JP2011184413A - Humidifying-type hair setting treatment preparation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a humidifying-type hair setting treatment preparation capable of making hair-waving set, and straight-set and hair correction etc. through eliminating strains inside the hair such as wavy hair and curly hair, by producing tannin linkages among the polypeptide chains of the hair using odorless and highly safe tannin, compared to cold perming treatment as a current method with a highly concentrated mercaptan-based reducing agent emitting intense odor as the main agent. <P>SOLUTION: The humidifying-type hair setting treatment preparation comprises: a tannin crosslinking agent with, as the main agent, a modified tannin obtained by oligomerizing, in the alkaline range of pH 8-10 and further activating, by reducing action with a sulfite, the original tannin; and a weakly acidic neutralizing agent to neutralize alkali compound(s) left inside the hair treated with the tannin crosslinking agent. Besides, a hair setting treatment method owing to the tannin crosslinking is provided, also serving as a highly effective means for repairing and ameliorating e.g. the declines in the mechanical strengths and elasticity of damaged hair caused by the chemical actions stemmed from current methods including cold perming, hair-coloring and hair-bleaching treatment methods. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a warming hair set treating agent.

  Conventional hair wave sets are mercaptan based reducing agents with thioglycolic acid, cysteine, acetylcysteine, cysteamine, thiolactic acid or their functional groups such as thiol groups (-SH) in the molecule. The second agent, which mainly breaks the cystine bond (-SS-) in hair keratin with the first agent mainly used as a main agent and has an oxidizing agent having strong oxidizing power such as bromate and hydrogen peroxide. A technology that depends on a simplified system, such as a room temperature or warming two-bath technique, in which a cystine bond that has been cleaved by recombination is recombined to form a wave has been put into practical use (see Patent Document 1, etc.).

In addition, a straight set of comb hair using a reducing agent and an oxidizing agent on the same principle and straightening of curly hair have been put into practical use.
In addition, a heating method technique for forming a wave using heat denaturation of hair protein using a heating device (105 to 110 ° C.) such as an electric hair perm has been put into practical use.

JP-A-10-87447

However, if the conventional permanent wave or straight permanent treatment is repeated as described above, the strong chemical action of the reducing agent and oxidizing agent causes damage to the hair structure and microstructure, and deterioration of the hair elasticity and strength. More cases.
That is, when the cystine bond is cleaved using one strong reducing agent as described above, the keratin molecules in the hair are greatly disturbed and the gap between the polypeptide chains is greatly expanded. Is prevented, and the portion where the cystine bond is still broken is increased, and the deterioration of the elasticity and strength of the hair is promoted.

  In addition to permanent waves and straight permanents, hair is damaged by improper treatment such as hair coloring, hair breaching, curly hair correction, and care and hairstyle such as combing, shampoo, and hair dryer. There are also many.

  In addition, the permanent liquid of the current method, which is mainly composed of a highly concentrated mercaptan reducing agent with strong odor, is masked by fragrance etc. for the time being, and has been devised to prevent unpleasant odor, but the problem of unpleasant odor is still solved. Not.

The present invention uses odorless and safer tannins, and generates new tannin crosslinks instead of cystine bonds between the polypeptide chains of the hair to release the hair set of the hair and the internal strain of the hair. An object of the present invention is to provide a warming hair set treating agent capable of straightening and straightening hair.
In addition, the above-mentioned hair set treatment by tannin cross-linking can be improved by repairing the decrease in strength and elasticity of damaged hair caused by the chemical action of cold perm, hair color, hair bleach treatment, etc. of the current method. It becomes a very effective means.

  In order to achieve the above object, the warming hair set treating agent according to the present invention (hereinafter referred to only as “hair set treating agent”) is reduced in molecular weight in an alkaline region having a pH of 8 to 10, and sulfite is used. A tannin crosslinking agent mainly comprising tannin activated by a reducing action, and a weakly acidic neutralizing agent neutralizing alkali remaining in the hair treated with the tannin crosslinking agent. Yes.

