JP2002338442A - Hair hard-treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair hard-treating agent which gives sufficient tension, sufficient stiffness, good touches (a proper bending hard touch and a proper volume touch), and excellent shampoo resistance. SOLUTION: This hair hard-treating agent is characterized by containing (I) 0.06 to 9.5 wt.% of vinyl caprolactam/vinylpyrrolidone/dimethylaminopropyl methacrylamide copolymer, (II) 0.06 to 9.5 wt.% of one or more compounds selected from the group consisting abietic acid, rosin, their salts, and their derivatives, and (III) 0.06 to 9.5 wt.% of an alkylpyridinium salt and/or a benzalkonium type quaternary ammonium salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a hair curing agent. More specifically, the present invention provides hair with firmness, firmness,
And a hair curing agent for imparting a feeling of bending hardness and the like.

[0002]

2. Description of the Related Art When hair is chemically treated with perm, bleach, hair color or the like, or is exposed to sunlight for a long time, the hair is damaged and weakened. As a result, the hair may lose moderate hardness and become too soft.
Also, the hair may be too soft due to the inherently thin hair.

[0003] However, for example, in order to maintain a set hairstyle, the hair must have a certain degree of firmness and firmness, and too soft hair is not preferred. On the other hand, excessively soft hair has a bad touch to the hair.

[0004] Therefore, various hair treatment agents or hair cosmetics for giving the hair firmness and firmness have been proposed. For example, Japanese Patent Application Laid-Open No. Hei 10-279436 proposes a hair cosmetic comprising a polyamide epichlorohydrin resin and a nonionic silicone and / or a nonionic surfactant.

[0005] However, since the above-mentioned hair cosmetic uses a polyamide epichlorohydrin resin which is a water-soluble resin, if the hair is shampooed after the hair treatment, the applied hair cosmetic is slightly washed away.
As a result, there is a problem in that tension and firmness imparted to the hair are reduced.

[0006] Japanese Patent No. 3024962 discloses a high-purity β-phosphate having a dinaphthyl sulfone content of 0.1% by weight or less.
A hair treatment agent comprising a naphthalene sulfonate is proposed.

However, when the above-mentioned β-naphthalene sulfonate is used, it can not be said that hair is firmly and firmly imparted as compared with the case where a high molecular weight resin is used.

Furthermore, Japanese Patent Application Laid-Open No. 2000-302645 proposes a hair cosmetic containing a specific amphoteric surfactant and a specific vegetable oil or fat.

However, since the amphoteric surfactant has a moisture retaining effect, if the hair is treated with this hair cosmetic and then exposed to the air for a long time, the hair absorbs the moisture in the air. Sometimes you do. As a result, the hair becomes moist and the tension and stiffness decrease. Therefore, it is not sufficiently satisfactory in terms of retention of firmness and stiffness.

[0010]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides hair with sufficient firmness and firmness, and a good tactile sensation (appropriate hardness and volume), and shampoo after the hair has been cured. An object of the present invention is to provide a hair hardening agent which does not lose these even after repeating (i.e., has excellent shampoo resistance).

[0011]

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, (I) vinyl caprolactam / vinyl pyrrolidone / dimethylaminopropyl methacrylamide copolymer, I
I) one or more selected from the group consisting of abietic acid, rosin, salts thereof, and derivatives thereof; and (II)
I) It has been found that the use of an alkylpyridinium salt and / or a benzalkonium-type quaternary ammonium salt is excellent, and the present invention has been accomplished.

That is, the present invention relates to (I) 0.06-9.5% by weight of a vinylcaprolactam / vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymer;
I) one or more selected from the group consisting of abietic acid, rosin, salts thereof, and derivatives thereof;
9.5% by weight, and (III) an alkylpyridinium salt and / or a benzalkonium-type quaternary ammonium salt.
The present invention provides a hair curing agent containing from 06 to 9.5% by weight.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The hair curing agent of the present invention includes (I) vinyl caprolactam /
It contains a vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymer (hereinafter sometimes simply referred to as “copolymer (I)”). The copolymer (I) imparts flexibility and setting properties to the hair. As the copolymer (I), for example, the structural formula

[0014]

Embedded image

[Wherein, x, y and z represent the degree of polymerization of each monomer. The sequence of each monomer in the copolymer is not particularly limited, and includes a copolymer having any monomer sequence. ] Are represented.

