JP2006104086A - Hair washing agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair washing agent composition capable of removing a frictional feeling of damaged hair, when the hair is washed and rinsed, and scarcely affecting the environment. <P>SOLUTION: This hair washing agent composition contains (A) a silicone emulsion in an amount of 0.01-20 wt%, (B) a detergent surfactant in an amount of 5-50 wt%, (C) a conditioning agent in an amount of 0.1-20 wt%, and (D) water, wherein the silicone emulsion (A) comprises a polyorganosiloxane emulsion which is obtained from (a) a silanol-terminated polydiorganosiloxane, (b) an anionic surfactant expressed by the formula: R<SP>2</SP>O(CH<SB>2</SB>CH<SB>2</SB>O)<SB>n</SB>SO<SB>3</SB>M (R<SP>2</SP>is an 8-20C saturated or unsaturated hydrocarbon group; M is ammonium or an organic amine; and (n) is an integer of 0 to 5), and water through emulsion polymerization. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hair cleaning composition, and in particular, a hair cleaning composition excellent in combability after drying without giving a squeaky feeling during washing and rinsing to damaged hair. About.

  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 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 in the emulsion after the emulsion polymerization, the cyclic siloxane oligomer is present 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, by using unsaturated aliphatic sodium sulfonate and / or sodium hydroxide aliphatic sulfonate as a surfactant, or using sodium alkyl sulfate, high molecular weight polyorgano Methods have been proposed for producing siloxane-containing emulsions. (For example, see Patent Document 2 and Patent Document 3)

However, the polyorganosiloxane emulsions obtained by these methods are also not fully satisfactory in terms of improving the feel such as eliminating the squeaky feeling on damaged hair during hair washing.
JP 7-138136 A JP-A-11-71522 JP 2002-20490 A

  The present invention was made to solve these problems, and can impart a smooth feel to the damaged hair and combability after drying, eliminating the squeaky feeling particularly during washing and rinsing, Furthermore, it aims at providing the hair cleaning composition with little influence on an environment.

  As a result of intensive studies to achieve the above object, the present inventor found that the use of a specific anionic surfactant is extremely effective in improving the feeling of use when washing damaged hair. The invention has been completed.

That is, the hair cleansing composition of the present invention comprises (A) 0.01 to 20% by weight of a silicone emulsion, (B) 5 to 50% by weight of a detersive surfactant, and (C) a conditioning agent of 0.1 to 0.1%. 20% by weight and (D) a composition each containing water, wherein the (A) silicone emulsion comprises (a) the general formula: HO [(R ¹ ) ₂ SiO] _m H (I) ( In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different from each other, and m represents the viscosity of the component (a) at 25 ° C. of 0.01 to 2.0 Pa. A value to be s.) And a (b) general formula: R ² O (CH ₂ CH ₂ O) _n SO ₃ M (wherein R ² is the number of carbon atoms) 8-20 saturated or unsaturated hydrocarbon groups M represents ammonium or an organic amine, n represents a number of 0 to 5, and (c) a polyorganosiloxane emulsion obtained by emulsion polymerization from water. It is characterized by that.

According to the hair cleansing composition of the present invention, the anionic surfactant represented by the general formula: R ² O (CH ₂ CH ₂ O) _n SO ₃ M as the component (b) is used to form a silicone polymer (polyorgano Since a stable silicone emulsion in which (siloxane) is emulsified (emulsified) and dispersed is contained, a smooth and moist feel can be imparted to the hair. In particular, it is possible to eliminate the squeaky feeling during washing and rinsing and give good combability to damaged hair.

  Hereinafter, embodiments of the hair cleaning composition according to the present invention will be described.

The hair cleansing composition of the embodiment of the present invention comprises (A) 0.01 to 20% by weight of a silicone emulsion, (B) 5 to 50% by weight of a detersive surfactant, and (C) a conditioning agent of 0.1 -20% by weight and (D) water, respectively. And (A) silicone emulsion is (a) general formula: HO [(R ¹ ) ₂ SiO] _m H (I) (wherein R ¹ may be the same or different from each other) A substituted or unsubstituted monovalent hydrocarbon group, and m is a value that makes the viscosity of component (a) at 25 ° C. 0.01 to 2.0 Pa · s.) 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 Represents an ammonium or an organic amine, n represents a number of 0 to 5.) and (c) a polyorganosiloxane emulsion obtained by emulsion polymerization from water.

First, the silicone emulsion as component (A) 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 (I) 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 2.0 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 2.0 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 general formula (I), R ¹ bonded to a silicon atom is (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, or 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, particularly 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-phenylpropoxy (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 selected from polyoxyethylene alkyl ether ammonium sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, alkyl sulfate ammonium, and alkyl sulfate triethanolamine.

