JP4257098B2 - Hair dye, method for producing the same and hair dyeing method using the same - Google Patents

Description

【００５４】
【表２】

【００５５】
表１から本発明の染毛剤は、製品（染毛剤）の安定性、色の濃さ（染毛力）、持続性（堅牢性）、シャンプー時の泡や水の色つき、色の質感のいずれにも優れていることが判る。
それに対して、比較例１の染毛剤は色の濃さ（染毛力）、持続性（堅牢性）および色の質感に劣り、比較例２の染毛剤は持続性（堅牢性）およびシャンプー時の泡や水の色つきに劣り、比較例３の染毛剤は持続性（堅牢性）、シャンプー時の泡や水の色つきおよび色の質感に劣り、比較例４の染毛剤は製品（染毛剤）の安定性、持続性（堅牢性）、シャンプー時の泡や水の色つきおよび色の質感に劣り、比較例５の染毛剤は色の濃さ（染毛力）、持続性（堅牢性）、シャンプー時の泡や水の色つき、色の質感のいずれにも劣る。
表２から本発明の染毛剤は、従来の(ｂ）染料を配合した染毛料（ヘアマニキュア）と同等の製品の安定性、染毛効果を有する上、より堅牢性が高く、色調の広がりの広い色の質感に優れた、染毛ができることが判る。
【００５６】
【発明の効果】
本発明の請求項１記載の染毛剤は、イオン性を持たない分子量１５０〜４００の直接染料（ａ）、陰イオンに電荷した分子量３５０〜１０５０の直接染料（ｂ）および陽イオンに電荷した分子量２５０〜５００の直接染料（ｃ）が塩基性水溶液中に安定に乳化分散してなるｐＨ７．５〜１０の１剤式染毛剤であって、前記染料（ａ）〜（ｃ）が同一水溶液に溶解しても反応しない濃度で、ノニオン系界面活性剤を用いて均一に乳化分散してなることを特徴とする染毛剤であり、構成が簡単で安価であり、肌にやさしく、頭皮や毛髪に対する刺激や損傷がない上、染料（ｂ）および染料（ｃ）が直接接触して反応することがないので、水不溶性のコンプレクッスが生成されることがなく、安定性、取り扱い性、貯蔵性などに優れており、毛髪に塗布、適用すると、毛髪に接した反応しない程度の濃度の水溶液が毛髪を膨潤するので、各染料や各種添加物の毛髪内部への浸透を促進でき、良好な染毛効果を得ることができるという顕著な効果を奏する。
また、染料（ｂ）は酸性下で皮膚への染着が非常に激しい染料であるが、反応しない程度の濃度の水溶液中に溶解して乳化分散しているためその発色を抑制でき、肌への染着がない。
【００５７】
本発明の請求項２記載の染毛剤は、請求項１記載の染毛剤において、塩基性アミノ酸およびアミンオキサイドから選択される少なくとも１種を含むことを特徴とするので、塩基性アミノ酸はアルカリ性下で毛髪に対する吸着能力に優れており、毛髪に補うことによりやさしいアルカリ剤としての効果と毛髪修復効果を得ることができる上、染色性の向上、シャンプーによる褪色を抑える効果があり、アミンオキサイドを添加することで、シャンプー時に色のついた泡や水の発生を抑制することが可能となるというさらなる顕著な効果を奏する。
【００５８】
本発明の請求項３は、同一水溶液に溶解しても反応しない濃度のイオン性を持たない直接染料（ａ）、陰イオンに電荷した直接染料（ｂ）および陽イオンに電荷した直接染料（ｃ）を添加して均一に溶解した水相に、ノニオン系界面活性剤を添加、攪拌して均一に乳化分散し、ｐＨ７．５〜１０にすることを特徴とするので、非水溶性のコンプレクッスの生成を抑えることができ、ノニオン系界面活性剤を添加するが、ノニオン系界面活性剤は（−）の電荷を有する直接染料（ｂ）や（＋）の電荷を有する直接染料（ｃ）と反応することがないので、直接染料（ａ）〜（ｃ）などが均一に乳化分散したエマルジョンを得ることができ、請求項１記載の染毛剤を容易に製造できるという顕著な効果を奏する。
【００５９】
本発明の請求項４は、同一水溶液に溶解しても反応しない濃度のイオン性を持たない直接染料（ａ）、陰イオンに電荷した直接染料（ｂ）および陽イオンに電荷した直接染料（ｃ）、および塩基性アミノ酸およびアミンオキサイドから選択される少なくとも１種を添加して均一に溶解した水相に、ノニオン系界面活性剤を添加、攪拌して均一に乳化分散し、ｐＨ７．５〜１０にすることを特徴とするので、非水溶性のコンプレクッスの生成を抑えることができ、次いで、ノニオン系界面活性剤を添加するが、ノニオン系界面活性剤は（−）の電荷を有する直接染料（ｂ）や（＋）の電荷を有する直接染料（ｃ）と反応することがないので、直接染料（ａ）〜（ｃ）や塩基性アミノ酸、アミンオキサイドなどが均一に乳化分散したエマルジョンを得ることができ、請求項２記載の染毛剤を容易に製造できるという顕著な効果を奏する。
【００６０】
本発明の請求項５は、請求項１あるいは請求項２記載の染毛剤を毛髪に均一に塗布してイオン性を持たない直接染料（ａ）を毛髪のコルテックスの深い層まで浸透させ、その後、加温することで、陰イオンに電荷した直接染料（ｂ）および陽イオンに電荷した直接染料（ｃ）をキューティクルの内側からコルテックスの浅い層にわたって浸透させると同時に反応させて、非水溶性のコンプレックスからなる褪色防止層を形成させることを特徴とする染毛方法であり、毛髪に、刷毛などで擦って均一に塗布し、手で揉み込むなどの刺激を与えることで物理的に乳化が破壊され染毛剤中の染料（ａ）が毛髪のコルテックスの深い層へ浸透し、そして、加温することで、分子の大きい染料（ｂ）と染料（ｃ）も毛髪内部のキューティクルの内側からコルテックスの浅い層にわたり浸透することで、２成分の濃度が高くなり、２成分は反応して、キューテイクルの内側からコルテックスの浅い層にわたって非水溶性コンプレクッスからなる褪色防止層が形成され、この褪色防止層は大きな分子により構成されているので例えシャンプーなどの物理的刺激を与えても毛髪の外部に流出することがない上、毛髪内部に浸透した染料（ａ）が毛髪の外部に流出するのを防止することで、堅牢性が向上するという顕著な効果を奏する。
【図面の簡単な説明】
【図１】 （イ）は染毛する前の毛髪の断面を模式的に説明する説明図であり、（ロ）は、染毛後の毛髪の断面を模式的に説明する説明図である。
【符号の説明】
１Ａ 染毛する前の毛髪
１Ｂ 染毛後の毛髪
２ キューテイクル
３ コルテックス
４ メデユラ
５ 褪色防止層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a one-component hair dye that can produce beautiful hair with excellent fastness properties but is very difficult to dye on human skin, a method for producing the same, and a hair dyeing method using the same. It is.
[0002]
[Prior art]
