JP2005075823A - Hair cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare a hair cosmetic which has high stability of the external appearance of a product and can impart good flexibility and smoothness to the hair from on wetting to after drying. <P>SOLUTION: This hair cosmetic comprises (A) a cationic group-containing copolymer obtained by radically polymerizing at least one nonionic group-containing vinyl monomer represented by formula (I) or formula (II), at least one cationic group-containing vinyl monomer, and a crosslinkable vinyl monomer having at least two groups selected from vinyl group, acryloyl group, methacryloyl group, and allyl group in the molecule as the essential constituting monomers and (B) an ether type cationic surface active agent represented by formula (V). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hair cosmetic composition that has high stability in product appearance and can impart good flexibility and slipperiness to the hair from wet to dry.

  Hair cosmetics are required to have flexibility and slipperiness to hair from wet to dry. Because of these requirements, quaternary ammonium salts such as stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, and distearyldimethylammonium chloride are used as cationic surfactants. However, hair that always satisfies these requirements is used. Cosmetics are not obtained. In particular, di-long-chain alkyl quaternary ammonium salts such as distearyldimethylammonium chloride are used for the purpose of improving flexibility when wet, but the problem is that the hair is inferior in slipperiness after drying and feels heavy. There is. Therefore, in order to improve the slipperiness after drying, a method using various additives such as silicone is known, but when these additives are used, the stability of the system is affected, so the amount of blending can be adjusted. There arises a problem that it is necessary or the formulation itself becomes complicated. Moreover, although the hair-treatment agent composition using the quaternary ammonium salt of an ethylene oxide addition type is known (for example, refer patent document 1 and patent document 2), these range in the addition mole number of ethylene oxide on manufacture. As a result, it was difficult to obtain a single addition mole number, and those having an addition mole number of 2 or more had a problem of adversely affecting the performance. On the other hand, depending on the components used in combination, some of the blended components in the system are separated, and there are many problems in terms of stability in appearance.

JP-A-6-107524 Japanese Patent Laid-Open No. 6-17728

  An object of the present invention is to provide a hair cosmetic that has a high product appearance stability and can impart good flexibility and slipperiness to the hair from wet to dry.

The present invention includes the following components (A) and (B):
(A) At least one nonionic group-containing vinyl monomer represented by the following general formula (I) or (II), at least one cationic group-containing vinyl monomer, vinyl group, acryloyl group A cationic group containing, obtained by radical polymerization with at least one crosslinkable vinyl monomer having at least two groups selected from a methacryloyl group and an allyl group in the molecule as an essential constituent monomer Copolymer [hereinafter referred to as copolymer (A)],

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms. ]

[Wherein, R ¹ has the same meaning as described above, and A ¹ and A ² are the same or different and each represents a group represented by the formula — (CH ₂ ) _n — (n represents an integer of 2 to 6). B represents —O— or —CH ₂ — group. ]
(B) The following general formula (V)

[Wherein, R ¹¹ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ¹² and R ¹⁴ represent an alkyl group having 1 to 6 carbon atoms or — (AO) _n H (a represents an alkylene group having 2 to 4 carbon atoms, n represents a number of 1 to 6, n pieces of a may be the same or different, the sequence is arbitrary.) indicates, R ¹³ is , An alkyl group having 1 to 6 carbon atoms, a benzyl group or — (A′O) _m H (A ′ represents an alkylene group having 2 to 4 carbon atoms, m represents a number of 1 to 6; 'May be the same or different, and the arrangement thereof is arbitrary.), And X ^1- represents an anion. A hair cosmetic containing an ether type cationic surfactant represented by the formula:

  The hair cosmetic composition of the present invention has high stability in product appearance, and can impart good flexibility and slipperiness to the hair from wet to dry.

