JP2809816B2 - Hair styling agent for aerosol - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a hair styling agent for aerosol. More specifically, the present invention relates to an aerosol hair styling agent having excellent compatibility with natural gas and exhibiting water solubility.

[Prior Art] Various hair styling agents have been developed to set hair into a desired shape. However, such hair styling agents are required to have water solubility in order to be able to be removed during washing. ing. Among such water-soluble hair styling agents, cationic hair styling agents have been used widely since they have excellent adhesion to hair.

By the way, when used in an aerosol, the cationic hair dressing is required to have excellent compatibility with a propellant in order to obtain a uniform spray state. Therefore, a conventional cationic hairdressing agent is used in combination with a CFC-based propellant having excellent compatibility with the hairdressing agent as a propellant.

However, the use of such chlorofluorocarbon-based propellants is not preferred, as these are currently being abolished worldwide as they destroy the ozone layer in the atmosphere.

As a propellant that can be substituted for the above-mentioned fluorocarbon propellant, for example, natural gas such as butane gas has attracted attention. Natural gas is a gas that is expected to be less likely to destroy the ozone layer, because unlike natural gas, natural gas or its decomposition product does not react with ozone under the influence of light or the like. However, when such a natural gas is used as a propellant, the cationic hair styling agent has poor compatibility with the natural gas, so that the cationic hair styling agent is dispersed in the natural gas in an aerosol container. However, it became difficult to obtain a uniform spray state.

[Problems to be Solved by the Invention] In view of the above-mentioned prior art, the present inventors have conducted intensive studies in order to develop a cationic hair styling agent having excellent compatibility with natural gas and exhibiting water solubility. As a result, a specific dimethylaminoalkyl (mear) acrylate diethyl sulfate monomer having another long-chain alkyl group (meth)
When the copolymer used in combination with acrylate is used as a hairdressing agent, it has excellent compatibility with natural gas,
In addition, they have found that they exhibit water solubility and are excellent in setting power and detergency, and have completed the present invention.

[Means for Solving the Problems] That is, the present invention provides a compound represented by the general formula (I): (Wherein, R ¹ is a hydrogen atom or a methyl group, and R ² is
3 represents an alkylene group)
5% by weight, general formula (II): (Wherein R ¹ is the same as above, and R ³ represents an alkyl group having 1 to 4 carbon atoms) A monomer B 5 to 60% by weight represented by the following general formula (III): (Wherein R ¹ is the same as above, and R ⁴ is an alkyl group having 5 to 24 carbon atoms or a cycloalkyl group having 5 to 24 carbon atoms).
The present invention relates to a hair styling composition for aerosol comprising a polymer obtained by copolymerizing 0 to 20% by weight of an ethylenically unsaturated monomer other than C.

[Action and Examples] As described above, the hair styling agent for aerosol of the present invention has the general formula (I): (Wherein, R ¹ is a hydrogen atom or an alkyl group, and R ² is a carbon atom 1
Which represents an alkylene group of 1 to 3)
~ 55% (% by weight, hereinafter the same), general formula (II): (Wherein R ¹ is the same as above, and R ³ represents an alkyl group having 1 to 4 carbon atoms).
I): Wherein R ¹ is the same as above, and R ⁴ represents an alkyl group having 5 to 24 carbon atoms or a cycloalkyl group having 5 to 24 carbon atoms, and the monomers A to C
And a polymer obtained by copolymerizing 0 to 20% of other ethylenically unsaturated monomers (hereinafter referred to as monomer D).

The monomer A used in the present invention is, as described above,
A derivative of acrylic acid and / or methacrylic acid represented by the general formula (I). In the present invention, there is a great feature in using the monomer A. When the monomer A is copolymerized with another alkyl (meth) acrylate, the monomer A exhibits excellent compatibility with natural gas. It exhibits excellent physical properties such as water solubility and good adhesion to hair.

Specific examples of the monomer A include dimethylaminomethyl acrylate diethyl sulfate, dimethylaminoethyl acrylate diethyl sulfate, dimethylaminopropyl acrylate diethyl sulfate, dimethylaminomethyl methacrylate diethyl sulfate, dimethylaminoethyl methacrylate diethyl sulfate, dimethyl Examples thereof include aminopropyl methacrylate diethyl sulfate, and these monomers are used alone or in combination of two or more. The amount of the monomer A used is desirably adjusted so as to be 30 to 55%, preferably 40 to 45%, based on all monomers to be subjected to polymerization. When the amount of the monomer A is less than 30%, the film formed by the obtained hair styling agent becomes sparingly soluble in water, which makes it difficult to wash and remove the hair at the same time. Affinity to hair, a characteristic attributed to the cationic nature of the hairdressing agent, is reduced, and as a result, it tends to cause a flaking phenomenon, and it is obtained when it exceeds 55% or more. The moisture resistance of the film formed by the hairdressing agent tends to decrease, and the solubility of the obtained hairdressing agent in natural gas tends to decrease.

