JPH0553771B2

JPH0553771B2 -

Info

Publication number: JPH0553771B2
Application number: JP59174523A
Authority: JP
Inventors: Hiroshi Kanayama; Hiromi Minamino; Masayoshi Inui
Original assignee: Kanebo Ltd
Current assignee: Kanebo Ltd
Priority date: 1984-08-21
Filing date: 1984-08-21
Publication date: 1993-08-10
Also published as: JPS6153211A

Description

[Detailed description of the invention]

（技術分野）本発明は、染色堅牢性に優れ、短時間にかつ均
一に染毛し得る染毛剤に関する。（従来技術）従来、汎用されている酸化染毛剤は、施術時、
アルカリ性下に過酸化水素を作用させるために、
扱い方によつては毛髪損傷や一次皮膚刺激を示す
危険性がある。このため酸性染料を用いた頭皮、
頭髪に対して影響の少ない染毛剤が開発されてき
た。しかしながら現在、市販されている酸性染料
を使用した染毛剤は、染着性や洗髪時の染色堅牢
性などが低い欠点があつた。従来、毛髪を酸性染料で染色する場合は、染毛
が完了するまで約30〜50分の長時間を必要として
いた。この間、被施術者は、染液が周囲へ飛び散
らないようにできるだけ不動静座の状態を保持し
なければならず、その精神的、肉体的負担は、は
かり知れないものがある。従つて、頭髪染色の所
要時間を少しでも短縮できれば、被施術者にとつ
て安楽これ以上のものはなく、その改良が需要者
等をして広く要望されている。尚、染毛所要時間を短縮する方法として、染毛
処理温度を高くする方法（染毛する間、頭髪部を
キヤツプ等により覆い、所要の染毛温度を永く保
持すること。）や染毛促進剤（例えば、スチレン
グリコール）の添加併用が知られているが、前者
の方法では非常に手間がかかり、しかも効果が少
ない等で実用性に乏しく、又後者の方法では、未
だ充分な効果が得られていない。（発明の目的）本発明の目的は、染色堅牢性に優れ、短時間
に、かつ均一に染毛し得る染毛剤を提供すること
である。（発明の構成）すなわち、本発明は下記一般式（式中で、R₁は水素原子、メチル基またはメト
キシ基、R₂は−CH₂OH基、−CH₂CH₂OH基、
(Technical Field) The present invention relates to a hair dye that has excellent color fastness and can dye hair uniformly in a short time. (Prior art) Conventionally, commonly used oxidative hair dyes are
In order to make hydrogen peroxide act under alkaline conditions,
Depending on how it is handled, there is a risk of hair damage or primary skin irritation. For this reason, the scalp using acid dyes,
Hair dyes that have less effect on hair have been developed. However, currently commercially available hair dyes using acidic dyes have drawbacks such as poor dyeability and dye fastness during hair washing. Conventionally, when dyeing hair with acid dyes, it took a long time of about 30 to 50 minutes to complete the dyeing. During this time, the person receiving the treatment must remain as still as possible to prevent the dye from scattering around them, and the mental and physical burden placed on them is immeasurable. Therefore, if the time required for hair dyeing can be shortened even a little, there is nothing more convenient and convenient for the person being treated, and improvements in this area are widely desired by consumers and the like. In addition, methods to shorten the time required for hair dyeing include increasing the hair dyeing temperature (during hair dyeing, cover the hair with a cap or the like to maintain the required hair dyeing temperature for a long time) and hair dyeing methods. It is known to use a combination of additives (for example, styrene glycol), but the former method is very time-consuming and has little effect, making it impractical, and the latter method has not yet been sufficiently effective. It has not been done. (Object of the Invention) An object of the present invention is to provide a hair dye that has excellent color fastness and can dye hair uniformly in a short time. (Structure of the invention) That is, the present invention has the following general formula (In the formula, R ₁ is a hydrogen atom, methyl group or methoxy group, R ₂ is -CH ₂ OH group, -CH ₂ CH ₂ OH group,

