JPH0552803B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a heating hair treatment agent that can be applied to hair and heated to give it semi-permanent waving and to semi-permanently improve the feel of the hair. [Prior art and its problems] Initially, as a method for giving semi-permanent waves to hair, sulfite is used and an aqueous alkaline solution with a high pH is heated. There was a method of transforming hair called so-called electric hair. Furthermore, the most common method in recent years is to first reduce and open the S-S bonds in the hair using a permanent wave first agent whose main ingredients are thioglycolic acid, cysteine, and sulfite reducing agents. Next, there is a so-called cold permanent wave method in which oxidative closure is performed using a permanent wave second agent whose main component is an oxidizing agent such as a bromate, a perborate, or a hydrogen peroxide solution.
However, according to these methods, the hair is exposed to adverse conditions such as high pH alkaline aqueous solutions, high temperature heating, reduction, and oxidation, resulting in a decrease in cysteine bonds (S-S bonds) and elution of keratin proteins. The drawbacks were a decrease in strength and a deterioration in feel. Therefore, after perm treatment, a so-called treatment agent containing a large amount of oil or protein hydrolyzate is applied to prevent hair damage. However, the effect of the treatment agent is temporary, and these ingredients are easily eluted from the hair when hair is washed, so it has been necessary to repeatedly treat the hair. [Means for Solving the Problems] Under these circumstances, the present inventor proposed a method for modifying hair, that is, without using a highly concentrated reducing agent that would damage the hair, and using an alkaline aqueous solution with a high pH. Alternatively, it can transform hair semi-permanently like conventional permanent waves without using any oxidizing agents, and it not only temporarily prevents hair damage caused by chemical treatments, but also actively We conducted intensive research on a treatment method that modifies hair so that its texture remains unchanged even when shampooed. As a result, when used at low concentrations at room temperature, the reducing power is low and it is difficult to form sufficient waves. Containing one or more selected cysteine derivatives and cationic polymers,
We discovered that by applying a hair treatment agent with a pH of 7 to 9 to the hair and heating it, it is possible to apply semi-permanent waves to the hair, and furthermore, it is possible to semi-permanently improve the feel of the hair. Completed the invention. That is, the present invention comprises the following two components (A) and (B), (A) a compound represented by the general formula () (In the formula, R ₁ represents hydrogen or an acyl group or alkyl group having 1 to 3 carbon atoms) and one or more cysteine derivatives (B) selected from the group of glutathione, containing a cationic polymer, and PH To provide a heating type hair treatment agent in which the hair loss is adjusted to 7 to 9. The cysteine derivative of component (A) used in the heating hair treatment agent of the present invention includes N-acetyl-3-
Examples include mercaptoalanine (hereinafter referred to as N-acetylcysteine), N-propyl-3-mercaptoalanine, N-ethyl-3-mercaptoalanine and glutathione. These cysteine derivatives can be used in combination or alone, and are preferably blended in the heating hair treatment agent of the present invention in an amount of 0.1 to 5.0% by weight (hereinafter simply expressed as %), particularly 0.5 to 3.0%. preferable. As the cationic polymer of component (B) used in the heating type hair treatment agent of the present invention, in addition to the water-soluble cationic polymer described in JP-A-56-92812, dimeric polymers of lysine, which is a basic amino acid, are used. Examples include homoamino acid polymers that are larger than the body. Examples of these cationic polymers include those shown below. The fourth derivative of cellulose ether described in French patent No. 1492597, represented by the following formula (1): [wherein Rcell is a group of anhydroglucose units, y is a number having a value of about 50 to about 20,000, and each R independently represents one substituent, which is a group of the following general formula: : (where a is an integer having a value of 2 or 3; b is an integer having a value of 2 or 3;
c is an integer having a value from 1 to 3; m is an integer having a value from 0 to 10; n is an integer having a value from 0 to 3; p is an integer from 1 to 3;
is an integer having a value of 10; q is an integer having a value of 0 or 1; R' is a group of the formula -H,

