, and Z ⁶ is a hydrocarbyl group, alkylcarboxy group or alkylamide group having 12 to 22 carbon atoms. A is a protein, preferably collagen, keratin, milk protein, silk, soy protein, wheat protein, or a hydrolyzed form thereof, and X is the salt-forming anion.

式中、ｂは２または３、Ｒ^１８およびＲ^１９は、それぞれ炭素数１〜３のヒドロカルビル基好ましくはメチル基であり、Ｘは前記塩形成アニオンである。

In the formula, b is 2 or 3, R ¹⁸ and R ¹⁹ are each a hydrocarbyl group having 1 to 3 carbon atoms, preferably a methyl group, and X is the salt-forming anion.

  Examples of useful hydrophilically substituted cationic surfactants include the following CTFA names: quaternium-16, quaternium-26, quaternium-27, quaternium-30, quaternium-33, quaternium-43, quaternium- 52, quaternium-53, quaternium-56, quaternium-60, quaternium-61, quaternium-62, quaternium-70, quaternium-71, quaternium-72, quaternium-75, quaternium-76 hydrolyzed collagen, quaternium-77, quaternium -78, quaternium-79 hydrolyzed collagen, quaternium-79 hydrolyzed keratin, quaternium-79 hydrolyzed milk protein, quaternium-79 hydrolyzed silk, quaternium-79 hydrolyzed soy protein And Quaternium -79 hydrolyzed wheat protein, quaternium -80, Quaternium -81, Quaternium -82, Quaternium -83, and materials and mixtures thereof having a quaternium -84 include, but are not limited to.

  Particularly preferred hydrophilically substituted cationic surfactants include dialkylamidoethylhydroxyethylmonium salts, dialkylamidoethyldimonium salts, dialkyloethylethylhydroxyethylmonium salts, dialkyloylethyldimonium salts, and These mixtures are mentioned.

  These are commercially available under the following trade names: Witco Chemical's VARISOFT 110, VariQuat K1215 and 638, McIntyre's MacPro KLP, MacPro WLW, MacPro MLP, MacPro NSP, MacPro NLW, MacPro WWP, MacPro NLP, MacPro SLP, Akzo's Etquad 18/25, Etquad 0 / 12PG, Etquad C / 25, Etquad S / 25, Etduqua, Such as Henkel's DEHYQUA SP and ICI America's ATLAS G265.

Primary, secondary, and tertiary aliphatic amine salts are suitable cationic surfactants. The alkyl group of such amines preferably has 12 to 22 carbon atoms and can be substituted or unsubstituted. Amidoamines represented by the general formula: R ²⁰ CONH (CH ₂ ) ₁ N (R ²¹ ) ₂ are particularly useful. In the formula, R ²⁰ represents a residue of a fatty acid having 11 to 24 carbon atoms, R ²¹ represents an alkyl group having 1 to 4 carbon atoms, and 1 is an integer of 1 to 4.

  Preferred amidoamines include stearoamidopropyldimethylamine, stearoamidopropyldiethylamine, stearoamidoethyldiethylamine, stearoamidoethyldimethylamine, palmitoamidopropyldimethylamine, palmitoamidopropyldiethylamine, palmitoamidoethyldiethylamine, Palmitoamidoethyldimethylamine, behenamidopropyldimethylamine, behenamidopropyldiethylamine, behenamidoethyldiethylamine, behenamidoethyldimethylamine, arachidoamidopropyldimethylamine, arachidoamidopropyldiethylamine, arachidoamidoethyldiethylamine, arachidoamidoethyldimethylamine And mixtures thereof. More preferably, stearoamidopropyldimethylamine, stearoamidoethyldiethylamine, and mixtures thereof are mentioned.

  Preferred amidoamines are acids selected from the group consisting of L-glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, L-glutamic acid hydrochloride, tartaric acid and mixtures thereof, particularly preferably L-glutamic acid, Partly quaternized with lactic acid, hydrochloric acid and mixtures thereof. The molar ratio of amidoamine to acid is preferably 1: 0.3 to 1: 1, more preferably 1: 0.5 to 1: 0.9.

  A cationic polymer useful in the second embodiment is described. In the present invention, the term “polymer” includes a substance produced by polymerization of one kind of monomer and a substance produced by two or more kinds of monomers.