【式】−CH₂CH₂CH₂OH基、[Formula] -CH ₂ CH ₂ CH ₂ OH group,

【formula】

【式】【formula】

【式】 −CH＝CHCH₂OH基または−OCH₂CH₂OH基
を表わす。）で表わされる芳香族アルコールを1.5〜79.2重量
％、キサンタンガムを0.5〜3.5重量％、ヒドロキ
シエチルセルロースを0.1〜3.0重量％、酸性染料
を0.01〜20重量％、水を10.0〜97重量％と酸を含
有しており、そして前記芳香族アルコールと水と
の重量比が３／97〜80／20であり、かつ最終PHが
1.2〜4.0であることを特徴とする染毛剤である。（構成の具体的な説明）本発明で使用される前記一般式で示される芳香
族アルコールとしては、例えばベンジルアルコー
ル、フエネチルアルコール、γ−フエニルプロピ
ルアルコール、桂皮アルコール、アニスアルコー
ル、Ｐ−メチルベンジンアルコール、α−α−ジ
メチルフエネチルアルコール、α−フエニルエタ
ノール、フエノキシエタノールなどが挙げられ
る。前記芳香族アルコールの含有量（配合量）
は、組成物全量に対して1.5〜79.2重量％である。水との重量比は３／97〜80／20であり、好まし
くは５／95〜60／40の範囲内である。前記一般式で示される芳香族アルコールと水と
の重量比を前記の特定量以外で用いると、前記染
毛完了時間は著るしく遅くなり、染色所要時間を
短縮する事ができず、染色堅牢度も著るしく低下
するため、好ましくない。本発明で使用するキサンタンガムは、Ｄ−グル
コース、Ｄ−マンノース、Ｄ−グルクロン酸から
成る多糖類で、その構成比は一般に2.8：２：２
であり、一部アセチル比（約4.7％）されており、
約３％のピルビン酸を含み、分子量は10⁶以上と
いわれている。例えば、米国KELCO社からケル
トロール（KELTROL）という商品名で市販さ
れている。キサンタンガムの含有量（配合量）は組成物全
量に対して0.5〜3.5重量％であり、好ましくは1.0
〜2.0重量％である。本発明に使用するヒドロキシエチルセルロース
は、セルロースに酸化エチレンを反応させて得ら
れる。ヒドロキシエチルセルロースの含有量（配合
量）は、組成物全量に対して、0.1〜3.0重量％で
あり、好ましくは0.5〜1.0重量％である。本発明で使用する酸性染料は、タール色素であ
り、化学構造から大別すると、ニトロ染料、アゾ
染料、ニトロソ染料、トリフエニルメタン染料、
キサンテン染料、キノリン染料、アントラキノン
染料、インジゴイド染料などが挙げられる。酸性染料の含有量（配合量）は、組成物全量に
対して通常0.01〜20重量％である。本発明のPH調整に使用する酸としては、例えば
酒石酸、酢酸、クエン酸、修酸等の有機酸及びリ
ン酸、塩酸等の無機酸などが挙げられるが、特に
これらに限るものではない。酸の含有量（配合
量）は、組成物のPHが1.2〜4.0に調整するにたる
必要量である。本発明に使用する水の含有量は、組成物全量に
対して10.0〜97重量％である。また、本発明の染毛剤は、系の安定性、PH値を
損わない範囲であれば、上記の必須成分の他に防
腐剤、キレート剤、香料などを配合する事も可能
である。（発明の効果）上記の如く、本発明の染毛剤は毛髪を短時間で
かつ均一に染着して、染色所要時間を短縮し、し
かも、染色堅牢度を向上し得るものであり、その
作用効果は著るしく、商品価値は極めて高い。（実施例）以下実施例によつて、本発明を更に詳細に説明
する。尚、実施例に示した部とは重量部を％とは
重量％を意味する。実施例に示した染毛完了時間（染着速度）、染
毛状態、染色堅牢度の試験法は下記の通りであ
る。 (1) 染色完了時間（染着速度）毛束（白色毛髪の束）２ｇを、試料染液（30
℃）の中に浸漬して、該染液を毛髪に含浸した
後、30℃の恆温室内に放置し、所定時間毎に取
出して、水洗し、風乾する。この染毛束につい
て高速色差計（村上色材(株)製）を用いて測色を
行ない、染毛束のＸ、Ｙ、Ｚ値をハンター
（Hunter）のLab表色系へ変換し、染色前の白
毛束との色差を測定し、色差がほぼ一定となつ
た時点（色差の変曲点）を染毛完了時間とし
た。表示した数値の小さい程（染色完了時間
（分）の短かい程）、毛髪の染色速度が早いこと
を意味する。 (2) 染色状態専門検査員３人によつて、染色した毛髪の色
相を肉眼観察すると共に均染状態（むら染めの
有無）および発色状態（正常に発色しているか
どうか）を調べた。 (3) 染色堅牢性（洗髪堅牢性）前記(1)の染色完了時間試験のところで得られ
た染色した毛髪をラウリル硫酸ナトリウムの５
％水溶液（30℃）の中に浸漬して、10回の手も
み洗いを行なつた後、水洗し、風乾した。これ
を１回として、20回繰り返した後、次式にて洗
髪試験後の褪色率を求めた。褪色率（％）＝（１−洗髪試験後の毛
髪と白髪との色差／洗髪試験前の毛髪と白髪との色差）
×100 褪色率20％までを「良好」、21〜50％未満を
「不良」、50％以上を「著るしく不良」として表
わした。実施例１キサンタンガム0.5部、ヒドロキシエチルセル
ロース1.0部、及び水71部を均一に溶解し、この
溶液の中にベンジルアルコール22部、酸性染料の
紫色401号（C.INo.60730）1.0部、クエン酸4.5部を
添加して、均一に攪拌混合して青色系の染毛剤を
調整した。得られた染毛剤のPHは3.3であつた。この染毛剤を使用して染着性、染色堅牢性など
の諸試験について評価した。その結果、染毛完了
時間は５分で、染着速度は極めて早く、毛髪は青
色（正常の色調）に均一に染色されていた。堅牢
性試験後も濃色を呈し、かつ正常の色調を保ち、
染色堅牢性は良好であつた。比較例１ヒドロキシエチルセルロースを使用しない他
は、実施例１と同様に行なつて比較の染毛剤を調
整した。この染毛剤を使用して染着性、染色堅牢性など
