JP2830114B2 - Hairdressing spray composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an aerosol spray composition for hair styling that exhibits an excellent hair styling effect and contains an anionic resin and uses a petroleum liquefied gas or the like as a propellant.

[Conventional technology]

As a hairdressing resin, an amphoteric ionic polymer which is a copolymer having a carboxybetaine moiety as a hydrophilic group.

A nonionic polymer which is a copolymer having vinylpyrrolidone or the like as a hydrophilic portion.

An anionic polymer which is a copolymer having a polymerizable unsaturated monomer having a carboxyl group such as acrylic acid and methacrylic acid or a salt thereof as a hydrophilic group.

 Etc. are known.

It is known that anionic polymers are excellent hair styling resins in terms of performance such as hair setting power and film hardness, and this polymer has already been disclosed in Japanese Patent Publication No. 44-3123.
8. It is known from Japanese Patent Publication No. 50-6538.

These hairdressing resins are generally used in the form of an aerosol spray, and trichloromonofluoromethane (F11) is used as a propellant in an alcoholic solution of the resin.
It has been common practice to inject halogenated hydrocarbons such as dichlorodifluoromethane (F12) and dichlorotetrafluoroethane (F114). However, in recent years, hydrocarbons such as propane and butane have been increasingly used as propellants instead of halogenated hydrocarbons due to global environmental problems.

However, when a conventional anionic polymer is used to form an aerosol spray using a hydrocarbon as a propellant, the solubility of the polymer in the solution decreases in the aerosol spray container, resulting in a non-uniform solution and a polymer. There is a problem in that the sprayed coating film becomes non-uniform due to the precipitation of the resin, or the valve is clogged.

[Problems to be solved by the invention]

The present invention solves the above problems and provides a hair styling spray composition having excellent performance as a hair styling aerosol spray using a hydrocarbon as a propellant.

[Specific means for solving the problem]

The present invention relates to (A) a (meth) acrylate monomer having an alkyl or alkenyl group having 1 to 7 carbon atoms (1); 30 to 70% by weight, an alkyl or alkenyl group having 9 to 24 carbon atoms (meth) ) Acrylate monomer (2): 10 to 50% by weight, polymerizable unsaturated monomer having a carboxyl group or a salt thereof (3); 10 to 40% by weight, and other than the above (1) to (3) Anionic resin obtained by copolymerizing 0 to 20% by weight of a polymerizable unsaturated monomer (4):
0.5 to 15% by weight [However, (meth) acrylate monomers (1) and (2)
In the above, the amount of the monomer whose alkyl group and alkenyl group have a branched structure is at least 50% by weight based on the total amount of the monomers (1) and (2). (B) ethanol, propanol, isopropanol,
A solvent selected from the group consisting of 1-methoxypropanol and a mixture thereof: 10 to 89.5% by weight, and (C) propane, normal butane, isobutane, 2,2-
An object of the present invention is to provide a hairdressing spray composition comprising 10 to 75% by weight of a propellant selected from the group consisting of dimethylpropane, isopentane and dimethyl ether.

(A) Anionic resin The anionic resin of the component (A) in the present invention comprises the above three kinds of essential monomers [monomer (1), (2), (3)], and an optional monomer. One type (monomer (4)) is copolymerized. These monomers can be used together in each group.

The monomer (1) is an alkyl or alkenyl ester of acrylic acid or methacrylic acid (hereinafter referred to as (meth) acrylic acid), wherein the alkyl or alkenyl group has 1 to 7 carbon atoms.

Specific examples of the monomer (1) include, for example, methyl (meth) acrylate, allyl (meth) acrylate,
Isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, hexyl (meth)
Acrylate and the like.

The amount of the monomer (1) to be used is 30 to 70% by weight, preferably 35 to 65% by weight, based on all monomers. If the amount is less than 30% by weight, the resulting copolymer resin film (hereinafter abbreviated as film) will exhibit a blocking feeling, and if it exceeds 70% by weight, the obtained film will have reduced flexibility and spreadability. Further, when the amount of the monomer (1) exceeds 70% by weight based on all the monomers, the solubility of the component (C) in the propellant decreases.