The monomer B used in the present invention is, as described above,
A derivative of acrylic acid and / or methacrylic acid represented by the general formula (II). In the present invention, the monomer B is used for improving physical properties such as blocking resistance and smoothness of a film formed by the obtained hair styling agent. In general formula (II),
It is preferable that R ¹ is a methyl group and R ³ is a butyl group because compatibility with natural gas is not easily impaired.

Specific examples of the monomer B include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and these monomers may be used alone or in combination of two or more. Used.

The amount of the monomer B used is desirably adjusted so as to be 5 to 60%, preferably 20 to 50%, based on all monomers to be subjected to polymerization. When the amount of the monomer B is less than 5%, blocking occurs or
If it exceeds 60%, the flexibility of the film formed by the obtained hair styling agent decreases and the solubility in natural gas tends to decrease.

The monomer C used in the present invention is, as described above,
An acrylic acid ester and / or a methacrylic acid ester represented by the general formula (III), wherein the alkyl group in the ester portion has a longer chain length than the monomer B. In the present invention, the monomer C is used for improving physical properties such as compatibility with natural gas and water resistance. In the general formula (III), R ¹ is preferably a methyl group, and R ⁴ is preferably an alkyl group or a cycloalkyl group having 5 to 18 carbon atoms from the viewpoint of improving the setting force under high humidity.

Specific examples of the monomer C include, for example, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, cyclohexyl acrylate,
-Ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate and the like, and these monomers are used alone or in combination of two or more.

The amount of the monomer C is desirably adjusted so as to be 5 to 45%, preferably 10 to 30%, based on all monomers to be subjected to polymerization. When the amount of the monomer C is less than 5%, the moisture resistance of the film formed by the obtained hair styling agent decreases, the flexibility of the film decreases, and the solubility in natural gas decreases.
If it exceeds 45%, blocking occurs in the film, and the smoothness and transparency of the film deteriorate,
In addition, they are poorly soluble in water and tend to be difficult to wash and remove during hair washing.

The monomer D used in the present invention is a component appropriately used for imparting flexibility and appropriate hardness to a film formed by the obtained hair styling agent and changing the feel.

Specific examples of the monomer D include, for example, N-vinylpyrrolidone, acrylonitrile, styrene, methylstyrene, chlorostyrene, vinyltoluene, vinyl acetate, polypropylene glycol mono (meth) acrylate, vinyltrichlorosilane, methacryloxypropyltrimethoxysilane, Acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Examples include acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and diacetone acrylamide. These monomers are used alone or in combination of two or more.

It is desirable to adjust the amount of the monomer D to be 0 to 20%, preferably 0 to 10%, based on all monomers to be subjected to polymerization. The amount of the monomer D used is
If it exceeds 20%, the compatibility with natural gas, which is the original purpose, tends to decrease.

The hair styling agent for aerosol of the present invention comprises the monomers A to D
Is obtained by adjusting a desired amount of the copolymer and copolymerizing in a hydrophilic solvent.

Here, the hydrophilic solvent has a solubility in water of 10 g / water 1
It refers to an organic solvent that is at least 00 g (25 ° C.). Specific examples of such a hydrophilic solvent include, for example, aliphatic mono- to tetra-hydric alcohols having 1 to 4 carbon atoms, ethyl cellosolve, butyl cellosolve, dioxane, methyl acetate, dimethylformamide and the like. Dihydric alcohols are particularly preferred for handling as cosmetic ingredients.

Specific examples of the monohydric alcohol include, for example, methanol, ethanol, isopropanol and the like. Specific examples of the dihydric alcohol include, for example, propylene glycol.

In addition, since the hair styling composition for aerosol of the present invention may adhere to human skin, in view of its safety, among the hydrophilic solvents, ethanol and isopropanol are particularly preferable.

The polymerization is carried out by dissolving the monomers A to D in the hydrophilic solvent, adding a polymerization initiator, and stirring while heating under an inert gas stream such as nitrogen gas.