In the present invention, the pH of the tannin cross-linking agent is limited to 8-10. The reason is that if the pH is less than 8, the tannin is not sufficiently reduced in molecular weight, and the tannin penetrates into the hair. This is because the formation of a cross-linking bond by tannin tends to be insufficient, and when the pH exceeds 10, the hair is easily damaged.
The alkali agent used for reducing the molecular weight of tannin is not particularly limited, and examples thereof include mono-, di- and triethanolamine, citrate, phosphate, carbonate and the like, and these are used alone. Or may be used in combination. Moreover, the sulfite which further activates the tannin reduced in molecular weight is sodium sulfite or potassium sulfite, and these may be used alone or in combination.

Tannin is a natural product and generally contains a non-tannin content extracted from plant raw materials simultaneously with tannin. The content of non-tannin is usually different depending on the type and location of plant raw materials and extraction conditions in the exporting country, and it is removed to some extent at the purification stage, but it cannot be completely separated and removed. is there.
Accordingly, the amount of sulfite used for activating tannin is determined according to the amount of tannin contained in the plant tannin, and is not particularly limited, but empirically 1 to 3 times the plant tannin used. It has been found that the weight of sulfite should be added.
That is, the reduction effect of tannin is that the tannin activation tends to be non-uniform under the specified conditions of 50 to 55 ° C. and 30 to 60 minutes, and the tannin activation is likely to be uneven when the sulfite is reduced to the same amount or less of the plant tannin. In addition to reducing the production, there are many cases where “slide unevenness” occurs between the peptide chains of the hair, and even when the amount used is more than 3 times, there is no significant change in the formation of tannin crosslinks. .

In the present invention, the tannin is not particularly limited, but catechol-based condensed tannin is preferably used.
In other words, since the degree of damage of general damaged hair cannot be ascertained in advance, the use of catechol-based condensed tannins with a large molecular weight results in damage to the hair keratin molecules that are greatly disturbed or the polypeptide chain gap is expanded. Even for hair, it is advantageous to produce a cross-linked three-dimensional network structure, and the cross-linking effect is enhanced.

Also, since the degree of damage varies depending on the root, middle, tip, etc. of hair, it is excellent to use a mixture of pyrogallol hydrolyzable tannin with a low molecular weight centered on catechol-based condensed tannin with a high molecular weight. A set effect can be obtained.
The mixing ratio of the catechol-based condensed tannin and pyrogallol-based hydrolyzed tannin in the above mixture is not particularly limited, but condensed tannin: hydrolyzed tannin = 7: 3 to 1: 1 (weight ratio) It is preferable that

The condensed tannin is not particularly limited, and examples thereof include quebracho tannin, wattle tannin, green tea tannin, mangrove tannin, Gambian tannin, and persimmon astringent tannin, which may be used alone or in combination. I do not care.
Although it does not specifically limit as said hydrolysis-type tannin, For example, a pentaploid tannin, a gallic tannin, a chestnut tannin, myrobalan tannin, oak tannin is mentioned, These may be used independently or may be used together.

The tannin concentration of the tannin crosslinking agent is not particularly limited, but is preferably 1 to 10% by weight, and more preferably 3 to 10% by weight.
In other words, the amount of tannin bound to the hair generally increases as the tannin concentration in the tannin cross-linking agent increases with increasing penetration rate. If the concentration is exceeded, it may decrease.
In the correction of abnormal hair such as curly hair with a strong water repellency and a lot of dry hair, spiral hair, etc., after releasing the strain inside the hair and softening the hair first, as in the above straight set treatment, The goal can be achieved by generating a new tannin cross-linked bond in a straight-line-fixed state, but in correcting abnormal hair, catechol such as Wat Lutannin or Kebracho Tannin is different from the straight set treatment described above. It is extremely effective to perform a heating treatment at 50 to 55 ° C. for 20 minutes using a 3 to 10% treatment solution having a relatively high concentration of the condensed tannin of the system, and an excellent setting effect can be obtained.

