JP4963581B2 - Method for producing temporary hair dye - Google Patents

Description

  The present invention relates to a temporary hair dye containing an inorganic pigment and an organic pigment, and a method for producing the same.

  Often hair is dyed on the hair to hide gray hair or change hair color to personal preference. Hair dyes include permanent hair dyes (hair colors) that are colored by coloring in the hair using an oxidative dye, semi-permanent hair dyes (hair manicure) that are colored by penetrating and adsorbing acid dyes to the hair, and pigments on the hair. It is classified as a temporary hair dye that forms a colored film to be colored. Of these, temporary hair dyes are preferred as being able to easily enjoy hair dyeing because they are less damaging to the hair, can be easily removed by washing the hair, and can be used easily. In the hair dye, it is preferable that the touch after application is excellent and that the hair can be given good gloss.

  As the pigment in the temporary hair dye, an inorganic pigment, an organic pigment, or a combination thereof is used (see, for example, Patent Documents 1 and 2).

  Usually, to improve the dispersion stability of a pigment, it is a common method to improve the dispersion by reducing the particle size of the pigment (Non-patent Document 1). On the other hand, the viscosity of the temporary hair dye is desired to be an appropriate viscosity from the viewpoint of easy attachment to the hair, ease of elongation at the time of application, and difficulty of dripping from the applicator. When the inorganic pigment and the organic pigment are used in combination, when the particle size of the pigment is reduced according to a conventional method, the storage stability decreases, the viscosity increases with time, and the feeling of use may be impaired. I found it.

Japanese Unexamined Patent Publication No. 63-218614 JP 09-208436 A Edited by Japan Pigment Technology Association: Handbook of Pigments 67-69, 186-187, Seibundo Shinkosha, 1989

  Accordingly, an object of the present invention is to provide a temporary hair dye which has a small increase in viscosity over time despite the combined use of an inorganic pigment and an organic pigment, is excellent in touch after application, and can impart good gloss to hair. And

  The inventor pulverized and mixed in the presence of a dispersion medium so that the maximum particle size of the pigment contained in the pigment paste to be used is 5 μm or more and less than 100 μm, which is larger than that of a conventional method, thereby allowing the inorganic pigment and the organic pigment to be mixed. It has been found that a temporary hair dye can be obtained that can suppress the thickening phenomenon over time due to the combined use, is excellent in touch after application, and can impart good gloss to the hair.

  That is, in the present invention, an inorganic pigment and an organic pigment are pulverized and mixed in the presence of a dispersion medium so that the maximum particle size of the pulverized pigment is 5 μm or more and less than 100 μm, and the resulting pigment paste is mixed with lower alcohol or The present invention provides a method for producing a temporary hair dye comprising a step of blending into a mixture containing a lower alcohol.

  Further, the present invention provides a temporary hair dye containing a pigment paste obtained by pulverizing and mixing an inorganic pigment and an organic pigment in the presence of a dispersion medium and having a maximum particle size of the pigment of 5 μm or more and less than 100 μm. It is.

  The temporary hair dye of the present invention has a small increase in viscosity over time in spite of the combined use of an inorganic pigment and an organic pigment, is excellent in touch after application, and can impart good gloss to hair. According to the production method of the present invention, such a temporary hair dye can be obtained.

  Examples of the inorganic pigment used in the present invention include black titanium oxide, zinc white, red bean, chromium oxide, black iron oxide, cobalt blue, alumina white, yellow iron oxide, viridian, zinc sulfide, lithopone, cadmium yellow, vermilion, and cadmium red. , Yellow lead, molybdate orange, zinc chromate, strontium chromate, ultramarine, lead white, bitumen, manganese violet, aluminum powder, brass powder, etc., among which black titanium oxide, brown rice, black iron oxide, yellow iron oxide Is preferable, and black titanium oxide is more preferable. Here, black titanium oxide refers to a mixture of titanium oxide and a titanium oxide / titanium nitride solid solution.