The polymerization initiator is not particularly limited as long as it is generally used in a solution polymerization method. Specific examples thereof include peroxides such as benzoyl peroxide and lauroyl peroxide, and azobisisobutyro. Examples include azo compounds such as nitriles.

In the present invention, since a monomer C that is an acrylate and / or a methacrylate is used as a monomer to be subjected to polymerization, a crosslinked gel is used when a peroxide is used as a polymerization initiator. It is preferable to use an azo-based compound, since azo compounds may be formed.

At the time of polymerization, it is preferable to use the hydrophilic solvent after adjusting the concentration of all the monomers to be used for copolymerization to be about 30 to 70%.

When the concentration of all the monomers to be used for the copolymerization is more than 50%, the polymerization is carried out by dividing the all the monomers and gradually adding them to avoid rapid generation of polymerization heat.
It is preferable for safe polymerization.

The polymerization temperature can not be determined unconditionally because it varies depending on the type of polymerization initiator used, but it is usually preferable to set the 10-hour half-life temperature of the polymerization initiator, particularly the reflux temperature of the hydrophilic solvent used. It is preferable that the distance is close because polymerization with higher reproducibility can be performed.

If the polymerization time is shorter than 8 hours, the polymerization may be incomplete and unreacted monomers may remain. Therefore, the polymerization time is desirably 8 hours or more, preferably 12 to 36 hours.

Whether or not the residual monomer is present can be determined by confirming whether or not a double bond exists by a general method, for example, the PSDB method.

The polymer thus obtained is used as a hairdressing agent in a state of a polymer solution or a state in which a solvent is removed.

When the hair styling agent of the present invention is used as an aerosol, the hair styling agent is dissolved in a hydrophilic solvent used as the polymerization solvent, for example, and a propellant is used as a propellant together with a natural gas, other additives, and an aerosol. The container may be filled under pressure and sealed. In this case, it is generally desirable that the mixing ratio of the various components to be filled in the aerosol container is appropriately adjusted according to the intended use.

Next, the hair styling agent for aerosol of the present invention will be described in more detail based on examples, but the present invention is not limited to only these examples. In each example, “parts” and “%” are based on weight unless otherwise specified.

Example 1 A five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet tube, a charging tube, and a stirrer was set to 85%.
47 parts of an ethanol solution of dimethylaminoethyl methacrylate diethyl sulfate, 40 parts of t-butyl methacrylate, 20 parts of lauryl methacrylate and 143 parts of anhydrous ethanol are added, and α, α'-azobisisobutyronitrile is added thereto.
0.3 parts was added, and the mixture was refluxed and heated at 80 ° C. under a nitrogen stream. Six hours after the start of the polymerization, 0.3 part of α, α'-azobisisobutyronitrile was added, and the reaction was completed by further polymerization for 12 hours to obtain a hairdressing agent (40% polymer ethanol solution). The weight average molecular weight of the resin contained in the obtained hairdressing agent is 70,000
Met.

The physical properties of the obtained hair dressing were examined for appearance, water solubility and compatibility with liquefied propane gas (hereinafter referred to as LPG) according to the following methods. Table 1 shows the results.

(Appearance) The obtained hair dressing was prepared so as to be an ethanol solution containing 30% of a resin component, and the appearance was visually observed.

(Water solubility) The obtained hair dressing was prepared to be an ethanol solution containing 30% of a resin component, and it was examined whether or not the hair was diluted by adding water while keeping the solution temperature at 25 ° C. The evaluation criteria are shown below.

(Evaluation criteria) ：: Infinite dilution.

 ×: Turbidity occurs when water is added.

(Compatibility with LPG) The obtained hair styling agent was prepared to be an ethanol solution containing 15% of a resin component, and LPG was dissolved while maintaining the solution temperature at 5 to 10 ° C. The amount of dissolution was determined.

Example 2 A hairdressing agent was prepared in the same manner as in Example 1 except that the monomer composition was changed to 85% diethylaminoethyl methacrylate diethylsulfate ethanol solution 58.8 parts, t-butyl methacrylate 30 parts and lauryl methacrylate 20 parts. I got The weight average molecular weight of the resin contained in the obtained hair dressing agent was 72,000.

The appearance, water solubility and compatibility with LPG were examined in the same manner as in Example 1 as physical properties of the obtained hair dressing agent. Table 1 shows the results.

Example 3 Example 1 was repeated except that the monomer composition was changed to 85% dimethylaminoethyl methacrylate diethyl sulfate ethanol solution (41.2 parts), t-butyl methacrylate (30 parts), lauryl methacrylate (20 parts) and N-vinylpyrrolidone (15 parts). A hairdressing agent was obtained in the same manner as in Example 1. The weight average molecular weight of the resin contained in the obtained hair dressing agent was 66,000.

