JP5243708B2 - Temporary hair dye - Google Patents

Description

  The present invention relates to a temporary hair dye.

  Temporary hair dyes that temporarily color hair by attaching a colorant to the surface of the hair are accepted and used by many consumers because of their ease. As the colorant, various pigments are used depending on the target hue, but carbon black is mainly used for concealing gray hair, etc., because it is excellent in color strength and concealment property and easy to disperse. I came.

  However, in recent years, since there is a concern about the safety problem of carbon black with respect to the human body, black titanium oxide having higher safety is attracting attention as a black pigment replacing carbon black. However, since black titanium oxide has a higher specific gravity than carbon black and is difficult to disperse well, there is a problem that the hue is not stable, for example, color unevenness occurs when it is contained in a temporary hair dye.

  To solve the above problem, a technique for improving the dispersibility of black titanium oxide has been studied so far. For example, Patent Document 1 listed below discloses an alcohol solvent and titanium black (of black titanium oxide). A temporary hair dye containing N-methacryloylethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / butyl methacrylate copolymer as a dispersing agent under the trade name) is disclosed.

Japanese Patent No. 3693437

  However, although the temporary hair dye described in Patent Document 1 is excellent in dispersibility of black titanium oxide, it tends to discolor due to insufficient fixing ability of the colorant, and the colorant on the hair due to moisture, sweat, etc. And secondary contamination such as soiling clothes. Further, such a temporary hair dye has a strong squeaky feeling after hair dyeing, and is still not sufficient in terms of the feeling of use.

  By the way, the temporary hair dye is used in various usage forms, but when hair is temporarily dyed on a part of concern such as a hairline, a type in which the hair dye is applied using a brush, comb or sponge is suitable. It is. With this type of hair dye, it spreads well on the hair, has good coatability that can be easily applied to the target site, and quick-drying that quickly dries after application and does not transfer the colorant to the hands. Good usability at the same time is required. And the level of consumer demand for such usability has been increasing recently. In addition, the feeling of use of the temporary hair dye is not limited to a squeaky feeling, and there is a demand for a little uncomfortable feeling. For this reason, it is necessary to improve the above-described color fading and secondary staining while preferably achieving both usability and feel.

  Therefore, the present invention has been made in view of the above circumstances, and while containing black titanium oxide with higher safety, it enables hair dyeing with sufficiently small color unevenness and discoloration, and secondary staining. An object of the present invention is to provide a temporary hair dye that has a sufficiently small amount and can achieve a good balance between usability and feel.

The temporary hair dye of the present invention that solves the above problems comprises 35 to 80% by mass of ethanol , 0.5 to 10% by mass of black titanium oxide, and 3 to (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer . It contains 15% by mass, 0.01-5.0% by mass of hydroxypropylcellulose, and 2-30% by mass of glycerin , and is applied to the target site of hair with a brush, comb or sponge. .

  According to the temporary hair dye of the present invention, by adopting the above-described configuration, even when black titanium oxide is contained, it is possible to perform hair dyeing with sufficiently little color unevenness and discoloration, and after hair dyeing, The secondary contamination can be reduced sufficiently, and a good feeling in use can be obtained with a feeling of squeakiness and stiffness. In addition, according to the temporary hair dye of the present invention, it is possible to achieve a balance between spreading on the hair, applicability and quick-drying, so that hair can be dyed more easily and more reliably in a shorter period of time. Can do.

  The temporary hair dye of the present invention is particularly suitable as a mascara type temporary hair dye because it can sufficiently reduce the scattering of liquid even when a brush or the like is used as an application tool.

  In the temporary hair dye of this invention, it is preferable that content of ethanol is 40-75 mass% from a viewpoint of achieving both a quick-drying property and little squeak feeling at a higher level.

  Moreover, in the temporary hair dye of this invention, from the viewpoint of obtaining the effect of this invention more reliably, content of hydroxypropyl cellulose is 0.01-5.0 mass%, and content of glycerin is 2. It is preferable that it is -30 mass%. Furthermore, the content of hydroxypropyl cellulose is more preferably 0.05 to 3.0% by mass. Moreover, it is more preferable that content of glycerol is 5-20 mass%.

  The temporary hair dye of the present invention preferably has a viscosity of 50 to 30000 mPa · s. According to the temporary hair dye of the present invention in such a viscosity range, the effect of the present application described above can be obtained more effectively, particularly when the hair dye is applied to the target site of hair using a brush, comb or sponge. Can do.

