JPH03206023A - Hair-dressing resin composition - Google Patents

Abstract

PURPOSE:To obtain a hair-dressing resin composition having excellent solubility in liquefied petroleum gas, free from tackiness and flaking tendency and exhibiting excellent setting performance by copolymerizing four specific kinds of polymerizable monomers at specific ratios and neutralizing the product with a water-soluble organic basic substance. CONSTITUTION:The objective composition can be produced by copolymerizing (A) 6-35wt.% of at least one kind of monomer (hereinafter abbreviated as a monomer) selected from acrylic acid, methacrylic acid and itaconic acid, (B) 15-50wt.% of a monomer selected from 10-18C aliphatic alcohol ester of acrylic acid and/or methacrylic acid, (C) 15-50wt.% of a monomer selected from 4-8C aliphatic alcohol ester of acrylic acid and/or methacrylic acid and (D) 0-25wt.% of other vinyl monomers and neutralizing the obtained copolymer with a water- soluble organic basic substance (e.g. ammonia water or formalin). The sum of the monomers B and C is preferably >=41wt.% to further improve the solubility in liquefied petroleum gas.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a hair styling resin composition that has excellent solubility especially in liquefied petroleum gas (LPG), adheres to hair, and exhibits excellent hair styling effects. relating to things.

[Conventional technology]

Conventionally, nonionic resins and anionic resins are known as hair styling resins.

Known examples of the nonionic resin include polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymer, and polyvinyl methyl ether. However, the physical properties of polyvinyl pyrrolidone-based materials change significantly between before and after moisture absorption, such that the film that contains them is hard before moisture absorption, but suddenly becomes soft after moisture absorption, and flakes when dry. It also has the disadvantage that it loses its curl and set in a short period of time when it is wet. Furthermore, a product obtained by copolymerizing vinyl pyrrolidone with vinyl acetate does not solve flaking, and the formed film has poor transparency, and cannot give a natural appearance to hair. Furthermore, since polyvinyl methyl ether is extremely sticky, it is only added as a plasticizer for polyvinylpyrrolidone.

On the other hand, the anionic resins include vinyl ether, maleic anhydride half ester, vinyl acetate/crotonic acid copolymer, (meth)acrylic acid/(meth)acrylic acid ester copolymer, etc., and the carboxyl in the polymer The current mainstream of hair styling resins is one in which water-solubility is imparted to the resin film by neutralizing the groups. However, many of the above-mentioned anionic resins have low solubility in liquefied petroleum gas, and when aerosolized in a formulation containing liquefied petroleum gas alone, insoluble matter may be produced when left at low temperatures. This has the disadvantage that it causes the air sole to malfunction and cause eye contact, resulting in the loss of the intended function.

In this specification, (meth)acrylic acid refers to acrylic acid and methacrylic acid, (meth)acrylic acid ester refers to acrylic ester and methacrylic ester, and (meth)acrylate refers to acrylate and methacrylic acid. Methacrylate is a general term, and (meth)acrylamito is a general term for acrylamide and metaxolamide.

[Problem to be solved by the invention]

The problem to be solved by the present invention is to provide a hair styling resin composition that does not produce insoluble matter even at low temperatures when aerosolized using liquefied petroleum gas alone, and exhibits excellent hair styling effects. .

[Means and effects for solving B oil] The hair styling resin composition according to the present invention has the following features: a. 6-35% by weight of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid b. Acrylic acid and/or methacrylic acid with 10 or more carbon atoms
15 to 50% by weight of at least 144 IIL polymers consisting of esters of 18 aliphatic alcohols, 4 to 8 carbon atoms of acrylic acid and/or methacrylic acid;
at least one monomer consisting of an ester of an aliphatic alcohol 1 5-50% by weight d. It is obtained by copolymerizing azd, a polymerizable monomer consisting of 0 to 25% by weight of other vinyl monomers, and neutralizing it with a water-soluble organic basic substance.

