JP5646204B2 - Hair cosmetic base material and method for producing the same - Google Patents

Description

The present invention relates to a hair cosmetic base material, and more specifically, after etherified starch is heated with water and a glycerin mixed solution, glycerin, ethylene glycol (hereinafter referred to as EG), propylene glycol (hereinafter referred to as PG). ), One or more additives of polyethylene glycol (hereinafter referred to as PEG) # 200, and by adding ethanol, for hair cosmetics that change the feel after being applied to the hair and washed. It relates to a substrate.

The effects required for hair cosmetics include so-called treatment effects that can improve and maintain the feel of the hair after shampooing, and good combing at the time of drying and styling after shampooing. In order to bring out these effects, modified silicon, cationized hydroxyethyl cellulose (cationized HEC), fats and oils and the like have been conventionally used for shampoos and treatment agents.

In addition, some of the hair treatment agents derived from starch use etherified (hydroxyalkylated) starch, esterified (acetylated) starch, or etherified phosphate-crosslinked starch. A method of adding other materials (oil, polyhydric alcohol, glycerin, surfactant, etc.) after heat gelatinization in a phase has been taken. (Special Tables 2000-514435, JP-A 2004-323425, JP-A 2005-270975, JP-A 2008-169183)

It is also known that starch can be used to prepare a paste solution using ethylene glycol or glycerin in addition to water. (Japanese Examined Patent Publication No. 49-35411, Japanese Unexamined Patent Publication No. 2000-265148)

Special Table 2000-514435 JP 2004-323425 A JP 2005-270975 A JP 2008-169183 A Japanese Patent Publication No.49-35411 JP 2000-265148 A

In general, modified silicones blended in shampoos and treatment agents as hair feel improvers have the effect of coating the hair surface and improving the feel. However, when a hair cosmetic compounded with modified silicon is used repeatedly, there is a problem that it cannot be removed cleanly and accumulated when it is washed, and the touch is worsened.

Moreover, about the thing which mix | blended cationized HEC and fats and oils, the problem that a touch becomes heavy or a comb passage worsens has arisen.

In order to solve such a problem, it is conceivable to use water-soluble starch, and patents are also disclosed (Patent Documents 1 to 4). When starch is gelatinized in an aqueous phase, If it is not heated and stirred at a high temperature such as 85 ° C. or higher, it will not become a uniform paste. In addition, considering the other ingredients to be added, when a thick starch suspension is heated, a complicated operation such as preparing a very viscous paste first is required. There was a drawback that the concentration could not be increased too much.

As a solution to this problem, Patent Documents 1 to 3 disclose a method in which pregelatinized starch is first prepared and then added to an aqueous phase or the like. However, pregelatinized starch must be prepared in advance, resulting in problems such as a large number of steps and economical addition.

Furthermore, in Patent Literatures 1 to 4, hydroxyalkylated or acylated, gelatinized and cross-linked (particularly phosphoric acid cross-linked) starches are used. Is hardly disclosed.

In addition, as disclosed in Patent Documents 5 and 6, when starch is gelatinized in a non-aqueous system using ethylene glycol or glycerin, a paste solution can be prepared unless heated at a high temperature of 95 ° C. or higher. There wasn't.

In order to solve such problems, the present inventors have intensively studied and, after heating the etherified starch with water and a mixed solution of glycerin, added glycerin or one or more of EG, PG, and PEG # 200. It was discovered that a cosmetic base material suitable for hair can be provided by adding an agent and ethanol.

As described above, according to the present invention, after etherified starch is heated with a mixed solution of water and glycerin, glycerin or one or more additives of EG, PG, PEG # 200, ethanol, By adding it, it is possible to prepare a viscous base material suitable for hair cosmetics. Furthermore, depending on the starch processing method, it can be applied to hair with various touches such as a dry touch, a firmness, and a voluminous feel. Can be improved.