In the present invention, the acid contained in the neutralizing agent is not particularly limited as long as it can neutralize the residual alkali in the hair treated with the tannin crosslinking agent. For example, citric acid, tartaric acid, lactic acid, Examples include weak acids such as phosphoric acid and acetic acid, and salts thereof, which may be used alone or in combination.
Moreover, the weak acid density | concentration of the said neutralizing agent is although it does not specifically limit, 0.5 to 1.0 weight% is preferable. That is, if the weak acid concentration is less than 0.5% by weight, unevenness in the setting effect and durability tends to occur, and if it exceeds 1.0% by weight, the hair becomes stiff and the tactile sensation tends to change. .

In the present invention, a penetrant such as an anionic surfactant or a nonionic surfactant may be added to the tannin crosslinking agent and the neutralizing agent in order to increase the penetration into the hair. Absent.
Furthermore, the tannin crosslinking agent and the neutralizing agent are generally used in hair cosmetics such as thickeners, gelling agents, coloring agents, and fragrances as long as they do not impair the object of the present invention. These additives may be appropriately added as necessary.
Incidentally, since curly hair is generally highly hydrophobic and many dry hairs are damaged, it is preferable to add an anionic surfactant having a strong osmotic effect and an oily component that imparts flexibility to the tannin crosslinking agent. . That is, an extremely excellent correction effect can be expected by addition.

  Moreover, although the form of the said tannin crosslinking agent and neutralizer is not specifically limited, For example, a lotion shape, cream shape, gel shape, etc. are mentioned.

  The hair setting treatment according to the present invention is a method in which the hair is preliminarily washed with shampoo to remove dirt, and then in the wave setting treatment, the hair is wound around a rod in advance to adjust the shape and uniformly apply the tannin crosslinking agent to the hair. In the straight set treatment, the hair is shaped in a stretched state so as to follow a flat holding plate and the tannin crosslinking agent is uniformly applied to the hair.

Although the processing temperature by the said tannin crosslinking agent is not specifically limited, The heating state of 40-55 degreeC is preferable.
That is, if the treatment temperature of the tannin crosslinking agent is less than 40 ° C., it takes a long treatment time because the penetration rate and reaction rate of tannin into the hair decreases, and if it exceeds 55 ° C., the tannin crosslinking agent If the scalp touches the user, the user may generally feel hot and feel uncomfortable, and if it is too hot, it may cause scalp burns.
The method for heating the tannin crosslinking agent is not particularly limited, but a method of holding the hair in a water vapor atmosphere using a steamer or the like used for normal permanent treatment during the treatment time is preferable.

  Since the treatment time with the tannin crosslinking agent varies depending on the properties of the hair, it needs 15 to 30 minutes in the temperature range of 40 to 55 ° C. In addition, it is preferable to raise processing temperature to 50-55 degreeC, to increase the tannin permeation | transmission rate and reaction rate, and to shorten processing time to about 10-20 minutes.

  The treatment temperature of the neutralizing agent is not particularly limited, and may be room temperature, but is preferably 30 to 40 ° C. in consideration of a cold district.

  Although the processing time by the said neutralizing agent will not be specifically limited if the inside of hair can be neutralized, 10 to 30 minutes are preferable.

  As described above, the hair set treating agent according to the present invention is a tannin cross-linking agent mainly composed of tannin that has been reduced in molecular weight in an alkaline region of pH 8 to 10 and further activated by reduction action with sulfite. It is characterized in that by generating a large number of three-dimensional network structures of tannin cross-linking between the polypeptide chains, hair set, hair straight set, curly hair correction and the like can be achieved. In addition, this hair set treatment agent is an extremely effective means for repairing and improving the reduction in strength and elasticity of damaged hair caused by the chemical action of current methods such as cold perm, hair color, and hair bleach treatment. Become.

  That is, the tannin cross-linking agent increases the permeability into the hair by reducing the molecular weight of tannin in the alkaline region of pH 8 to 10, further hydrophilizing and activating tannin through the reduction action of sulfite. After applying to the skin, heating with a steamer increases the reaction rate to the hair and generates a large number of strong tannin cross-linked three-dimensional networks mainly composed of hydrogen bonds and covalent bonds in the polypeptide chain. In addition, the hair setting effect is exhibited, and in the case of damaged hair, a repairing effect for increasing elasticity and strength is also shown.