【formula】

【formula】

[expression] or

[Formula] When q is 0, R' represents -H; R ₂ ,
R ₃ and R ₄ are treated independently and are respectively alkyl, aryl, aralkyl, alkaryl,
represents a cycloalkyl, alkoxyalkyl or alkoxyaryl group and each R ₂ , R ₃
and R ₄ groups may contain up to 10 carbon atoms, provided that if the group is an alkoxyalkyl group there are at least two carbon atoms separating the oxygen atom from the nitrogen atom. , and also the total number of carbon atoms present in the radicals represented by R ₂ , R ₃ and R ₄ is 3
and 12; or R ₂ ,
R ₃ and R ₄ together with the nitrogen atom to which they are attached can represent one of the following groups: pyridine, α-methylpyridine,
3,5-dimethylpyridine, 2,4,6-trimethylpyridine, N-methylpiperidine, N-
Ethylpiperidine, N-methyl-morpholine,
or N-ethyl-morpholine; X is an anion and V is an integer equal to the valence of X; and the average value of n is between 0.01 and about 1 per anhydroglucose unit of the cellulose ether; And for each anhydroglucose unit of this cellulose ether (m+n
+p+q) is between about 0.01 and about 4)] The most particularly desirable polymers are those corresponding to formula (1) given above, where a and b
is 2, q is 0, m, n and p have the values given above, R' denotes hydrogen and
R ₂ , R ₃ and R ₄ represent methyl. Average value per anhydroglucose unit is 0.35 for n
and 0.45 and 1 to 2 for the sum of m+p and X represents chloride. Desirable ethers according to the invention are:
Measured by the method of ABTMD-2364-65 (model LVF Bruckfield viscometer, 30 revolutions/min, spindle number 2) in a 2% concentration aqueous solution at 25°C.
and which have a viscosity of 50 to 35,000 centipoise and are particularly desirable are those manufactured by Union Carbide Corporation, called "JR-
125'', ``JR-400'' and ``JR-30M'', which are 125 centipoise and 125 centipoise, respectively.
Denotes polymers of the above type with viscosities of 400 centipoise and 30000 centipoise. Water-soluble copolymers having a molecular weight of 20,000 to 1,000,000, selected from the homopolymers and copolymers given below:
Homopolymer numbers contain units corresponding to the following formula (2) or (2') as the main component of the chain: (wherein R ₅ represents hydrogen or methyl and
R ₂ ′ and R ₃ ′ independently each represent an alkyl group having 1 to 22 carbon atoms, a hydroalkyl group or a lower amidoalkyl group, where the alkyl group preferably has 1 to 5 carbon atoms; R ₂ ′ and R ₃ ′ together with the nitrogen atom to which they are attached can then represent a heterocyclic group such as piperidinyl or morpholinyl in association with a cosmetically acceptable anion. ) The copolymers can be of acrylamide or of diacetone-acrylamide and of monomers which give units corresponding to formula (2) in the resulting copolymer. These polymers are in the acetate, borate, bromide, chloride, citrate, tartrate, sulfite, hyposulfite, sulfate, phosphate or succinate form. Among quaternary ammonium polymers of the type defined above, more particularly preferred are homopolymers of dimethyldiallylammonium chloride, sold under the name MERQOAT 100 and having a molecular weight of less than 100,000, and 500,000. Melcoat by MERCK has a molecular weight greater than
It is a copolymer of dimethyldiallylammonium chloride and acrylamide sold under the name 550. Quaternized polymers represented by the following formula (3): [wherein R ₆ , R ₇ , R ₈ and R ₉ are the same or different and represent an aliphatic, cycloaliphatic or araliphatic group containing at most 20 carbon atoms, or a lower hydroxy aliphatic group; Representation,
or R ₆ and R ₇ and R ₈ and R ₉ together or separately form a heterocyclic structure with the nitrogen atom to which they are attached, which may include a second heteroatom other than nitrogen. can or
R ₆ , R ₇ , R ₈ and R ₉ are groups: (However, R ₄ ′ represents hydrogen or lower alkyl,
and R ₅ ′ is −CN,

【formula】

【formula】

【formula】

[expression] or

[Formula], R ₆ ′ represents lower alkyl, R ₇ ′ represents hydrogen or lower alkyl, R ₈ ′ represents alkylene, and D represents a quaternary ammonium group), and A
and B can represent a polymethylene group containing from 2 to 20 carbon atoms and which may be straight-chained or branched and saturated or unsaturated and with one or more interleaved aromatic ring or one or more −
CH ₂ -Y-CH ₂ - group (where Y is O, S, SO,
SO ₂ , -S-S-,

【formula】

【formula】

【formula】 【formula】

【formula】 or

[formula] in which R ₉ ' represents hydrogen or lower alkyl and R ₁₀ ' represents lower alkyl), or A and
R ₆ and R ₈ together with the two nitrogen atoms to which they are attached form a piperazine ring, X is an anion derived from a mineral or organic acid, and l is a molecular weight between 1000 and 100000. ]. Copolymers of vinylpyrrolidone represented by the following formula (4): [wherein d is between 20 and 99 mol% and preferably
between 40 and 90 mol% and e is between 1 and 80 mol% and preferably between 5 and 40 mol%; f represents 0 to 50 mol% and d+
e+f=100; R ₁₀ represents H or CH ₂ ; y′ represents 0 or 1; R ₁₁ is −CH ₂ −
CHOH−CH ₂ − or CxH ₂ x (where x is 2 to 18); R ₁₂ is CH ₃ , C ₂ H ₅ or