The raw materials of etherified starch that can be used in the present invention include potato starch, corn starch, waxy corn starch, sweet potato starch, tapioca starch, sago starch, rice starch, glutinous starch, amaranthus starch and other untreated (natural) starches, Examples include treated starch (acid-treated starch, enzyme-treated starch, dextrin, oxidized starch, wet-heat treated starch, etc.), but untreated corn starch is preferred in terms of viscosity after the processing.

Examples of the etherified starch that can be used in the present invention include carboxymethylated starch, hydroxyalkyl (hydroxyethyl, hydroxypropyl) -ized starch, cationized starch and the like, and hydroxypropylated starch and / or carboxymethylated starch are particularly preferred. Although it can be suitably used in terms of viscosity after processing, it can be appropriately changed depending on the feel.

The degree of substitution of etherified starch that can be used in the present invention (the number of functional groups per glucose unit that is a constituent of starch, hereinafter referred to as DS) improves the gelatinization start temperature and viscosity of raw starch. It becomes an important factor when heating together with the mixed solution of water and glycerin used in the invention. For example, when DS <0.02, heating with a mixed solution of water and glycerin does not turn into a paste, and when DS> 0.15, it does not extend uniformly when applied to hair.

The film elongation of the etherified starch that can be used in the present invention is an important factor for the feel of the hair after application. For example, if the film elongation is 23% or less, the hair feel becomes hard, which is not preferable. The film elongation used in the present invention is measured by the following procedure.

<Film elongation>
20 mL of an anhydrous 2% starch paste solution (prepared after heating at 85 ° C. for 10 minutes and then correcting for moisture) was poured into a mold adhered on a PET film of 100 mm × 100 mm, 20 ° C., 65% A film was prepared by air-drying for 2 days in RH. The film was cut into 10 mm × 30 mm, sandwiched so that the distance was 10 mm, a tensile test was performed with Tensilon under the following conditions, and the film elongation was determined by the following formula.

Measurement conditions: Tensile speed 20 mm / min, measurement temperature 20 ° C., measurement humidity 65% RH
Load cell 5kgf, measurement range 40%, chuck width 10mm

The amount of etherified starch used in the present invention is not particularly limited. For example, when the dosage form of the hair cosmetic is cream, it can be applied to the hair even if it has a relatively high viscosity, but if it is a spray (mist) type, it is uniform when sprayed. Viscosity should be as wide as possible. For example, when preparing a hair cream using hydroxypropyl corn starch (DS: about 0.1), the viscosity is 6-15% by mass (hereinafter referred to as%) that can be applied to the hair to some extent with fingers, 8 to 12% can be suitably used in terms of elongation when applied to hair and feel after washing.

The glycerin used in the present invention can be uniformly gelatinized by mixing with water prior to heating, adding and heating. It is also possible to add a part after heat gelatinization, but even if etherified starch is heat gelatinized only with water and all necessary glycerin is added later, a uniform and stable substrate cannot be prepared.

In the present invention, in order to adjust the viscosity suitable for hair cosmetics and improve the elongation to hair and the feel after washing, after preparing a paste with etherified starch, water and glycerin, glycerin or EG, PG Add additives such as diethylene glycol, PEG, polypropylene glycol. Preferably, EG, PG, and PEG # 200 can be used, and these can be suitably used alone or in a mixture.

The amount of one or more of glycerin or EG, PG, PEG # 200 used in the present invention is not particularly limited. However, when PG and PEG # 200 are added too much, the viscosity decreases or separation / precipitation occurs. For example, when 10% of hydroxypropyl corn starch (DS: about 0.1) is used, a range of 2 to 15% can be preferably used.

In the present invention, ethanol is added in order to adjust the viscosity suitable for hair cosmetics and to improve the elongation to hair and the feel after washing. The amount is not particularly limited. However, if it is added too much, the viscosity will decrease or separation / precipitation will occur. Therefore, when 10% of hydroxypropyl corn starch (DS: about 0.1) is used, it can be suitably used within the range of 2 to 12%.