  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 (2) octyl ether sulfate triethanolamine, polyoxyethylene (8) decyl ether sulfate triethanolamine, polyoxyethylene (3) lauryl ether sulfate triethanol as polyoxyethylene alkyl ether sulfate system Amine, polyoxyethylene (2) octyl ether ammonium sulfate, polyoxyethylene (8) decyl ether ammonium sulfate, polyoxyethylene (3) ammonium lauryl ether sulfate, etc. are alkyl sulfates such as lauryl sulfate triethanolamine, myristyl sulfate triethanol. Examples thereof include amines, cetyl sulfate triethanolamine, ammonium lauryl sulfate, myristyl ammonium sulfate, and cetyl ammonium sulfate.

  Of these, triethanolamine salts are preferable from the viewpoint of feeling during use in rinsing, and lauryl sulfate triethanolamine and polyoxyethylene (3) lauryl ether sulfate triethanolamine are particularly preferable.

  The above-mentioned component (b) is used as an emulsifier in the form of a water-soluble salt or neutralized salt, and then an acid is added to produce an acid-type component (b) in the reaction system as an emulsion polymerization catalyst. Make it work. 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 initially used as a surfactant and thereafter used 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 the embodiment of the present invention, it is preferable to use two or more kinds of the (b) anionic surfactant together, and the blending ratio is 1:10 when two kinds of anionic surfactant are used in combination. It is in the range of 10: 1, preferably in the range of 1: 5 to 5: 1. Outside the range of 1:10 to 10: 1, the stability is deteriorated and sufficient effects cannot be obtained. Moreover, the mixture ratio in the case of using 3 types together is the range of (1-10) :( 1-10) :( 1-10), Preferably (1-5) :( 1-5) :( 1-5).

  The amount of the component (b) used can be any amount as long as it meets the object of the present invention in consideration of the use as a polymerization catalyst. 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 (A) silicone emulsion according to the embodiment of the present invention is obtained by polymerizing the component (a) with respect to the emulsion containing the components (a) to (c). As long as the emulsion contains the components (a) to (c) as essential components, various auxiliary components may be dissolved or dispersed as long as the gist of the present invention is not impaired. Such 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 auxiliary components before or during the polymerization because the dispersibility thereof is improved.

  The (A) silicone emulsion of the embodiment can be produced as follows. That is, the above-mentioned polydiorganosiloxane whose molecular chain terminal is blocked with a silanol group, (b) the anionic surfactant, 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.

  In this way, a stable emulsion containing a high molecular weight polyorganosiloxane 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 50 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.

  Reactivity such as methyldimethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane to form a firm film on hair with polyorganosiloxane emulsion obtained by emulsion polymerization N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-to give silane and good slipperiness and flexibility on the surface of the substrate Reactivity such as aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltris (trimethylsiloxy) silane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane Silane, during emulsion polymerization or emulsification It is also possible to add a small amount after engagement. 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 hair cleansing composition of the embodiment of the present invention, the (B) detersive surfactant that is blended with the silicone emulsion as the component (A) is a component that is blended for the purpose of imparting detergency to the composition. Yes, it contains a surfactant selected from anionic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants 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 (B) 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 cleansing composition.

  In the embodiment of the present invention, a known conditioning agent can be used as the (C) conditioning agent. Suitable (C) conditioning agents include cationic polymers, fatty compounds, non-volatile dispersed silicones, hydrocarbons, proteins and mixtures thereof. Of these, the use of a cationic polymer is preferred.

  The cationic polymer is preferably a water-soluble cationic polymer. “Water-soluble” cationic polymers are sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1% in 25 ° C. water (distilled water or equivalent water). Means a 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 still 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 includes a copolymer or polymer of quaternary ammonium or cationic amine substituted monomer units and other non-cationic units 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 the general formula: RX. Here, R 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. .

  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 (for example, Rubiquat FC 370); copolymer of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (“CTFA”) Is called Polyquaterium-11), trade name 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); in US Pat. No. 4,009,256 Mention may be made of the mineral acid salts of aminoalkyl esters of the homopolymers and copolymers of unsaturated carboxylic acids having 3 to 5 carbon atoms as described. “CTFA” represents Cosmetics, Toiletry, and Fragrance Association, Inc.

