JP3693437B2 - Temporary hair dye and its manufacturing method - Google Patents

Description

【００３８】
【発明の効果】
本発明により、人体に安全な着色材であるチタンブラックの分散性が良好で、且つ他の着色顔料、特に酸化鉄系顔料との併用でそれらの分散安定性を向上させ、塗布後の風合いも良好な一時染毛料が提供される。
【図面の簡単な説明】
【図１】本発明の実施例および比較例の染毛料を充填した塗布具の断面図である。
【符号の説明】
１ 塗布部（刷毛）
２ 口金（プラスティック製）
３ 液導入部
４ 外軸
５ バルブ
６ 塗布液
７ 塗布液収容管（内軸）
８ ノック部
９ 抜け止め
１０ バルブ中のバネ
１１ 塗布液収容管キャップ
１２ 弁座
１３ 弁棒
ａ 摺接面
ｂ 摺接面
ｃ 摺接面
ｄ 摺接面[0001]
BACKGROUND OF THE INVENTION
For hair dyes that mainly dye hair, oxidative hair dyes that color and color in the hair, acidic hair dyes that dye by adsorbing the dye to the hair, and temporary hair dyes that color by forming a colored film on the hair. There is.
The present invention relates to a temporary hair dye, particularly a temporary hair dye that does not use carbon black or graphite.
[0002]
[Prior art]
Conventional temporary hair dyes mainly contain white hair by dispersing carbon black in water or ethanol and using a resin to form a so-called dark colored film such as black or brown on the hair. There are those that use white and a coloring pigment such as a tar dye together to conceal the color of the hair and color it in an arbitrary color.
Carbon black is mainly used for concealing gray hair because it has high color strength, excellent concealment, easy dispersibility, low specific gravity, so it does not settle even during long-term storage, and is inexpensive. It is.
Conventionally, in Japan, carbon black is allowed to be used in cosmetics, but in the United States, carbon black is not allowed in cosmetics because it may be carcinogenic. Temporary hair dyes that do not use hair are desired.
Titanium white, i.e., titanium oxide, is a pigment that has a strong hiding power so as to mask the black color of the hair. The hiding power of titanium white improves the coloring of pigments other than titanium white.
However, titanium oxide is white and the gray hair cannot be hidden in a dark color.
[0003]
From these facts, it is conceivable that dark-colored titanium oxide, such as titanium black, can be used to obtain a dark temporary hair dye that does not use carbon black, but titanium oxide has a higher specific gravity than carbon black and is not stable in dispersion. Remarkably inferior. The coloring power of titanium black is stronger than that of other pigments, but is weaker than that of carbon black. In order to obtain the same level of coloring power on white hair, 3 to 4 times the weight ratio of carbon black is required.
[0004]
A resin is used to disperse the pigment. However, in the case of a conventional dispersion resin, when the amount of the dispersion resin is small, the binding force of the pigment particles in the film on the hair is weak and is easily removed by rubbing. In order to obtain a binding force, a large amount of dispersion resin is required, and there is a drawback that the film on the hair is thick and the feeling of stickiness is large.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a temporary hair dye that is safe for the human body, has good dispersibility of the pigment, has excellent fixability, has a remarkably slow sedimentation rate, or is easily redispersed by shaking or the like.
[0006]
[Means for Solving the Problems]
As a result of diligent research on the above problems, the inventors of the present invention have used N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer to produce titanium black, that is, titanium. Stable dispersion against sedimentation and agglomeration by dispersing titanium oxide sintered product (“Cosmetic raw material non-standard ingredient standard” (common name “Cosmetic group”) name of titanium black) in alcoholic solvent, mainly ethanol The present inventors have succeeded in obtaining a liquid and have found that there is an effect of suppressing aggregation and sedimentation of iron oxide pigments when dispersed simultaneously with iron oxide pigments such as petals, and the present invention has been completed.
[0007]
In this temporary hair dye, it is essential to disperse titanium black using N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer, and carbon black and It is characterized by not using graphite.
Titanium black colors gray hair alone, but a natural hair color is obtained by using red or yellowish black to brown in combination with petal or yellow iron oxide or iron black.
[0008]
N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer is generally 0% of the whole hair dye, although it depends on the type and required amount of titanium black and other dispersed pigments. Effective at 1% or more as a dispersant. Below this range, a stable dispersion effect cannot be obtained, or a necessary amount of pigment cannot be dispersed.
[0009]
When a large amount of N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer is added, water resistance, strength against scuffing, and precipitation stability of the pigment are excellent. As the coating solution becomes slightly inferior in stability over time, the coating film becomes too thick and the hair becomes stiff, and the viscosity becomes high and the applicability becomes poor. Is the maximum addition amount.
