JP3881688B2 - Hair dye and method for producing the same - Google Patents

Hair dye and method for producing the same Download PDF

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JP3881688B2
JP3881688B2 JP2005518104A JP2005518104A JP3881688B2 JP 3881688 B2 JP3881688 B2 JP 3881688B2 JP 2005518104 A JP2005518104 A JP 2005518104A JP 2005518104 A JP2005518104 A JP 2005518104A JP 3881688 B2 JP3881688 B2 JP 3881688B2
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力 川田
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/23—Sulfur; Selenium; Tellurium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A61K2800/438—Thermochromatic; Photochromic; Phototropic

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  • Life Sciences & Earth Sciences (AREA)
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Description

本発明は、容易に染毛ができる染毛料及びその製造方法に関する。  The present invention relates to a hair dye that can be easily dyed and a method for producing the same.

頭髪を染めるものとして、まず、カラースプレーやカラースティックなどと称される一時的に着色する一時染毛料がある。また、ヘアマニキュア，カラーリンス，カラートリートメントといわれる毛髪のタンパク質と酸性染料とのイオン結合を利用した半永久染毛料や、ヘアカラー，ヘアダイ，白髪染めに代表される酸化染毛剤などがある。最近では、染めた色の高い耐久性などにより、酸化染毛剤が好まれる傾向にある（特許文献１参照）。  First, there are temporary hair dyes for temporarily coloring the hair, such as color sprays and color sticks. In addition, there are semi-permanent hair dyes that use ionic bonds between hair proteins and acid dyes, which are called hair manicures, color rinses, and color treatments, and oxidative hair dyes that are typified by hair colors, hair dyes, and white hair dyes. Recently, there is a tendency that an oxidative hair dye is preferred due to high durability of the dyed color (see Patent Document 1).

上記酸化染毛剤は、例えば、パラフェニレンジアミンやトルエン−２．５−ジアミンなどの酸化染料に、アンモニアなどのアルカリ剤を加えた第１液と、過酸化水素などの酸化剤からなる第２液とから構成されている。使用にあたっては、毛髪を染めようとする直前に上記２つの液を混合し、混合した液を毛髪に塗布する。酸化染毛剤による染毛では、毛髪中に浸透した酸化染料が、加えられた酸化剤により酸化重合し、酸化重合により不溶性色素が生成され、生成された不溶性色素が毛髪中に定着することにより、毛髪に染色が行われる。  The oxidative hair dye is, for example, a first liquid in which an alkaline agent such as ammonia is added to an oxidative dye such as paraphenylene diamine or toluene-2.5-diamine, and a second oxidant such as hydrogen peroxide. It is composed of liquid. In use, the two liquids are mixed just before hair is dyed, and the mixed liquid is applied to the hair. In hair dyeing with an oxidative hair dye, the oxidative dye that has penetrated into the hair undergoes oxidative polymerization with the added oxidant, and an insoluble pigment is formed by the oxidative polymerization, and the insoluble pigment produced is fixed in the hair. The hair is dyed.

一方、硝酸銀，乳酸銀，難溶性の硫酸銀，酢酸銀などの銀塩を用い、光による反応や酸化などにより染色する染毛剤も提案されている（特許文献２，特許文献３参照）。また、アンモニア銀錯塩又はエタノールアミン銀錯塩溶液を毛髪に付着させた後、還元剤を用いて染色する２液を用いる染毛方法も提案されている（特許文献４参照）。また、エタノールアミン銀錯塩とジアミン系染料を用いた染毛方法も提案されている（特許文献５参照）。  On the other hand, hair dyes that use silver salts such as silver nitrate, silver lactate, sparingly soluble silver sulfate, and silver acetate and that are dyed by light reaction or oxidation have also been proposed (see Patent Documents 2 and 3). In addition, a hair dyeing method using two liquids in which ammonia silver complex salt or ethanolamine silver complex salt solution is attached to hair and then dyed with a reducing agent has also been proposed (see Patent Document 4). Moreover, the hair dyeing method using ethanolamine silver complex salt and diamine type dye is also proposed (refer patent document 5).