The copolymer (A) of the present invention has a viscosity at 25 ° C. when added to ion-exchanged water so as to be 0.5% by weight in order to express the good feeling desired by the present invention. when 1 sec ^-1, a 0.3~20Pa · s, when the shear rate 10 sec ^-1, a 0.01~5Pa · s, and the viscosity at a shear rate of 1 sec ^-1 is a shear rate 10 sec ^-1 It is preferable to exhibit thixotropy that is higher than the viscosity at the time. A copolymer having a viscosity behavior within the above range can be easily applied to the skin and the like, can feel a residual feeling on the skin, and can provide a good feeling in use.

Further preferred viscosity behavior as a copolymer (A) of the present invention, the viscosity at 25 ° C. upon addition to 0.5% by weight of ion-exchanged water, when the shear rate 1sec ^-1, 0.4~10Pa · a s, when the shear rate 10 sec ^-1, a 0.05～3Pa · s, and the viscosity at a shear rate of 1 sec ^-1 is higher than the viscosity at a shear rate 10 sec ^-1.
The copolymer (A) used in the present invention has a 0.5% by weight hydrogel having a complex elastic modulus ε ₁ , loss tangent tan δ _{1 at} 25 ° C., strain frequency 6.28 rad / sec, strain 1%, The complex elastic modulus ε ₂ and the loss tangent tan δ ₂ at a strain of 500% are 1 ≦ ε ₁ ≦ 300 (N / m ² ), tan δ ₁ ≦ 2, and 0.01 ≦ ε ₂ ≦ 30 (N / m ^2). ), When tan δ ₂ ≧ 1, a cleaner composition having a more preferable feel can be obtained. Here, as the loss tangent of the copolymer (A) becomes tan δ ₁ ≦ 1.5, and further tan δ ₁ ≦ 1.0, a cleaner composition having a more preferable feel can be obtained.

In addition, the copolymer (A) of the present invention can also be thickened (provided with thixotropy) by a hydrophilic solvent such as ethanol or isopropyl alcohol. In these organogels, in order to develop the desired feeling of use desired by the present invention, when the viscosity at 25 ° C. when added to ethanol to 2.0% by weight is a share rate of 1 sec ⁻¹ , a 0.3~20Pa · s, when the shear rate 10 sec ^-1, a 0.01~5Pa · s, and the viscosity at a shear rate of 1 sec ^-1 is higher than the viscosity at a shear rate of 10 sec ^-1 It is preferable to show thixotropic properties.

Further, the copolymer (A) of the 2.0 wt% ethanol gel, 25 ° C., the viscosity eta ₁ of shear rate 1 sec ^-1, the viscosity eta ₂ of the shear rate 10 sec ^-1, 0.3 ≦ eta ₁ ≦ 20 (Pa · s), 0.01 ≦ η ₂ ≦ 5 (Pa · s), and η ₁ > η ₂ , excellent in touch and capable of maintaining the touch even when used in combination with ethanol A composition can be obtained.
η ₁ and η ₂ are measured by the following method. The measurement method is the same for both samples 1 and 2.
Sample 1: A 0.5 wt% hydrogel prepared by adding a powder sample (average particle size of 50 μm or less) to ion-exchanged water and holding it at 50 ° C. for half a day.
Sample 2: A 2.0 wt% ethanol gel prepared in the same manner as described above using ethanol instead of water.
Measuring apparatus: HAAKE viscometer, Rotovisco RV-20.
Measurement conditions: Measurement head M10, coaxial double cylindrical rotor, measurement temperature 25 ° C., sample amount 15 ml.
Increases from 0 sec ^-1 to 15 sec ^-1 in 2 minutes; shear rate.
Number of measurement points: 60 points measured over the above share rate range.
Calculation method: Calculated by the Rotation Version 2.8 program from the above measured values.
Measurement of δ ₁ , δ ₂ , ε ₁ , ε ₂ is performed by the following method.
Sample: Same as Sample 1 above.
Measuring apparatus: Fluids Spectrometer RFS-II manufactured by Rheometrics.
Measurement conditions: Dynamic Strain Sweep mode Cone plate: diameter 50 mm, gap 0.05 mm, angle 0.04 rad, strain frequency 6.2 rad / sec, strain 0.5-500%. Measurement temperature: 25 ° C.