Specifically, the copolymer (I) has the formula x: y: z = 1: (0.5-2) :( 0.5-2)
And the like satisfying the following.

The average molecular weight of the copolymer (I) is, for example, preferably 10,000 to 100,000, particularly preferably 25,000 to 50,000. If the average molecular weight is less than 10,000, it may be difficult to impart sufficient bending stiffness to the hair. Conversely, if the average molecular weight exceeds 100,000, the feel of the hair tends to be impaired.

The hair curing agent of the present invention includes (II) at least one selected from the group consisting of abietic acid, rosin, salts thereof, and derivatives thereof (hereinafter, simply referred to as “component (II)”). May be included). The component (II) imparts shampoo resistance.

The rosin is steam-distilled from turpentine collected from a pine genus plant to remove turpentine oil, and the residue is purified. Wood rosin is used, but any of these can be used.
Furthermore, the main component of rosin is a resin acid such as abietic acid and pimaric acid, and this resin acid can also be used.

The "salts" include alkali metal salts (eg, sodium and potassium salts of abietic acid, rosin and its resin acids, sodium and potassium salts), amine salts (eg, abietic acid). Ethanolamine, diethanolamine, rosin or its resin acid ethanolamine, diethanolamine, etc.)
Is mentioned.

The "derivatives thereof" include these esters and the like. Specifically, as the ester,
Alkyl esters (eg, abietic acid methyl ester, ethyl ester, rosin or its resin acid methyl ester, ethyl ester, etc.), and hydroxyalkyl esters (eg, abietic acid hydroxymethyl ester, hydroxyethyl ester, rosin or its resin acid) Hydroxymethyl esters, hydroxyethyl esters, etc.), polyhydric alcohol esters (for example,
Polyethylene glycol ester of abietic acid, glyceryl ester, pentaerythritol ester, polyethylene glycol ester of rosin or its resin acid, glyceryl ester, pentaerythritol ester, etc.) and hydroxy acid ester (for example, hydroxyethyl sulfonic acid ester of abietic acid, hydroxy Acetic acid ester, rosin or its resin acid, such as hydroxyethylsulfonic acid ester and hydroxyacetic acid ester). Incidentally, as the abietic acid ester, an ester gum or the like can be further used.

Other "derivatives" include amides thereof. Specifically, as the amide,
An amide of abietic acid or rosin or its resin acid with ethanolamine, diethanolamine, glycine and the like can be mentioned.

As the compounding component (II), preferably, abietic acid, rosin, sodium abietic acid, glyceride abietic acid, pentaerythritol rosin acid and the like are used, and more preferably, glyceride abietic acid and the like are used.

The component (II) comprises the above abietic acid,
It contains at least one selected from the group consisting of rosin, salts thereof, and derivatives thereof. Preferably, the blending component (II) is abietic acid, rosin, sodium abietic acid, ester gum, pentaerythritol rosinate, or the like, or two or more thereof.

The hair curing agent of the present invention comprises (III)
An alkylpyridinium salt and / or a benzalkonium type quaternary ammonium salt (hereinafter simply referred to as “component (II)
I) ". ). Ingredient (I
II) not only enhances the adsorptivity of the hair treatment agent to the hair, but also imparts a good tactile sensation to the hair (ie, moderate bending stiffness and voluminous feel, further smoothness, good combability, etc.). Is to be granted.

Usually, the cationic surfactant imparts flexibility to the hair. However, the present inventors have found that the combination of the component (III) with the components (I) and (II) allows the hair to be reversely treated. Has been found to impart bending hardness to hair.