なお、出願人は、本明細書に記載した先行技術文献情報で特定される先行技術文献以外には、本発明に関連する先行技術文献を出願時までに発見するには至らなかった。
特開平１０−１７５８３０号公報 特開２００２−３４８２２１号公報 特開昭５２−１２５６３８号公報 特開昭４８−０１８４３８号公報 特開平４−３１２５１４号公報 The applicant has not yet found prior art documents related to the present invention by the time of filing other than the prior art documents specified by the prior art document information described in this specification.
JP-A-10-175830 JP 2002-348221 A JP-A-52-125638 JP-A-48-018438 Japanese Patent Laid-Open No. 4-31514

しかしながら、上述した酸化染毛剤は、使用直前に２液を混合する必要があるため、手間がかかり、またアンモニア臭があるなどの問題があった。また、ジアミン系物質やこの重合体などからなる酸化染料は、発ガン性や肝臓障害、また、胎児への影響など、人体の健康面への影響や、アルカリや酸化反応などによる毛髪の傷みなどが指摘されている。  However, the above-mentioned oxidative hair dye needs to mix two liquids immediately before use, and thus takes time and has a problem such as an ammonia odor. In addition, oxidative dyes made of diamine-based substances and this polymer can cause carcinogenicity, liver damage, effects on the health of the human body, such as effects on the fetus, and hair damage caused by alkalis and oxidation reactions. Has been pointed out.

また、銀塩を利用するものは、銀塩水溶液が非常に不安定なため、容器に収容した状態で放置すると、自然に黒く着色してしまい、毛髪に対する付着能力や付着した状態の堅牢性が低くなるなどの問題がある。
本発明は、以上のような問題点を解消するためになされたものであり、より簡便に安定した状態で染毛できるようにすることを目的とする。In addition, those using silver salts are very unstable in silver salt aqueous solution, so if left in a container, they will naturally color black, and the ability to adhere to hair and the fastness of the attached state will be reduced. There are problems such as lowering.
The present invention has been made to solve the above-described problems, and an object of the present invention is to make it possible to more easily and stably dye hair.

上述した問題を解消するために、本発明に係る染毛料は、水分を有する基質材料に硫酸銀及びクエン酸が混合されているようにしたものである。
従って、上記染毛料は、紫外線や可視光線の照射などにより還元されて金属銀を析出する銀塩である硫酸銀が、水溶液の状態で含まれている。
また、本発明に係る染毛料の製造方法は、クエン酸が溶解している水溶液に硫酸銀を加えることで、水分を有する基質材料に硫酸銀及びクエン酸が混合されているようにしたものである。
従って、銀塩が析出することなく染毛料が製造できる。In order to solve the above-described problems, the hair dye according to the present invention is such that silver sulfate and citric acid are mixed with a substrate material having moisture.
Therefore, the hair dye contains silver sulfate, which is a silver salt that is reduced by irradiation with ultraviolet rays or visible light to deposit metallic silver, in an aqueous solution state.
Further, the method for producing a hair dye according to the present invention is such that silver sulfate is added to an aqueous solution in which citric acid is dissolved, so that silver sulfate and citric acid are mixed with a substrate material having moisture. is there.
Therefore, the hair dye can be produced without the silver salt being precipitated.