  The copolymer (A) of the present invention having such performance is extremely useful as a thickener in an aqueous medium, a hydrophilic medium of a lower alcohol having 1 to 3 carbon atoms (ethanol, isopropyl alcohol, etc.) or a mixed medium thereof. It is.

The copolymer (A) exhibiting such rheological properties includes, for example, at least one cationic group-containing vinyl monomer (hereinafter referred to as monomer (a ₁ )) and a general formula (I) or (II ):

[Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different,
A hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms is shown. ]

[Wherein, R ¹ has the same meaning as described above, and A ¹ and A ² are the same or different and each represents a group represented by the formula — (CH ₂ ) _n — (n represents an integer of 2 to 6). B represents —O— or —CH ₂ — group. ] Nonionic group-containing vinyl monomer [hereinafter referred to as monomer (a ₂ )] and a crosslinkable vinyl monomer having 2 or more vinyl groups in the molecule [hereinafter referred to as Monomer (a ₃ )] is an essential constituent monomer and is obtained by radical polymerization.

Among the monomers constituting the copolymer (A), as the monomer (a ₁ ), (meth) acrylic acid ester or (meth) acrylamides having a dialkylamino group, (meth) acryloylalkyltri Alkyl quaternary ammonium salts, styrenes having a dialkylamino group, vinyl pyridines, N-vinyl heterocyclic compounds, acid neutralized or quaternary ammonium salts of amino groups, diallyl-type quaternary ammonium salts Etc.

Of these monomers (a ₁ ), compounds represented by the general formula (III) or (IV) are preferred.

[Wherein, R ¹ represents the same meaning as described above, R ⁴ and R ⁵ are the same or different and represent an alkyl group or alkenyl group having 1 to 4 carbon atoms, and R ⁶ represents a hydrogen atom or 1 to 4 carbon atoms. Y represents —O—, —NH—, —CH ₂ — or —O—CH ₂ CH (OH) —, and Z represents a linear or branched alkylene having 1 to 4 carbon atoms. A group (provided that when Y is —CH ₂ —, a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms), X is an acid conjugate base, a halogen atom or an alkyl having 1 to 4 carbon atoms. Indicates a sulfate group. ]

[Wherein, R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or a methyl group; R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; The same meaning as above is shown. ]

  Preferred acids used for obtaining the salt of compound (III) or (IV) include hydrochloric acid, sulfuric acid, acetic acid, citric acid, succinic acid, adipic acid, sulfamic acid, etc., for obtaining a quaternary ammonium salt. Preferred quaternizing agents include alkyl halides such as methyl chloride and methyl iodide, diethyl sulfate, di-n-propyl sulfate and the like.

Preferable specific examples of the monomer (a ₁ ) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, or diethylaminopropyl (meth) acrylamide as described above. Quaternary ammonium salts quaternized with an agent, dimethyl diallyl ammonium chloride, and the like.

As the monomer (a ₂ ), N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N- Examples thereof include t-butylacrylamide, N- (meth) acryloylmorpholine and the like. Among these, a feeling of use is preferable when N, N-disubstituted acrylamide is used, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like are particularly preferable.

Examples of the monomer (a ₃ ) include (meth) acrylic acid esters of polyhydric alcohols or unsaturated alcohols, divinyl compounds, polyallyl compounds, and the like. Among these, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, allyl etherified product of pentaerythritol, vinyl (meth) acrylate, allyl (meth) acrylate, etc. Particularly preferred.

A preferable blending ratio of the monomer (a ₁ ) to the monomer (a ₂ ) is 2/98 to 98/2 in terms of a molar ratio of (a ₁ ) / (a ₂ ), and more preferably 3 / 97 to 60/40. When the molar ratio is small, the expression of thixotropic properties is facilitated, and when the molar ratio is large, the viscosity can be easily maintained at a low share rate. However, it is preferable that both properties are within the above ranges.