  On the other hand, the neutralizing agent is a weakly acidic treatment solution that neutralizes residual alkali in the hair treated with the tannin crosslinking agent to make it near the isoelectric point (pH 5 to 6) of the hair protein. It is effective to stabilize the three-dimensional network structure of the tannin crosslinking as described above.

  Tannin, which is the main ingredient of the hair set treating agent of the present invention, is a plant polyphenol compound that has been widely used in the food and medical fields for a long time. Compared with mercaptan-based reducing agents having a strong unpleasant odor of the current method. It is expected to be applied to hair set treatment agents that are odorless and safer.

It is a graph which compares and shows the load extension | expansion curve of the hair processed only by the sulfite of each density | concentration, and the hair set-treated with the tannin. It is a graph which compares and shows the load elongation curve of the hair which carried out the hair set process by the tannin similar to FIG. 1 to the damaged hair by the conventional cold permanent, and the damaged hair. It is a graph which shows the relationship between the binding amount of Kebracho tannin and pentaploid tannin to hair, and the pH of a tannin crosslinking agent. It is a graph which shows the relationship between the amount of tannin bonds to hair, and processing temperature and time. It is a graph which shows the relationship between the kind and density | concentration of tannin, and the amount of tannin binding. It is a wave model figure used for evaluation of the wave effect etc. of hair.

  Hereinafter, the present invention will be described in detail with reference to experimental examples.

(Experimental example 1)
Using quebracho tannin, 5 wt% sodium sulfite was added to 3 wt% tannin aqueous solution adjusted to pH 9 with mono and triethanolamine and allowed to act at 50 ° C for 30 minutes to reduce and activate tannin. A tannin crosslinking agent was obtained.
After immersing Japanese untreated hair (I) in the obtained 45 ° C. tannin crosslinking agent for 20 minutes, a neutralizing agent (around pH 4) containing 0.5% by weight of citric acid is applied to the removed hair. And left at room temperature for 20 minutes to neutralize the alkali remaining in the hair and make it near the isoelectric point (pH 5 to 6) of the hair protein.
The hair treated with the neutralizing agent was removed from the rod, washed with water and dried to obtain treated hair (II).

(Experimental example 2)
Instead of the tannin cross-linking agent of Experimental Example 1, 1 wt% sodium sulfite was added to a liquid that did not contain tannin and was adjusted to pH 9 using mono- and triethanolamine to obtain a comparative treatment liquid A.
After immersing untreated hair (I) in the obtained comparative treatment liquid A at 45 ° C. for 20 minutes, a neutralizing agent (around pH 4) containing 0.5% by weight of citric acid is applied to the taken out hair. The mixture was allowed to stand at room temperature for 5 minutes to neutralize the alkali remaining in the hair and bring it close to the isoelectric point (pH 5-6) of the hair protein.
The hair treated with the neutralizing agent was removed from the rod, washed with water and dried to obtain treated hair (III).

(Experimental example 3)
Instead of the tannin cross-linking agent of Experimental Example 1, 3 wt% sodium sulfite was added to a solution containing no tannin and adjusted to pH 9 using mono- and triethanolamine to obtain a comparative treatment solution B.
After immersing untreated hair (I) in the obtained comparative treatment liquid B at 45 ° C. for 20 minutes, a neutralizing agent (about pH 4) containing 0.5% by weight of citric acid is applied to the taken-out hair. The mixture was allowed to stand at room temperature for 5 minutes to neutralize the alkali remaining in the hair and bring it close to the isoelectric point (pH 5-6) of the hair protein.
The hair treated with the neutralizing agent was removed from the rod, washed with water and dried to obtain treated hair (IV).