The appearance, water solubility and compatibility with LPG were examined in the same manner as in Example 1 as physical properties of the obtained hair dressing agent. Table 1 shows the results.

Example 4 Hairdressing was performed in the same manner as in Example 1 except that the monomer composition was changed to 47 parts of an 85% dimethylaminoethyl methacrylate diethyl sulfate ethanol solution, 47 parts of t-butyl methacrylate and 20 parts of stearyl methacrylate. I got the drug. The weight average molecular weight of the resin contained in the obtained hair dressing was 65,000.

The appearance, water solubility and compatibility with LPG were examined in the same manner as in Example 1 as physical properties of the obtained hair dressing agent. Table 1 shows the results.

Example 5 A hairdressing agent was prepared in the same manner as in Example 1 except that the monomer composition was changed to 47 parts of an 85% dimethylaminoethyl methacrylate diethyl sulfate ethanol solution, 47 parts of methyl methacrylate and 20 parts of lauryl methacrylate. I got it. The weight average molecular weight of the resin contained in the obtained hair dressing was 70,500.

The appearance, water solubility and compatibility with LPG were examined in the same manner as in Example 1 as physical properties of the obtained hair dressing agent. Table 1 shows the results.

Example 6 Example 1 was repeated except that the monomer composition was changed to 47 parts of 85% dimethylaminoethyl methacrylate diethyl sulfate ethanol solution, 20 parts of ethyl acrylate, 30 parts of 2-ethylhexyl methacrylate and 10 parts of hydroxyethyl methacrylate. A hairdressing preparation was obtained in the same manner as in 1. The weight average molecular weight of the resin contained in the obtained hair dressing agent was 58200.

The appearance, water solubility and compatibility with LPG were examined in the same manner as in Example 1 as physical properties of the obtained hair dressing agent. Table 1 shows the results.

Example 7 Example 1 was repeated except that the monomer composition was changed to 58.8 parts of an 85% dimethylaminoethyl methacrylate diethyl sulfate ethanol solution, 30 parts of t-butyl methacrylate, 10 parts of cyclohexyl methacrylate and 10 parts of vinyl acetate. A hairdressing agent was obtained in the same manner as described above. The weight average molecular weight of the resin contained in the obtained hair dressing was 63,800.

The appearance, water solubility and compatibility with LPG were examined in the same manner as in Example 1 as physical properties of the obtained hair dressing agent. Table 1 shows the results.

Comparative Example 1 A hairdressing agent was obtained in the same manner as in Example 1, except that the composition of the monomers was changed to 53 parts of an 85% dimethylaminoethyl methacrylate diethyl sulfate ethanol solution and 55 parts of lauryl methacrylate. The weight average molecular weight of the resin contained in the obtained hair dressing was 68,000.

The appearance, water solubility and compatibility with LPG were examined in the same manner as in Example 1 as physical properties of the obtained hair dressing agent. Table 1 shows the results.

Comparative Example 2 A hairdressing agent was obtained in the same manner as in Example 1 except that the composition of the monomer was changed to 53 parts of an 85% dimethylaminoethyl methacrylate diethyl sulfate ethanol solution and 55 parts of t-butyl methacrylate. The weight average molecular weight of the resin contained in the obtained hair dressing was 64,000.

The appearance, water solubility and compatibility with LPG were examined in the same manner as in Example 1 as physical properties of the obtained hair dressing agent. Table 1 shows the results.

From the results shown in Table 1, it can be seen that the hair dressings obtained in Examples 1 to 7 of the present invention are all excellent in appearance, water solubility and compatibility with LPG.

Formulation Examples 1 to 7 and Comparative Formulation Examples 1 to 2 An aerosol container containing 10 g of an ethanol solution containing 10% of a resin component of the hairdressing agent obtained in Examples 1 to 7 and Comparative Examples 1 to 2 and 10 g of LPG as a propellant ( (Full injection amount: 80 ml), and a valve was attached thereto to produce a hair aerosol product.

Using the obtained aerosol product, the setting power of the hairdressing agent and the physical properties of the formed film were examined according to the following methods. Table 2 shows the results.