The proportion of the monomer (a ₃ ) is preferably 0.002 to 5% by weight, particularly preferably 0.002% by weight or more and less than 0.1% by weight, based on the total amount of monomers. If the proportion of the monomer (a ₃ ) is 0.002% by weight or more, the viscosity of the hydrogel formed from the copolymer (A) is sufficient, and if it is 5% by weight or less, the hydrogel The touch is soft and slippery.

  The copolymer (A) can contain, as a constituent component, one or more of the above-mentioned three kinds of vinyl monomers, which are essential structural units, as well as other vinyl monomers copolymerizable therewith. . Examples of other vinyl monomers include (meth) acrylic acid derivatives such as methyl (meth) acrylate and ethyl (meth) acrylate; anionic group-containing monomers such as acrylic acid and methacrylic acid; N- (3 Examples include betaines such as -sulfopropyl) -N-acryloyloxyethyl-N, N-dimethylammonium betaine and N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine.

  The method for producing the copolymer (A) is preferably an aqueous solution polymerization method, reverse phase suspension polymerization method, precipitation polymerization method or the like. For example, in the case of using an aqueous solution polymerization method as described in JP-A-4-230250, page 12, column 22, lines 28 to 34, the polymerization start temperature is 20 to 90 ° C. and the reaction time is about 1 to 10 hours. Is preferred. As the polymerization initiator, an azobis-based compound as described in JP-A-4-230250, page 12, column 22, line 46 to page 13, column 23, line 18, can be used alone or in combination with a reducing agent. Used. For the production of the copolymer (A) by the aqueous solution polymerization method, for example, a container having a rotating stirring arm described in JP-A-53-34101, page 3, upper right column, line 14 to lower right column, line 8 Is used.

  One or more kinds of the copolymer (A) can be used, and 0.01 to 20% by weight, particularly 0.1 to 10% by weight, and further 0.5 to 3% by weight are incorporated in the total composition. From the viewpoints of touch, stability, and usability.

  As the ether type cationic surfactant of the component (B) used in the present invention, the general formula (V):

[Wherein, R ¹¹ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ¹² and R ¹⁴ represent an alkyl group having 1 to 6 carbon atoms or — (AO) _n H (a represents an alkylene group having 2 to 4 carbon atoms, n represents a number of 1 to 6, n pieces of a may be the same or different, the sequence is arbitrary.) indicates, R ¹³ is , An alkyl group having 1 to 6 carbon atoms, a benzyl group or — (A′O) _m H (A ′ represents an alkylene group having 2 to 4 carbon atoms, m represents a number of 1 to 6; 'May be the same or different, and the arrangement thereof is arbitrary.), And X ^1- represents an anion. ] An ether type cationic surfactant represented by the formula:

R ¹¹ preferably has 12 to 22 carbon atoms, particularly 16 to 18 carbon atoms, and is preferably a linear alkyl group.
R ¹² and R ¹⁴ are preferably an alkyl group having 1 to 6 carbon atoms and — (CH ₂ CH ₂ O) _n H (n is preferably 1 to 3, particularly 1), more preferably a methyl group and an ethyl group, A methyl group is particularly preferable.
R ¹³ is preferably a methyl group, an ethyl group or a benzyl group, more preferably a methyl group or an ethyl group, particularly preferably a methyl group.
Examples of X ¹⁻ include halide ions and ethyl sulfate ions, and chloride ions are particularly preferable.

[Wherein, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and X ¹⁻ represent the same meaning as described above. ]
That is, first, in the presence of an alkali metal hydroxide, alcohol (2) is reacted with acrylonitrile to give alkoxypropionitrile (3) and then hydrogenated using a hydrogenation catalyst to obtain alkoxypropylamine (4). Get. Subsequently, a tertiary agent (formaldehyde or a combination of alkylaldehyde having 2 to 6 carbon atoms and hydrogen, or alkylene oxide having 2 to 4 carbon atoms) is added to the alkoxypropylamine (4) in the presence of a catalyst. A tertiary amine (5) is obtained by reaction, and an ether type cationic surfactant (1) can be obtained by reacting this with a quaternizing agent in an appropriate solvent.