以上説明したように、本発明では、染毛料に、紫外線の照射などにより還元されて金属銀を析出する銀塩が、クエン酸により酸性とされた水溶性の状態で含まれているようにしたので、上記染毛料を頭髪に塗布するだけで染毛が可能となっている。また、クエン酸を用いて酸性領域としているので、暗反応により酸化するなどのことが抑制され、硫酸銀が安定して溶解した状態が得られる。
このように、本発明によれば、使用直前に２液を混合するなどの必要がないなど、簡便に染毛ができる。またアンモニア臭もなく、人体の健康面への影響や、アルカリや酸化反応などによる毛髪の傷みなどもない。As described above, in the present invention, the hair dye contains a silver salt that is reduced by ultraviolet irradiation or the like to precipitate metallic silver in a water-soluble state made acidic with citric acid. Therefore, hair can be dyed only by applying the hair dye to the hair. Moreover, since it is set as the acidic area | region using a citric acid, it is suppressed that it oxidizes by dark reaction etc., and the state which silver sulfate melt | dissolved stably is obtained.
As described above, according to the present invention, hair can be easily dyed, for example, it is not necessary to mix the two liquids immediately before use. There is no odor of ammonia, and there is no effect on the health of the human body or hair damage due to alkali or oxidation reaction.

以下、本発明の実施の形態について説明する。
本実施の形態の染毛料は、水分を有する所定の基質材料をクエン酸により酸性の状態とし、この基質材料に水溶性の銀塩である硫酸銀を混合（添加）させ、クエン酸により酸性とされた基質材料に硫酸銀が溶解している状態としたものである。基質材料は、水溶性成分に油成分が乳化された乳液状であればよい。また、基質材料は、所定の分散媒体中に高分子材料が分散したゲルであってもよく、アルコールを含む水溶液であってもよい。Embodiments of the present invention will be described below.
The hair dye of the present embodiment makes a predetermined substrate material having moisture acidic with citric acid, and mixes (adds) silver sulfate, which is a water-soluble silver salt, to the substrate material to make it acidic with citric acid. Silver sulfate is dissolved in the prepared substrate material. The substrate material may be an emulsion in which an oil component is emulsified in a water-soluble component. The substrate material may be a gel in which a polymer material is dispersed in a predetermined dispersion medium, or an aqueous solution containing alcohol.

上記染毛料を頭髪に塗布し、ここに紫外線や可視光線などの光照射がなされると、染毛料に溶解している銀イオンが金属銀に還元され、還元された金属銀の微粒子が毛髪の表面に析出・付着して発色する。このようにして染毛された毛髪は、通常の洗髪では毛髪の着色状態に何ら変化が確認されない。光照射により析出して毛髪の表面に付着した金属銀は、洗髪などでは毛髪の表面より離脱しない強固なものと考えられる。  When the hair dye is applied to the hair and irradiated with light such as ultraviolet rays or visible light, the silver ions dissolved in the hair dye are reduced to metal silver, and the reduced metal silver fine particles are added to the hair. Colored by depositing on the surface. In the hair dyed in this way, no change in the coloring state of the hair is confirmed in normal hair washing. The metallic silver deposited by the light irradiation and adhering to the surface of the hair is considered to be strong that does not separate from the surface of the hair during hair washing or the like.

硫酸銀（Ａｇ２ＳＯ４）は、分子量３１１．７９の白色固体であり、水に対する溶解度は低く、２０℃で０．８％であり、酸性とした状態やアルコールの存在により溶解度はわずかに向上する。例えば、酸性の状態とすることで、溶解度は０．９％程度に向上する。
溶解している銀塩の濃度が０．４〜０．６％程度の低い濃度では、毛髪が赤みの入った着色状態となる。例えば、白髪に適用した場合、銀塩の濃度が０．４〜０．６％程度では、ピンク色から赤色を帯びた茶色に染毛され、あまり濃い茶色には染毛されない。ただし、染毛の対象が女性の場合などは、ライトブラウンが好まれる場合もあり、銀塩濃度である程度色調を調整すればよい。Silver sulfate (Ag 2 SO 4 ) is a white solid with a molecular weight of 311.79, has low solubility in water, is 0.8% at 20 ° C., and is slightly improved in the acidified state and presence of alcohol. To do. For example, the solubility is improved to about 0.9% by setting the acid state.
When the concentration of the dissolved silver salt is as low as about 0.4 to 0.6%, the hair becomes colored with redness. For example, when applied to gray hair, when the silver salt concentration is about 0.4 to 0.6%, the hair is dyed from pink to reddish brown, and not so dark brown. However, when the subject of hair dyeing is a woman, light brown may be preferred, and the color tone may be adjusted to some extent by the silver salt concentration.