〔Effect of the invention〕

By using the heating type hair treatment agent of the present invention, it is possible to semi-permanently improve the feel of hair in a relatively low temperature and short time by simple operation, and furthermore, it is possible to apply semi-permanent waves. In addition, since high-concentration alkaline agents, reducing agents, and oxidizing agents are not used, hair damage caused by elution of hair proteins can be reduced, and the handling problems of conventional permanent waving agents can be solved. There is an advantage. [Examples] Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples. Example 1 A heating hair treatment agent having the composition shown in Table 1 was prepared,
The degree of hair damage was evaluated by reducing agent concentration, wave forming effect, and sensory evaluation. The results are also shown in the same table. (1) Wave formation effect [Measurement method] Wave degree and wave retention force measurement test; 15
A bundle of 10 healthy Japanese hairs measuring 1 cm in diameter was wound around a glass tube (10 mm in diameter), and 30 μ of the treatment solution was applied to the bundle, followed by treatment at 50° C. for 10 minutes. After treatment, the hair bundle is removed from the glass tube after rinsing thoroughly with ion-exchanged water, and the hair becomes coiled. The length of the hair coil at this time was measured. The wave degree was calculated from the following formula. Wave degree (%) = Y/X-Y×100 Evaluation of degree of damage (evaluation criteria) Compared to untreated hair ○Good △Same ×Poor

【table】

[Table] Example 2 A heating hair treatment agent having the composition shown in Table 2 was prepared,
adsorption of water-soluble cationic polymers to hair;
The removability and feel by shampooing and acid rinsing were evaluated. (1) Treatment solution N-acetylcysteine 1.0% Water-soluble cationic polymer (listed in Table 2) 2.5×10 ^-3 M 0.2M phosphate buffer PH8.0 100.00 (2) Treatment method 1 g of healthy Japanese hair tresses Treatment liquid (Table 2)
and treated at each temperature (30°C, 50°C) for 10 minutes. Next, it was washed with water, dried, immersed in a 1% sodium lauryl sulfate aqueous solution at 40°C for 10 minutes, rinsed with water, and placed in an acid rinse (1N acetic acid aqueous solution) at 40°C for 10 minutes.
Soaked for minutes. Next, wash with water and then heat at 100℃ for 80 minutes.
% formic acid aqueous solution for 1 hour. After the shampoo solution, acid rinse solution, and formic acid solution were evaporated to dryness, the eluate was dissolved in ion exchange water, and the polymer desorbed from the hair was purified using a cation exchange resin and quantified by colloid titration. (3) Sensory evaluation After treatment with a heating hair treatment agent, shampoo, and acid rinse, the feel was evaluated. (Evaluation criteria) Compared to untreated hair ○Good △Same × Bad (4) Cationic polymer used (i) Polycationic polymer (In the formula, n ₁ = 2 to 6. m ₁ = 2 to 6, average molecular weight
300-11000) (ii) Polylysine (Average molecular weight 4000) (iii) Diallyl quaternary ammonium salt (Commercial name: Marquat 100, (manufactured by Merck & Co.),
molecular weight 100000)

【table】

[Table] Example 3 A heating hair treatment agent having the following compositions was prepared. Formulation 1 A N-propyl-3-mercaptoalanine
2.0 (%) B Cationized cellulose (commercial product name: Polymer JR125UCC, molecular weight 125,000) 1.5 C Ascorbic acid 0.5 D Setanol 1.0 E Stearyltrimethylammonium chloride
2.0 F Propylene glycol 2.0 G Ammonium bicarbonate 3.0 H Arginine Adjust to PH9.0 I Fragrance 0.2 J Ion exchange water Balance 100.0 Dissolve A, B, C, and G in nitrogen-substituted ion exchange water, add F, D, Add a solution in which E and I are dissolved, and finally adjust the pH with H to produce. Formulation 2 A N-ethyl-mercaptoalanine 0.5 (%) B Ascorbic acid 0.5 C Calcium chloride 1.0 D Diallyl quaternary ammonium salt (commercial product name
Marquat 550 (manufactured by Merck, molecular weight 100,000) 2.0 E Glycine 3.0 F Monoethanolamine Adjusted to PH8.5 G Fragrance 0.2 H Ion exchange water Balance 100.0 Add A, B, C, E, to ion exchange water replaced with nitrogen.
Dissolve G in D, add the solution in which G is dissolved, and finally adjust the pH with F to produce. Formulation 3 A Glutathione 0.5 (%) B Ascorbic acid 0.5 C Calcium chloride 1.0 D Diallyl quaternary ammonium salt (commercial product name
Marquat 550 (manufactured by Merck, molecular weight 100,000) 2.0 E Glycine 3.0 F Ammonia water (28%) Adjusted to PH8.0 G Fragrance 0.2 H Ion exchange water Balance 100.0 Add A, B, C, E, to the nitrogen-substituted ion exchange water
Dissolve G in D, add the solution in which G is dissolved, and finally adjust the pH with F to produce.

Claims (1)

[Claims] 1. The following two components (A) and (B), (A) a compound represented by the general formula () (In the formula, R ₁ represents hydrogen or an acyl group or alkyl group having 1 to 3 carbon atoms) and one or more cysteine derivatives (B) selected from the group of glutathione, containing a cationic polymer, and PH A heating hair treatment agent with a temperature of 7 to 9. 2. The heating hair treatment agent according to claim 1, wherein the cysteine derivative is represented by the general formula (), and R ₁ is an acyl group.