  The content of the inorganic pigment is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 6% by mass in the total amount of the temporary hair dye of the present invention from the viewpoint of dispersion stability.

  As organic pigments used in the present invention, red 201, red 202, red 203, red 204, red 205, red 206, red 207, red 208, red 219, red 220, Red 221, Red 228, Red 404, Orange 203, Orange 204, Yellow 205, Red 405, Orange 401, Yellow 401, Blue 404, etc. Of these, Red 202 Red 404, yellow 205, yellow 401 and blue 404 are preferred.

  The content of the organic pigment is preferably 0.1 to 20% by mass in the total amount of the temporary hair dye of the present invention from the viewpoint of dispersion stability.

  In the temporary hair dye of the present invention, the total amount of the inorganic pigment and the organic pigment is 0.1 to 20% by mass in the total amount of the temporary hair dye in terms of hair dyeability, white hair concealment, and touch after application, It is preferably 1 to 15% by mass, particularly 5 to 12% by mass. Moreover, the content mass ratio (inorganic pigment mass / organic pigment mass) of the inorganic pigment and the organic pigment in the temporary hair dye of the present invention can be in the range of 0.001 to 1000 in terms of color design. Is preferably 0.005 to 100, more preferably 0.01 to 5, and particularly preferably 0.5 to 2.5.

  The dispersion medium used for pulverization and mixing is not particularly limited as long as it is moderately viscous and can disperse inorganic pigments and organic pigments. In particular, it is one of polyols such as glycerin, dipropylene glycol, 1,3-butylene glycol, and sorbit. Species or two or more species may be mentioned, and those having a viscosity of 10 to 10,000 mPa · s are preferable, and those having a viscosity of 50 to 5000 mPa · s are particularly preferable.

  The pigment can be pulverized and mixed using a ball mill, bead mill, sand mill, roll mill, kneader, homogenizer, ultrasonic disperser, or the like.

  In the production method of the present invention, pulverization and mixing are performed so that the maximum particle size of the pulverized inorganic pigment and organic pigment is 5 μm or more and less than 100 μm. By setting the maximum particle size to 5 μm or more, change the viscosity of the obtained temporary hair dye after storage for 1 month at 40 ° C. (Δ viscosity = (viscosity after storage) − (viscosity at the start of storage)) In terms of the coating performance, it is possible to set a change range that does not give the consumer a sense of discomfort. Specifically, as shown in FIG. 1, even after one month, the Δ viscosity can be 1700 mPa · s or less. The maximum particle size is more preferably 10 μm or more so that the Δ viscosity is 1500 mPa · s or less, and particularly preferably 20 μm or more so that the Δ viscosity is 1200 mPa · s or less. On the other hand, when particles that are thicker than the hair are mixed, the hand feels uncomfortable, but the diameter of the hair is a maximum of 100 μm in the case of Mongolian including the Japanese, and the maximum particle diameter of the pigment is less than 100 μm as described above. A temporary hair dye with little discomfort can be obtained. The maximum particle size of the pigment is more preferably 80 μm or less, which is the average diameter of Mongolian hair including Japanese, and even more preferably, 50 μm or less, which is the average diameter of Caucasian hair.

  In the present invention, the pulverization and mixing so that the maximum particle size of the pigment is 5 μm or more and less than 100 μm is performed by controlling the pulverization conditions while measuring the maximum particle size with a grind gauge specified in JIS K 5101. To do. For specific measurements, use a BYK-GARDNER grind gauge and take 1.0 (± 0.1) g of sample paste, and measure it at room temperature three times (except for values that are clearly considered abnormal values). , Additional measurement is made for that amount), and the average value of three times is taken as the measurement value. Regarding reading of numerical values, in the present invention, the value at which the first continuous line formed by the motion of the scraper appears is read regardless of the JIS regulations.