Conventionally, the direct dye (a) having no ionicity has a nitro group in the molecular structure and penetrates into the cortex of the hair even though there is little dyeing to the skin due to the low molecular weight. This dye (a) has no ionic character, so it does not cause ionic bonds inside the hair, and since it is a direct dye, it does not cause oxidative polymerization, so it is robust. There is a problem in that the dye (a) itself easily flows out of the hair and fades after physical dyeing such as shampoo after hair dyeing (for example, see Non-Patent Document 1).
[0003]
Further, the direct dye (b) charged with anions is used as hair nail polish and the like, but it is very dyed to the skin, and when it comes into contact with the skin, the skin is dyed and difficult to remove. There is a problem that the fastness is poor and, for example, the hair is easily discharged to the outside by treating the hair with a treatment using a surfactant charged with a cation (for example, Non-Patent Document 2). reference).
[0004]
In addition, the direct dye (c) charged with a cation has poor fastness, and easily flows out of the hair by treating the hair with a shampoo using a surfactant charged with an anion, for example. (For example, refer nonpatent literature 3).
[0005]
[Non-Patent Document 1]
Publisher: Akemi Nagao, Editor: Shigeru Chiba “MARCEL”
Publisher: Shin Beauty Publishing Co., Ltd., July issue, issued July 1, 2001,
(This is all you need to know * Basic knowledge on relaxation of cosmetic regulations, p.70-73)
[Non-Patent Document 2]
Publisher: Isao Tsunoda, Editor: Fumio Mohri “Fragrance JOURNAL (Fragrance Journal), Publisher: Fragrance Journal, 2001-8, Recent functions and development trends of temporary and semi-permanent hair dyes, p. 33-38
[Non-Patent Document 3]
Publisher: Isao Tsunoda, Editor: Fumio Mohri "Fragrance JOURNAL (Fragrance Journal), Publisher: Fragrance Journal, 2002-6, Effects of ceramide components in hair dyes, p.54-59
[0006]
[Problems to be solved by the invention]
The first object of the present invention is to have a hair dyeing effect equivalent to that of a hair dye (hair manicure) containing a direct dye (b) charged with a conventional anion, and has high fastness and adheres to the skin. It is to provide a novel one-component hair dye that is hard to be dyed, can be easily removed even if the skin is dyed, is gentle to the skin, and does not irritate or damage the scalp or hair.
The second object of the present invention is to provide a production method for easily producing such a hair dye.
[0007]
The third object of the present invention is to provide a method for dyeing hair using such a hair dye.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to improve the problems and drawbacks of the prior art, the present inventors have obtained a direct dye (a) having no ionicity that can penetrate deep into the cortex of hair, and a negative dye. A basic aqueous solution of a direct dye (b) that is charged to ions and penetrates only to a shallow layer of cortex, and a direct aqueous solution that is charged to cations and penetrates only to a shallow layer of cortex (c) It has been found that the problem can be solved by using a one-component hair dye emulsified and dispersed using an activator, and the present invention has been accomplished.