The monomer a is involved in the wood-philicity and hair washing properties of the resin, and the amount used is 6 to 35% by weight, preferably 10 to 30% by weight. When the amount used is less than 6%, the resulting film is poorly soluble in water and has poor hair washability;
If it exceeds 5% by weight, the amount of moisture absorbed increases and stickiness becomes noticeable, resulting in poor solubility in petroleum scum.

As monomer a, unsaturated carboxylic acid monomers selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid can be used alone or in combination.

Monomer b is involved in the lipophilicity, flexibility, and washability of the resin, and the amount used is 15 to 50% by weight, preferably 20 to 45% by weight. When the amount used is less than 15% by weight, the resulting film is hard, causes flaking, and has poor solubility in liquefied petroleum gas. On the other hand, it is 50
If the weight percentage is exceeded, the resulting film becomes very soft and sticky, resulting in poor hair washability.

Specific examples of monomer b include decyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, valmityl (meth)acrylate, stearyl (meth)acrylate, oleyl (meth)acrylate, and tridecyl (meth)acrylate. ) Synthetic alcohol (meth)acrylates such as acrylates can be used alone or in combination.

Monomer C is also involved in the lipophilicity, flexibility, and washability of the resin, and the amount used is 15 to 50% by weight, preferably 20 to 45% by weight. When the amount of stool is less than 15% by weight + 1%, the solubility in liquefied petroleum gas becomes poor, while when it exceeds 50% by weight, the hair washing properties become poor.

As a specific example of monomer C, for example, n-butyl (meth)
acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (
Meth) acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. can be used alone or in combination.

Comparing the monomer b and the ridge member C, the contribution to the lipophilicity of the resin and the effect of impairing hair washability are greater than the former or the latter, but the former also contributes to the solubility in liquefied petroleum gas. is larger than the latter. In order to further improve the solubility in liquefied petroleum scum, the total amount of monomer b and monomer C is preferably 41% by weight or more.

Monomer d is involved in the hardness of the film and the solubility in liquefied petroleum scum, and the amount used is O to 25% by weight, and is used as necessary. The amount used is preferably 1% by weight or more in order to fully obtain the desired effect, but if it exceeds 25% by weight, the solubility in liquefied petroleum gas becomes poor.

Specific examples of monomer d include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, ethoxyethyl (meth)acrylate, acrylonitrile, (meth)acrylamide, vinyl acetate, styrene, vinylpyrrolidone, etc. can be used alone or in combination. Among the monomers d, methyl acrylate, ethyl acrylate, probyl acrylate, ethoxyethyl acrylate, acrylonitrile,
Relatively flexible films are obtained when acrylamide and vinylpyrrolidone are used; methyl methacrylate,
When ethyl methacrylate, proyl methacrylate, ethoxyethyl methacrylate, methacrylamide, vinyl acetate, or styrene is used, a film that is harder and less sticky can be obtained than the former.

The above copolymerization of monomers a''-d can be carried out by ordinary solution polymerization in a hydrophilic solvent. For example, each monomer is dissolved in a hydrophilic solvent, a polymerization initiator is added, and the solvent is heated under a nitrogen stream. This can be carried out by stirring at or near the boiling point of the monomer.All types and amounts of the monomers may be present from the beginning of the polymerization, or the types and/or amounts of the monomers may be added in portions. The solvent is preferably used so that the solid content in the resin solution is 30 to 60% by weight.

Examples of hydrophilic solvents include water-soluble aliphatic alcohols such as methyl alcohol, ethyl alcohol, isobrobyl alcohol, butyl alcohol, hydrous alcohols such as 95% ethyl alcohol, acetone, methyl cellosolve, ethyl cellosolve, dioxane, etc. Methyl acetate, ethyl acetate, dimethylformamide, etc. can be used alone or in combination.

In addition, as a polymerization initiator, for example, penzoyl peroxide,
It is recommended to use peroxides such as lauroyl peroxide and azo compounds such as azobisisobutyronitrile.