  The cationic polymer is preferably a water-soluble cationic polymer. A “water-soluble” cationic polymer is sufficiently soluble in water to form a substantially transparent solution in water at 25 ° C. (distilled or equivalent water) at a concentration of 0.1%. Means polymer. Preferred cationic polymers are sufficiently soluble to form a substantially clear solution at a concentration of 0.5%, more preferably at a concentration of 1.0%.

  Also, the cationic polymer of embodiments has an average molecular weight of at least 5,000, typically at least 10,000 and less than 10,000.000. A preferred average molecular weight is 100,000 to 2,000,000. It has a cationic nitrogen-containing moiety such as a quaternary ammonium moiety and / or a cationic amino moiety.

  The cationic charge density is preferably 0.1 meq / g or more, more preferably 0.5 meq / g or more, still more preferably 1.1 meq / g, and even more preferably 1.2 meq / g or more. The cationic charge density of the cationic polymer can be measured by the Kjeldahl method. Since the charge density of the amino-containing polymer varies depending on the pH and the isoelectric point of the amino group, the charge density is set within the above range at the pH of the desired application.

  Any anion counterion can be utilized for the cationic polymer as long as the water solubility criteria is met. Suitable counterions include halides (eg, Cl, Br, I or F compounds, preferably Cl, Br or I compounds), sulfates and methyl sulfates, although others can be used.

  The cationic nitrogen-containing moiety is present as a substituent on all monomer units of the cationic polymer. Thus, the cationic polymer contains quaternary ammonium or cationic amine substituted monomer units, and other non-cationic unit copoly or polymers referred to as spacer monomer units. Such polymers are already known in the art and are described, for example, in the International Cosmetic Ingredient Dictionary, 3rd edition, 1982.

  Suitable cationic polymers include acrylamide, methacrylamide, alkyl acrylamide and dialkyl acrylamide, alkyl methacrylamide and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and water-soluble spacer monomers such as vinyl pyrrolidone, cationic amines or Mention may be made of copolymers with vinyl monomers having secondary ammonium functional groups.

  The alkyl-substituted monomer and dialkyl-substituted monomer preferably have an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Other suitable spacer monomers include vinyl esters, vinyl alcohol obtained by hydrolysis of polyvinyl acetate, maleic anhydride, propylene glycol and ethylene glycol.

  The cationic amine can be a primary, secondary or tertiary amine. Secondary and tertiary amines are preferred, and tertiary amines are particularly preferred.

Amine-substituted vinyl monomers can be polymerized in the amine form and then optionally converted to ammonium by a quaternization reaction. The amine can be quaternized in the same way after the polymer is formed. For example, a tertiary amine functional group can be quaternized by reacting with a salt of formula R ⁰ X. Here, R ⁰ is a short-chain alkyl group, preferably an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and X is an anion that forms a water-soluble salt with quaternized ammonium. is there.

  Suitable cationic amino monomers and quaternary ammonium monomers include, for example, dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkylmethacryloxyalkylammonium salt, trialkylacryloxyalkyl Ammonium salts, vinyl compounds substituted with diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers and quaternized pyrrolidones having cyclic cation nitrogen-containing rings such as pyridinium, imidazolium and quaternized pyrrolidones such as alkyl vinyl imidazolium, alkyl vinyl Examples include pyridinium and alkyl vinyl pyrrolidone salts.

  The alkyl part of these monomers is preferably a lower alkyl group such as an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. Suitable amine substituted vinyl monomers include dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, dialkylaminoalkyl acrylamides, and dialkylaminoalkyl methacrylamides. Here, the alkyl group is preferably a hydrocarbyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

  The cationic polymer can comprise a mixture of monomer units derived from amines and / or quaternary ammonium substituted monomers and / or compatible spacer monomers.

  Suitable cationic polymers include, for example, copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (eg, chloride) (referred to as polyquaterium-16 in “CTFA”), BASF Wyandotte (BASF Wyandotte Corp., Parsippany, NJ, USA) under the trade name LUVIQUAT (e.g. RUQUIQUAT FC 370); copolymer of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate ("CTFA") In the trade name of GAFQUAT (for example, Gafquat 755N) commercially available from Gaf Corporation (Wayne, NJ, USA); dimethyldiallylammonium chloride; Homopolymers and cationic diallyl quaternary ammonium containing polymers, including acrylamide and dimethyldiallylammonium chloride copolymer (referred to in the “CTFA” industry as polyquaternium 6 and polyquaternium 7); US Pat. No. 4,009 , 256 amino acid ester mineral acid salts of unsaturated carboxylic acid homopolymers and copolymers having 3 to 5 carbon atoms.