(2) → (3)
In the reaction of alcohol (2) with acrylonitrile, the amount of acrylonitrile used is preferably 0.9 to 1.2 equivalents, particularly preferably 0.95 to 1.1 equivalents, relative to alcohol (2). Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. The amount of the alkali metal hydroxide used does not require removal of the alkali metal hydroxide after the reaction, and alkoxypropionitrile. From the viewpoint of the purity of (3), it is preferably 0.01 part by weight or more and less than 0.05 part by weight, particularly 0.01 to 0.04 part by weight with respect to 100 parts by weight of the alcohol (2).
The reaction temperature in this step is preferably 45 to 70 ° C, particularly 50 to 65 ° C. The reaction time is preferably 2 to 5 hours.

(3) → (4)
In the hydrogenation reaction of alkoxypropionitrile (3), if the amount of alkali metal hydroxide used in the previous step is in the above range, the reaction product can be used as it is. As the hydrogenation catalyst, a cobalt-based catalyst, a nickel-based catalyst, a copper-based catalyst, a noble metal-based catalyst, etc., preferably a catalyst based on Ni, Co and / or Ru, more preferably a Raney-type catalyst is used. In addition, those having these metals supported on a carrier can also be used. The amount of the hydrogenation catalyst used is preferably 0.05 to 5 parts by weight, particularly 0.1 to 3 parts by weight, based on 100 parts by weight of the alkoxypropionitrile (3).
This step is preferably performed at a hydrogen pressure of 0.3 to 10 MPa. The reaction temperature is preferably 50 to 250 ° C, particularly 70 to 180 ° C. The reaction time is preferably about 2 to 15 hours.
In this step, an alkali metal hydroxide may be used, and the amount used is preferably 0.4 parts by weight or less, particularly preferably 0.2 parts by weight or less, based on 100 parts by weight of nitrile (3). Moreover, you may react by adding water, The addition amount is 0.5-20 weight part with respect to 100 weight part of a nitrile (3), Especially 3-15 weight part is preferable. In this case, the alkali metal hydroxide is preferably used after being dissolved in water.
Alkoxypropylamine (4) is produced by the method described in J. Am. Chem. Soc., 57, 1505 (1945), British Patent No. 869405, Japanese Patent Laid-Open No. 48-103505, etc. However, it is preferable to use the above method from the viewpoint of easy operation and yield.
The obtained amine (4) can be used as it is as a raw material for the next step as it is, but it is preferable to purify it by a method such as distillation.