By adding a water-soluble organic basic material to the resin-containing liquid obtained by the copolymerization, the copolymerized network resin is preferably
Neutralize with a neutralization rate of 0 to 100% and make it water-soluble.

Examples of water-soluble organic basic substances include ammonia water,
Morpholine, (mono-, di- or tri)ethanolamine,
(Mono, di, or tri) isobrobanolamine, aminomethylbrobanolamine, aminoethylbrobanolamine, aminomethylpropanediol, aminoethylpropanediol, and the like can be used alone or in combination. In particular, when an organic amine is used, a water-free resin composition can be obtained, which is suitable for producing an aerosol that avoids water.

The resin composition obtained as described above has a copolymer having an average molecular weight of about 5,000 to 200,000, and can be used as a solution in a hydrophilic solvent obtained by the copolymerization or in a water-containing solvent. It can be used as a system.

The resin composition according to the present invention includes an aliphatic alcohol having 1 to 4 carbon atoms, a hydrous alcohol such as 95% ethyl alcohol,
It can be dissolved in a hydrophilic solvent such as acetone, methyl cellosolve, ethyl cellosolve, dioxane, methyl acetate, and ethyl acetate, and sealed in a container under pressure with a propellant to form an aerosol.

The propellants include liquefied petroleum gas (LPG) whose main components are propane, butane and isobutane, trichloromonofluoromethane (Freon 11), cyclosifluoromethane (Freon 12), and cyclotetrafluoroethane (Freon 114). , halogenated hydrocarbons containing methylene cyclolite, etc., dimethyl ether, carbon dioxide gas, etc. can be used singly or in mixtures thereof. 15% by weight
Solution 2 obtained by dissolving in a hydrophilic organic solvent so that
An aerosol can be obtained by sealing 5 to 80% by weight of the propellant and 75 to 20% by weight of the propellant in a pressure vessel.

The resin composition according to the present invention can be dissolved in water and a hydrophilic organic solvent and added with various additives for hair styling products, and used as a component of hair styling products such as hair creams, hair lotions, and non-gas aerosols (hair mist). I can do it.

In addition, the reticulum composition can be used as a hair coloring fixing agent in hair cosmetic colorants such as color sprays, color foams, mascara types, etc. by combining hair colorants. In addition to the above uses, the resin composition may also include:
It can also be suitably used as a film-forming component for facial cosmetics and as a coating agent for skin wounds.

[Examples 1 to 6] The present invention will be described below based on Examples. In addition, both "%" and "part" described in F below are based on weight.

Table 1 lists the monomer composition, neutralization rate, average molecular weight, etc. of the resin in each example and its corresponding comparative example, and Table 2
Performance evaluation of each resin composition shown in Table 1 is described below.

<Manufacture of resin composition> 200 parts of polymerizable monomers a to d, 100 parts of ethyl alcohol, and a polymerization initiator to a tIL four-flask equipped with a reflux condenser, thermometer, glass tube for nitrogen substitution, dropping funnel, and stirrer. Add 0.5 to 4 parts and reflux under nitrogen stream (
Polymerization is carried out at a temperature of about 80° C. for 5 hours. After polymerization, cool
An ethyl alcohol solution of a water-soluble organic basic substance is added at 0° C. and diluted with ethyl alcohol to a solid content of 50%.

<Preparation of aerosol (hair spray)> Using the resin compositions (solid content 50%) of each example and comparative example, three types of aerosol (hair spray) ANC consisting of the following composition were prepared in a pressure-resistant glass bottle for aerosol. Prepared in

ABC 10% factorial content of resin composition 45 50 55
Ethyl alcohol solution liquefied petroleum gas* 55 50 45
*Liquefied petroleum gas consists of 25% propane and 75% butane, and has a temperature of about 3.5% at 20°C. 'OKg/Cm' was used.