  Other cationic polymers that can be used include polysaccharide polymers such as cationic cellulose derivatives and cationic starch derivatives. Suitable cationic polysaccharide polymers include those having the following formula:

In the formula, A is an anhydroglucose residue such as a starch anhydroglucose residue or a cellulose anhydroglucose residue, and R is an alkyleneoxyalkylene group, a polyoxyalkylene group, a hydroxyalkylene group, or a combination thereof. R ²² , R ²³ and R ²⁴ are each independently selected from an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group, or an alkoxyaryl group, each group having 18 or fewer carbons. The total number of carbons in each cation moiety (that is, the total number of carbon atoms of R ²² , R ²³ and R ²⁴ ) is preferably 20 or less. X is an anion counter ion as described above.

  Cationic cellulose is commercially available from Amerchol Corp. (Edison, NJ, USA) as a salt obtained by reacting hydroxyethylcellulose with a trimethylammonium substituted epoxide under the trade name polymer JR and LR series. In this case, it is called polyquaternium 10. Other types of cationic cellulose include polymeric quaternary ammonium salts reacted with hydroxyethyl cellulose and lauryldimethylammonium substituted epoxide, what is called polyquaternium 24 in the “CTFA” industry. These substances are commercially available from Amercor as trade name polymer LM-200.

  Other cationic polymers include cationic guar rubber derivatives such as guar hydroxypropyltrimonium chloride (trade name Jaguar® series commercially available from Celanese Corp.). Also included are quaternary nitrogen-containing cellulose ethers (such as those described in US Pat. No. 3,962,418), and etherified celluloses and starches (such as those described in US Pat. No. 3,958,581). It is done.

  In the second embodiment of the present invention, water as component (D) is used as a dispersion medium for (A) silicone emulsion, (B) high melting point aliphatic compound (melting point 25 ° C. or higher) and (C1) cation conditioning agent. Used. (D) A uniform hair cosmetic composition can be obtained by blending water.

  The hair cosmetic composition of the third embodiment of the present invention comprises 0.01 to 20% by weight of the (A) silicone emulsion, 5 to 50% by weight of (E) a detersive surfactant, 1 to 20% by weight of (C2) conditioning agent and (D) water are contained.

  In the third embodiment, (E) the detersive surfactant is intended to give the composition a detergency, and is an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a zwitterionic surfactant. And a surfactant selected from agents and mixtures thereof.

  The term “detergent surfactant” is intended to distinguish these from surfactants that mainly emulsify the surfactant, ie, surfactants that provide emulsification benefits and have low detergency. ing. However, since many surfactants have both detergency and emulsifying properties, emulsifying surfactants are not excluded from the detersive surfactants of the present invention. Further, the detersive surfactant of the component (B) may be the same as or different from the surfactant contained in the silicone emulsion as the component (A).

  This (E) detersive surfactant is contained in a proportion of 5 to 50% by weight, preferably 8 to 30% by weight, more preferably 10 to 25% by weight of the hair cosmetic composition.

  In the third embodiment, a known conditioning agent can be used as the (C2) conditioning agent. Suitable (C2) conditioning agents include (A) cationic surfactants, water-soluble cationic polymers, fatty compounds, non-volatile dispersion silicones, hydrocarbons, proteins, and There is a mixture of them. These conditioning agents are contained in a proportion of 0.1 to 20% by weight of the hair cosmetic composition.

  Water as component (D) is used as a dispersion medium for the aforementioned (A) silicone emulsion, (E) detersive surfactant, and (C2) conditioning agent. (D) A uniform hair cosmetic composition such as a shampoo composition can be obtained by blending water.

  According to the hair cosmetic composition of the embodiment of the present invention, it exhibits an excellent conditioning effect on the hair, improves the squeaky feeling during rinsing, and imparts excellent fingering properties to dry hair. be able to.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. In these examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. Moreover, the viscosity of the high molecular weight polyorganosiloxane contained in the emulsion obtained by emulsion polymerization and the content of the cyclic siloxane oligomer were measured as follows.

[Polymer viscosity]
200 parts of isopropyl alcohol was added to 100 parts of the obtained emulsion, and the mixture was sufficiently stirred and allowed to stand for 24 hours to separate into two layers. Then, only the oil layer was transferred to a petri dish and placed in an oven at 150 ° C. for 45 minutes. . Thus, the remaining isopropyl alcohol and water were completely evaporated to obtain polyorganosiloxane. This was cooled to 25 ° C., and the viscosity at this time was measured using a rotational viscometer.