The monomer (2) is an alkyl or alkenyl ester of (meth) acrylic acid, wherein the alkyl or alkenyl group has 9 to 24 carbon atoms.

Specific examples of the monomer (2) include, for example, lauryl (meth) acrylate, branched tridecyl (meth) acrylate, palmityl (meth) acrylate, branched pentadecyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) ) Acrylate, behenyl (meth) acrylate and the like.

The amount of the monomer (2) used is 10 to 50% by weight, preferably 15 to 45% by weight, based on all monomers. If it is less than 10% by weight, the solubility of the component (C) in the propellant decreases,
If it exceeds 50% by weight, the resulting film will exhibit a blocking feeling.

As these (meth) acrylate monomers, those in which the monomer (1) or (2) is an alkyl methacrylate are preferred, and those in which both are alkyl methacrylates are more preferred.

In the monomer (1) and the monomer (2), a monomer in which the alkyl group and the alkenyl group of the ester have a branched structure is the same as the (meth) acrylate monomers (1) and (2). When the amount is 50% by weight or more based on the total amount, and the amount of the ester monomer having a branched structure is less than 50% by weight, the solubility in the propellant as the component (C) decreases.

The monomer (3) is a polymerizable unsaturated monomer having a carboxyl group or a salt thereof. Specific examples of the monomer (3) include, for example, (meth) acrylic acid, maleic acid,
Maleic anhydride, itaconic acid, fumaric acid, vinyl acetic acid,
Polymerizable unsaturated carboxylic acids such as crotonic acid, and polybasic anhydrides (eg, phthalic anhydride, oxalic anhydride, etc.) and hydroxyl group-containing unsaturated monomers (eg, hydroxyethyl (meth) acrylate, hydroxypropyl ( And a salt of a polymerizable unsaturated monomer having a carboxyl group.

If necessary, the polymerizable unsaturated monomer having a carboxyl group can be partially neutralized or completely neutralized in the monomer stage or the post-polymerization stage, and can be used as a basic compound used for neutralization. Is, for example, aqueous ammonia, lithium hydroxide, potassium hydroxide, sodium hydroxide; mono-, di-, or triethanolamine; mono-, di-, or triisopropanolamine; morpholine, aminomethylpropanol, aminoethylpropanediol , Lysine and the like.

The amount of the monomer (3) to be used is 10 to 40% by weight, preferably 15 to 35% by weight, based on all monomers. If it is less than 10% by weight, the resulting film will be poorly soluble in water, causing problems during shampooing. If the content exceeds 50% by weight, the solubility of the component (C) in the propellant decreases, and the resulting film has an increased hygroscopicity and exhibits a blocking feeling, and the hair styling effect (setting power) decreases. I do.

The monomer (4) is a polymerizable unsaturated monomer other than the above (1) to (3), and imparts appropriate hardness, appropriate flexibility, and the like to the obtained film to change the feel. Can be used as one component of the copolymer as required.

Specific examples of the monomer (4) include, for example, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane, (meth) acrylamide, diacetone acrylamide and the like. (Meta)
There are acrylic-based derivatives, aromatic polymerizable vinyl monomers such as styrene, chlorostyrene, and vinyltoluene, and polymerizable vinyl monomers such as N-vinylpyrrolidone and vinyl acetate.

The amount of the monomer (4) to be used is 0 to 20% by weight, preferably 0 to 15% by weight, based on all monomers.

The anionic resin as the component (A) of the present invention can be obtained by copolymerizing the above monomer in a hydrophilic solvent.
Here, “hydrophilic solvent” means that the solubility in water is 10 g / g
100 g / 25 ° C.] or higher.

Suitable hydrophilic organic solvents are preferably aliphatic alcohols having 1 to 4 carbon atoms, particularly monohydric alcohols such as methanol, ethanol, propanol and isopropanol. In addition, dihydric alcohols such as ethylene glycol and the like, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, dioxane, methyl acetate, dimethylformamide and the like are used.

The “hydrophilic solvent” may be in a water-containing state. The degree of water content is free within the range in which all the monomers used are dissolved at a predetermined concentration from the viewpoint of the polymerization solvent. For example, there is 5% aqueous ethanol.