The water and glycerin mixed solution used in the present invention may be any ratio that allows the etherified starch to gelatinize at a predetermined temperature. However, when water accounts for the majority, even if glycerin is added later, a uniform paste is not obtained. Moreover, when glycerin accounts for most, starch cannot be gelatinized at the temperature of 65 to 80 degreeC.

Examples of the method for producing the hair cosmetic base material of the present invention include the following methods. First, a predetermined amount of water and glycerin are mixed and prepared. Thereafter, a predetermined amount of etherified starch is added and heated with mixing and stirring. The heating temperature may be in the range of 65 to 80 ° C, but it is preferably heated at 65 to 70 ° C. When the temperature is lower than 65 ° C, the starch does not gelatinize and does not become a paste. Moreover, when it heats at 80 or more, a viscosity will fall and it will not become the viscosity suitable when applying to hair. While maintaining the temperature, the mixture is stirred for a certain time to complete the gelatinization. After cooling to room temperature, one or more additives of EG, PG, and PEG # 200 are added and mixed. When uniform, ethanol is added and mixed to prepare a paste solution.

In addition to the above, surfactants (nonions, anions, cations, amphoteric surfactants), other water-soluble polymers, hair protecting agents such as seaweed extracts and keratin derivatives, moisturizers, drugs as necessary , Pigments, preservatives, fragrances, antioxidants, ultraviolet absorbers, and the like can be appropriately blended. As a matter of course, these components must be in a qualitative and quantitative range that does not impair the effects of the present invention.

Regarding the dosage form and application method of the base material for hair cosmetics that can be used in the present invention, for those having a high viscosity, a method for uniformly applying to the hair with fingers like a cream, and for those having a low viscosity, Examples of the method include a method of extending the shape (mist) with a comb or fingers, and the like, but can be appropriately selected according to the viscosity of the substrate.

EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited only to these Examples.

<Examples of making modified starch>
Various modified starches (etherified and esterified starch) were prepared according to the following formulation. Table 1 shows the starch used, the processing method, the amount of chemicals added (parts) to 1000 parts of starch, the degree of substitution, and the film elongation. In addition, since it cannot measure by the concept of a substitution degree about the crosslinking degree of crosslinked starch, data was abbreviate | omitted.
A. To 1300 parts of hydroxypropylated starch water, 300 parts of sodium sulfate and 10 parts of caustic soda were added and dissolved. To the slurry prepared by adding 1000 parts of starch with stirring, propylene oxide was added and reacted at 40 ° C. for 15 hours. . Thereafter, neutralization, washing with water, dehydration, drying and fine powder were performed to obtain hydroxypropylated starch.
B. To 1300 parts of carboxymethylated starch water, 300 parts of sodium sulfate and 3.5 parts of caustic soda are added and dissolved. To a slurry prepared by adding 1000 parts of starch with stirring, sodium monochloroacetate is added, and pH 11.5-12. The mixture was reacted at 45 ° C. for 6 hours while maintaining at 0.0. Thereafter, neutralization, washing with water, dehydration, drying and fine powder were performed to obtain carboxymethylated starch.
C. To 1300 parts of cationized starch water, 4 parts of caustic soda was added and dissolved, and under stirring, a slurry prepared by adding 1000 parts of starch was added to an 80% 2,3-epoxypropyltrimethylammonium chloride solution (manufactured by Sakamoto Pharmaceutical Co., Ltd.). SY-GTA80) was added and reacted at 40 ° C. for 24 hours. Thereafter, neutralization, washing with water, dehydration, drying and fine powder were performed to obtain cationized starch.
D. To a slurry prepared by adding 1000 parts of corn starch to 1300 parts of acetylated starch water, 3% aqueous sodium hydroxide solution was added with stirring to maintain pH at 8.5 to 9.0, while acetic anhydride was added dropwise. In addition, the reaction was carried out for 1 hour after completion of the dropwise addition. Thereafter, neutralization, washing with water, dehydration, drying and fine powder were performed to obtain acetylated corn starch.
E. To 1300 parts of hydroxypropylated phosphoric acid crosslinked starch water, 300 parts of sodium sulfate and 10 parts of caustic soda were added and dissolved, and to a slurry prepared by adding 1000 parts of starch with stirring, sodium trimetaphosphate and propylene oxide were added, and 40 The reaction was carried out at 15 ° C. for 15 hours. Then, neutralization, washing with water, dehydration, drying and fine powder were performed to obtain hydroxypropylated phosphate cross-linked starch.
F. Epichlorohydrin was added to a slurry prepared by adding 5 parts of caustic soda to 1300 parts of epichlorohydrin-crosslinked starch water, and 1000 parts of starch was added with stirring, and reacted at 40 ° C. for 15 hours. Thereafter, neutralization, washing with water, dehydration, drying and fine powder were performed to obtain hydroxypropyl crosslinked starch.
G. Using 1000 parts of hydroxypropylated starch decomposition product water, 1000 parts of hydroxypropylated starch prepared by the formulation of 1 and 1 part of α-amylase were added and liquefied at 80 to 97 ° C. while maintaining the pH at 6.0 to 7.0. Thereafter, the viscosity was adjusted, and deactivation, neutralization, diatomaceous earth and activated carbon filtration, microfiltration, concentration, and spray drying were performed to obtain a hydroxypropylated starch degradation product.