[0009]
In order to solve the above problem, the hair dye according to claim 1 does not have ionicity. With a molecular weight of 150-400 Directly charged to dye (a), anion With a molecular weight of 350-1050 Directly charged to dye (b) and cation With a molecular weight of 250-500 Direct dye (c) is stably emulsified and dispersed in a basic aqueous solution. pH 7.5-10 A one-component hair dye, which uses a nonionic surfactant at a concentration that does not react even when the dyes (a) to (c) are dissolved in the same aqueous solution. Uniform milk It is characterized by being dispersed.
[0010]
In the hair dye of the present invention, the direct dyes (a) to (c) dissolved in a basic aqueous solution at a concentration that does not react even when dissolved in the same aqueous solution are independent of each other using a nonionic surfactant. It is a one-component hair dye that is stably emulsified and dispersed. In the hair dye of the present invention, the direct dye (b) and the direct dye (c) do not react with each other directly, so that no water-insoluble complex is formed, and the stability and handleability are improved. Excellent storage stability. Since the hair is swollen by setting the pH of the hair dye of the present invention to basic, penetration of each dye and various additives into the hair can be promoted, and a good hair dyeing effect can be obtained. Further, the direct dye (b) is a dye that is very intensely dyed to the skin under acidic conditions, but since it is basic, the color development can be suppressed and there is no dyeing to the skin. The hair dye of the present invention is simple and inexpensive, is gentle to the skin, and does not irritate or damage the scalp or hair.
[0011]
The hair dye according to claim 2 of the present invention is characterized in that in the hair dye according to claim 1, it contains at least one selected from basic amino acids and amine oxides.
[0012]
Basic amino acids have excellent ability to adsorb hair under alkaline conditions, and supplementing the hair can provide an effect as a gentle alkaline agent and a hair repair effect, as well as an improvement in dyeability and an effect of suppressing discoloration due to shampoo. There is.
By adding amine oxide, generation of colored bubbles and water during shampooing can be suppressed.
[0013]
Claim 3 of the present invention provides a direct dye (a) having no ionicity at a concentration that does not react even when dissolved in the same aqueous solution, a direct dye (b) charged with an anion, and a direct dye (c) charged with a cation. ) Is added to the water phase that is uniformly dissolved, and a nonionic surfactant is added and stirred to uniformly emulsify and disperse. To pH 7.5-10 The method for producing a hair dye according to claim 1.
[0014]
Since the direct dye (b) and the direct dye (c) are dissolved in the basic aqueous solution at a concentration that does not react even when dissolved in the same aqueous solution, the formation of water-insoluble complex can be suppressed. Next, a nonionic surfactant is added, but the nonionic surfactant does not react with the direct dye (b) having a charge of (−) or the direct dye (c) having a charge of (+). An emulsion in which the direct dyes (a) to (c) and the like are uniformly emulsified and dispersed can be obtained. The hair dye according to claim 1 can be easily produced by the production method of the present invention.
[0015]
According to a fourth aspect of the present invention, there is provided a direct dye (a) having a concentration that does not react even when dissolved in the same aqueous solution, a direct dye (b) charged with an anion, and a direct dye charged with a cation (c) ), And at least one selected from basic amino acids and amine oxides, a non-ionic surfactant is added to the aqueous phase uniformly dissolved and stirred to uniformly emulsify and disperse. To pH 7.5-10 A method for producing a hair dye according to claim 2.
[0016]
Since the direct dye (b) and the direct dye (c) are dissolved in an aqueous solution having a concentration that does not react even when dissolved in the same aqueous solution, the formation of water-insoluble complex can be suppressed. Next, a nonionic surfactant is added, but the nonionic surfactant does not react with the direct dye (b) having a charge of (−) or the direct dye (c) having a charge of (+). In addition, an emulsion in which direct dyes (a) to (c), basic amino acids, amine oxides and the like are uniformly emulsified and dispersed can be obtained. The hair dye according to claim 2 can be easily produced by the production method of the present invention.
[0017]
Claim 5 of the present invention uniformly applies the hair dye according to claim 1 or claim 2 to the hair and allows the direct dye (a) having no ionic properties to penetrate into the deep cortex layer of the hair, By heating, the direct dye (b) charged to the anion and the direct dye (c) charged to the cation are allowed to permeate from the inside of the cuticle to the shallow layer of the cortex and react with each other at the same time. It is a hair dyeing method characterized by forming an anti-fading layer comprising a complex.
[0018]
The hair dye of the present invention is applied uniformly to the hair by rubbing with a brush or the like, and emulsification is physically broken by giving a stimulus such as swallowing by hand, so that the dye (a) in the hair dye is Penetrates deep into cortex. By heating, dyes (b) and (c) having large molecules also permeate from the inside of the cuticle inside the hair over the shallow layer of cortex, thereby increasing the concentration of the two components. The components react to form an anti-fading layer consisting of water-insoluble complex from the inside of the cuticle to the shallow layer of cortex. This anti-fading layer is composed of large molecules, so even if a physical stimulus such as shampoo is applied, it does not flow out of the hair, and the dye (a) that has penetrated into the hair flows out of the hair. By preventing this, the robustness is improved.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
FIGS. 1A and 1B are explanatory views schematically illustrating a cross section of hair dyed by the hair dyeing method of the present invention.