The polymerization is carried out by a usual solution polymerization method, for example, a method comprising dissolving each monomer in the solvent, adding a radical polymerization initiator, and heating and stirring under a nitrogen stream. As the radical polymerization initiator, peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile are preferable. Usually, all kinds and amounts of the monomers are present from the initial stage of the polymerization, but it is also possible to carry out divisional addition with respect to the kind and / or the amount of the monomers. The amount of solvent used is such that the concentration of the resulting copolymer solution is 30 to 65.
It is preferable that the amount is about weight%.

The polymerization conditions such as the method of adding the monomer and the polymerization initiator, and the amount of the solvent used can be appropriately selected, but it is preferable that the molecular weight of the obtained polymer be in the range of 5,000 to 500,000.

The hydrophilic solvent solution of the anionic resin thus obtained can be used as it is, and if the solvent is removed, the anionic resin can be taken out as a solid, and the following (B) It can be used after diluting with the solvent of the component.

(B) Solvent The solvent of the component (B) is used to dilute the anionic resin of the component (A) or a solution of the anionic resin in a hydrophilic solvent. This solvent is a solvent selected from the group consisting of the lower alcohols and mixtures thereof, and may contain water in a range of 20% by weight or less.

Preferred diluting solvents include ethanol, mixed solvents of ethanol and isopropanol, and ethanol containing 5% by volume of water.

(C) Propellant The hair styling spray composition of the present invention puts a solution obtained by diluting the component (A) with the component (B) in a spray container, and pressurizes and seals the propellant of the component (C). This can be used as a spray.

The propellant of the component (C) is a liquefied gas selected from the group consisting of propane, normabutane, isobutane, 2,2-dimethylpropane, isopentane, dimethyl ether, and a mixture thereof.
It may be used in combination with fluorocarbons such as fluorotrichloromethane, chlorinated hydrocarbons such as methylene chloride, nitrogen, carbon dioxide and the like.

Preferred propellants include petroleum-based liquefied gas whose main component is a mixture of propane, normal butane, and isobutane, and a mixture of the petroleum-based liquefied gas and dimethyl ether, and the filling pressure is ^{2 to} 10 kg / cm ² G (20 ° C) is preferred.

Component (A) (anionic resin) is used in an amount of 0.5 to 15% by weight based on the total amount of components (A) to (C).
Preferably it is 1 to 10% by weight. If the amount is less than 0.5% by weight, the set of hair (curl retention) becomes insufficient, and if the amount exceeds 15% by weight, uncomfortable feeling such as stiffness is given to the hair. Component (B) (solvent) is used in an amount of 10 to 89.5% by weight, preferably 10 to 89.5% by weight, based on the total amount of components (A) to (C).
30 to 84% by weight. If the amount is less than 10% by weight, uncomfortable feeling such as stiffness is given to the hair, and if the amount exceeds 89.5% by weight, there arises a problem that the drying speed becomes slow when spray-applied to the hair. The amount of component (C) (propellant) used is from component (A) to component (C).
10 to 75% by weight, preferably 15 to 65% by weight, based on the total amount of If the amount is less than 10% by weight, fine spraying is difficult to be performed at the time of spraying, and there are problems such as a slow drying rate when applied to hair. If the amount exceeds 75% by weight, the drying rate is too fast when spray applied to hair. Therefore, there is a problem that uniform application to hair cannot be performed.

The spray composition of the present invention comprises known additives or auxiliaries, for example, esters such as isopropyl myristate and ethyl phthalate, polyhydric alcohols such as glycerin and polyethylene glycol, silicone compounds, oils such as paraffin and squalane. , Cationic, anionic, amphoteric, nonionic surfactants, cationic, amphoteric, nonionic hairdressing resins, dyes, pigments and other coloring agents, UV absorbers, preservatives, perfumes, etc. as required It is possible to use it additionally.

〔Example〕

Hereinafter, the present invention will be described with reference to Production Examples and Examples.
In these examples, “parts” and “%” are used.
Is represented on a weight basis, and the blending amount of the (A) anionic resin in Tables 1 and 2 is represented by% by weight as the amount of the active ingredient.