  According to the present invention, while containing higher safety black titanium oxide, it is possible to dye hair with sufficiently small color unevenness and discoloration, and there is a sufficient amount of secondary contamination, balancing usability and feel. Temporary hair coloring that can be achieved well can be provided.

  Hereinafter, the temporary hair dye of the present invention will be described in detail.

  Examples of the black titanium oxide used in the present invention include those obtained by reducing titanium oxide by heating at a temperature of about 800 ° C. in ammonia gas and comprising a mixture of a solid solution of titanium oxide and titanium nitride. As such black titanium oxide, commercially available products can be used. For example, titanium black 12S, titanium black 13M (manufactured by Mitsubishi Materials Corporation, trade name), Tilac D (Ako Kasei Co., Ltd.) Product name).

  The content of the black titanium oxide contained in the temporary hair dye of the present invention is preferably 0.5 to 10% by mass and more preferably 1 to 6% by mass based on the total amount of the temporary hair dye.

  The (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer (hereinafter simply referred to as “copolymer”) used in the present invention is obtained by copolymerizing methacryloyloxyethylcarboxybetaine and an alkyl methacrylate. . As such a copolymer, a commercially available product can be used. For example, R205, R205S, 510, SM, 301, AMPHOSET, 104D and 202 (trade name, manufactured by Mitsubishi Chemical Corporation) of Yuka Former series. Etc.

  In this invention, it is preferable that the alkyl group of the said copolymer is a C1-C18 aliphatic hydrocarbon group.

  The weight average molecular weight of the copolymer is preferably 10,000 to 200,000, and more preferably 50,000 to 150,000. In addition, the weight average molecular weight as used in this specification is measured by gel permeation chromatography (GPC), and converted using a standard polystyrene calibration curve.

  The content of the copolymer contained in the temporary hair dye of the present invention is preferably 3 to 15% by mass based on the total amount of the temporary hair dye. In addition, when the said copolymer is mix | blended with a temporary hair dye in the form of a resin solution, it is preferable that solid content (copolymer) in a solution becomes in the said density | concentration range on the basis of the total amount of temporary hair dye.

  As the hydroxypropyl cellulose used in the present invention, commercially available products such as HPC-M (trade name, manufactured by Nippon Soda Co., Ltd.) and Crucell G (trade name, manufactured by Aqualon Co., Ltd.) can be used.

  The content of the hydroxypropyl cellulose contained in the temporary hair dye of the present invention is 0.01 to 5.00% by mass based on the total amount of the temporary hair dye from the viewpoint of improving the usability and fixing power of the temporary hair dye in a balanced manner. It is preferable that it is 0.05 to 3.00 mass%.

  A commercially available thing can be used as glycerol used by this invention. Moreover, the content is 2-30 mass% on the basis of the total amount of the temporary hair dye, from the viewpoint of satisfying all of the less stiff feeling of the temporary hair dye, the secondary anti-fouling property and the quick drying property at a higher level. It is preferable that it is 5-20 mass%.

  It does not specifically limit as ethanol used by this invention, A commercially available thing can be used. However, in the present invention, it is necessary that the total content of ethanol contained in the temporary hair dye is 35 to 80% by mass based on the total amount of the temporary hair dye. If the total content of ethanol is less than 35% by mass, quick-drying properties cannot be obtained sufficiently. On the other hand, if the total content exceeds 80% by mass, the squeaky feeling becomes too strong and the feeling of use becomes insufficient. . Moreover, in the temporary hair dye of this invention, it is preferable that content of ethanol is 40-75 mass% from a viewpoint of satisfying both quick-drying property and little squeak feeling at a higher level.

  In the temporary hair dye of the present invention, if necessary, pigments other than black titanium oxide, hydrocarbons, waxes, fats and oils, cationic polymers, anionic polymers, amphoteric polymers, nonionic polymers, higher alcohols , Higher fatty acids, organic solvents or penetration enhancers, esters, ethers, silicones, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, preservatives, chelating agents , Stabilizers, antioxidants, pH adjusters, protein hydrolysates, amino acids, various plant extracts, herbal extracts, fragrances, and UV absorbers.