(4) → (5) (Tertiary process)
When aldehyde and hydrogen are used as the tertiary agent, the ether tertiary amine (5) can be produced by a reductive alkylation reaction such as a so-called reductive methylation reaction of alkoxypropylamine (4). Examples of the aldehyde include formaldehyde and alkyl aldehydes having 2 to 6 carbon atoms such as acetaldehyde, propanal, butanal, pentanal, hexanal, 2-methylpentanal, and among them, formaldehyde and acetaldehyde are preferable. Here, as the formaldehyde, an aqueous solution (formalin or the like) or a polymer such as paraformaldehyde can be used. The amount of the aldehyde to be used is preferably 1.0 to 1.5 times mol, particularly 1.0 to 1.2 times mol for one active hydrogen group of nitrogen of amine (4).
As the catalyst, an element selected from Pd, Pt, Rh, Re and Ru, particularly a metal catalyst containing Pd is preferable. As the metal catalyst, the metal powder may be used, but it is preferable to use the metal supported on a carrier. The amount of metal supported is preferably 0.01 to 20% by weight, particularly 0.1 to 10% by weight, based on the total weight of the catalyst. As the catalyst, as described in JP-A-64-16751, a Raney nickel catalyst adjusted to be acidic with an organic acid can be used, but separation of the compound (5) from the reaction product is easy. From this point, it is preferable to use the metal catalyst.
The amount of the metal catalyst used varies depending on the compound type of amine (4), reaction conditions, and the like, but usually, the metal is preferably 2 to 2000 ppm, particularly preferably 5 to 500 ppm based on the weight of amine (4).
This reaction is usually performed by supplying aldehyde to a reaction system charged with amine (4) and a metal catalyst in hydrogen gas. The hydrogen pressure (gauge pressure) is preferably 0.5 MPa or more, particularly 1 to 10 MPa. The reaction temperature is preferably 60 to 200 ° C, particularly 110 to 180 ° C. The aldehyde may be added to the reaction system continuously or intermittently, and the addition rate may be adjusted to the reaction rate, but it is preferable to add the aldehyde continuously at a constant rate. This addition time is essentially a reaction time, usually 1 to 10 hours. After completion of the supply of aldehyde, aging is preferably performed for 10 to 60 minutes.
Further, when R ¹² and R ¹⁴ are — (AO) nH, the alkylene oxide having 2 to 4 carbon atoms is used as the tertiary agent, and the tertiary alkylene is added to the amine (4) by usual addition of alkylene oxide. can do.
In this way, various tertiary amines (5) are obtained. The resulting tertiary amine (5) can be used as it is as a raw material for the next step as it is, but is preferably purified by a method such as distillation.

(5) → (1)
Examples of the quaternizing agent used for the quaternization of the tertiary amine (5) include alkyl halides having 1 to 6 carbon atoms in the alkyl group and dialkyl sulfuric acid. Further, after the reaction, the acid salt may be further neutralized in a suitable solvent using hydrogen halide, sulfuric acid, organic acid or the like. Further, addition of alkylene oxide having 2 to 4 carbon atoms to the acid salt of the tertiary amine (5) can also give a quaternized product.
The obtained ether type cationic surfactant (1) can be used as it is as a compounding component of the product of the present invention, but can also be used after being purified by a usual purification means. The ether type cationic surfactant (1) can be produced by other methods, but is preferably produced by the method described above.

  One or more ether type cationic surfactants as the component (B) can be used in the hair cosmetic composition of the present invention, and 0.01 to 20% by weight, particularly 0.1 to 10% by weight in the total composition. % Is preferable.

  In addition to the above essential components, the hair cosmetic of the present invention includes anionic surfactants, amphoteric surfactants, nonionic surfactants, anionic polymers, and nonionic polymers that are used in ordinary cosmetics. , Ethylene oxide / propylene oxide block copolymers, alcohols, oils, powders, functional beads / capsules, silicones, metal chelators, antioxidants, UV absorbers, moisturizers, perfumes, etc. .

  The hair cosmetic composition of the present invention can be produced according to an ordinary method, and its dosage form is not particularly limited. For example, shampoo, hair rinse, conditioner, hair treatment, hair cream, styling agent, hair gel, set agent, hair liquid, hair restorer It can be applied as a permanent agent, hair dye, etc.

Production Example 1
In a reaction vessel, N, N-dimethylaminoethyl diethyl methacrylate sulfate (MOEDES: manufactured by Nitto Chemical Industry Co., Ltd.) 23.85 g, N, N-dimethylacrylamide 71.37 g, polyethylene glycol dimethacrylate (NK-9G: new) (Nakamura Chemical Co., Ltd.) 0.0429 g of nitrogen-exchanged monomer aqueous solution consisting of 350 g of ion-exchanged water was added, and nitrogen was further blown for 20 minutes. Next, 0.22 g of a polymerization initiator (2,2′-azobis (2-amidinopropane) dihydrochloride) was added. Polymerization started after 30 minutes to 1 hour, and the whole became a soft gel. Stirring was continued as it was, and the polymerization was stopped 4 hours after the addition of the polymerization initiator. The bowl-shaped contents were taken out, washed with stirring in 5 liters of ethanol for 10 minutes, and dried. Thereafter, the mixture was pulverized with a coffee mill and a jet mill, and the pulverized particles were classified with a high voltor. 1 was obtained.