FIG. 1 (a) is an explanatory view schematically explaining a cross section of hair 1A before dyeing hair. Hair 1A has a cuticle (hair skin) 2 in the surface layer, and cortex in the interior thereof. (Fur quality) 3 and medeura (hair pulp) 4 are provided. FIG. 1 (b) is an explanatory view schematically illustrating a cross section of hair 1B after hair dyeing. Cuticle 2 and cortex 3 of hair 1B are dyed with dye (a). An anti-fading layer 5 made of water-insoluble complex is formed from the cuticle 2 to the inside of the cuticle 2 (shallow layer of the cortex 3). The anti-fading layer 5 prevents the dye (a) dyed by penetrating deep inside the hair 1B from flowing out to the outside of the hair 1B, and the dye (a) is not affected by physical stimulation such as shampoo. Does not flow out of 1B.
[0020]
As the (a) dye used in the present invention, known dyes can be used. Since the dye (a) used in the present invention has a very small molecule (for example, a molecular weight of about 150 to 400) and is not ionic, it easily penetrates into hair and easily penetrates into cortex through a cuticle. On the contrary, after hair dyeing, it tends to come out of the hair and, for example, it flows out of the hair due to physical stimulation such as shampoo, but there is also an advantage that there is little dyeing on the skin. In the present invention, this dye (a) is used as a main dye for hair dyeing.
[0021]
The dye (a) used in the present invention is, for example, a (a) dye having a molecular weight of 150 to 400 having no ionicity, having a nitro group in the structure and penetrating into the cortex of the hair. There may be mentioned one or more selected from direct dyes. Specific examples include 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, nitroparaphenylenediamine hydrochloride, nitroparaphenylenediamine, paranitroorthophenylenediamine. And sulfur Acid 2-amino-5-nitrophenol, nitroparaphenylenediamine sulfate, paranitrometaphenylenediamine sulfate, paranitroorthophenylenediamine sulfate, 4-hydroxypropylamino-3-nitrophenol, HC BLUE NO.2, HC BLUE NO .4, HC BLUENO.5, HC BLUE NO.6, HC BLUE NO.9, HC BLUE NO.11, HC BLUE NO.12, HC ORANGE NO.2, HC ORANGENO.3, HC RED N O.3, HC RED NO.7, HC RED NO.10, HC RED NO.13, HC VIOLET NO.1, HC VIOLE T NO.2, HC YELLOW NO.2, HC YELLOWNO.4, HC YELLOW NO.5, HC YELLOW NO.9, HC YELLOW NO.10, HC YELLOW NO.11, HC YELLOW NO.12, HC YELLOW NO.14 and HC YELLOW NO.15. These dyes (a) can be used alone or in combination of two or more.
[0022]
If the molecular weight of the dye (a) used in the present invention is less than 150, there is a possibility that there is no commercially available and inexpensive dye, and if the molecular weight exceeds 400, it is difficult to penetrate into the hair, and the cut take There is a risk that it will not penetrate the cortex via
[0023]
The dye (b) used in the present invention is, for example, one or more selected from direct dyes which are dyes having a molecular weight of 350 to 1050 charged to anions and penetrate only from the inside of the cuticle to a shallow layer of cortex. Can be mentioned. Specific examples include Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, Blue No. 2, Red No. 201, Red No. 227, Red No. 230 (1), Red No. 230 (2), Red No. 231, Red No. 232, Orange No. 205, Orange No. 207, Yellow No. 202 (1), yellow 202 (2), yellow 203, green 201, green 204, green 205, blue 202, blue 203, blue 205, brown 201, red 401, red 502, Red 503, Red 504, Red 506, Orange 402, Yellow 402, Yellow 403 (1), Yellow 406, Yellow 407, Green 401, Green 402, Purple 401 And black 401, etc. It can be. These dyes (b) can be used alone or in admixture of two or more.
[0024]
When the molecular weight of the dye (b) used in the present invention is less than 350, there is a fear that there is no commercially available and inexpensive dye, and when the molecular weight exceeds 1050, it may be difficult to penetrate into the hair. .
[0025]
The dye (c) used in the present invention is, for example, a dye having a molecular weight of 250 to 500 charged to a cation, and one or more selected from direct dyes that penetrate only from the inside of the cuticle to a shallow layer of cortex Can be mentioned. Specific examples include Rhodamine B, Rhodamine B acetate, BASIC BLUE 3, BASIC BLUE 6, BASIC BLUE 7, BASIC BLUE 9, BASIC BLUE 26, BASIC BLUE 41, BASICBLUE 99, BASIC BROWN 16, BASIC BROWN 17, BASIC GREEN 1 , BASIC GREEN 4, BASIC ORANGE 1, BASIC RED 1, BASIC RED 2, BASIC RED 22, BASIC RED 46, BASIC RED 51, BASIC RED 76, BASIC RED 118, BASIC VIOLET 2, BASIC VIOLET 3, BASIC VIOLET 4, BASIC VIOLET 14, BASIC VIOLET 16, BASIC YELLOW 11, BASIC YELLOW 28, BASIC YELLOW 40, BASIC YELLOW 57, and BASIC YELLOW 87. These dyes (c) can be used alone or in combination of two or more.