In the alkylpyridinium salt, "alkyl" includes C8 to C22, and salts include halides such as chloride and bromide. Specifically, examples of the alkylpyridinium salt include laurylpyridinium chloride, cetylpyridinium chloride, and the like.

Examples of the benzalkonium type quaternary ammonium salt include an alkyldimethylbenzylammonium salt and an alkyldimethyl (alkylbenzyl) ammonium salt.

As the alkyl in the above "alkyldimethyl", those having C8 to C19, "alkylbenzyl"
Examples of the alkyl in the above include C1 to C12.

Specifically, examples of the alkyldimethylbenzylammonium salt include benzalkonium chloride, myristyldimethylbenzylammonium chloride, and stearyldimethylbenzylammonium chloride. Specific examples of the alkyldimethyl (alkylbenzyl) ammonium salt include lauryldimethyl (ethylbenzyl) ammonium chloride.

As the compounding component (III), the above-mentioned alkylpyridinium salt or benzalkonium-type quaternary ammonium salt may be used alone or in combination. For example, as the compounding component (III), laurylpyridinium chloride, cetylpyridinium chloride, benzalkonium chloride, myristyldimethylbenzylammonium chloride, or stearyldimethylbenzylammonium chloride is used alone, or two or more of these are used in combination. May be.

In the composition of the hair curing agent of the present invention,
The compounding component (I) is contained in an amount of 0.06 to 9.5% by weight.
Preferably, it is 0.6 to 3.6% by weight. If the amount is less than 0.06% by weight, sufficient firmness and firmness cannot be imparted to the hair. Conversely, if it exceeds 9.5% by weight, the hair becomes stiff and impairs the feel of the hair.

In the composition of the hair curing agent of the present invention,
The compounding component (II) is contained in an amount of 0.06 to 9.5% by weight. Preferably, it is 0.5 to 3% by weight. If the amount is less than 0.06% by weight, shampoo resistance and hair firmness and stiffness will not be sufficiently obtained, while if it exceeds 9.5% by weight, the feel of the hair will be impaired.

In the composition of the hair curing agent of the present invention,
The compounding component (III) is contained in an amount of 0.06 to 9.5% by weight. Preferably, it is 0.5 to 3% by weight. When the amount is less than 0.06% by weight, the hair treating agent does not sufficiently adhere to the hair, and the feel of the hair is poor. On the other hand, when the amount exceeds 9.5% by weight, sufficient firmness and firmness may be imparted to the hair. Can not.

The hair treatment composition of the present invention may contain various additives depending on the product form of the hair treatment composition described below or for various other purposes. Examples of the additive include alcohols such as higher alcohols (cetyl alcohol, stearyl alcohol, behenyl alcohol, etc.) and polyhydric alcohols (eg, glycols, glycerins), and glycerin fatty acid esters (eg, glyceryl monostearate, glyceryl monolaurate, monomyristin). Nonionic surfactants such as glycerin acid), polyoxyethylene alkyl ethers (eg, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, etc.), waxes (carnauba wax, polyethylene wax, polyolefin wax, etc.), Preservatives such as decomposed silk and parabens,
Water, cationic-, anionic-, nonionic-, and amphoteric polymer resin polymers, cationic-, anionic-, and amphoteric surfactants, silicone oils (e.g., methylpolysiloxane, methylphenylpolysiloxane, amino-modified silicone, Polyether-modified silicone, etc.), organic acids and salts thereof such as citric acid and succinic acid, amino acids such as glycine and alanine, polypeptides and derivatives thereof, bactericides, ultraviolet absorbers, antioxidants, hydrocarbons, animal and vegetable oils,
Examples thereof include ester oils, coloring agents, fragrances, solvents such as ethanol, fatty acids, and the like, and one or more of these can be used.

The product form of the hair curing agent of the present invention is not particularly limited, and may be prepared as a liquid, foam, gel, cream, powder, etc. according to a conventional method, and further as a spray product. May be.