A hair cosmetic base material was prepared using various starches and starch degradation products listed in Table 1 prepared according to modified starch preparation examples. The manufacturing method of a base material is shown below.

<Manufacturing method>
1. Mix and prepare a predetermined amount of water and glycerin.
2. A predetermined amount of various modified starches are added and heated to 70 ° C. with mixing and stirring.
3. Once at 70 ° C., stir for 5 minutes while maintaining temperature to complete gelatinization.
4). After cooling to room temperature, additional correction of evaporated water is made and mixed to homogenize.
5. When a predetermined amount of the additive is added and mixed to become uniform, a predetermined amount of ethanol is added and mixed to obtain a substrate.

<Comparison of substitution degree 1>
A hair cosmetic base material was prepared by the above-described production method using hydroxypropylated starch (HPS-CS1 to 4) or raw corn starch having different degrees of substitution. However, the base material No. Since 4 and 5 cannot be prepared by the above-described production method of the present invention, first, the mixed solution of water and glycerin was not prepared, gelatinization was similarly completed with water and starch, and after cooling to room temperature, it evaporated Water was further corrected and mixed to homogenize. Thereafter, when a predetermined amount of glycerin and a polyhydric alcohol were added and mixed, and a uniform amount of ethanol was added and mixed, a substrate was prepared. Table 2 shows various blending amounts, viscosities of B-type rotational viscometers at 30 ° C. or 20 rpm (upper right *) of the base material, and stability on the next day of preparation.

From the results in Table 2, when hydroxypropylated starch is used, the substrate can be prepared by the production method of the present invention. However, for HPS-CS4 and raw corn starch having a substitution degree of 0.04, The substrate could not be prepared by the production method of the present invention. Furthermore, when gelatinized with water and then prepared by adding glycerin and polyhydric alcohol, the substrate No. using HPS-CS4 was prepared. 4 could be prepared stably, but the base material No. 4 using raw corn starch was used. As for No. 5, a stable product could not be prepared.

<Comparison of substitution degree 2>
A hair cosmetic base material was prepared by the above-described production method using carboxymethylated starches (CMS-CS1 to 3) having different degrees of substitution. Table 3 shows various blending amounts and viscosities of B-type rotational viscometers at 30 ° C. or 20 rpm (upper right *) of the base material and stability on the next day of preparation.

From the results shown in Table 3, when carboxymethylated starch is used, the substrate can be prepared by the production method of the present invention. However, in CMS-CS3 having a substitution degree of 0.02, only a substrate having no stability could be prepared even if the substrate could be prepared by the production method of the present invention.