[0026]
When the molecular weight of the dye (c) used in the present invention is less than 250, there is a fear that there is no commercially available and inexpensive dye, and when the molecular weight exceeds 500, there is a possibility that it will be difficult to penetrate into the hair. .
[0027]
In order to prevent the dye (a) from flowing out in the hair that has been dyed, the present inventors have tried a method of coating the outside of the cuticle with silicon, various polymers, etc. It was weak against irritation and could not prevent the dye (a) from flowing out. Therefore, in the present invention, it has been devised to form an anti-fading layer around the outside of the cortex inside the cuticle.
[0028]
First, the dye (b) (tar pigment) that could be used as a cosmetic dye from before the relaxation of cosmetic regulations (Ministerial Ordinance to determine tar pigments that can be used for pharmaceuticals, etc. announced by the former Ministry of Health and Welfare in 1966) An attempt was made to use the defined dye (b)).
Since this dye (b) has a minus (−) charge and a large molecular weight, it can penetrate inside the cuticle, but cannot penetrate into the cortex part of the hair. In addition, since this dye (b) is water-soluble, it is very vulnerable to hair care agents containing a large amount of cationic components such as hair treatments and hair conditioners, sweat, etc., and easily flows out of the hair. It is known that the fall is intense. Therefore, in order to make this water-soluble dye (b) stay in the hair and make it difficult to flow out, it was examined to make it water-insoluble.
[0029]
Therefore, like the dye (a), an attempt was made to use the dye (c) that has become usable in Japan after the relaxation of cosmetic regulations. This dye (c) has a positive (+) charge, has a large molecular weight almost equal to that of the dye (b), and can penetrate inside the cuticle, but penetrates to the cortex part of the hair. I can't.
[0030]
Since the dye (c) has a positive (+) charge, the dye (c) and the dye (b) react with each other in the aqueous solution of the dye (b) and the aqueous solution of the dye (c) having a negative (−) charge. It was found that a water-insoluble complex was formed only by mixing under such conditions that the concentration was higher than that, and once this complex was formed, it was never dissolved in water. If this water-insoluble complex could be formed between the cuticle and the cortex, the dye (a) in the hair was prevented from flowing out and the fastness was improved. Thereafter, as a result of intensive studies, the object of the present invention was achieved.
The concentration at which the dye (c) and the dye (b) react with each other is, for example, when 100 g of the same aqueous solution at room temperature dissolves 0.5 g or more of the (b) dye and 2.0 g or more of the (c) dye. Reacts to form a water-insoluble complex. Therefore, for example, both (b) less than 0.2 g of dye and (c) less than 1.0 g of dye do not react with 100 g of aqueous solution at room temperature. Of course, since these concentrations change depending on the temperature of the seasons, it is necessary to appropriately select a concentration at which the two do not react.
[0031]
Various known additives can be added to the hair dye of the present invention. For example, it is preferable to add at least one selected from basic amino acids and amine oxides.
[0032]
Basic amino acids include L-Arg, L-Lys, and L-His. Among these, L-Arg may act as an alkaline agent, but has an excellent hair repair effect under high pH conditions. Therefore, it can be preferably used, and it can obtain an effect as a hair-friendly alkaline agent and a hair repair effect, and also has an effect of suppressing discoloration due to shampoo after hair dyeing.
[0033]
Amine oxide has an effect of suppressing generation of colored bubbles and water during shampooing. Among amine oxides, laurylamine oxide has a strong effect and suppresses generation of colored bubbles and water.
[0034]
By adjusting the pH of the aqueous dye solution to a basic region (the basic region is pH 7 or higher, preferably 7.5 to 10, more preferably 7.8 to 10), hair can be swollen, Can penetrate into the hair. In addition, by setting the pH of the aqueous dye solution in the basic region, it is possible to prevent the dye (b), which is intensely attached to the skin in the acidic region, from developing color. Furthermore, by making the pH of the dye aqueous solution into the basic region, more L-Arg can penetrate into the hair.
[0035]
The nonionic surfactant used in the present invention is not particularly limited as long as it is a nonionic surfactant and may be an ether type or an ester type. Specific examples thereof include: polyoxyethylene alkyl ether, polyoxyethylene alkylphenol Sorbitan, sucrose esters (sorbitan fatty acid esters, sucrose fatty acid esters), monoglycerides of glycerin derivatives, and the like. These can be used alone or in combination of two or more.