  On the other hand, when measuring the maximum particle size of the pigment contained in the temporary hair dye, which is the final object of the present invention, it is measured by optical microscopy. For specific measurement, shake the hair dye solution at 25 ° C, make it uniform, drop it on a slide glass, extend the solution thinly until it can be observed with a microscope, and leave it at room temperature. dry. This is magnified 200 times with a Nikon optical microscope (model ECLIPSE E800), and five locations are photographed with a Polaroid microscope digital camera (model PDMCIIi) and the software (PDMCII) attached thereto. From this photograph, the maximum particle size of the pigment present in each one photographing is measured using a scale, and the average of the five photographed images is taken as the maximum particle size of the pigment contained in the temporary hair dye.

  The production method of the present invention includes a step of blending the pigment paste thus obtained into a lower alcohol or a mixture containing a lower alcohol. Examples of the lower alcohol include methanol, ethanol, n-propanol, isopropanol and the like, and ethanol and isopropanol are particularly preferable. The mixture preferably contains water.

  Two or more kinds of lower alcohols may be used in combination, and the content thereof is preferably 35% by mass to 80% by mass in the total amount of the temporary hair dye.

  The viscosity of the temporary hair dye of the present invention is preferably 50 mPa · s to 30000 mPa · s from the viewpoint of easy attachment to the hair, ease of elongation during application, and difficulty in dripping from the applicator. Particularly when the temporary hair dye of the present invention is applied to the hair with a mascara brush, a more preferable viscosity is 60 mPa · s to 15000 mPa · s, particularly 70 mPa · s to 10000 mPa · s, more preferably 80 mPa · s, in terms of elongation. ~ 5000mPa · s. Here, the mascara brush refers to an applicator in which brush hairs are attached to a core body as shown in FIG. 1 of JP-A-2004-229748.

  In addition to these, components that are usually used in hair dyes can be added to the temporary hair dye of the present invention. For example, a film-forming polymer; a surfactant; a fragrance; an oil and fat; a hardly volatile hydrocarbon; Oils; thickeners such as hydroxyethylcellulose, hydroxypropylcellulose, carboxyvinyl polymer; antiseptics; ultraviolet absorbers; chelating agents; antioxidants; plant extracts and the like.

  The film-forming polymer forms a film on the surface of the hair and exhibits hair setting properties. Examples of the film-forming polymer include nonionic polymers, cationic polymers, anionic polymers and amphoteric polymers, and two or more kinds may be used in combination.

  Nonionic polymers include, for example, polyvinylpyrrolidone such as Rubiscol K12, 17, 30, 60, 80, 90 (above BASF), PVP K15, 30, 60, 90 (above GAF); Lubiscol VA28, 37 , 55, 64, 73, VA37E (above, BASF), PVP / VA E-735, E-635, E-535, E-335, S-630, W-735 (above, GAF) etc. Pyrrolidone / vinyl acetate copolymer; Polyvinylpyrrolidone / vinyl acetate / vinyl propionate ternary copolymer such as Rubiscol VAP343 (BASF); Vinyl acetate / N-vinyl-5-methyl-2- such as Dowtex (Dow Chemical) Examples include oxazoline copolymers.

  Examples of the cationic polymer include vinyl imidazolium chloride / vinyl pyrrolidone copolymers such as Ruby Cut FC370, FC550, FC905, HM552, MonoCP (above, BASF); Cellcut H-100 (viscosity 1000 cps), L-200 (viscosity 100 cps) (National Starch Co., Ltd.) Hydroxyethyl cellulose / dimethyl diallylammonium chloride such as Guffcut 734, 755N, 755 (above, GAF Co.) vinyl pyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer; Rubiflex (BASF) Polyvinylpyrrolidone / alkylaminoacrylate copolymers such as copolymers 845, 937, 958 (above GAF); polyvinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymers such as copolymer VC-713 (GAF); Guffcut HS-100 (ISP Etc.) Lidon / methacrylamidopropyl trimethylammonium chloride copolymer; alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymer such as water-soluble polymer compound described in JP-A-2-809911, N-propionyl polyethyleneimine / methyl poly Examples thereof include siloxane copolymers, acrylic acid amide / acrylic acid / alkyl methacrylic acid / methoxypolyethylene glycol copolymers, and acrylic acid amide / acrylic acid ester copolymers.