The hair curing treatment with the hair curing agent of the present invention may be performed in combination with other hair treatments. For example, before or with a shampoo, a hair tonic, a hair conditioner (including rinsing, treatment, etc.), a hair dye, a waving agent, a finishing agent, and other hair treatment agents, or a hair treatment with these hair treatment agents After that, the hair may be cured with the hair curing agent of the present invention.

Specifically, as a hair treatment agent for hair treatment performed in such a combination, for example, 4 to 15% by weight of a higher alcohol, 1 to 10% by weight of dimethyl stearylamine, hydrogenated rice oil 0.1-5% by weight,
And 0.2 to 3% by weight of glycolic acid.

More specifically, in the composition, 5.5% by weight of myristyl alcohol, 1% by weight of behenyl alcohol, 0.2% by weight of myristic acid, 0.5% by weight of shea butter, 2% by weight of dimethyl stearylamine, Hexyldecanol 0.1 wt%, diisobutyl adipate 0.7 wt%, hydrogenated rice oil 0.5 wt%, glycolic acid 0.56
% By weight, 0.1% by weight of methylparaben, 0.05% by weight of propylparaben, and a treatment comprising the remaining amount of water.

As another hair treatment agent for another hair treatment performed in combination, for example, a cold wave treatment agent described in JP-A-2000-297017 can be mentioned.

Of course, the hair curing treatment with the hair curing agent of the present invention may be used alone without being combined with the hair treatment with another hair treatment agent.

Further, the hair hardening agent of the present invention may be used as a hair conditioner, a hair dye, a waving agent (for example, the above-mentioned special treatment) for shampoo, hair tonic, rinse or treatment (for example, the treatment exemplified in the above-mentioned combination treatment). And the like may be used in combination with a finishing agent, other hair treatment agents, and the like.

As a method of using the hair hardening agent of the present invention, a case where the hair hardening agent is used after shampooing will be exemplified. First, the hair is shampooed, towel-dried and semi-dried, and then the hair curing agent of the present invention is applied.
The hair may then be left for 15 minutes, if necessary under warming, then cooled, rinsed and dried.

[0044]

The present invention will be described more specifically with reference to the following examples. (Preparation of Hair Hardening Agent) Examples 1-3, Comparative Examples 1 and 2, Ester gum, lauryl pyridinium chloride, cetyl alcohol, glyceryl monostearate, polyoxyethylene cetyl ether, carnauba wax, methyl paraben, and propyl paraben 85 The mixture was heated to ９０90 ° C., mixed with stirring, and uniformly dissolved.

A mixture of the copolymer (I) and 1,3-butylene glycol heated to 85 to 90 ° C. was added to the homogeneous solution, and the mixture was uniformly stirred and mixed to prepare an oily composition.

Next, the initial water 6 heated to 85 to 90 ° C.
The above oily composition was added to 0 kg with stirring to obtain a uniform emulsion. Thereafter, the emulsion was cooled to 48 ° C., hydrolyzed silk was added, and water (replenishing water) was further added to adjust the total weight to 100 kg, and the mixture was uniformly stirred and mixed to obtain a hair hardening agent (Example 1). ~ 3, Comparative Examples 1 and 2) were prepared. Table 1 shows the components and the amount (kg).

Examples 4 to 9, Comparative Examples 3 and 4, except that 1 kg of ester gum was replaced with the amount of ester gum, rosin, pentaerythritol rosinate, abietic acid or sodium abietic acid shown in Table 2. Prepared hair hardening agents (Examples 4 to 9, Comparative Examples 3 and 4) in the same manner as in Example 2. Table 2 shows the components and the amount (kg).

Examples 10 to 15 and Comparative Examples 5 to 7 Instead of 1 kg of laurylpyridinium chloride, the following amounts of laurylpyridinium chloride, cetylpyridinium chloride, benzalkonium chloride, myristyldimethylbenzylammonium chloride, stearyl chloride Hair curing agents (Examples 10 to 15 and Comparative Examples 5 to 7) were prepared in the same manner as in Example 2, except that dimethylbenzylammonium or stearyltrimethylammonium chloride was used. Table 3 shows the components and the amount (kg).