Production Example 1 In a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a glass tube for nitrogen replacement, and a stirrer, 50 parts of isobutyl methacrylate and methyl methacrylate 5 were added.
Parts, 15 parts of stearyl methacrylate, 5 parts of behenyl acrylate, 25 parts of methacrylic acid, and 100 parts of ethanol, and 0.6 parts of azobisisobutyronitrile was added. Done.

Next, under cooling, a 40% ethanol solution of aminomethylpropanol corresponding to 70% of equimolar methacrylic acid was added dropwise to the flask, and ethanol was further added to obtain a 40% ethanol solution of the anionic resin “A-1”. Was. Incidentally, the average molecular weight of the obtained resin was 80,000.

Production Example 2 In the same apparatus as in Production Example 1, isobutyl acrylate 20
Part, tert-butyl methacrylate 20 parts, branched tridecyl methacrylate 20 parts, stearyl methacrylate
10 parts, 30 parts of methacrylic acid, and 150 parts of ethanol were added, and 0.9 parts of benzoyl peroxide was added.
And refluxed for 6 hours to carry out polymerization.

Next, under cooling, a 40% ethanol solution of aminomethylpropanol corresponding to 70% of an equimolar amount of methacrylic acid was dropped into the flask, and ethanol was further added to obtain a 40% ethanol solution of the anionic resin “A-2”. Was. The average molecular weight of the obtained resin was 45,000.

Production Example 3 Isobutyl methacrylate was added to the same apparatus as in Production Example 1.
40 parts, tertiary butyl acrylate 5 parts, lauryl methacrylate 10 parts, stearyl methacrylate 20 parts,
18 parts of methacrylic acid, 7 parts of acrylic acid, and 80 ethanol
, And 0.6 parts of azobisisobutyronitrile was added, and the mixture was refluxed and heated at 80 ° C under a nitrogen stream to carry out polymerization for 8 hours.

Next, under cooling, the mixture was added dropwise to a flask of a 40% ethanol solution of triethanolamine corresponding to 70% of an equimolar amount of the acid used.
3 "was obtained as a 40% ethanol solution. The average molecular weight of the obtained resin was 150,000.

Production Example 4 In the same apparatus as in Production Example 1, 5 parts of isopropyl methacrylate, 35 parts of isobutyl methacrylate, 5 parts of cyclohexyl methacrylate, 15 parts of decyl methacrylate, 15 parts of behenyl methacrylate, 15 parts of methacrylic acid, 10 parts of diacetone acrylamide and 100 parts of ethanol Part, add 0.6 parts of benzoyl peroxide, and add
And refluxed for 6 hours to carry out polymerization.

Then, under cooling, a 40% ethanol solution of aminomethylpropanol corresponding to an equimolar amount of methacrylic acid was added dropwise to the flask, and ethanol was further added to the anionic resin “A-
4 "was obtained as a 40% ethanol solution. The average molecular weight of the obtained resin was 75,000.

Production Example 5 Isobutyl methacrylate was added to the same apparatus as in Production Example 1.
60 parts, 15 parts of methyl methacrylate, 20 parts of stearyl methacrylate, 5 parts of methacrylic acid, and 100 parts of ethanol were added, and 0.6 part of azobisisobutyronitrile was added.
Polymerization and aminomethylpropanol neutralization were carried out in the same manner as in "Production Example 1" to obtain a 40% ethanol solution of the anionic resin "A-5". The average molecular weight of the obtained resin was 85,0.
00.

Production Example 6 Isobutyl methacrylate was added to the same apparatus as in Production Example 1.
30 parts, 20 parts of normal butyl methacrylate, 5 parts of methyl methacrylate, 20 parts of stearyl methacrylate, 25 parts of methacrylic acid and 100 parts of ethanol were added, and 0.6 parts of azobisisobutyronitrile was added. And aminomethylpropanol neutralization to obtain a 40% ethanol solution of the anionic resin "A-6".
Incidentally, the average molecular weight of the obtained resin was 80,000.