Production Examples 2-14
Using the monomers shown in Table 1, a cationic group-containing copolymer No. 1 was prepared in the same manner as in Production Example 1. 2-No. 14 was produced.

Test example 1
About the cationic group containing copolymer obtained by manufacture example 1-14, the viscosity in 25 degreeC and dynamic viscoelasticity of 0.5 weight% hydrogel were measured by the said method. The results are shown in Table 1.

Examples 1-3, Comparative Examples 1-2
Cationic group-containing copolymers No. 1 to 3 shown in Table 1, ether type cationic surfactants No. 1 to 3 produced by the method described in Table 2 and other ether types Using cationic surfactant No. 4, hair conditioners (Examples 1 to 3 and Comparative Examples 1 and 2) having the compositions shown in Table 3 were produced by a conventional method. The numerical values in Table 3 are “% by weight”.
The obtained sample was evaluated by 10 panelists for coating performance, rinsing performance and dry performance, and appearance of the sample stored at 50 ° C. for 1 month. For each, the average score was obtained, 4.5 or more points, ◎, 4 points to less than 4.5 points, ○, 2.5 points to less than 4 points, △, less than 2.5 points x, and Table 3 also shows the results of external appearance evaluation when stored at 50 ° C for 1 month.
(Evaluation methods)
(1) Application performance: Sensory evaluation of the feel of stretch, familiarity and slip when 1 g of hair cosmetic was applied to 20 g of tress was performed according to the following criteria.
(2) Rinsing performance: The smoothness, softness, and touch feeling of the hair when the tress coated with the hair cosmetic in (1) was rinsed with running water was subjected to sensory evaluation based on the following criteria.
(3) Dry performance: When the tress rinsed in (2) was dried with a drier, the moist feeling of the hair, the unity, the fingering, and the smooth feel were subjected to sensory evaluation based on the following criteria.
(4) Storage appearance evaluation: 100 mL of the blended cosmetic was put in a glass bottle and visually evaluated for appearance after storage at 50 ° C. for 1 month.
<Evaluation criteria>
Evaluation items (1) to (3): 5; Very good. 4; Good. 3; Usually. 2; Somewhat bad. 1; bad.
Evaluation item (4): A: No change before storage. ○: A slight change is recognized. X: A change is clearly recognized.

Example 4
A hair rinse agent having the following composition was produced.
(weight%)
Ether type cationic surfactant No.4 1.5
Cationic group-containing copolymer No. 4 1.0
Cetanol 3.5
Isopropyl myristate 1.0
Dimethylpolysiloxane (500cs) 0.5
Propylene glycol 3.5
Hydroxyethyl cellulose 0.1
Ethanol 2.0
Methylparaben 0.3
Perfume Trace amount purified water Balance total 100.0
*: SH200C, manufactured by Toray Dow Corning Silicone Co., Ltd. This rinsing agent has a high appearance stability, good flexibility and slipperiness from wet to dry, especially without any stickiness after drying. It was excellent in nature.

Example 5
A transparent hair rinse agent having the following composition was produced.
(weight%)
Ether type cationic surfactant No.1 1.0
Cationic group-containing copolymer No. 7 0.5
Isopropyl myristate 1.0
Dimethylpolysiloxane (500cs) 0.5
Propylene glycol 3.5
Hydroxyethyl cellulose 0.1
Dipropylene glycol 5.0
Ethanol 5.0
Methylparaben 0.3
Perfume Trace amount purified water Balance total 100.0
This rinse agent had high stability in the appearance of the product, good flexibility and slipperiness from wet to dryness, and was particularly free from stickiness and excellent slippery after drying.