  As pigments other than black titanium oxide, red No. 2, red No. 3, red No. 102, red No. 104 (1), red No. 105 (1), red No. 106, red No. 227, red No. 230 ( 1), red 230 (2), red 231, red 232, yellow 4, yellow 5, yellow 202 (1), yellow 202 (2), yellow 203, green 3 , Barium of water-soluble dyes such as green 201, green 204, green 205, blue 1, blue 2, blue 202, blue 205, orange 205, orange 207, brown 201, Calcium, zirconium or aluminum lake pigment, red 201, red 202, red 203, red 204, red 205, red 206, red 207, red 208, red 215, red 218, Red 219, Red 220, Red 221, Red 223, Red 225, Red 226, Red 228, Yellow 201, Yellow 204, Yellow 205, Green 202, Blue 201, Blue 204 , Blue 404, orange 201, orange 203, orange 204, orange 206, orange 401, orange 402, orange 403, purple 201 and other organic pigments, and yellow Examples thereof include inorganic pigments such as iron oxide, black iron oxide, bengara, gunjo, koji, chromium oxide, chromium hydroxide, carmine and shikonin.

  A pigment other than the black titanium oxide can be appropriately selected according to the desired color tone, and an appropriate amount can be blended with the temporary hair dye.

  The temporary hair dye of the present invention preferably has a viscosity of 50 to 30000 mPa · s. The viscosity of the temporary hair dye is a value (mPa · s) when measured at a predetermined rotational speed and a temperature of 25 ± 1 ° C. with a B-type viscometer using a rotor corresponding to the measurement adaptation range. . Specifically, when the viscosity is 100 mPa · s or less, the rotor no. No. 2 and a rotational speed of 60 rpm, a range of 100 to 2000 mPa · s, rotor No. No. 2 and a rotational speed of 12 rpm, 2000 to 8000 mPa · s. 3 and the rotational speed of 12 rpm, the rotor No. in the range of 8000 to 40000 mPa · s. 4, the viscosity of the temporary hair dye is measured under the condition of a rotational speed of 12 rpm.

  In the temporary hair dye of this invention, it is possible to adjust a viscosity by adjusting content of hydroxypropyl cellulose, and to obtain the effect of this application.

  The form of the temporary hair dye of the present invention is not particularly limited, but is preferably a gel from the viewpoint that it can be easily applied to a target site. By using a gel shape, it becomes easy to temporarily dye hair that is worrisome such as hairline using a brush, comb or sponge.

  The temporary hair dye of the present invention can be prepared according to a conventional method by blending the above-described components. For example, purified water, ethanol, and hydroxypropyl cellulose are mixed, and this mixture is mixed with black titanium oxide, glycerin, (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer, and, if necessary, a pigment other than black titanium oxide. A temporary hair dye can be obtained by adding a mixture of other components such as and stirring.

  For the above mixing and stirring, a normal stirrer can be used, but if necessary, it may be pulverized and mixed with a homogenizer, a ball mill, a sand mill, a roll mill, a disper mill or the like. Moreover, although mixing and stirring can be normally implemented at room temperature, you may heat and cool as needed.

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

(Examples 1-13 and Comparative Examples 1-8)
Gel-like temporary hair dyes having the compositions shown in Tables 1 to 3 were prepared by the following method, usability (liquid splashing, ease of application, spreading, quick drying), feeling of use (feeling of stickiness, squeaking), color Each item of unevenness, adhesion, and secondary adhesion was evaluated and determined by the following evaluation method and criteria. Furthermore, the viscosity of the prepared temporary hair dye was measured. These results are shown in Tables 1-3. In addition, the unit of each component in a table | surface is the mass% unless there is particular notice.

(Manufacturing method)
First, purified water (1), absolute ethanol (2) and component (3) were mixed. Next, a mixture of titanium black 12S (4), pigment (5) other than titanium black 12S, component (6), and Yucaformer 202 (7) is added to this mixed solution and stirred to obtain a gel-like solution. A temporary hair dye was obtained. In addition, said mixing and stirring were performed at room temperature.