[0010]
The range of the amount to which N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer is added is preferably 0.3% to 10% in practice.
This is because the amount of pigment such as titanium black is about 1% to 10% when white hair is colored to an inconspicuous level and natural hue and texture are desired, and about 1% of the pigment is stably dispersed. The amount of resin blended is 0.3%, and when it is blended in a large amount to improve the durability of the coating film as a measure against rubbing off, the hair becomes stiff or unnatural luster appears. This is because the added amount that does not lose the natural texture important for hiding gray hair is 10%, but a more preferable range is 2% to 8%. Within this range, the balance of water resistance, resistance to rubbing, and natural texture is the best.
[0011]
As a main solvent of the temporary hair dye of this invention, C4 or less alcohol is preferable, and especially ethanol is preferable. However, any solvent may be used as long as it is safe for the human body and can dissolve the N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer. However, those having better volatility than water are more advantageous in terms of quick drying.
Further, since water can be the safest main solvent, it is meaningless to use a solvent having lower volatility than this in consideration of safety.
[0012]
As a coloring component, titanium black is used as an essential component, but if necessary, zinc white, brown, chromium oxide, iron black, cobalt blue, alumina white, iron oxide yellow, viridian, zinc sulfide, lithopone, cadmium yellow, Red, cadmium red, yellow lead, molybdate orange, zinc chromate, strontium chromate, white carbon, ultramarine, lead white, bitumen, manganese violet, aluminum powder, brass powder and other inorganic pigments, C.I. I. 16185, C.I. I. 45430, C.I. I. 16255, C.I. I. 45410, C.I. I. 45440, C.I. I. 45100, C.I. I. 19140, C.I. I. 15985, C.I. I. 42053, C.I. I. 42090, C.I. I. 73015, C.I. I. 15850, C.I. I. 15585, C.I. I. 15630, C.I. I. 45170, C.I. I. 15800, C.I. I. 15880, C.I. I. 12120, C.I. I. 45380, C.I. I. 26100, C.I. I. 73360, C.I. I. 17200, C.I. I. 12085, C.I. I. 45370, C.I. I. 12075, C.I. I. 21110, C.I. I. 15510, C.I. I. 45425, C.I. I. 45350, C.I. I. 47005, C.I. I. 47000, C.I. I. 21090, C.I. I. 61570, C.I. I. 61565, C.I. I. 59040, C.I. I. 42095, C.I. I. 73000, C.I. I. 42052, C.I. I. 69825, C.I. I. 42090, C.I. I. 2013, C.I. I. 60725, C.I. I. 45190, C.I. I. 15865, C.I. I. 26105, C.I. I. 16155, C.I. I. 16150, C.I. I. 14700, C.I. I. 12140, C.I. I. 15620, C.I. I. 11725, C.I. I. 14600, C.I. I. 12100, C.I. I. 11680, C.I. I. 18950, C.I. I. 10316, C.I. I. 11380, C.I. I. 11390, C.I. I. 13065, C.I. I. 18820, C.I. I. 10020, C.I. I. 42085, C.I. I. 61520, C.I. I. 74160, C.I. I. 60730, C.I. I. Pearl pigments such as organic pigments such as 20470 and lake dyes of acidic dyes, fish scale foil, various mica titanium, sericite, mascobite, pearl oyster shell powder, abalone shell powder, hawk shellfish powder and the like can be used.
[0013]
Since these coloring components are used as cosmetics, safety to the human body must be fully considered. It is selected from those permitted to be used as cosmetics, more specifically, those recognized as food additives and those having low oral toxicity.
Iron black, petal, yellow iron oxide and the like are excellent in safety, and when dispersed simultaneously with titanium black, stability against sedimentation and agglomeration increases.
[0014]
Resins, surfactants, fragrances, fats and oils, hardly volatile hydrocarbons, silicone oil, water, and the like can be added to the temporary hair dye of the present invention as necessary.
N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer has the best pigment dispersion stability, and also has good durability and texture on the hair. Excellent resin. Among durability, there are various elements such as adhesion, strength against rubbing, and water resistance, and even if the dispersion stability of the pigment is not good, sufficient resin to improve any of those elements and texture Use it as needed.
The surfactant exhibits favorable effects such as an effect of improving the wettability of the temporary hair dye and the hair and facilitating the application, and an effect of improving the water resistance at the interface between the film and the gas and liquid (sweat, etc.).
The perfume has the effect of masking the odor of ethanol, N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer or pigment, and conversely improving the feeling of use. is there.