酸性の状態とするためには、酸を加えればよいが、例えば、硫酸や硝酸などの強酸は、人体に用いる染毛料には適切ではない。また、塩酸は、塩化銀を生成するので、用いることができない。
上述した強酸に対し、弱酸は人体に対する影響もなく、塩を形成することもないので、酸性とするために添加する材料として適している。しかしながら、例えば酢酸は、強い臭いがあるため、染毛料に添加する材料としては適切ではない。In order to obtain an acidic state, an acid may be added. For example, strong acids such as sulfuric acid and nitric acid are not suitable for hair dyes used for the human body. Also, hydrochloric acid cannot be used because it produces silver chloride.
In contrast to the strong acid described above, the weak acid has no influence on the human body and does not form a salt, so it is suitable as a material to be added to make it acidic. However, for example, acetic acid is not suitable as a material to be added to the hair dye because it has a strong odor.

以上の知見に対し、クエン酸，リンゴ酸，乳酸，グリコール酸などが、前述した酸性にするための材料として、上述したような問題が発生しない。
これらの材料を調査すると、リンゴ酸，乳酸，グリコール酸などを用いて酸性とした基質材料に硫酸銀を加えた場合、製造時あるいは経時に伴い徐々に着色する現象が確認された。また、用いた酸によっては、製造後に沈殿物が確認された。In contrast to the above knowledge, citric acid, malic acid, lactic acid, glycolic acid and the like do not cause the above-described problems as materials for making them acidic.
When these materials were investigated, it was confirmed that when silver sulfate was added to a substrate material acidified with malic acid, lactic acid, glycolic acid, or the like, it gradually colored during production or over time. Depending on the acid used, precipitates were confirmed after production.

これらに対し、クエン酸を用いて酸性領域とすると、着色を発生させることなく、安定した状態で硫酸銀を溶解させる状態が得られた。加えて、クエン酸を用いた場合、硫酸銀の溶解度を０．９％まで高くすることが可能となる。ここで、緩衝剤としてクエン酸ナトリウムを用いるようにしてもよいことは、いうまでもない。
また、銀塩水溶液は非常に不安定であるが、上述したようにクエン酸を加えることで酸性域としておくことで、安定した状態が得られ、放置により黒化するという暗反応が抑制できるようになる。On the other hand, when an acidic region was formed using citric acid, a state in which silver sulfate was dissolved in a stable state was obtained without causing coloring. In addition, when citric acid is used, the solubility of silver sulfate can be increased to 0.9%. Here, it goes without saying that sodium citrate may be used as a buffering agent.
In addition, the silver salt aqueous solution is very unstable, but as described above, by adding citric acid to make it an acidic region, a stable state can be obtained and the dark reaction of blackening by standing can be suppressed. become.

クエン酸を用いない場合、暗所に保管した場合であっても徐々に黒化が進行し、また、毛髪に対する付着の能力や堅牢性が低下する。
これに対し、本実施の形態における染毛料では、クエン酸によりｐＨ４．０以下としておくようにしたので、溶解している銀塩の酸化が抑制され、硫黄などの還元性物質と組み合わせることなく、黒色の酸化銀の生成を抑制できる。例えば、上記染毛料は、４０℃以上の高温状態で保管されていても、着色の発生（暗反応）がおきない。ただし、予めクエン酸が添加されている状態で、硫酸銀を加える必要がある。硫酸銀を溶解した後にクエン酸を加えても効果が得られない。When citric acid is not used, blackening gradually proceeds even when stored in a dark place, and the ability and fastness to adhere to the hair decrease.
On the other hand, in the hair dye in this Embodiment, since it was made to be pH 4.0 or less with citric acid, the oxidation of the dissolved silver salt is suppressed, without combining with reducing substances such as sulfur, Generation of black silver oxide can be suppressed. For example, even if the hair dye is stored at a high temperature of 40 ° C. or higher, coloring (dark reaction) does not occur. However, it is necessary to add silver sulfate in a state where citric acid has been added in advance. Even if citric acid is added after silver sulfate is dissolved, no effect is obtained.