<Comparison of starch content>
A hair cosmetic base material was prepared by the above-described production method using hydroxypropylated starch (HPS-CS1). Table 4 shows various blending amounts and viscosities of B-type rotational viscometers at 30 ° C. or 20 rpm (upper right *) of the base material and stability on the next day of preparation.

From the results in Table 4, it is possible to prepare a substrate by the production method of the present invention when hydroxypropylated starch is used from 6% to 15%.

<Comparison of processing methods>
A base material for hair cosmetics was prepared by the above-described production method using corn starch as a raw material and differently processed starch. Table 4 shows various blending amounts and viscosities of B-type rotational viscometers at 30 ° C. or 20 rpm (upper right *) of the base material and stability on the next day of preparation.

From the results shown in Table 5, when hydroxypropylated starch, carboxymethylated starch, and cationized starch are used, the substrate can be prepared by the production method of the present invention. However, other processing methods could only be prepared with no stability.

<Comparison of raw materials>
A hair cosmetic base material was prepared by the above-described production method using hydroxypropylated starches of different raw materials. Table 6 shows various blending amounts and viscosities of B-type rotational viscometers at 30 ° C. or 20 rpm (upper right *) of the base material and stability on the next day of preparation.

From the results in Table 6, it is possible to prepare the substrate by the method of the present invention even if the raw materials are different.

<Comparison 1 of additives>
A hair cosmetic base material was prepared by the above-described production method using hydroxypropylated starch (HPS-CS1). Table 7 shows various blending amounts and viscosities of B-type rotational viscometers at 30 ° C. or 20 rpm (upper right *) of the base material and stability on the next day of preparation.

From the results in Table 7, when glycerin, EG, PG, PEG # 200, and PEG # 400 are used as additives, the substrate can be prepared by the production method of the present invention.

<Comparison of additive content>
A hair cosmetic base material was prepared by the above-described production method using hydroxypropylated starch (HPS-CS1) and PEG # 200. Table 8 shows various blending amounts and viscosities of B-type rotational viscometers at 30 ° C. or 20 rpm (upper right *) of the base material and stability on the next day of preparation.

From the results of Table 8, when PEG # 200 is used as the polyhydric alcohol, the substrate can be prepared by the production method of the present invention, but when the blending amount is 20 parts or more, a stable substrate is prepared. I couldn't do that either.

<Comparison of ethanol blending amount>
A hair cosmetic base material was prepared by the above-described production method using hydroxypropylated starch (HPS-CS1) and PEG # 200. Table 9 shows various blending amounts and viscosities of B-type rotational viscometers at 30 ° C. or 20 rpm (upper right *) of the base material and stability on the next day of preparation.

From the results shown in Table 9, when ethanol is added, the substrate can be prepared by the production method of the present invention.

<Comparison of heating temperature>
A hair cosmetic base material was prepared using hydroxypropylated starch (HPS-CS1) by the same production method as described above except that the heating temperature was changed. Table 10 shows various blending amounts, viscosities of B-type rotational viscometers at 30 ° C. or 20 rpm (upper right *) of the base material, and stability on the next day of preparation.

From the results shown in Table 10, when the heating temperature was 60 ° C., the hydroxypropylated starch did not become paste, so that the substrate could not be prepared by the production method of the present invention. Further, at 80 ° C., the viscosity is lowered despite the same addition amount, which is not economically preferable.

A touch test after application and shampooing was performed using a base material that was stably prepared using 50% decolorized damaged hair. The touch test method and evaluation contents are shown below.

<Feel test I>
1. 1 g of damaged hair bundle is washed with 40 ° C. hot water for 15 seconds.
2. Lightly squeeze the washed hair bundle with Kim Towel (registered trademark) and place it on the wrap.
3. The prepared base material is applied onto 1 g of hair, wrapped with a wrap, and blended well into the whole hair bundle.
After leaving still for 4.5 minutes, peel off the wrap, make 40 ° C. hot water into a shower, and wash the hair bundle for 15 seconds while rubbing the hair bundle with fingers.
5. The hair bundle that has been washed is lightly sandwiched with a Kim towel and dried for 1 minute while combing up and down with a hair dryer wind (HOT).
6). A hair bundle that had been shampooed and dried without applying the substrate was used as a blank, and the touch when touched with a finger was compared and evaluated according to the evaluation content. The results are shown in Table 9.