[0015]
In addition, N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine is used for surfactants, fragrances, and the like that are hardly volatile, oils and fats, refractory hydrocarbons or silicone oils.・ There are also useful plasticizers for butyl methacrylate copolymers, and when exerted to a reasonable degree, the brittleness of the film on the hair is suppressed, and it is soft and has a good texture as well as improved adhesion to the hair. It is a highly adherent and highly durable film.
Water is a poor solvent for N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer, but has the effect of blending hair and temporary hair dye to improve the texture. Therefore, a preferable result is obtained with moderate addition. In this case, the term “appropriate” means 20% or less of the total amount and about 3% to 12%.
[0016]
One of the features of the present invention is that the handle, iron black, yellow iron oxide (hereinafter referred to as iron oxide pigment) and titanium black are simultaneously dispersed.
In short, dispersibility has the ability to suppress the pigment sedimentation itself and maintain a uniform suspension system, while the pigment sediments, but allows the sediment to re-diffuse by simple operations such as shaking. is there. In the case of inorganic pigments, especially titanium oxide pigments such as titanium white and titanium black and pigments with high true specific gravity such as iron oxide pigments, it is impossible to prevent sedimentation at all. The case where re-diffusion is easy means that “dispersibility is good”.
[0017]
N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer is an excellent dispersant and iron oxide pigments are well dispersed, but iron oxide pigments are agglomerated. -It tends to settle, and once it settles, it tends to form hard deposits (hereinafter referred to as hard cake) that are difficult to re-diffusion.
However, when titanium black and iron oxide pigments are simultaneously dispersed in the presence of N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer, this hard cake is formed. It becomes difficult and the re-diffusion property of the sediment becomes very good.
[0018]
It is not clear what principle this is based on, but the titanium black particles and the iron oxide pigment particles, which are sheared by dispersion, associate at the secondary or tertiary aggregation stage, and the aggregate of titanium black and iron oxide pigments. It is speculated that it will stabilize after that.
[0019]
Therefore, even when the already dispersed titanium black liquid and iron oxide pigment dispersion are combined, it is preferable to apply the dispersion to a dispersing machine such as a ball mill, a bead mill, a sand mill, a roll mill, a kneader, a homogenizer, or an ultrasonic dispersing machine. Is obtained.
[0020]
Titanium black can also be used as a dispersion stabilizer for iron oxide pigments. That is, even when a small amount of titanium black is dispersed in the iron oxide pigment, the effect of preventing hard cake formation of the iron oxide pigment is exhibited.
As a quantitative measure, the effect can be sufficiently obtained with about 10% titanium black with respect to the petal by weight. As long as titanium black is added at a higher ratio, generation of a hard cake is not recognized. The same applies to yellow iron oxide.
With iron black, the hard cake of iron black itself is softer than that of petal or yellow iron oxide, so it is effective in a smaller amount.
[0021]
This property is effective for industrial production of temporary hair dyes. For example, as a method of suppressing the hue variation, four colors of a titanium black single dispersion and a petrol and titanium black mixed dispersion, an iron black and titanium black mixed dispersion, or a yellow iron oxide and titanium black mixed dispersion are used. If it is made, browning can be done freely even with simple work such as stirring with a blade without using a disperser again after color mixing.
[0022]
The temporary hair dye of the present invention is prepared by dissolving N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer in ethanol, and then adding a pigment such as titanium black. In addition, a pigment dispersion is made by dispersion treatment with a ball mill, bead mill, sand mill, roll mill, kneader, homogenizer, ultrasonic disperser, etc., and considering the performance as a temporary hair dye such as durability and texture after application. Although it is based on adding resin and surfactant, a fragrance | flavor, a pigment, its dispersion, etc. as needed, there is no problem even if it mixes and disperses all the materials at once.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail by way of examples.
In Examples and Comparative Examples, N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer is supplied under the trade name “Yuka Former AM75” and is 30% or 40%. Ethanol solution.
[0024]
【Example】
Example 1
Tilac D (Titanium Black; Ako Kasei Co., Ltd. trade name) 5.0 parts by weight Bengala 211 (Valent; Daito Kasei Co., Ltd. trade name) 1.0 〃
Yuka Former AM75 202
(30% ethanol solution; trade name of Mitsubishi Chemical Corporation) 15.0
KF-56
(Polyether-modified silicone; trade name of Shin-Etsu Chemical Co., Ltd.) 0.5 〃
Ethanol 78.5〃
The above was stirred with a bead mill for 1 hour to obtain hair dye 1.