(Experimental example 4)
Instead of the tannin cross-linking agent of Experimental Example 1, 5 wt% sodium sulfite was added to a solution containing no tannin and adjusted to pH 9 using mono- and triethanolamine to obtain a comparative treatment solution C.
After dipping the untreated hair (I) in the obtained comparative treatment liquid C at 45 ° C. for 20 minutes, the removed hair was coated with a neutralizing agent (around pH 4) containing 0.5% by weight of citric acid. The mixture was allowed to stand at room temperature for 5 minutes to neutralize the alkali remaining in the hair and bring it close to the isoelectric point (pH 5-6) of the hair protein.
The hair treated with the neutralizing agent was removed from the rod, washed with water and dried to obtain treated hair (V).

For each of the untreated hair (I) and the treated hairs (II to V) obtained in Experimental Examples 1 to 4, a load elongation curve was obtained using a constant speed elongation type Instron tensile tester, and the results were obtained. It was shown in FIG.
FIG. 1 suggests that tannin crosslinks are generated between the polypeptide chains of the hair that have been “slided” by cleavage by the reducing action of sodium sulfite.

(Experimental example 5)
For the damaged hair with normal cold perm and the hair with the damaged hair set with tannin using the same tannin crosslinking agent and neutralizing agent as in Experimental Example 1, the load by a constant speed extension type Instron tensile tester An elongation curve was obtained, and the result is shown in FIG.
From FIG. 2, in the hair setting treatment using the hair setting treatment agent of the present invention, the strength of the hair is reduced even in the normal damaged hair damaged by the chemical action due to strong reduction / oxidation by cold perm, hair color, hair dibleach, etc. It proved to be a very effective means to repair and improve the increase in elongation.

(Experimental example 6)
3 weights using quebracho tannins and pentaploid tannins and changing hair to pH 1-10 (adjusted to 8 levels of pH 1, 3, 5, 6, 7, 8, 9, 10) with Clark Labs buffer The hair was dipped in an aqueous solution of 100% tannin at 45 ° C. for 20 minutes, and the amount of tannin bound to the hair was examined. The result is shown in FIG.
(Measurement method of tannin binding amount)
The amount of tannin bound in each pH range was determined by titration with 0.1 N potassium permanganate using the Indigo Carmine solution as an indicator by the Lebental method, and the amount consumed was determined from the amount of tannin before and after treatment. The amount (mg) was shown as a converted value.
The amount of tannin bound was also measured in the following experimental examples.
From FIG. 3, in any tannin, the tannin binding amount shows a minimum value in the vicinity of pH 5 to 6 (the isoelectric point of the hair protein), and shows a maximum value in the vicinity of pH 1, but in particular, the condensed quebracho tannin. Then, it became clear that the amount of tannin binding increased specifically in the alkaline region near pH 9, and showed a maximum value.

(Experimental example 7)
Using the same Kebracho tannin cross-linking agent as in Experimental Example 1, the temperature was first adjusted to 35 ° C., 45 ° C. and 55 ° C., and the treatment time was changed in the range of 5 to 60 minutes, respectively. The amount of binding was examined, and the results are shown in FIG.
As shown in FIG. 4, when the treatment temperature is increased, the penetration rate and reaction rate of tannin to the hair generally increases and the amount of tannin binding increases, but the amount of binding sharply increases in the treatment time of 10 to 20 minutes, particularly at the treatment temperature of 55 ° C. It became clear that it showed an almost constant value.

(Experimental example 8)
Using three types of hydrolyzable tannins such as pentaploid, chestnut, and milobaran, and four types of condensed tannins such as quebracho, wattle, mangrove, and gambia, the pH is adjusted to 9 and the tannin concentration is changed to a range of 5 to 25% by weight. The hair was immersed in the tannin aqueous solution for 20 minutes at 45 ° C., and the amount of tannin bound to the hair was examined. The result is shown in FIG.
From FIG. 5, the amount of tannin bound to the hair varies greatly depending on the type of tannin, but in particular, quebracho and wattle tannin show a large amount of binding when the tannin concentration is increased, and a maximal value is obtained at a concentration of 10 to 15% by weight. It became clear to show.