  Examples of anionic polymers include methyl vinyl ether / alkyl maleic anhydride alkyl half ester copolymers such as Gantrez ES-225, ES-425, and SP-215 (above, GAF); Resin 28-1310 (National Starch), Rubyset CA Vinyl acetate / crotonic acid copolymer such as (BASF); Vilni acetate / crotonic acid / neodecanoic acid vinyl copolymer such as resin 28-2930 (National Starch); Vinyl acetate / crotonic acid such as Rubyset CAP (BASF) / Vinyl propionate copolymer; Vinyl acetate / maleic acid monobutyl ester / isopolonyl acrylate copolymer such as ADVANTAGECP (ISP); Plus size L53P, L-75CB, L-9540B (Kyoto Chemical Co.), Diamond (Mitsubishi Chemical Co., Ltd.) ) And other (meth) acrylic acid / (meth) acrylic acid ester copolymers; Ultrahold 8 Acrylic acid / alkyl acrylate / alkyl acrylamide copolymers such as Ultrahold Strong (above, BASF) and Anformer V-42 (National Starch); Polyvinylpyrrolidone such as Rubiflex VBM35 (BASF) / Examples include acrylate / (meth) acrylic acid copolymers.

  Examples of amphoteric polymers include (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymers such as Yucaformer R205, R205S, 510, SM, 301, AMPHOSET, 104D, 202 (and above, Mitsubishi Chemical); Amformer 28-4910 , LV-71 (above, National Starch Co., Ltd.) and the like, and the like, such as hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymer.

  Among these film-forming polymers, (meth) acrylic polymers are preferable, and among these, (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymers (for example, Yucaformer 202, Mitsubishi Chemical Corporation) are preferable.

  In the case of using a film-forming polymer, the content thereof is preferably 3% by mass to 15% by mass in the total amount of the temporary hair dye of the present invention, from the viewpoint of stickiness and hair feel.

  From the viewpoint of the dispersion and mixing efficiency of the pigment, these components are obtained by previously pulverizing and mixing the pigment paste, and then included in the mixture containing the lower alcohol, or separately from this, or a mixture with other components. However, all these components may be mixed at one time and pulverized and mixed.

  The temporary hair dye container of the present invention is not particularly limited as long as it is suitable for applying an appropriate amount of the hair dye to the hair, but it is preferably dyed like a commercially available mascara container from the viewpoint of simplicity. Examples include a container composed of a resin container body filled with hair material and a cap integrated with an applicator.

Test example 1
5 parts by mass of black titanium oxide, 4.5 parts by mass of yellow No. 401 and 1.5 parts by mass of red No. 202 SG are mixed with 12 parts by mass of concentrated glycerin and pulverized and mixed with a roll mill. Pigment pastes of 5, 10, 20, 30, and 40 μm were obtained. The maximum particle size was measured using a grind gauge (BYK-GARDNER). 23 parts by mass of each of the obtained pigment pastes were mixed with 30 parts by mass of absolute ethanol, (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer solution (solid content: 30% by mass, ethanol: 70% by mass; trade name “Yukaformer 202”) , Mitsubishi Chemical Corporation) 20 parts by mass, purified water 23 parts by mass, and hydroxypropylcellulose (trade name “HPC-M”, Nippon Soda Co., Ltd.) 0.1 part by mass to obtain a temporary hair dye. The obtained temporary hair dye was stored at 40 ° C. for 1 month, and the viscosity of the hair dye after storage and the hair dye before the start of storage was measured. The viscosity before storage was subtracted from the viscosity after storage, and the resulting value was taken as the viscosity change (Δ viscosity). Viscosity was measured by putting 40g of each temporary hair dye into a screw tube No. 7 (50cc) (Marem) and using a BM viscometer (VISCOMETER, TOKIMEC) for 1 minute at 25 ° C. This was done after rotating. In addition, the rotor and the number of rotations in the viscosity measurement are rotor No. 2 when the viscosity of the temporary hair dye is less than 100 mPa · s, 60 rpm, and rotor No. 2 when the viscosity is 100 mPa · s or more and less than 2000 mPa · s. , 12 rpm, and those with 2000 mPa · s or more and less than 8000 mPa · s were set to rotor No. 3 and 12 rpm, and those with 8000 mPa · s to less than 40000 mPa · s were set to rotor No. 4 and 12 rpm. The viscosity change (Δ viscosity) obtained for each temporary hair dye is shown in FIG.
As shown in FIG. 1, in the temporary hair dye that uses both an organic pigment and an inorganic pigment, when the maximum particle size of the pigment in the contained pigment paste is 1 μm, the increase in viscosity over time due to storage is large, whereas the increase in viscosity is It was found that the maximum particle size was suppressed as it increased.