[0025]
Example 2
<Liquid A>
Titanium Black 10S (trade name of Mitsubishi Materials Corporation) 4.0 parts by weight Yuka Former AM75 201
(40% ethanol solution; trade name of Mitsubishi Chemical Corporation) 10.0
Ethanol 50.0 〃
The above was stirred with a bead mill for 1 hour to obtain Liquid A.
<Liquid B>
TODA Yellow48
(Yellow iron oxide; trade name of Toda Kogyo Co., Ltd.) 2.0 parts by weight Yucaformer AM75 201 5.0
Ethanol 23.0 〃
The above was stirred with a bead mill for 1 hour to obtain Liquid B.
<Liquid C>
Water 5.0 parts by weight Rubiscol K15
(Polyvinylpyrrolidone; trade name of BASF) 1.0 〃
The above was stirred with a magnetic stirrer to obtain liquid C.
<Liquid A> 64.0 parts by weight <Liquid B> 30.0 〃
<Liquid C> 6.0 〃
The above was mixed and irradiated with ultrasonic waves for 1 hour to obtain hair dye 2.
[0026]
Example 3
Titanium Black 20M (trade name of Mitsubishi Materials Corporation) 5.0 parts by weight Red No. 202 (manufactured by Tsubaki Kasei Co., Ltd.) 0.5 〃
Yuka Former AM75 R205S
(30% ethanol solution; trade name of Mitsubishi Chemical Corporation) 10.0
Ethanol 84.5 〃
The above was stirred with a sand mill for 1 hour to obtain hair dye 3.
[0027]
Example 4
Iron Black BL-100 (Daito Kasei Co., Ltd. trade name) 4.5 parts by weight Tilac D 0.5 〃
Yuka Former AM75 204
(40% ethanol solution; trade name of Mitsubishi Chemical Corporation) 12.5
Ethanol 82.5 〃
The above was stirred with a bead mill for 1 hour to obtain hair dye 4.
[0028]
Example 5
<Liquid D>
Tilack D 4.5 parts by weight Yuca Former AM75 202 7.5 〃
KF-56 0.25mm
Ethanol 39.25〃
The above was stirred with a bead mill for 1 hour to obtain Liquid D.
<Liquid E>
Tilac D 0.5 parts by weight Bengala 211 1.0 〃
Yuka Former AM75 202 7.5 〃
KF-56 0.25mm
Ethanol 39.25〃
The above was stirred with a bead mill for 1 hour to obtain Liquid E.
<Liquid D> 51.5 parts by weight <Liquid E> 48.5
The above was stirred with a magnetic stirrer to obtain hair dye 5.
[0029]
Comparative Example 1
Tilac D 5.0 parts by weight Bengala 211 1.0 〃
PVP K-15 (polyvinylpyrrolidone; trade name of GAF) 4.5 〃
KF-56 0.5 〃
Ethanol 89.0 〃
The above was stirred with a bead mill for 1 hour to obtain Hair Color A.
[0030]
Comparative Example 2
<Liquid F>
Titanium Black 10S 4.0 parts by weight Jurimer AT-960P
(Ethylene acrylic resin; Nippon Pure Chemicals Co., Ltd. trade name) 4.0 〃
Ethanol 56.0〃
The above was stirred with a bead mill for 1 hour to obtain Liquid F.
<Liquid G>
TODA Yellow48 2.0 parts by weight Jurimer AT-960P 2.0 〃
Ethanol 26.0 〃
The above was stirred with a bead mill for 1 hour to obtain Liquid G.
<Liquid C>
Water 5.0 parts by weight Rubiscol K15 1.0 〃
The above was stirred with a magnetic stirrer to obtain liquid C.
<Liquid F> 64.0 parts by weight <Liquid G> 30.0 〃
<Liquid C> 6.0 〃
The above was mixed and irradiated with ultrasonic waves for 1 hour to obtain hair dye B.
[0031]
Comparative Example 3
Bengala 211 3.0 parts by weight bitumen 302 (bituminous; trade name of Daito Kasei Co., Ltd.) 2.0
Red No. 202 0.5 〃
Yuka Former AM75 R205S 10.0 〃
Ethanol 84.5 〃
The above was stirred with a sand mill for 1 hour to obtain hair dye C.
[0032]
Comparative Example 4
Iron Black BL-100 5.0 parts by weight Yuka Former AM75 204 12.5 〃
Ethanol 82.5 〃
The above was stirred with a bead mill for 1 hour to obtain hair dye D.
[0033]
Comparative Example 5
<Liquid H>
Tilack D 5.0 parts by weight Yuka Former AM75 202 7.5 〃
KF-56 0.25mm
Ethanol 39.25〃
The above was stirred with a bead mill for 1 hour to obtain liquid H.