[Content of cyclic siloxane oligomer]
Five parts by volume of the emulsion was collected, and 50 parts by volume of methanol, 100 parts by volume of n-hexane and 50 parts by volume of water were added thereto, and the mixture was shaken vigorously and left to stand for 24 hours to separate into two layers. Thereafter, the n-hexane layer was collected with a microsyringe and subjected to gas chromatography to quantify the cyclic siloxane oligomer in the sample. From this value and the amount of polyorganosiloxane obtained by volatilizing n-hexane separately from the n-hexane layer, the content of the cyclic siloxane oligomer in the polyorganosiloxane was calculated.

{Preparation of emulsion}
(Synthesis Example 1)
2 parts of polyoxyethylene (3) lauryl ether triethanolamine sulfate and 3 parts lauryl sulfate triethanolamine were uniformly dispersed in 455 parts of deionized water. To this, 500 parts of α, ω-dihydroxypoly (dimethylsiloxane) having a viscosity of 0.085 Pa · s containing 1.3% of a cyclic siloxane oligomer was added, premixed by stirring, and then a pressure homogenizer (pressure 500 kgf / cm ² ) twice to obtain an emulsion containing α, ω-dihydroxypoly (dimethylsiloxane).

  Next, 0.5 part of sulfuric acid was added to the emulsion, and the reaction was performed at 25 ° C. for 8 hours with stirring. Thereafter, the polymerization reaction was stopped by adding dropwise a 10% aqueous sodium carbonate solution until the pH reached 7 while continuing the stirring, and an emulsion containing polyorganosiloxane was obtained. To 100 parts of this emulsion, 2 parts of polyethylene glycol (PEG) having a molecular weight of 600 was added and dispersed uniformly, and then 2 parts of stearyltrimethylammonium chloride was further added and dispersed uniformly to obtain an emulsion (E-1). .

  The average particle size of the polyorganosiloxane in this emulsion (E-1) was 0.17 μm, the viscosity (polymer viscosity) was 950 Pa · s, and the content of the cyclic siloxane oligomer was 1.6%.

(Synthesis Example 2)
Polyoxyethylene (3) lauryl ether 2 parts triethanolamine sulfate and 3 parts ammonium lauryl sulfate were uniformly dispersed in 455 parts deionized water. To this, 500 parts of α, ω-dihydroxypoly (dimethylsiloxane) having a viscosity of 0.085 Pa · s containing 1.3% of a cyclic siloxane oligomer was added, premixed by stirring, and then a pressure homogenizer (pressure 500 kgf / cm ² ) twice to obtain an emulsion containing α, ω-dihydroxypoly (dimethylsiloxane).

  Next, 0.5 part of sulfuric acid was added to the emulsion and reacted at 25 ° C. for 5 hours with stirring. Thereafter, the polymerization reaction was stopped by dropwise addition of a 10% aqueous sodium carbonate solution until the pH reached 7 while continuing the stirring, and an emulsion containing polyorganosiloxane was obtained. To 100 parts of this emulsion, 2 parts of PEG having a molecular weight of 1000 was added and dispersed uniformly, and then 2 parts of stearyltrimethylammonium chloride was further added and dispersed uniformly to obtain an emulsion (E-2).

  The average particle diameter of the polyorganosiloxane in this emulsion (E-2) was 0.21 μm, the polymer viscosity was 560 Pa · s, and the content of the cyclic siloxane oligomer was 1.2%.

(Synthesis Example 3)
2 parts of sodium polyoxyethylene (3) lauryl ether sulfate and 3 parts of sodium lauryl sulfate were uniformly dispersed in 455 parts of deionized water. To this, 500 parts of α, ω-dihydroxypoly (dimethylsiloxane) having a viscosity of 0.085 Pa · s containing 1.3% of a cyclic siloxane oligomer was added, premixed by stirring, and then a pressure homogenizer (pressure 500 kgf / cm ² ) twice to obtain an emulsion containing α, ω-dihydroxypoly (dimethylsiloxane).