一方、クエン酸により酸性とされていなくアルカリ領域とされている場合、光を遮断しておいても、室温（例えば２０〜２５℃）の状態で放置しておくと、銀イオンが徐々に酸化して酸化銀が生成し、徐々に黒化する。この場合、還元剤として硫黄が添加されていると、アルカリ領域であっても上記暗反応を抑制することが可能となる。しかしながら、アルカリ領域で硫黄が添加されているものでは、光に対する反応性（感度）が低下する。  On the other hand, when it is not made acidic by citric acid and is in the alkaline region, silver ions are gradually oxidized when left at room temperature (for example, 20 to 25 ° C.) even if light is blocked. As a result, silver oxide is formed and gradually becomes black. In this case, when sulfur is added as a reducing agent, the dark reaction can be suppressed even in the alkaline region. However, when sulfur is added in the alkaline region, the reactivity (sensitivity) to light is lowered.

なお、硫酸銀は、０．５〜０．９％程度の溶解量であっても、水溶液であれば、前述した染毛状態が得られる。ただし、例えば、油成分中に硫酸銀を分散させた状態など、銀イオンがほとんど発生していない状態では、光による反応が非常に遅く、上述した染毛効果が得られない。  In addition, even if silver sulfate is about 0.5-0.9% of dissolution amount, if it is aqueous solution, the hair dyeing state mentioned above will be obtained. However, in a state where silver ions are hardly generated, for example, in a state where silver sulfate is dispersed in an oil component, the reaction by light is very slow and the above-described hair dyeing effect cannot be obtained.

次に、上述した染毛料の製造方法について説明する。
まず、以下に示す各成分により、作製物Ａを作製する。
真空乳化釜において、精製水８１．４ｋｇを入れて９０℃に加温し、ここにクエン酸を追加して酸性の状態とした上で、硫酸銀０．６ｋｇを加え、撹拌して硫酸銀を溶解させて作製物Ａとする。ここで、緩衝剤としてクエン酸ナトリウムを当量加えておいてもよい。Next, the manufacturing method of the hair dye mentioned above is demonstrated.
First, the product A is prepared using the following components.
In a vacuum emulsification pot, add 81.4 kg of purified water and heat to 90 ° C., add citric acid to make it acidic, add 0.6 kg of silver sulfate, and stir to add silver sulfate. Dissolve to make Product A. Here, an equivalent amount of sodium citrate may be added as a buffering agent.

次に、以下に示す各成分を混合し、作製物Ｂを作製する。
油槽釜に、シリコーンオイル１２ｋｇ、セタノール４ｋｇ、ステアリン酸ソルビタン１．５ｋｇ、ステアリルジメチルアンモニウムクロライド０．３ｋｇ、メチルパラベン０．１ｋｇを収容し、これらを８０℃に加温して各々溶解させ、作製物Ｂとする。Next, the following components are mixed to prepare a product B.
In an oil tank kettle, 12 kg of silicone oil, 4 kg of cetanol, 1.5 kg of sorbitan stearate, 0.3 kg of stearyldimethylammonium chloride and 0.1 kg of methylparaben are stored and heated to 80 ° C. to dissolve them. And

次に、真空乳化釜中に収容されている作製物Ａを８０℃に保ち、これを激しく撹拌した状態とし、撹拌している状態に、作製物Ｂを徐々に添加する。ついで、作製物Ａに作製物Ｂが全て添加された後、真空乳化釜を密閉して減圧環境とする。減圧環境とした後、３０００ｒｐｍのホモミクサーにより、真空乳化釜の内容物を８分間撹拌し、この後、撹拌速度を低下させながら内容物の温度を３５℃まで冷却する。  Next, the product A stored in the vacuum emulsification kettle is kept at 80 ° C., and this is vigorously stirred. The product B is gradually added to the stirred state. Next, after all the product B is added to the product A, the vacuum emulsification pot is sealed to create a reduced pressure environment. After the reduced pressure environment, the contents of the vacuum emulsification pot are stirred for 8 minutes by a 3000 rpm homomixer, and then the temperature of the contents is cooled to 35 ° C. while the stirring speed is reduced.