(Experimental example 9)
Appropriate methods for evaluating and expressing the wave effect of hair have not yet been established, and each depends on its own method. In a series of experiments in the present invention, strict evaluation was made as much as possible, and as one means, a five-stage wave model diagram shown in FIG. 6 was prepared and expressed by comparison with this. Specifically, five types of materials with different wave conditions were prepared using 17-18 cm Japanese normal hair bundles and φ6 mm rods, and expressed in a five-step system from 1 to 5.
Also, the durability of the set effect has not been established at present, and each depends on its own method. Therefore, the durability of the set effect was also evaluated using the 5-stage wave model diagram shown in FIG. 6 after the hair evaluated for the wave effect was further dipped in warm water of 40 ± 2 ° C. for 20 minutes and dried. did.

(Experimental example 10)
A mixture of wattle tannin and pentaploid tannin (1: 1 by weight) was added to 3 wt% tannin aqueous solution adjusted to pH 9 with monoethanolamine and disodium hydrogenphosphate to add 5 wt% sodium sulfite to 50%. The tannin crosslinking agent was obtained by reducing the tannin by allowing it to act at 30 ° C. for 30 minutes.
The obtained tannin cross-linking agent was uniformly applied to the hair, and then set to a warm treatment using a 50 ° C. steamer for 20 minutes.
After the set treatment is completed, a neutralizing agent containing 0.5% by weight tartaric acid and 0.5% by weight phosphoric acid is sufficiently applied to the hair bundle, and further left at room temperature for 20 minutes to neutralize the alkali remaining in the hair. The hair bundle was adjusted to near the isoelectric point (pH 5-6) of the hair protein, the hair bundle was removed from the rod, washed with water and dried.
The hair after the completion of the treatment was evaluated for the hair wave effect, and as a result, the 4th to 5th class excellent wave set effect as shown in FIG. 6 was exhibited.

(Experimental example 11)
Using a mixture of quebracho tannin and gambian tannin (7: 3 by weight), adding 5 wt% potassium sulfite to 3 wt% tannin aqueous solution adjusted to pH 9 with monoethanolamine and citrate at 50 ° C, A tannin crosslinking agent activated by reducing tannin for 60 minutes was obtained.
And after apply | coating uniformly the obtained said tannin crosslinking agent to hair, it left to warm for 20 minutes using a 55 degreeC steamer, and set processing of the hair.
After the set treatment is completed, a neutralizing agent containing 0.5% by weight citric acid and 0.5% by weight tartaric acid is sufficiently applied to the hair, and further left at room temperature for 20 minutes to neutralize the alkali remaining in the hair. Then, the hair was removed from the rod near the isoelectric point (pH 5-6) of the hair protein, washed with water and dried.
The hair after the treatment was evaluated for the wave effect of the hair. As a result, even for the hair which is difficult to be subjected to the conventional wave set, the excellent wave set effect of the 4th to 5th class durable as shown in FIG. 6 is exhibited. It was.

(Experimental example 12)
Using a mixture of wattle tannin and green tea tannin (1: 1 by weight), adding 5 wt% sodium sulfite to 3 wt% tannin aqueous solution adjusted to pH 9 by adding triethanolamine and sodium carbonate to 50 ° C For 60 minutes to obtain a tannin crosslinking agent activated by reducing tannin.
Next, the tannin cross-linking agent was applied to the hair in a state where the hair with a habit was held in a straight line using a jig, and then set for a heating treatment using a steamer at 55 ° C. for 20 minutes.
After the set treatment is completed, a neutralizing agent consisting of 0.5% by weight citric acid is sufficiently applied to the hair, and is further allowed to stand at room temperature for 20 minutes to neutralize the alkali remaining in the hair, thereby isolating the hair protein isoelectric point. After adjusting the pH to around (pH 5-6), the hair was removed from the jig, washed with water and dried.
The hair after the treatment was completed did not have any habit and was almost linear.