As shown in Tables 1 to 3, hydroxypropylcellulose, carboxyvinyl polymer, hydroxycellulose, titanium black 12S, yellow No. 401, red No. 202 SG and Yuka Former 202 were used as shown below.
Hydroxypropylcellulose: Nippon Soda Co., Ltd., trade name “HPC-M”
Carboxyvinyl polymer: manufactured by Sumitomo Seika Co., Ltd., trade name “Apeck HV-505E”
Hydroxyethyl cellulose: manufactured by Hercules Co., Ltd., trade name “Natrozole 250HR”
Yellow 401: Red Chemical No. 202 manufactured by Kasei Kasei Co., Ltd. SG: Titanium Black 12S manufactured by Kasei Kasei Co., Ltd. Yucaformer 202 manufactured by Mitsubishi Materials Corporation: (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer, Made by Mitsubishi Chemical Corporation

(Evaluation method)
[Liquid fly]
Temporary hair dye was put in a plastic mascara container whose application part was made of a mascara brush, and the degree of scattering of the temporary hair dye when the mascara brush was pulled out was evaluated visually based on the following criteria.
A: The hair dye does not scatter at all.
○: Almost no hair dye is scattered.
Δ: Hair dye is slightly scattered.
X: The amount of hair dye scattered is large.

[Ease of application (applicability)]
Test subjects (20 people) use a mascara brush to dye the target area of the hair, and the target area from the viewpoint of familiarity with the hair and less adherence to the target area Asked if it was easy to dye hair. And the ease of application | coating was evaluated based on the following reference | standard.
A: More than 17 people answered that they could easily dye their target area.
○: 12 or more and less than 17 responded that “the target site could be easily dyed”.
Δ: 8 or more and less than 12 responded that “the target site could be easily dyed”.
×: Less than 8 responded that “the target site could be easily dyed”.

[Nobi]
Based on the following criteria, the hair dye was evaluated by visual observation when the temporary hair dye was applied once to a goat hair bundle (length 10 cm, weight 1 g) with a mascara brush.
A: The hair dye is very good.
○: The hair dye spreads well.
Δ: Slightly poor hair dyeing
X: The hair dye does not spread well.

[Color unevenness]
The color of the hair bundle when a temporary hair dye was applied once to the goat hair bundle (length 10 cm, weight 1 g) with a mascara brush was visually evaluated based on the following criteria.
A: There is no color unevenness.
○: There is almost no uneven color.
Δ: Some uneven color.
X: There is uneven color.

[Stuck]
A temporary hair dye 0.5 g was applied to a goat hair bundle (length 10 cm, weight 1 g) with a brush for mascara, and allowed to dry at room temperature (25 ° C. ± 1 ° C.) for 30 minutes. Stiffness of the hair bundle after drying was evaluated based on the following criteria based on the touch feeling with a hand.
A: There is no wrinkle.
○: Almost no wrinkle.
Δ: There is a little wrinkle.
X: There is a sensation.

[Squeaking]
A temporary hair dye 0.5 g was applied to a goat hair bundle (length 10 cm, weight 1 g) with a brush for mascara, and allowed to dry at room temperature (25 ° C. ± 1 ° C.) for 30 minutes. The squeak of the hair bundle after drying was evaluated based on the following criteria based on the touch feeling with the hand.
A: There is no squeak.
○: Almost no creaking
Δ: Slightly squeaky.
X: There is a squeak.

[Fixing strength]
A temporary hair dye 0.5 g was applied to a goat hair bundle (length 10 cm, weight 1 g) with a brush for mascara, and allowed to dry at room temperature (25 ° C. ± 1 ° C.) for 30 minutes. Next, a cotton cloth was rubbed against the dried hair bundle, the degree of color fading of the hair bundle was visually confirmed, and the fixing strength of the hair dye was evaluated based on the following criteria.
(Double-circle): The dye | dye of the hair | bristle bundle has not fallen at all.
○: The hair bundle is hardly dyed.
Δ: The hair bundle is slightly dyed.
X: The hair bundle is almost dyed.

[Secondary adhesion]
A temporary hair dye 0.5 g was applied to a goat hair bundle (length 10 cm, weight 1 g) with a brush for mascara, and allowed to dry at room temperature (25 ° C. ± 1 ° C.) for 30 minutes. Next, a cotton cloth was rubbed against the hair bundle after drying, the degree of transfer of the pigment adhered to the cloth was visually confirmed, and the secondary staining property of the hair dye was evaluated based on the following criteria.
(Double-circle): Transfer of the pigment to cloth is not seen at all.
○: Almost no transfer of the pigment onto the fabric.
(Triangle | delta): Transfer of the pigment to cloth is seen a little.
X: Many transfer of the pigment to cloth is seen.