(Setting power) After spraying a hairdressing agent onto 2g of 25cm long hair from a distance of 20cm for 10 seconds, wind the hair around a curler with an outer diameter of 1.2cm and dry it with hot air at 40 ° C for 60 minutes. Remove the hair from the curlers, measure the length (l ₁ ) immediately after hanging vertically in an atmosphere at a temperature of 30 ° C. and a relative humidity of 80% and the length (l ₂ ) after leaving for 1 hour, and determine the curl retention. It was calculated from the following equation.

In addition, those having a curl retention of 60% or more were regarded as passing (marked with "O" in the table), and those having less than 60% were rejected (marking with "x" in the table).

(Physical properties of the film)
And spray-dried at 20 ° C. for 3 hours to form a film. This glass plate was immersed in warm water containing 0.2% shampoo at 40 ° C., and the change with time in the dissolved state of the film was examined.

(Evaluation criteria) ○ Dissolves completely within 30 minutes.

 Δ: Completely dissolved within 40 minutes.

 ×: The film remains after 40 minutes.

(B) Water resistance The above hair styling agent is placed on a glass plate 2.5cm long and 7.5cm wide for 20cm.
And spray-dried at 20 ° C. for 3 hours to form a film. This glass plate was immersed in warm water at 40 ° C., and the change over time in the dissolved state of the film was examined, and evaluated according to the following evaluation criteria.

(Evaluation criteria) ○: Does not dissolve at all even for 60 minutes or more.

 Δ: Partial dissolution was observed within 40 to 60 minutes.

 ×: Partial dissolution was observed within 40 minutes.

(C) Blocking resistance 3 g of a hairdressing agent was uniformly applied to 2 g of hair having a length of 25 cm by spraying. The hair was dried with warm air at 40 ° C. for 60 minutes, and the state of the comb was evaluated using a commercially available comb based on the following evaluation criteria.

(Evaluation criteria) ：: There is no snagging, and the comb passes smoothly.

 △: Comb can be passed though it is caught.

 ×: Comb does not pass.

(D) Smoothness The hair styling agent was sprayed onto a glass plate of 2.5 cm × 7.5 cm from a distance of 20 cm for 5 seconds, and then air-dried at 20 ° C. for 3 hours to form a film. Next, the tactile sensation of the formed film surface was examined with a finger, and the smoothness was evaluated based on the following evaluation criteria.

(Evaluation criteria) ：: Completely smooth.

 Δ: There is slight roughness.

 ×: There is considerable roughness.

(E) Transparency The above hair styling agent is placed on a glass plate of 2.5cm in length and 7.5cm in width.
After spraying from a distance of 5 hours, the film was air-dried at 20 ° C. for 3 hours to form a film. Next, the state of the formed film was visually observed and evaluated based on the following evaluation criteria.

(Evaluation criteria) ：: Completely transparent.

 Δ: Partly whitened.

 ×: The entire surface is whitened.

From the results shown in Table 2, it can be seen that the hair styling preparations obtained in Examples 1 to 7 of the present invention are all excellent in setting power, detergency, blocking resistance, smoothness and transparency. .

[Effects of the Invention] The hair styling agent for aerosol of the present invention is soluble in water and a hydrophilic organic solvent and has excellent compatibility with natural gas used as a spraying agent. It can be ejected from inside with a propellant in a homogeneous state. Further, the hair styling agent for aerosol of the present invention can be easily removed by a shampoo and has excellent blocking resistance.

Further, since the hair styling composition for aerosol of the present invention is cationic, it has excellent affinity for hair and the low moisture resistance, which is a drawback of the conventional cationic hair styling, is markedly reduced by using the monomer C. It has been improved.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Toyoyuki Sugiura 2272-5, Mise-cho, Kashihara-shi, Nara (56) References JP-A-2-223509 (JP, A) JP-A 1-223611 (JP, A) JP-A-57-165311 (JP, A) JP-A-56-92809 (JP, A) JP-A-3-178923 (JP, A) JP-A-59-172413 (JP, A) 500912 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) A61K 7/00-7/50

Claims (1)

(57) [Claims] 1. A compound of the general formula (I): (Wherein, R ¹ is a hydrogen atom or a methyl group, and R ² is
3 represents an alkylene group)
5% by weight, general formula (II): (Wherein R ¹ is the same as described above, and R ³ represents an alkyl group having 1 to 4 carbon atoms) A monomer represented by the following formula: Wherein R ¹ is the same as above, and R ⁴ represents an alkyl group having 5 to 24 carbon atoms or a cycloalkyl group having 5 to 24 carbon atoms, and the monomer A
An aerosol hair styling agent comprising a polymer obtained by copolymerizing 0 to 20% by weight of an ethylenically unsaturated monomer other than -C.