Example 6
A non-washing type hair treatment having the following composition was produced.
(weight%)
Ether type cationic surfactant No.3 0.8
Cationic group-containing copolymer No. 10 0.1
Cetanol 2.5
Isopropyl myristate 1.0
Dipropylene glycol 5.0
Ethanol 2.0
Methylparaben 0.3
Perfume Trace amount purified water Balance total 100.0
This hair treatment agent has high stability in the appearance of the product, and has good flexibility and slipperiness from wet to dry, and has no stickiness and excellent slippery especially after drying.

Example 7
A hair tonic having the following composition was produced.
(weight%)
Ether type cationic surfactant No.2 0.2
Cationic group-containing copolymer No. 14 0.1
l-Menthol 0.2
Acetic acid dl-α-tocopherol 0.05
Polyoxyethylene (60) hardened castor oil 1.0
Ethanol 55.0
Perfume Trace amount purified water Balance total 100.0
This hair tonic had high stability in product appearance, good flexibility and slipperiness, and excellent usability.
Each of the hair cosmetics obtained in Examples 1 to 7 had high stability in product appearance, and was able to impart good flexibility and slipperiness to the hair from wet to dry. .

Claims (3)

The following components (A) and (B):
(A) At least one nonionic group-containing vinyl monomer represented by the following general formula (I) or (II), at least one cationic group-containing vinyl monomer, vinyl group, acryloyl group A cationic group containing, obtained by radical polymerization with at least one kind of a crosslinkable vinyl monomer having at least two groups selected from a methacryloyl group and an allyl group in the molecule. Copolymer,

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms. ]

[Wherein, R ¹ has the same meaning as described above, and A ¹ and A ² are the same or different and each represents a group represented by the formula — (CH ₂ ) _n — (n represents an integer of 2 to 6). B represents —O— or —CH ₂ — group. ]
(B) The following general formula (V):

[Wherein R ¹¹ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ¹² and R ¹⁴ represent an alkyl group having 1 to 6 carbon atoms or — (AO) _n H (a represents an alkylene group having 2 to 4 carbon atoms, n represents a number of 1 to 6, n pieces of a may be the same or different, the sequence is arbitrary.) indicates, R ¹³ is , An alkyl group having 1 to 6 carbon atoms, a benzyl group or — (A′O) _m H (A ′ represents an alkylene group having 2 to 4 carbon atoms, m represents a number of 1 to 6; 'May be the same or different, and the arrangement thereof is arbitrary.), And X ^1- represents an anion. A hair cosmetic containing an ether type cationic surfactant represented by the formula: The hair cosmetic according to claim 1, wherein the cationic group-containing vinyl monomer is represented by the following general formula (III) or (IV).

[Wherein, R ¹ represents the same meaning as described above, R ⁴ and R ⁵ are the same or different and represent an alkyl group or alkenyl group having 1 to 4 carbon atoms, and R ⁶ represents a hydrogen atom or 1 to 4 carbon atoms. Y represents —O—, —NH—, —CH ₂ — or —O—CH ₂ CH (OH) —, and Z represents a linear or branched alkylene having 1 to 4 carbon atoms. A group (provided that when Y is —CH ₂ —, a single bond or a linear or branched alkylene group having 1 to 3 carbon atoms), X is an acid conjugate base, a halogen atom or an alkyl having 1 to 4 carbon atoms. Indicates a sulfate group. ]

[Wherein, R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or a methyl group; R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; The same meaning as above is shown. ] When the cationic group-containing copolymer is added to ion-exchanged water so as to be 0.5% by weight, the viscosity at 25 ° C. is 0.3 to 20 Pa · s when the share rate is 1 sec ⁻¹ , and the share is rate when 10 sec ^-1, a 0.01~5Pa · s, and high claim 1 or 2 hair cosmetic according than the viscosity when the viscosity is shear rate 10 sec ^-1 when the shear rate 1 sec ^-1.