<Performance Evaluation> (1) Aerosol Stability Hair Spray A. B and C were left in a -10°C freezer for 24 hours, and the state of the solution was evaluated as follows.

O: Transparent, △: Slightly cloudy, ×: Separates or produces precipitate (2) Curl retention length 22 cm,
After washing approximately 2g of hair with a commercially available shampoo, treating it with a commercially available conditioner and air drying, attach a 10g clip to the bottom end of the hair, and attach it to a motor that rotates at 30 revolutions per minute to prevent the hair from scattering when sprayed. Ta. Next, while rotating the hair, spray Hairbrae evenly for 10 seconds from a distance of about 15 cm, immediately smooth out the attached droplets with your fingers, and wind them into a 1.2 cm diameter lot.
It was fixed with a clip and dried at 55 to 60°C for 30 minutes. Furthermore, after cooling it well in a desiccator, it was unraveled into a spiral shape, and a glass plate (0.5
Attach a scale to a 1-digit scale every cm, and heat at 30°C.
The hair was left in a temperature and humidity chamber adjusted to 90% RH, and the position of the tip of the hair after 10 hours was recorded, and curl retention was measured based on the following formula.

L, -L. L ・Length when the test piece is stretched (L = 2 2
cm) Lo: Constant temperature drying I. i Position of the tip of the test piece L before placing it in the humidity chamber, ・Position of the tip of the test piece in ↓5 after leaving it in a constant temperature and humidity chamber for 10 hours (3) Same as in the case of flaking cell force value The amount of resin that fell off when the hair prepared in 1 was combed was evaluated as 34i as in Shimokita.

○: Almost no falling off, △. Little shedding, ×: Major shedding (4) Smoothness When evaluating flaking, the difficulty of combing was rated on a 5-point scale as in F-E.

0: Easy to comb, △: Slightly difficult to comb, ×: Difficult to comb. Spread the solution with a glass rod etc. so that it is 1.5 cm). The glass plate is left in an atmosphere of 20° C. and 60% RH all day and night, and then dried at 60° C. for 1 hour.

Regarding the cleanability, the glass plate was immersed in a 0.5% commercially available shampoo ice-containing aqueous solution at 40° C., and the dissolution state of the film was evaluated as follows.

○: Dissolved within 1 hour, △: A small amount remained after 1 hour,
×: After 1 hour, if there is a large amount of residual blocking (adhesiveness), the glass plate
Humidity controlled to 0℃ and 90%RH! After being left in a lI temperature and humidity chamber for a day and night, it was evaluated by touch as described above.

0: No adhesion, △: Slight adhesion, ×: Adhesiveness 71 people (6) Feeling When the hair was prepared in the same manner as in the evaluation of feel setting, the feel of the hair was evaluated as follows.

O: Soft and soft to the touch, △: Slightly stiff or stale, ×: Very stiff or sagging (hereinafter referred to as the margin of this page) [Effects of the Invention] As described above, the present invention has the following advantages: Such hair styling resin compositions have particularly excellent solubility in liquefied petroleum gas, are free from adhesion and flaking, have excellent smoothness, exhibit excellent setting properties even at high temperatures and under heavy rubbing, and do not impair its feel. It has a hair styling effect and can be easily removed by washing.

that's all

Claims (2)

[Claims] (1) A hair styling resin composition obtained by copolymerizing the following polymerizable monomers a to d and neutralizing the resultant with a water-soluble organic basic substance. a. 6-35% by weight of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid b. Acrylic acid and/or methacrylic acid with 10 or more carbon atoms
15-50% by weight of at least one monomer consisting of esters of 18 aliphatic alcohols c. Acrylic acid and/or methacrylic acid having 4 to 8 carbon atoms
15-50% by weight of at least one monomer consisting of an ester of an aliphatic alcohol d. Other vinyl monomers 0-25% by weight (2) The hair styling resin composition according to claim 1, wherein the total amount of monomer b and monomer c is 41% by weight or more.