  Next, 0.5 part of sulfuric acid was added to the emulsion and reacted at 25 ° C. for 6 hours with stirring. Thereafter, the polymerization reaction was stopped by adding dropwise a 10% aqueous sodium carbonate solution until the pH reached 7 while continuing the stirring, and an emulsion containing polyorganosiloxane was obtained. To 100 parts of this emulsion, 2 parts of PEG having a molecular weight of 600 was added and dispersed uniformly, and then 2 parts of stearyltrimethylammonium chloride was further added and dispersed uniformly to obtain an emulsion (E-3).

  The average particle size of the polyorganosiloxane in this emulsion (E-3) was 0.23 μm, the viscosity (polymer viscosity) was 1,450 Pa · s, and the content of the cyclic siloxane oligomer was 2.2%.

(Synthesis Example 4)
Emulsion (E-4) was obtained in the same manner as in Synthesis Example 3 except that PEG having a molecular weight of 600 was replaced with polyethylene glycol glyceryl ether having a molecular weight of 450. The average particle size of the polyorganosiloxane in this emulsion (E-4) was 0.17 μm, the polymer viscosity was 950 Pa · s, and the content of the cyclic siloxane oligomer was 1.6%.

(Synthesis Example 5)
2 parts of polyoxyethylene (2) sodium lauryl ether sulfate and 3 parts of sodium lauryl sulfate were uniformly dispersed in 455 parts of deionized water. To this, 500 parts of α, ω-dihydroxypoly (dimethylsiloxane) having a viscosity of 0.085 Pa · s containing 1.3% of a cyclic siloxane oligomer was added, premixed by stirring, and then a pressure homogenizer (pressure 500 kgf / cm ² ) twice to obtain an emulsion containing α, ω-dihydroxypoly (dimethylsiloxane).

  Next, 0.5 part of sulfuric acid was added to the emulsion and reacted at 25 ° C. for 8 hours with stirring. Thereafter, while continuing stirring, a 10% aqueous sodium carbonate solution was added dropwise until the pH reached 7, whereby the polymerization reaction was stopped to obtain an emulsion (E-5) containing polyorganosiloxane.

  The average particle size of the polyorganosiloxane in this emulsion (E-5) was 0.23 μm, the polymer viscosity was 2,100 Pa · s, and the content of the cyclic siloxane oligomer was 2.4%.

(Synthesis Example 6)
30 parts of dodecylbenzenesulfonic acid was uniformly dispersed in 455 parts of deionized water. To this, 500 parts of octamethylcyclotetrasiloxane was added, premixed by stirring, and then treated twice with a pressure homogenizer (pressure 500 kgf / cm ² ) to obtain an emulsion containing octamethylcyclotetrasiloxane. .

  Next, the emulsion was kept at 85 ° C. for 3 hours with stirring, and further cooled to 25 ° C. over 3 hours, and then reacted at 25 ° C. for 5 hours with stirring. Thereafter, a 10% sodium carbonate aqueous solution was added dropwise until the pH reached 7 while continuing the stirring, whereby the polymerization reaction was stopped to obtain an emulsion (E-6) containing polyorganosiloxane.

  The average particle diameter of the polyorganosiloxane in this emulsion (E-6) was 0.20 μm, the polymer viscosity was 270 Pa · s, and the content of the cyclic siloxane oligomer was 9.6%.

(Synthesis Example 7)
To 100 parts of the emulsion (E-6), 2 parts of PEG having a molecular weight of 400 are added and dispersed uniformly, and then 2 parts of stearyltrimethylammonium chloride is further added and dispersed uniformly to obtain an emulsion (E- 7) was obtained.

  The average particle diameter of the polyorganosiloxane in this emulsion (E-7) was 0.19 μm, the polymer viscosity was 270 Pa · s, and the content of the cyclic siloxane oligomer was 9.6%.

(Synthesis Example 8)
When 2 parts of ethylene glycol is added to 100 parts of the emulsion (E-5) and dispersed uniformly, 2 parts of stearyltrimethylammonium chloride is further added thereto, and a gel is formed in the emulsion. However, a good emulsion could not be obtained.

Examples 1-4, Comparative Examples 1-3 [Hair conditioner composition]
Using the silicone emulsions (E-1) to (E-7) obtained in Synthesis Examples 1 to 7, hair conditioner compositions having the compositions shown in Table 1 were prepared. And about the prepared conditioner composition, the characteristic evaluation was performed according to the method and reference | standard shown below.