[0036]
In the present invention, an oil agent or a cationic surfactant can be further blended for the purpose of increasing added value. The oil agent is not particularly limited, and specific examples thereof include animal and vegetable oils such as lanolin, mink oil, horse oil, almond oil, castor oil, jojoba oil, medford oil and olive oil; Sterols derived from animals and plants such as phosphorus, lanolin alcohol, and phytosterol, and their derivatives; minerals such as solid paraffin, ceresin, whale wax, beeswax, carnauba wax, waxes derived from animals and plants; liquid paraffin, squalane, etc. Hydrocarbon oils; higher alcohols such as lauryl alcohol, cetanol, cetostearyl alcohol, and oleyl alcohol; higher fatty acids such as lauric acid, stearic acid, and oleic acid; polyoxyethylene polyoxypropylene glycol, isopropyl myristate, isopropyl palmitate Le, isooctane acid cetostearyl, there may be mentioned synthetic oils such as isostearic acid alkyl esters, these may be used alone or in admixture.
[0037]
In addition, the hair dye of the present invention includes anionic or amphoteric surfactants other than nonionic surfactants, glycerin, sorbit, propylene glycol, 1,3-butylene glycol as long as the effects thereof are not impaired. Polyhydric alcohols such as ethanol; lower alcohols such as ethanol; hyaluronic acid salts, pyrrolidone carboxylates, hydrolyzed collagen, hydrolyzed keratin, hydrolyzed silk, trehalose and other moisturizers; alkyltrimethylammonium chloride, cationized dextran, etc. Cationized formulations of: aloe, chamomile, licorice, chlorella, comfrey, cinnamon, shiitake, jasmine, sage, carrot, garlic, tea, peppermint, marigold, lavender, rosemary, seaweed and other plant ingredients, sucrose, Glucose, Bulking agents such as sugars and sugars such as oligosaccharides and / or excipients, plant components such as guar gum, seaweed extract and refined extract, and thickeners derived from animals such as silk protein, celluloses, alginates and polysaccharides Viscosity ingredient consisting of the group of, in particular, methylcellulose, ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, polyvinyl alcohol, carboxyvinyl polymer, alginic acid, sodium alginate, alginic acid A thickening ingredient selected from the group consisting of ammonium, calcium alginate, gum arabic, xanthan gum, carrageenan, and their cationic derivatives, parabens for improving stability over time, and repose Fungicides such as salt, preservatives and / or antioxidants, pH adjusting agents, ultraviolet absorbers, and the like can be added additives selected from chelating agents.
[0038]
The addition amount of additives such as parabens, bactericides such as benzoates, preservatives and / or antioxidants, pH adjusters, ultraviolet absorbers, chelating agents, etc., is the desired effect of the hair dye of the present invention. Although it will not specifically limit if it is a range which does not impair, Usually, it is the range of 0.01-1.0 mass% with respect to the whole hair dye. If it is less than 0.01% by mass, the stability over time may not be obtained, and even if added over 1.0% by mass, the stability over time will not be obtained, which is uneconomical.
[0039]
Moreover, the hair dye of this invention can add an appropriate amount of fragrance | flavor. The fragrance is an important component for making the product attractive and increasing the commercial value, and for masking the odor of other components.
[0040]
In the present invention, the mixing ratio of water, dye (a), dye (b), dye (c), nonionic surfactant, and oil agent can be changed according to the purpose, and is not particularly limited. In 100% by mass of the hair dye, about 65% by mass or more of water, the dye (a), the dye (b), the dye (c) (for example, the mass ratio of the dye (a): the dye (b): the dye (c) = 60 to 70: to 20: to 50) in total, 2 mass% or less, nonionic surfactant 1 to 10 mass%, oil agent 1 to 10 mass%, cationic surfactant 1 to 10 mass%, other An example of a small amount of additive can be given.
[0041]
The form of the hair dye of the present invention is not particularly limited, but usually a cream form is preferable, and a form excellent in stability, handleability, storage property and the like is preferable.
[0042]
The hair dye of the present invention is packaged, for example, by using a plastic film bag, tube or glass bottle that does not transmit moisture, stored, transported and stored, and the hair dye inside is taken out and used as it is.
[0043]
Next, an embodiment of the hair dyeing method of the present invention in which hair is dyed using the hair dye of the present invention will be described.
A necessary amount of the hair dye of the present invention is applied to the hair and uniformly applied to the hair using a brush or the like.
The hair dyeing conditions are not particularly limited. For example, after uniformly applying to hair, the dye (a) is allowed to penetrate into the hair by allowing it to stand for 10 to 15 minutes while heating at about 35 to 45 ° C., Dye (b) and dye (c) also penetrate to the inside of the cuticle inside the hair, so that the concentration of the two components is increased, and the two components react and extend from the inside of the cuticle to the shallow layer of cortex. An anti-fading layer comprising a water-insoluble complex is formed. After dyeing in this way, the hair is rinsed with water, dried and finished. By determining the concentration of hair dye, temperature, and time of hair dyeing, the shade can be adjusted and the range of color tone can be expanded.
[0044]
【Example】
EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
[0045]
Example 1
The hair dye of the present invention having the composition shown in Table 1 was prepared, and the hair dye of the present invention was uniformly applied to the sample hair bleached by bleaching about 1 g of a human hair bundle using a necessary amount of brush. Thereafter, the hair was dyed by standing for 10 to 15 minutes while heating at about 35 to 45 ° C., and then the hair was rinsed with water, dried and finished. The following evaluation methods were used to evaluate the stability of the product (hair dye), color strength (hair dyeing power), durability (fastness), the color of bubbles and water during shampooing, and the texture of the color. . The evaluation results are shown in Table 1.