Examples 16 to 20 The procedure of Example 2 was repeated, except that the copolymer (I) having an average molecular weight shown in Table 4 was used instead of the copolymer (I) having an average molecular weight of 37,500. Hair curing treatment agents (Examples 16 to 20) were prepared. Table 4 shows the components and the amount (kg).

(Sensory test of stiffness of hair) Feeling test hair bundle without chemical treatment history (Female adult hair, about 2 lengths)
0.5 g of the hair hardening agent (Examples 1 to 20 or Comparative Examples 1 to 7) was applied to half of the hair (5 cm, weight of about 8 g), and was not applied to the other half of the hair. Then
Put this hair bundle in a polyethylene bag,
%, R. H. (Constant temperature / humidity chamber) for 15 minutes.
Thereafter, the mixture was cooled for 2 minutes, rinsed with running water, and dried with a hair dryer.

Thereafter, the hair of the part to which the hair hardening agent was applied and the hair of the part to which the hair hardening agent was not applied were bent by fingers by ten panelists. The hair to which the hair hardening agent was not applied was used as a control, and the applied hair was subjected to a sensory evaluation of the stiffness of the applied hair. Table 1 shows the evaluation results.
Are shown in FIGS.

(Measurement of change in bending stress of hair) After the hair is cured, the hair is cured and the shampoo is performed once, or the hair is cured and the shampoo is performed twice, and then the hair is bent. It was examined how the stress changed compared to before the hair hardening treatment.

That is, the hair before the hair curing treatment, the hair after the hair curing treatment, the hair after the hair curing treatment and the shampooing once, and the hair after the hair curing treatment and the shampooing twice. For each of the above, a measurement test of the bending stress of the hair (hereinafter, sometimes referred to as “B value”) is performed, and the amount of change in the bending stress of the hair (in this specification, , "BS value").

(BS value after hair curing treatment) = (B value after hair curing treatment) − (B value before hair curing treatment).

(BS value after hair curing treatment and shampooing once) = (B value after hair curing treatment and shampooing once)-(B value before hair curing treatment).

(BS value after hair curing treatment and further shampooing twice) = (B value after hair curing treatment and shampooing twice) − (B value before hair curing treatment).

The higher the BS value, the greater the bending stiffness imparted to the hair.

The curing treatment of the hair was performed as follows. That is, 200 female adult hairs (about 40 cm in length) having no chemical treatment history are arranged in a 3.5 cm width so as not to overlap, and the length of the hair is 3 cm so that both ends are 1 cm width tape. Is fixed in a hair curing agent (each of Examples 1 to 20, or each of Comparative Examples 1 to 7).
After immersion at 5 ° C for 30 minutes, water
Rinse for 0 seconds.

Then, the sample was newly rinsed with hot water at 40 ° C. for 30 seconds, and further rinsed with hot water at 40 ° C. for 60 seconds. Then, at 50 ° C., 45% humidity, R. H. Inside
Dried for 30 minutes and stored in a silica gel pot. The B value of the hair was measured the next day.

The hair was shampooed as follows. That is, after washing the hair with stirring in an aqueous solution of sodium lauryl sulfate at 40 to 50 ° C. for 5 minutes,
The mixture was stirred and washed with water at 50 ° C. for 5 minutes. Next, 4 new
After stirring and washing with water of 0 to 50 ° C for 5 minutes, 50 ° C, 45% humidity, R. H. , And dried in a silica gel pot for 30 minutes. The B value of the hair was measured the next day.

Further, the B value was measured as follows. That is, the hair was applied to a hair stiffness tester (KES-FB2-S type, manufactured by Kato Tech Co., Ltd.), and the stress [B value (gf · cm ² / cm)] at the time of bending was measured. The B value is a numerical value indicating the bending hardness when one of the hairs is fixed and bent at a constant speed, and the larger the numerical value, the harder the hair.