<Evaluation details>
The ease of application to the hair and the touch when touched with a finger after washing and drying were evaluated by the average of three panelists, and the overall evaluation was expressed as follows.
<Ease of painting>
○: Elongates cleanly when applied to the hair bundle.
Δ: It spreads neatly when applied to the hair bundle, but the substrate hangs down from the hair when peeled off from the wrap.
X: When applied to the hair bundle, it does not stretch neatly.
<Feel>
A: The feeling is remarkably improved as compared with the blank.
○: The touch is improved compared to the blank. (◎ somewhat inferior)
Δ: Slightly better than blank.
X: worse than blank.
<Comprehensive evaluation>
G: Easier to apply and feel △ or more F: Either ease of application or feel x

From the results shown in Table 11, those having a high viscosity (base Nos. 12, 18, and 19) were slightly inferior in terms of ease of application of the base. On the other hand, those with low viscosities (base materials No. 3, 20, 34, 36) were poorly evaluated by this coating method. On the other hand, when cationized starch was used, the base material could be manufactured properly by the method of the present invention, but in the touch test, it was worse than the blank. When the heating temperature was 65 ° C., 75 ° C., and 80 ° C. (base materials No. 36, 37, and 38), even if there was a problem in the ease of application and the feel test, the overall evaluation was generally suitable. About the film elongation, about the modified starch which is less than 23%, even if a base material can be prepared stably, evaluation is inferior in the point of a touch. (Substrate Nos. 3 and 4) In addition, the etherified starch that was actually produced by the production method of the present invention also used a hydroxypropylated starch, whereas it had a lighter feel. Those using carboxymethylated starch had a firm feel and differed depending on the starch processing method.

With respect to the type and amount of the polyhydric alcohol, if the base material can be stably prepared by the method of the present invention, both the ease of application and the feel are good. However, for PEG # 400 (base No. 24), a stable base can be prepared by the method of the present invention, but it is inferior in terms of ease of application. Regarding the amount of ethanol, even if the substrate could be stably prepared by the method of the present invention, when the blending amount was 0, the touch was not much different from the blank. Moreover, when 15 parts were added, the evaluation at the time of application was inferior.

<Feel test II>
Of the feel test of Example 3, the substrate No. 1 with “ease of application” being Δ and feel being “◯” was used. 3, 20, and 36 were put into a spray spray with a trigger and applied to 50% damaged hair. Since the base material 20 was uniformly applied, the “ease of application” could be evaluated as “◯”. , Substrate No. As for Nos. 3 and 36 , no fog was generated from the spray bottle , and therefore, “x” was evaluated. Subsequently, the substrate No. was sprayed. When the hair bundle to which No. 20 was applied was evaluated in the same manner as in <Feeling Test I> 4 and the subsequent steps, the evaluation was "」 ". Therefore, the base material No. For 20 it was found that it was better to apply it to the hair in the form of a mist (mist) and stretch it with a comb or fingers, instead of applying it directly with fingers like a cream.

Claims (1)

8-12% by weight of hydroxypropylated starch derived from corn starch having a substitution degree of 0.05-0.13 or waxy corn starch and / or corn starch or waxy corn having a substitution degree of 0.03-0.04 Carboxymethylated starch derived from starch is gelatinized by heating to 65 ° C. to 85 ° C. with a mixed solution of 25 to 48% by weight of water and 25 to 40% by weight of glycerol, 2 to 12% by weight of ethanol, and 0 -15% by weight for hair characterized by being prepared by adding and mixing one or more additives selected from glycerin, ethylene glycol (EG), propylene glycol (PG) or polyethylene glycol (PEG) # 200 Cosmetic base material.