[0046]
[Product stability]: The stability of the product is judged by a aging test (40 ° C).
A: Stable for 3 months or more
○ Stable for more than 1 month
Δ: Stable for more than 1 week
×: Does not form hair dye
[0047]
[Color intensity (dyeing power)]: The color intensity is visually determined.
A: Pretty dark
○: dark
Δ: thin
×: Almost no color
[0048]
[Durability (fastness)]: After hair dyeing, shampoo is performed 10 to 20 times, and the degree of fading after 10 times of shampooing is determined.
○: Almost no fading
Δ: Scarlet is seen
×: Fading
[0049]
[Color of bubbles and water during shampooing]: After dyeing hair, the color of bubbles and water during shampooing is visually determined.
○: Color is not applied
Δ: Slightly colored
X: Very dark and colored
[0050]
[Color texture]
A: Nearly natural color
○: Close to natural color
Δ: Slightly artificial color
×: Artificial color
[0051]
(Comparative Examples 1-5)
After hair dyeing was performed in the same manner as in Example 1 except that a hair dye for comparison of the formulations shown in Table 1 was prepared, the hair was rinsed with water, dried, finished, and the product (hair dye) stabilized. The color, the color strength (hair dyeing power), the durability (fastness), the color of bubbles and water during shampooing, and the color texture were evaluated. The evaluation results are shown in Table 1.
[0052]
(Comparative Example 6)
(A) Dye or (c) Dye is not blended, (b) Dye is blended in the conventional hair dye (hair manicure) (trade name: Real Herb Color <6OB>, manufactured by Real Chemical Co., Ltd.) After the hair is dyed in the same manner as in Example 1, the hair is rinsed with water, dried, finished, the stability of the product (hair dye), the color strength (hair coloring power), the durability (fastness), The color and texture of bubbles and water during shampoo were evaluated. The evaluation results are shown in Table 2 together with the results of Example 1.
[0053]
[Table 1]

[0054]
[Table 2]

[0055]
From Table 1, the hair dye of the present invention has the stability of the product (hair dye), the color strength (hair dyeing power), the durability (fastness), the color of bubbles and water during shampooing, It turns out that it is excellent in any of the textures.
On the other hand, the hair dye of Comparative Example 1 is inferior in color strength (hair dyeing power), durability (fastness) and color texture, and the hair dye of Comparative Example 2 is durable (fastness) and The hair dye of Comparative Example 4 is inferior in the color of foam and water at the time of shampooing, and the hair dye of Comparative Example 3 is inferior in durability (fastness), the color of the foam and water at the time of shampooing, and the color texture. Is inferior in the stability (fastness) of the product (hair dye), the color of foam and water during shampooing, and the color texture, and the hair dye of Comparative Example 5 is dark (hair dyeing power) ), Durability (fastness), color of foam and water during shampooing, and color texture are inferior.
From Table 2, the hair dye of the present invention has the same product stability and hair dyeing effect as the hair dye (hair manicure) blended with the conventional (b) dye, has higher fastness, and spreads color tone. It can be seen that the hair color is excellent with a wide color texture.
[0056]
【The invention's effect】
The hair dye according to claim 1 of the present invention has no ionicity. With a molecular weight of 150-400 Directly charged to dye (a), anion With a molecular weight of 350-1050 Directly charged to dye (b) and cation With a molecular weight of 250-500 Direct dye (c) is stably emulsified and dispersed in a basic aqueous solution. pH 7.5-10 A one-component hair dye, which uses a nonionic surfactant at a concentration that does not react even when the dyes (a) to (c) are dissolved in the same aqueous solution. Uniform milk A hair dye characterized by being dispersed and dispersed, is simple and inexpensive in construction, is gentle to the skin, has no irritation or damage to the scalp and hair, and dye (b) and dye (c) are directly used. Since it does not react upon contact, water-insoluble complex is not generated, and it is excellent in stability, handleability, storability, etc. When applied to and applied to hair, it does not react with hair. Since an aqueous solution of a certain concentration swells the hair, penetration of each dye and various additives into the hair can be promoted, and a remarkable effect that a good hair dyeing effect can be obtained is achieved.
Dye (b) is a dye that is very intensely dyed to the skin under acidic conditions, but it can be dissolved and emulsified and dispersed in an aqueous solution at a concentration that does not react, and the color development can be suppressed. There is no dyeing.
[0057]
The hair dye according to claim 2 of the present invention is characterized in that, in the hair dye according to claim 1, it contains at least one selected from basic amino acids and amine oxides. It has an excellent ability to adsorb hair, and supplementing the hair can provide an effect as a gentle alkaline agent and a hair repair effect, as well as improving dyeability and suppressing discoloration due to shampoo. By adding, it is possible to further suppress the generation of colored bubbles and water during shampooing.