Table 1 shows the calculation results of the BS value after the hair curing treatment, the BS value after the hair curing treatment and one shampooing, and the BS value after the hair curing treatment and the shampooing twice. To Table 4 below.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

In Tables 1 to 3, 1) represents the trade name "Aquaflex SF-40" (manufactured by International Specialty Products, average molecular weight 37500). In Tables 1 to 3, 2) and in Table 4, 1) represents a degree of ethylene oxide (EO) polymerization of 40.

In Tables 1 to 4, in the column of the feeling of stiffness after the hair hardening treatment, "」 "indicates that the hair to which the hair hardening treatment was applied by at least 8 out of 10 panelists was the hair hardening treatment agent. Indicates that the stiffness felt greater than that of the hair not coated, and "O" indicates that 5 to 7 out of 10 panelists applied the hair hardening agent to the hair to which the hair hardening agent was applied. This indicates that the user felt a greater degree of bending stiffness than the hair that had not been treated, and “△” indicates that 1 to 4 out of 10 panelists did not apply the hair hardening agent to the hair to which the hair hardening agent was applied. It indicates that the hair felt greater bending hardness than the hair, and `` x '' indicates that none of the panelists felt that the hair to which the hair curing agent was applied had a greater bending hardness than the hair to which the hair curing agent was not applied. Indicates that there was no.

As shown in Table 1, as the copolymer (I) is added in a larger amount, the BS value after the hair curing treatment increases (Examples 1 to 3 and Comparative Examples 1 and 2). That is, the copolymer (I)
It can be understood that は imparts bending hardness to hair.

Furthermore, hair cosmetics which give hair firmness and firmness generally have insufficient shampooing resistance, and the BS value gradually decreases when shampooing is repeated. However, as shown in Example 2, the present inventors combined the copolymer (I) with the compounding components (II) and (III), and when the shampooing treatment was repeated, the BS value conversely increased ( That is, the bending hardness is imparted to the hair more).

As shown in Table 2, by blending an appropriate amount of the compounding component (II), the BS value can be maintained at a high value (0.04 to 0.07) even after repeated shampooing. (Examples 4 to 9). That is, the shampoo resistance can be effectively provided by blending the blending component (II) in an appropriate amount.

As shown in Table 3, it can be seen that blending of the blending component (III) imparts a good feeling (moderate bending hardness) to the hair (Examples 10 to 15;
Comparative Example 5).

Further, generally, a cationic surfactant imparts flexibility to hair (Comparative Example 5). That is, generally, when the amount of the cationic surfactant is increased, the BS value gradually decreases. However, the present inventors increase the BS value by increasing the blending amount of the blending component (III) by combining the blending component (III) with the blending components (I) and (II) (that is, the BS value is increased). It was found that a greater bending hardness was imparted to the hair (Example 10).
And Comparative Example 6).

As shown in Table 4, the average molecular weight was about 250
From about 50,000 to about 50,000 copolymer (I)
Value, indicating that the hair is effectively imparted with bending stiffness and also has a good feel (appropriate bending stiffness).

[0075]

EFFECTS OF THE INVENTION The hair hardening agent of the present invention is damaged or weakened and softened by chemical treatment of perm (for example, cold perm, etc.), hair bleach, hair color, etc., and exposure to sunlight. Alternatively, fine and soft hair can be given elasticity, stiffness, and good tactile sensation (appropriate bending stiffness and voluminous feel) with aging. Moreover, even when shampoo is repeated, such firmness, firmness, and good tactile sensation can be maintained.

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Claims (1)

[Claims] 1. A composition comprising: (I) 0.06-9.5% by weight of a vinylcaprolactam / vinylpyrrolidone / dimethylaminopropylmethacrylamide copolymer; and (II) abietic acid, rosin, salts thereof, and derivatives thereof. At least one selected from the group consisting of 0.06 to 9.5% by weight, and (III) an alkylpyridinium salt and / or a benzalkonium type quaternary ammonium salt of 0.06 to 9.5% by weight. Hair curing agent.