Examples 1-4 and Comparative Examples 1-4
A pigment (black titanium oxide, yellow No. 401, red No. 202 SG) is mixed with a dispersion medium (concentrated glycerin) at the ratio shown in Table 1, and pulverized by a roll mill so that the maximum particle size of the pigment becomes the value shown in Table 1. Mixing was performed to obtain a pigment paste. The maximum particle size was measured using a grind gauge (BYK-GARDNER). The obtained pigment paste was mixed with a (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer solution, purified water, absolute ethanol, and hydroxypropyl cellulose to obtain a temporary hair dye having the composition shown in Table 1.

  About the obtained temporary hair dye, "feel after application" and "gloss" were evaluated according to the following evaluation methods.

(1) Feel after application 0.2 g of each temporary hair dye was applied to 1 g of Japanese tress with a mascara brush (model number PH-1E, Shinoharasha), and after drying, five professional panelists evaluated. Each was evaluated in 5 stages of 1 to 5, and the average value was used as the score of the touch. If the value X is 4 <X ≦ 5, ◎ if 3 <X ≦ 4, Δ if 2 <X ≦ 3, and x if 1 ≦ X ≦ 2. The results are also shown in Table 1.

(2) Gloss 0.1 g of each temporary hair dye was applied to the slide glass with the above-mentioned mascara brush, and after drying, five specialist panelists evaluated the gloss. Each was evaluated in 5 stages of 1 to 5, and the average value was used as the score of the touch. If the value X is 4 <X ≦ 5, ◎ if 3 <X ≦ 4, Δ if 2 <X ≦ 3, and x if 1 ≦ X ≦ 2. The results are also shown in Table 1.

Viscosity The obtained temporary hair dye was stored at 40 ° C. for 1 month, and the viscosity of the hair dye after storage and the hair dye immediately after production was measured. The viscosity of the product immediately after production was subtracted from the viscosity of the product after storage, and the obtained value was defined as a viscosity change (Δ viscosity). The results are also shown in Table 1. The viscosity was measured in the same manner as in Test Example 1.

  As shown in Table 1, the temporary hair dyes of the examples have a small increase in viscosity over time despite the combined use of inorganic pigments and organic pigments, have excellent touch after application, and can impart good gloss to hair. Met.

It is a figure which shows the viscosity change of the temporary hair dye containing the pigment from which a largest particle size differs.

Claims (4)

Inorganic pigment and organic pigment are pulverized and mixed in the presence of a dispersion medium so that the maximum particle size of the pulverized inorganic pigment and organic pigment is 20 μm or more and less than 80 μm. The manufacturing method of the temporary hair dye including the process mix | blended with a lower alcohol or the mixture containing a lower alcohol so that content of the lower alcohol in it may be 35-80 mass%.   The method for producing a temporary hair dye according to claim 1, wherein the content ratio of the inorganic pigment and the organic pigment in the temporary hair dye (inorganic pigment mass / organic pigment mass) is 0.01 to 5.   The manufacturing method of the temporary hair dye of Claim 1 or 2 which grind | pulverizes and mixes with a roll mill.   The method according to any one of claims 1 to 3, wherein the inorganic pigment is black titanium oxide.

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