最後に、上述したことにより作製物Ａと作製物Ｂとを混合して得られた乳化物を、２０メッシュのフィルターにより濾過し、９８ｋｇの白色のクリーム（染毛料）を得る。
これらの作製は、ほぼ光が遮断した状態で行い、還元による金属銀の析出がないようにする。Finally, the emulsion obtained by mixing the product A and the product B as described above is filtered through a 20-mesh filter to obtain 98 kg of white cream (hair dye).
These preparations are performed in a state where light is almost blocked so that there is no precipitation of metallic silver due to reduction.

得られた白色・クリーム状の染毛料は、ｐＨ４程度である。この染毛料を、光を遮断して室温にした状態で放置すると、１０ヶ月以上黒色化することなく安定している。また、この染毛料を、光を遮断して４０℃にした状態で放置しても、６ヶ月以上黒色化することなく安定している。  The resulting white / creamy hair dye has a pH of about 4. When this hair dye is allowed to stand at room temperature with light blocked, it is stable without being blackened for more than 10 months. Moreover, even if this hair dye is left in a state of 40 ° C. while blocking light, it is stable without blackening for 6 months or more.

次に、上述した本発明の染毛料の染毛作用について、より詳細に説明する。
本発明の染毛料は、例えば、硫酸銀による水溶性銀塩を、ヘアクリームなどの水分を有する基質材料に混合したものである。このような染毛料を毛髪に塗布し、この状態で毛髪を日光（紫外線）に晒すと、染毛料中の銀イオンが光により還元されて金属銀が析出し、析出した金属銀が毛髪に付着する。このように金属銀が析出して毛髪に付着することで、毛髪が染毛される。析出して毛髪に付着した金属銀の一部は、毛髪中のイオウと反応して黒色の硫化銀に変化することや、空気中の酸素により徐々に酸化されて黒色の酸化銀に変化することも予想される。Next, the hair dyeing action of the hair dye of the present invention described above will be described in more detail.
The hair dye of the present invention is obtained, for example, by mixing a water-soluble silver salt of silver sulfate with a substrate material having moisture such as a hair cream. When such a hair dye is applied to the hair and the hair is exposed to sunlight (ultraviolet rays) in this state, the silver ions in the hair dye are reduced by light and metal silver is deposited, and the deposited metal silver adheres to the hair. To do. Thus, the metal silver is deposited and adhered to the hair, so that the hair is dyed. Part of the metallic silver deposited on the hair reacts with sulfur in the hair and changes to black silver sulfide, or is gradually oxidized by oxygen in the air and changes to black silver oxide. Is also expected.

本発明の染毛料は、毛髪を染色するもととなる銀を、銀塩として混合してあり、水に溶解した状態すなわち水溶性の銀イオンの状態で頭髪に塗布するものとした。この結果、本発明の染毛料によれば、毛髪内部にまで銀が浸透しやすい状態となっており、毛髪表面に接触した状態や毛髪内部で金属銀の微粒子が析出するので、色が定着しやすいものとなっている。また、ジアミンや鉛などを含むことが無いので、アレルギー反応を起こすことや健康を害することもない。さらに、本発明の染毛料によれば、金属銀が毛髪表面を被覆することによる毛髪の保護効果も期待でき、勿論、毛髪などに損傷を与えることもない。  The hair dye of the present invention is prepared by mixing silver as a silver salt for dyeing hair as a silver salt and applying it to the hair in a state dissolved in water, that is, in a state of water-soluble silver ions. As a result, according to the hair dye of the present invention, the silver is easily penetrated into the hair, and since the metal silver fine particles are deposited in the state of contact with the hair surface or inside the hair, the color is fixed. It is easy. Moreover, since it does not contain diamine or lead, it does not cause allergic reactions or harm health. Furthermore, according to the hair dye of the present invention, the protective effect of hair by coating the surface of the hair with metallic silver can be expected, and of course, the hair is not damaged.