[Quick drying]
A temporary hair dye 0.5 g was applied to a goat hair bundle (length 10 cm, weight 1 g) with a brush for mascara and left under conditions of room temperature (25 ± 1 ° C.) and humidity 50 ± 1%. The time until the pigment did not touch the hand even when the hair bundle was touched was measured as the drying time, and the quick drying property of the hair dye was evaluated based on the following criteria.
A: Drying time is within 1 minute.
○: Drying time exceeds 1 minute and is within 3 minutes.
Δ: Drying time exceeds 3 minutes and is within 10 minutes.
X: Drying time exceeds 10 minutes.

(Measurement of viscosity)
Using a B-type viscometer (manufactured by TOKIMEC Co., Ltd., VISCOMETER BM type), the viscosity of the temporary hair dye was measured at a temperature of 25 ± 1 ° C. When the viscosity is 100 mPa · s or less, the rotor No. No. 2 and a rotational speed of 60 rpm, a range of 100 to 2000 mPa · s, rotor No. No. 2 and a rotational speed of 12 rpm, 2000 to 8000 mPa · s. 3 and the rotational speed of 12 rpm, the rotor No. in the range of 8000 to 40000 mPa · s. 4, the viscosity of the temporary hair dye was measured under the condition of a rotational speed of 12 rpm. The obtained values are shown in Tables 1-3. The unit of the numbers shown in the table is mPa · s.

  As shown in Tables 1-3, it contains ethanol, black titanium oxide, (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer, hydroxypropyl cellulose, and glycerin, and the ethanol content is 35-80. According to the temporary hair dyes of Examples 1 to 13 in the range of mass%, they achieve a good balance without causing a major problem in usability and feeling of use, and have sufficiently small color unevenness, fixing strength and It was confirmed that the hair dyeing excellent in secondary adhesion was made.

  On the other hand, the temporary hair dye of Comparative Example 1 that does not contain hydroxypropyl cellulose has a problem of discoloration due to liquid splashing or insufficient fixing power, and the temporary hair dye of Comparative Example 2 using carboxyvinyl polymer instead of hydroxypropyl cellulose. The temporary hair dye of Comparative Example 3 using hair dye or hydroxyethyl cellulose was insufficient in spreading and coating properties and inferior in usability.

  Moreover, the temporary hair dye of the comparative example 4 which does not contain glycerin had a feeling of stickiness, and was inferior in use feeling. Furthermore, in the temporary hair dye of Comparative Example 5 containing dipropylene glycol instead of glycerin, secondary staining is often observed, and in the temporary hair dye of Comparative Example 6 containing 1,3-butylene glycol instead of glycerin, There were problems such as uneven color.

  In addition, the temporary hair dyes of Comparative Examples 7 and 8 whose ethanol content is not in the range of 35 to 80% by mass are insufficient in either quick-drying or squeaky feeling, so that both usability and use feeling are compatible. I couldn't.

  Hereinafter, examples of the temporary hair dye of the present invention will be shown.

(Example 14) Tube type temporary hair dye (component) (mass%)
1. 1. Purified water remaining Absolute ethanol 46.5
3. Hydroxypropylcellulose 4.0
4). Titanium Black 12S 5.0
5. Yellow No. 4.0 4.0
6). Blue No. 404 0.5
7. Red No. 202 SG 2.0
8). Concentrated glycerin 8.0
9. Yuka Former 202 20.0

(Manufacturing method)
The tube type temporary hair dye of Example 14 was obtained by melt | dissolving the component 3 in the component 1 and the component 2, and adding the mixed dispersion liquid of the components 4-9 there.

  When the above-mentioned evaluation was performed on the obtained tube-type temporary hair dye, it was confirmed that the color unevenness, color fading, and secondary staining were sufficiently small, and the usability and feel were sufficiently excellent.

Claims (3)

0.01 ethanol and a 35 to 80 wt%, and 0.5 to 10% by mass of black titanium oxide, (methacryloyloxyethyl carboxymethyl betaine / alkyl methacrylate) and 3 to 15 wt% of the copolymer, hydroxypropyl cellulose Temporary hair dye containing 5.0% by mass and 2-30% by mass of glycerin , and applying to a target site of hair with a brush, comb or sponge. The temporary hair dye of Claim 1 whose content of the said ethanol is 40-75 mass%. The temporary hair dye of Claim 1 or 2 whose viscosity is 50-30000 mPa * s.