<Liquid I>
Bengala 211 1.0 parts by weight Yuka Former AM75 202 7.5 〃
KF-56 0.25mm
Ethanol 39.25〃
The above was stirred with a bead mill for 1 hour to obtain Liquid I.
<Liquid H> 52.0 parts by weight <Liquid I> 48.0 〃
The above was stirred with a magnetic stirrer to obtain hair dye E.
[0034]
Comparative Example 6
Red No. 227 aluminum lake (manufactured by Kasei Kasei Co., Ltd.) 1.8 parts by weight Yellow No. 5 aluminum lake (manufactured by Sakai Kasei Co., Ltd.) 2.3
Bitumen 302 (bituminous; trade name of Daito Kasei Co., Ltd.) 1.4
Titanium oxide CR 50 (trade name of Ishihara Sangyo Co., Ltd.) 0.5 〃
Yuka Former AM75 202 15.0 〃
KF-56 0.5 〃
Ethanol 78.5〃
The above was stirred with a bead mill for 1 hour to obtain hair dye F.
[0035]
The following tests were performed using hair dyes 1 to 5 and hair dyes A to F.
Test 1: Redispersibility test (Actual use test over time)
The hair coloring materials 1 to 5 and the hair coloring materials A to F are filled in the applicator shown in FIG. 1 and left to stand for 1 month in an upward direction. Then, write on a glass plate with the applicator (brush), compare the initial stroke and the hue / density, and visually determine the difference.
{○} ... Almost unchanged. {△}: Some change in hue or density.
{X} ... It is extremely thin or cannot be written.
Test 2: Using the hair dyes 1 to 5 and the hair dyes A to F after finishing the texture investigation test 1, the hair was applied to the hair of 20 monitors, and the texture was examined.
{○}… Natural shades and tension, but supple and natural finish.
{△}: Somewhat unnatural hue or stiff feeling is felt.
{X} ... The hue is separated into two or more colors, or the hair is stiff enough to become a rod shape.
[0036]
The results of Tests 1 and 2 are summarized in Table 1.
Those having a poor test 1 result are poorly colored and thus are applied in a large amount, have a strong sense of stiffness, and test 2 also gives a bad result.
[0037]
[Table 1]

[0038]
【The invention's effect】
According to the present invention, the dispersibility of titanium black, which is a coloring material that is safe for the human body, is good, and in combination with other colored pigments, particularly iron oxide pigments, their dispersion stability is improved, and the texture after coating is also improved. A good temporary hair dye is provided.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of an applicator filled with hair dyes of Examples and Comparative Examples of the present invention.
[Explanation of symbols]
1 Application part (brush)
2 Base (made of plastic)
3 Liquid introduction part 4 Outer shaft 5 Valve 6 Coating liquid 7 Coating liquid storage tube (inner shaft)
8 Knock part 9 Retaining stopper 10 Spring in valve 11 Coating liquid containing pipe cap 12 Valve seat 13 Valve rod a Sliding surface b Sliding surface c Sliding surface d Sliding surface

Claims (7)

At least 0.1 to 20% by weight of an alcohol solvent having 4 or less carbon atoms and N-methacryloylethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / butyl methacrylate copolymer as a dispersant. Ingredients: (1) 0.5 to 5% by weight of titanium black and (2) 0.5 to 4.5% by weight of pigment other than titanium black excluding carbon black
Temporary hair dye characterized by including.   The temporary hair dye according to claim 1, wherein the alcohol solvent having 4 or less carbon atoms is ethanol.   3. The temporary dyeing according to claim 1, comprising 0.3 to 10% by weight of the N-methacryloylethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / butyl methacrylate copolymer. Hair.   The temporary hair dye according to claim 3, comprising 2 to 8% by weight of the N-methacryloylethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / butyl methacrylate copolymer.   The temporary hair dye according to any one of claims 1 to 4, comprising at least one pigment selected from the group consisting of petal, iron black and yellow iron oxide as the pigment of (2).   Liquid in which N-methacryloylethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / butyl methacrylate copolymer is dissolved as a dispersant in ethanol, and then added with titanium black and dispersed (A) And at least one pigment selected from the group consisting of petal, iron black and yellow iron oxide, and a liquid (B) in which titanium black is dispersed in ethanol with the above-mentioned dispersant are mixed and stirred. Item 6. A method for producing a temporary hair dye according to Item 5.   In the dispersion liquid (B), the mixing ratio of at least one pigment selected from the group consisting of petal, iron black and yellow iron oxide and titanium black is 10% by weight or more of titanium black with respect to the former pigment. The manufacturing method of the temporary hair dye of Claim 6 characterized by the above-mentioned.

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