上述した本発明の染毛料によれば、染毛料が塗布された段階の毛髪は、染色された状態とはなっていないが、染毛料中の銀イオンが還元された金属銀として析出した段階で、毛髪が染色された状態となる。
ところで、上述では、乳液状とした基質材料に硫酸銀を溶解させて染毛料としたが、これに限るものではない。例えば、所定の分散媒体中に高分子材料が分散しているゲルとした基質材料に、硫酸銀を溶解させて染毛料としてもよい。According to the hair dye of the present invention described above, the hair at the stage where the hair dye is applied is not in a dyed state, but at the stage where silver ions in the hair dye are deposited as reduced metallic silver. The hair is dyed.
In the above description, the hair dye is prepared by dissolving silver sulfate in an emulsion base material. However, the present invention is not limited to this. For example, a hair dye may be obtained by dissolving silver sulfate in a base material that is a gel in which a polymer material is dispersed in a predetermined dispersion medium.

例えば、精製水８２．１ｋｇ、クエン酸０．１ｋｇ、クエン酸ナトリウム０．１ｋｇに硫酸銀０．６ｋｇを溶解させ、これに、カルボキシビニルポリマー０．５ｋｇ、ポリビニルピロリドン誘導体四級アンモニウム塩０．５ｋｇ、トリイソプロパノールアミン０．８ｋｇ、エタノール１４．０ｋｇ、ポリオキシエチレンラウリルエーテル（２３Ｅ・Ｏ）０．８ｋｇ、エチルパラベン０．５ｋｇを加え、これらで透明なゲルを得て染毛料としてもよい。なお、当然ではあるが、この染毛料の製造においても、ほぼ光が遮断した状態で行い、還元による金属銀の析出がないようにする。  For example, 0.6 kg of silver sulfate is dissolved in 82.1 kg of purified water, 0.1 kg of citric acid and 0.1 kg of sodium citrate, and 0.5 kg of carboxyvinyl polymer and 0.5 kg of polyvinyl pyrrolidone derivative quaternary ammonium salt are added thereto. Further, 0.8 kg of triisopropanolamine, 14.0 kg of ethanol, 0.8 kg of polyoxyethylene lauryl ether (23E · O) and 0.5 kg of ethyl paraben may be added to obtain a transparent gel to be used as a hair dye. Needless to say, this hair dye is also manufactured in a state where light is almost blocked so that metallic silver is not precipitated by reduction.

また、基質材料として、所定の香料などが溶解した水溶液を用いてもよい。
基質材料として乳状液を用いた場合、一般にヘアクリームと称されるものとなり、基質材料としてゲルを用いた場合、一般にヘアジェルと称されるものとなる。また、基質材料として水溶液を用いた場合、ヘアローションと称されるものとなり、基質材料に粘度の高い乳化物を用いた場合、ヘアワックスと称されるものとなる。また、これらの染毛料は、例えばスプレー缶などに充填し、泡立てたクリーム状のいわゆるヘアムース（登録商標）として提供することができる。
また、上記染毛料に、０．０１〜０．５０％のコロイド硫黄が添加されていてもよい。コロイド硫黄が添加・混合されていることで、上記染毛料による着色が、より濃い状態となる。An aqueous solution in which a predetermined fragrance is dissolved may be used as the substrate material.
When a milky liquid is used as the substrate material, it is generally referred to as a hair cream, and when a gel is used as the substrate material, it is generally referred to as a hair gel. In addition, when an aqueous solution is used as the substrate material, it is referred to as a hair lotion, and when a highly viscous emulsion is used as the substrate material, it is referred to as a hair wax. Moreover, these hair dyes can be provided as, for example, a so-called hair mousse (registered trademark) in the form of a cream filled in a spray can.
Moreover, 0.01 to 0.50% of colloidal sulfur may be added to the hair dye. By adding and mixing colloidal sulfur, the coloring by the hair dye becomes darker.