[0058]
Claim 3 of the present invention provides a direct dye (a) having no ionicity at a concentration that does not react even when dissolved in the same aqueous solution, a direct dye (b) charged with an anion, and a direct dye (c) charged with a cation. ) Is added to the water phase that is uniformly dissolved, and a nonionic surfactant is added and stirred to uniformly emulsify and disperse. To pH 7.5-10 Therefore, it is possible to suppress the formation of water-insoluble complex, and a nonionic surfactant is added. The nonionic surfactant is a direct dye having a charge of (-) (b) Since it does not react with the direct dye (c) having a charge of or (+), an emulsion in which the direct dyes (a) to (c) are uniformly emulsified and dispersed can be obtained. The remarkable effect that a hair agent can be manufactured easily is produced.
[0059]
According to a fourth aspect of the present invention, there is provided a direct dye (a) having a concentration that does not react even when dissolved in the same aqueous solution, a direct dye (b) charged with an anion, and a direct dye charged with a cation (c) ), And at least one selected from basic amino acids and amine oxides, a non-ionic surfactant is added to the aqueous phase uniformly dissolved and stirred to uniformly emulsify and disperse. To pH 7.5-10 Therefore, the formation of water-insoluble complex can be suppressed, and then a nonionic surfactant is added. The nonionic surfactant is a direct dye having a charge of (−) ( Since it does not react with the direct dye (c) having the charge of b) or (+), an emulsion in which the direct dyes (a) to (c), basic amino acids, amine oxides and the like are uniformly emulsified and dispersed is obtained. The hair dye according to claim 2 can be easily produced.
[0060]
Claim 5 of the present invention uniformly applies the hair dye according to claim 1 or claim 2 to the hair and allows the direct dye (a) having no ionic properties to penetrate into the deep cortex layer of the hair, Then, by heating, the direct dye (b) charged to the anion and the direct dye (c) charged to the cation are allowed to permeate through the shallow layer of the cortex from the inside of the cuticle and react with each other at the same time. This is a hair dyeing method characterized by forming an anti-fading layer composed of a natural complex, and is physically emulsified by applying a stimulus such as rubbing the hair evenly with a brush and applying it by hand. Is destroyed, the dye (a) in the hair dye penetrates into a deep layer of cortex of the hair, and is heated, so that the dye (b) and the dye (c) having large molecules are also contained in the cuticle inside the hair. From the inside By penetrating over the shallow layer of lutex, the concentration of the two components increases and the two components react to form an anti-fading layer consisting of water-insoluble complex from the inside of the cuticle to the shallow layer of cortex. The anti-fading layer is composed of large molecules, so that even if a physical stimulus such as shampoo is applied, the anti-fading layer does not flow out of the hair, and the dye (a) that has penetrated into the hair is exposed to the outside of the hair. By preventing it from flowing out, there is a remarkable effect that the fastness is improved.
[Brief description of the drawings]
FIG. 1A is an explanatory diagram schematically illustrating a cross section of hair before hair dyeing, and FIG. 1B is an explanatory diagram schematically illustrating a cross section of hair after hair dyeing.
[Explanation of symbols]
1A Hair before dyeing
1B Hair after dyeing
2 Cuticle
3 Cortex
4 Medleyra
5 Anti-fading layer

Claims (5)

A direct dye (a) having a molecular weight of 150 to 400 having no ionicity, a direct dye (b) having a molecular weight of 350 to 1050 charged to an anion, and a direct dye (c) having a molecular weight of 250 to 500 charged to a cation are basic. A one- component hair dye having a pH of 7.5 to 10 that is stably emulsified and dispersed in an aqueous solution, wherein the dyes (a) to (c) do not react even when dissolved in the same aqueous solution. hair dye, characterized in that formed by uniformly emulsifying dispersion using a surfactant.   The hair dye according to claim 1, comprising at least one selected from a basic amino acid and an amine oxide for the purpose of enhancing the anti-fading effect. Dissolve uniformly by adding direct dye (a) having no ionicity at a concentration that does not react even when dissolved in the same aqueous solution, direct dye (b) charged with anion, and direct dye (c) charged with cation The method for producing a hair dye according to claim 1, wherein a nonionic surfactant is added to the aqueous phase and stirred to uniformly emulsify and disperse to pH 7.5-10 . Direct dye (a) having no ionicity at a concentration that does not react when dissolved in the same aqueous solution, direct dye (b) charged with anion and direct dye (c) charged with cation, and basic amino acid and amine A nonionic surfactant is added to an aqueous phase uniformly dissolved by adding at least one selected from oxides, and the mixture is stirred and uniformly emulsified and dispersed to a pH of 7.5 to 10. Item 3. A method for producing a hair dye according to Item 2.   Applying the hair dye according to claim 1 or 2 to the hair uniformly, infiltrating the direct dye (a) having no ionicity into a deep layer of cortex of the hair, and heating the anion, Directly charged direct dye (b) and positively charged direct dye (c) are allowed to permeate from the inside of the cuticle through a shallow layer of cortex and react to form an anti-fading layer comprising a water-insoluble complex. A hair dyeing method characterized by causing the hair to dye.

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