[Evaluation methods]
Each of the 12 panelists dipped 10 g of 25 cm long hair in 40 ° C. water, spread 2 g of the conditioner composition on the wet hair, and rinsed with 40 ° C. water for 30 seconds after 1 minute. Subsequently, it dried with the dryer and the hair sample was created. In the hair sample preparation stage, each panelist was given a five-point score based on the following criteria: “No squeaky feeling when rinsing”, “Finger feeling after drying” and “Moist feeling after drying”. The average value was calculated.

[Evaluation criteria]
5 ... excellent 4 ... excellent 3 ... good 2 ... slightly inferior 1 ... poor evaluation results are shown in Table 1.

Examples 5-8, Comparative Examples 4-6 [Shampoo Composition]
Using the silicone emulsions (E-1) to (E-7) obtained in Synthesis Examples 1 to 7, shampoo compositions were prepared with the compositions shown in Table 2. And about the prepared shampoo composition, the characteristic evaluation was performed according to the method and reference | standard shown below.

[Evaluation methods]
Each of the 12 panelists dipped 10 g of 25 cm long hair in 40 ° C water, washed with 2 g of shampoo composition for 1 minute, rinsed with 40 ° C water for 30 seconds, and dried with a drier to make a hair sample did. At the hair sample preparation stage, each panelist was given 5 levels of “no squeaking feeling during washing and rinsing”, “feeling of fingering after drying” and “moist feeling after drying”. The score was calculated and the average value was calculated.

[Evaluation criteria]
5 ... excellent 4 ... excellent 3 ... good 2 ... slightly inferior 1 ... poor evaluation results are shown in Table 2.

  The hair cosmetic composition of the present invention exhibits an excellent effect on hair, improves the squeaky feeling during washing or rinsing, and can impart excellent fingering properties to dry hair. So it is suitable as a hair conditioner and shampoo.

Claims (5)

(A) General formula: HO [(R ¹ ) ₂ SiO] _m H (1)
(In the formula, ^{R 1} rather good even though it or different mutually identical, (1) an alkyl group having 1 to 30 carbon atoms, (2) a cycloalkyl group having 4 to 7 carbon atoms, (3) the number of carbon atoms 2 to 8 alkenyl groups, (4) the aryl moiety is a phenyl group or a lower alkyl-substituted phenyl group having up to 4 carbon atoms, the alkyl moiety is an aralkyl group having up to 4 carbon atoms, (5) the phenyl group or up to 4 carbon atoms 1 represents a monovalent hydrocarbon group selected from an alkyl-substituted phenyl group and (6) the alkyl group of (1) substituted with a halogen, and m represents the viscosity of the component (a) at 25 ° C. of 0.01 to A silanol group-terminated polydiorganosiloxane represented by the following formula:
(B) the general _{^{formula: R 2 O (CH 2 CH}} 2 O) n SO 3 M
(In the formula, R ² represents a saturated or unsaturated hydrocarbon group having 8 to 20 carbon atoms, M represents an alkali metal, an alkaline earth metal, ammonium or an organic amine. N is 0 to 5). And (c) a polyorganosiloxane emulsion obtained by emulsion polymerization from water,
(D) one or more polyethylene glycols or derivatives thereof selected from polyethylene glycol having a molecular weight of 200 to 3,000 or polyethylene glycol glyceryl ether, and (e) a cationic surfactant. A silicone emulsion.   When the component (b) contains two kinds of anionic surfactants, the blending ratio thereof is 1:20 to 20: 1, and when it contains three kinds of anionic surfactants, the blending ratio is 2. The silicone emulsion according to claim 1, wherein (1-20) :( 1-20) :( 1-20). The silicone emulsion according to claim 1 or 2, wherein the polyorganosiloxane in the polyorganosiloxane emulsion has a viscosity at 25 ° C of 10 to 2,000 Pa · s . (A) 0.01 to 20% by weight of a silicone emulsion, (B) 0.1 to 15% by weight of a high melting point aliphatic compound having a melting point of 25 ° C. or higher, and (C1) 0.1 to 10% by weight of a cation conditioning agent. And (D) each containing water,
A hair cosmetic composition, wherein the silicone emulsion (A) is the silicone emulsion according to any one of claims 1 to 3. (A) 0.01 to 20% by weight of silicone emulsion, (E) 5 to 50% by weight of detersive surfactant, (C2) 0.1 to 20% by weight of conditioning agent, and (D) water. A composition to
A hair cosmetic composition, wherein the silicone emulsion (A) is the silicone emulsion according to any one of claims 1 to 3.