Claims (6)

水分を有する基質材料と、
この基質材料に混合された硫酸銀及びクエン酸と
から構成されたことを特徴とする染毛料。A substrate material having moisture;
A hair dye comprising silver sulfate and citric acid mixed with the substrate material. 請求項１記載の染毛料において、
前記基質材料に、コロイド硫黄が混合されている
ことを特徴とする染毛料。In the hair dye according to claim 1,
A hair dye comprising colloidal sulfur mixed in the substrate material. 請求項１記載の染毛料において、
前記基質材料は、水溶性成分に油成分が乳化された乳状液であることを特徴とする染毛料。In the hair dye according to claim 1,
The hair dye characterized in that the substrate material is a milky liquid in which an oil component is emulsified in a water-soluble component. 請求項１記載の染毛料において、
前記基質材料は、所定の分散媒体中に高分子材料が分散したゲルであることを特徴とする染毛料。In the hair dye according to claim 1,
The hair dye characterized in that the matrix material is a gel in which a polymer material is dispersed in a predetermined dispersion medium. 請求項１記載の染毛料において、
前記基質材料は、水溶液であることを特徴とする染毛料。In the hair dye according to claim 1,
The hair dye characterized in that the substrate material is an aqueous solution. 水分を有する基質材料と、この基質材料に混合された硫酸銀及びクエン酸とから構成された染毛料の製造方法であって、
クエン酸が溶解している水溶液に硫酸銀を加える
ことを特徴とする染毛料の製造方法。A method for producing a hair dye comprising a substrate material having moisture, and silver sulfate and citric acid mixed in the substrate material,
A method for producing a hair dye, comprising adding silver sulfate to an aqueous solution in which citric acid is dissolved.
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KR101228416B1 (en) * 2010-08-18 2013-02-22 주식회사 코스메카코리아 Hair color composition of matter including silver dye
JP2014051479A (en) * 2012-09-10 2014-03-20 Kawata Rikiya Method for using silver ion containing photosensitive hair dye
CN108697605A (en) * 2016-02-17 2018-10-23 株式会社雅邬乐 Photosensitive hair dye

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JP5026862B2 (en) * 2006-07-28 2012-09-19 富士フイルム株式会社 Hair dye
JP4985926B2 (en) * 2006-09-15 2012-07-25 株式会社加美乃素本舗 Photosensitive acid hair dye composition
WO2010137103A1 (en) * 2009-05-25 2010-12-02 Kawata Tsutomu Photosensitive hair dye and method for producing the same
JP4804573B2 (en) * 2009-12-04 2011-11-02 株式会社ピカソ美化学研究所 Photosensitive hair dye

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GB1518874A (en) * 1976-04-06 1978-07-26 Beecham Group Ltd Hair colourant
CH673225A5 (en) * 1986-04-22 1990-02-28 Sanosil Ag
FR2838050B1 (en) * 2002-04-08 2006-07-14 Oreal KERATIN FIBER-CONTAINING METAL SINKING PROCESS OF COSMETIC PROPERTIES RESPONSIVE TO SHAMPOO
JP2004099502A (en) * 2002-09-09 2004-04-02 Tsutomu Kawada Hair dye

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Publication number Priority date Publication date Assignee Title
KR101228416B1 (en) * 2010-08-18 2013-02-22 주식회사 코스메카코리아 Hair color composition of matter including silver dye
JP2014051479A (en) * 2012-09-10 2014-03-20 Kawata Rikiya Method for using silver ion containing photosensitive hair dye
CN108697605A (en) * 2016-02-17 2018-10-23 株式会社雅邬乐 Photosensitive hair dye

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