Production Example 7 Isobutyl methacrylate was added to the same apparatus as in Production Example 1.
60 parts, methyl methacrylate 15 parts, methacrylic acid 25 parts,
And 100 parts of ethanol, 0.6 parts of azobisisobutyronitrile was added, and polymerization and neutralization with aminomethylpropanol were carried out in the same manner as in Production Example 1.
-7 "in a 40% ethanol solution. The average molecular weight of the obtained resin was 75,000.

Production Example 8 Isobutyl methacrylate was added to the same apparatus as in Production Example 1.
30 parts, stearyl methacrylate 20 parts, methacrylic acid 50
And 100 parts of ethanol, and 0.6 part of azobisisobutyronitrile was added. Polymerization and aminomethylpropanol neutralization were carried out in the same manner as in Production Example 1 to give 40% ethanol of the anionic resin "A-8". A solution was obtained. The average molecular weight of the obtained resin was 65,000.

Example 1 8 parts of anionic resin "A-1" and 72 parts of ethanol were placed in a pressure-resistant glass spray bottle, and then a propellant 20 in which propane / normanbutane / isobutane was mixed at a weight ratio of 20/50/30. The part is pressed into a spray bottle to obtain a spray sample.

When this spray sample was evaluated, it showed excellent performance as shown in Table 1.

Examples 2 to 7 Using the spray compositions shown in Table 1, the same operations as in Example 1 were performed to obtain spray samples. When this spray sample was evaluated, it showed excellent performance as shown in Table 1.

Comparative Examples 1 to 7 Using the spray compositions shown in Table 2, the same operations as in Example 1 were performed to obtain spray samples. When this spray sample was evaluated, there was a problem in performance as shown in Table 2.

In Tables 1 and 2, the abbreviation of the propellant (C) in the spray composition means the following gas composition.

<Gas composition (weight ratio)> Gas-1: propane / normanbutane / isobutane = 20/50
/ 30 Gas-2: propane / normanbutane / isobutane = 30/44
/ 26 Gas-3: propane / isobutane = 20/80 The performances in Tables 1 and 2 are evaluated as follows.

は: good; △: insufficient; ×: poor <Low-temperature stability> The spray sample was left at −10 ° C. for 3 days, and the state of the liquid content (white turbidity or polymer precipitation) was evaluated.

<Dryability> Spray the spray sample on a glass plate for 3 seconds,
The dry state at every hour is visually evaluated.

<Film smoothness> Spray sample on glass plate for 3 seconds,
Leave it in an atmosphere of 20 ° C and 60% RH (relative humidity) for one day,
Evaluation is made visually and visually.

<Washability> A glass plate prepared in the same manner as the film
The evaluation is made based on the state of film dissolution at each time when the film is immersed in warm water containing shampoo containing% shampoo.

<Set power> Spray the spray sample on hair of 23cm, 2g for 10 seconds, wind it on a curler of 1.2cm diameter, and after drying, 30 ℃, 90% RH
(Relative humidity) Hang under an atmosphere and measure curl retention.

<Flaking> In the same manner as in the evaluation of the setting force, the amount of the release resin from the hair when the hair was combed was evaluated.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-167307 (JP, A) JP-A-63-48315 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A61K 7/06-7/155

Claims (1)

(57) [Claims] (A) a (meth) acrylate monomer having an alkyl or alkenyl group having 1 to 7 carbon atoms (1): 30
(Meth) acrylate monomer having an alkyl or alkenyl group having 9 to 24 carbon atoms (2): 10 to 50% by weight; polymerizable unsaturated monomer having a carboxyl group (3): 10 To 40% by weight, and an anionic resin obtained by copolymerizing 0 to 20% by weight of a polymerizable unsaturated monomer (4) other than the above (1) to (3): 0.5 to 15% by weight [however, , (Meth) acrylate monomers (1) and (2), wherein the alkyl group and alkenyl group of the monomer have a branched structure, based on the total amount of monomers (1) and (2) Not less than 50% by weight. (B) ethanol, propanol, isopropanol,
A solvent selected from the group consisting of 1-methoxypropanol and a mixture thereof: 10 to 89.5% by weight, and (C) propane, normal butane, isobutane, 2,2-
A hairdressing spray composition comprising 10 to 75% by weight of a propellant selected from the group consisting of dimethylpropane, isopentane and dimethyl ether.