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 ³ , R ⁴ and R ⁵ are each independently selected from alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxyalkyl groups, or alkoxyaryl groups, 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 ³ , R ⁴ and R ⁵ ) 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 hydroxyethyl cellulose with a trimethylammonium substituted epoxide under the trade name polymer JR and LR series. Is called polyquaternium-10. Other types of cationic cellulose include polymeric quaternary ammonium salts reacted with hydroxyethyl cellulose and lauryldimethylammonium substituted epoxides, referred to in the “CTFA” industry as polyquaternium-24. 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 an embodiment, these (C) conditioning agents are contained in a proportion of 0.1 to 20% by weight of the hair cleansing composition.

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

  According to the hair cleansing composition of the embodiment of the present invention, it exerts an excellent conditioning effect on the hair, improves the squeaky feeling at the time of washing and rinsing, and has excellent fingering properties for dry hair Can be granted.

  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, 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-1) containing polyorganosiloxane. The average particle size of the polyorganosiloxane in this emulsion was 0.18 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) 2 parts ammonium lauryl ether 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, while continuing stirring, a 10% aqueous sodium carbonate solution was added dropwise until the pH became 7, thereby terminating the polymerization reaction, and an emulsion (E-2) containing polyorganosiloxane was obtained. The average particle size of the polyorganosiloxane in this emulsion 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)
Emulsion containing polyorganosiloxane (E-3) in the same manner as in Synthesis Example 1 except that the polymerization reaction stopped by dropping and neutralizing the aqueous sodium carbonate solution was replaced by stopping the reaction by dropping and neutralizing triethanolamine. Got. The average particle size of the polyorganosiloxane in this emulsion was 0.17 μm, the polymer viscosity was 950 Pa · s, and the content of the cyclic siloxane oligomer was 1.5%.

(Synthesis Example 4)
In Synthesis Example 1, an emulsion (E-4) containing polyorganosiloxane was obtained in the same manner as in Synthesis Example 1 except that the polymerization time of 8 hours was changed to 3 hours. The average particle size of the polyorganosiloxane in this emulsion was 0.19 μm, the polymer viscosity was 310 Pa · s, and the content of cyclic siloxane oligomer was 0.8%.

(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 diameter of the polyorganosiloxane in this emulsion was 0.23 μm, the polymer viscosity was 2100 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 size of the polyorganosiloxane in this emulsion was 0.20 μm, the polymer viscosity was 270 Pa · s, and the content of the cyclic siloxane oligomer was 9.6%.

Examples 1-4 and Comparative Examples 1-2
Using the silicone emulsions (E-1) to (E-6) obtained in Synthesis Examples 1 to 6, shampoo compositions were prepared with the compositions shown in Table 1. 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 dryer to prepare a hair sample. did. At the hair sample preparation stage, each panelist was given 5 levels of “no squeaky feeling during washing and rinsing”, “finger feeling 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.

  When the hair cleanser composition of the present invention is used as a shampoo, it exhibits an excellent conditioning effect on the hair, improves the squeaky feeling during washing and rinsing, and is excellent for dry hair Gives fingering.

Claims (5)

(A) 0.01 to 20% by weight of silicone emulsion, (B) 5 to 50% by weight of detersive surfactant, (C) 0.1 to 20% by weight of conditioning agent, and (D) each containing water A composition to
The (A) silicone emulsion is
(A) General formula: HO [(R ¹ ) ₂ SiO] _m H (......) (I)
(Wherein R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different from each other, and m represents the viscosity of component (a) at 25 ° C. of 0.01 to 2. 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
(Wherein R ² represents a saturated or unsaturated hydrocarbon group having 8 to 20 carbon atoms, M represents ammonium or an organic amine, and n represents a number of 0 to 5). A hair cleansing composition, which is a polyorganosiloxane emulsion obtained by emulsion polymerization from a water-soluble surfactant and (c) water.   In the (A) silicone emulsion, when the component (b) contains two types of anionic surfactants, the blending ratio thereof is 1:10 to 10: 1, and three types of anionic surfactants are used. 2. The hair cleansing composition according to claim 1, wherein when it is contained, the blending ratio thereof is (1-10) :( 1-10) :( 1-10).   The hair cleansing composition according to claim 1 or 2, wherein the (A) silicone emulsion contains a polyorganosiloxane having a viscosity at 25 ° C of 10 to 2,000 Pa · s.   The hair cleansing composition according to any one of claims 1 to 3, wherein the (A) silicone emulsion contains silicone polymer particles having an average particle size of 0.15 to 0.5 µm.   In the anionic surfactant of said (b) component, M in general formula (I) is a triethanolamine, The hair cleansing composition of any one of Claims 1 thru | or 4 characterized by the above-mentioned.