(Experimental example 13)
Using a mixture of wattle tannin and quebracho tannin (7: 3 by weight), adding 5 wt% sodium sulfite to 3 wt% tannin aqueous solution adjusted to pH 9 with triethanolamine and disodium hydrogenphosphate. It was allowed to act at 50 ° C. for 60 minutes to reduce and activate tannin. Further, sodium lauryl sulfate as a penetrating agent was added at 0.5% by weight and squalane at 0.2% by weight to obtain a tannin crosslinking agent.
Next, the tannin cross-linking agent was applied to the hair in a state where the hair with a habit was held in a straight line using a jig, and then set for a heating treatment using a steamer at 55 ° C. for 20 minutes.
After the set treatment is completed, a neutralizing agent containing 0.5% by weight citric acid and 0.5% by weight lactic acid is sufficiently applied to the hair, and further left at room temperature for 20 minutes to neutralize the alkali remaining inside the hair. After the hair protein was brought to the vicinity of the isoelectric point (pH 5-6), the hair was removed from the jig, washed with water and dried. The hair after the treatment was completed did not have any habit and was almost linear.

(Experimental example 14)
Using the same tannin crosslinking agent and neutralizing agent as the hair setting treatment agent of Experimental Example 1, the concentration of quebracho tannin in the tannin crosslinking agent was changed in the range of 0.5 to 15% by weight, and the hair was set. Processed. Each hair after completion of the treatment was evaluated for wave effect, durability, and touch feeling. The results are shown in Table 1.
The wave effect and durability were evaluated in the same manner as in Experimental Examples 9-11. As for tactile sensation, +++ was evaluated as extremely good, ++ was good, + was slightly bad, and − was bad.

From Table 1 above, in the hair setting treatment with quebracho tannin, when the tannin concentration is 1.0 wt% or less, the hair setting effect and durability are reduced, but the concentration of 1.0 to 10.0 wt% In the range, excellent wave effect and durability can be obtained. On the other hand, when the concentration is 10.0% by weight or more, not only the wave effect and durability are weakened, but also the hair feel tends to deteriorate. Accordingly, it was found that the tannin concentration contained in the tannin crosslinking agent is preferably in the range of more than 1% by weight and less than 10% by weight without unnecessarily increasing.
It should be noted that the wave effect and durability vary from grade 5 to grade 4 and grade 3 to 2 depending on the judge. This includes variations due to hair, and the 5th and 3rd grades underlined are close to the 5th and 3rd grades (the same applies hereinafter).

(Experimental example 15)
The hair effect and durability were evaluated after the hair setting treatment was performed in the same manner as in Experimental Example 10 except that the mixing ratio of watt tannin and pentaploid tannin in the tannin crosslinking agent was changed. The results are shown in Table 2.

As is apparent from Table 2, the hair effect using the tannin cross-linking agent of A to F with a high mixing ratio of wattle tannin was determined, and the hair using the tannin cross-linking agent of D to F was determined. It was determined to show excellent durability.
Therefore, from this result, when the condensed tannin having different tannin characteristics and the hydrolyzed tannin are mixed and used, the blending ratio of the condensed tannin and the hydrolyzed tannin is within the following range: condensed tannin: hydrolyzed It was determined that tannin was preferably 7: 3 to 1: 1 (weight ratio).

Claims (4)

a tannin cross-linking agent mainly composed of tannin that has been reduced in molecular weight in an alkaline region of pH 8 to 10 and further activated by the reduction action of sulfite;
A warming hair set treating agent comprising: a weakly acidic neutralizing agent that neutralizes alkali remaining in hair treated with a tannin crosslinking agent.   The warming hair set treating agent according to claim 1, wherein the tannin is a catechol-based condensed tannin.   The warming hair set treating agent according to claim 1, wherein the tannin is a mixture of a catechol-based condensed tannin and a pyrogallol-based hydrolyzed tannin. The mixing ratio of condensed tannin and hydrolyzed tannin is by weight,
The heating-type hair set treatment agent according to claim 3, wherein condensed tannin: hydrolyzed tannin = 7: 3 to 1: 1.