の諸試験について評価した。その結果、染毛完了
時間は10分で、染着速度は早く、毛髪は青色（正
常の色調）に均一に染色されていた。堅牢性試験
後も濃色を呈し、かつ正常の色調を保ち、染色堅
牢性は良好であつた。比較例２キサンタンガムを使用しない他は、実施例１と
同様に行なつて、比較の染毛剤を調整した。この染毛剤を使用して前記の諸試験を行なつた
結果、染毛完了時間は30分で染着速度は遅かつ
た。毛髪は略々均一に、かつ青色に染色されてい
たが、堅牢性試験後に褐色を認め、堅牢性は不良
であつた。又、この染毛剤の長期保存品（35℃、６カ月）
は、さらに著るしく染色性、堅牢性が低下した。実施例２ベンジルアルコールと水の総量は一定としたま
ま、比率を第１表の如く、種々変化させる他は実
施例１と同様に行ない、その結果を第１表に示し
た。[Formula] -CH=CHCH ₂ OH group or -OCH ₂ CH ₂ OH group. ) 1.5 to 79.2% by weight of aromatic alcohol represented by and the weight ratio of the aromatic alcohol to water is 3/97 to 80/20, and the final pH is
It is a hair dye characterized by having a color density of 1.2 to 4.0. (Specific description of the structure) Examples of the aromatic alcohol represented by the above general formula used in the present invention include benzyl alcohol, phenethyl alcohol, γ-phenylpropyl alcohol, cinnamon alcohol, anise alcohol, P- Examples include methylbenzine alcohol, α-α-dimethylphenethyl alcohol, α-phenylethanol, and phenoxyethanol. Content (blended amount) of the aromatic alcohol
is 1.5 to 79.2% by weight based on the total amount of the composition. The weight ratio with water is from 3/97 to 80/20, preferably from 5/95 to 60/40. If the weight ratio of aromatic alcohol and water shown by the above general formula is used in a ratio other than the above specified amount, the hair dyeing completion time will be significantly delayed, the dyeing time cannot be shortened, and the dyeing fastness will be reduced. It is not preferable because the temperature also decreases markedly. The xanthan gum used in the present invention is a polysaccharide consisting of D-glucose, D-mannose, and D-glucuronic acid, and the composition ratio thereof is generally 2.8:2:2.
and has a partial acetyl ratio (approximately 4.7%),
It contains approximately 3% pyruvic acid and is said to have a molecular weight of 10 ⁶ or more. For example, it is commercially available from the American company KELCO under the trade name KELTROL. The content (amount) of xanthan gum is 0.5 to 3.5% by weight based on the total amount of the composition, preferably 1.0% by weight.
~2.0% by weight. Hydroxyethyl cellulose used in the present invention is obtained by reacting cellulose with ethylene oxide. The content (amount) of hydroxyethylcellulose is 0.1 to 3.0% by weight, preferably 0.5 to 1.0% by weight, based on the total amount of the composition. The acidic dyes used in the present invention are tar dyes, and can be roughly classified according to their chemical structures as nitro dyes, azo dyes, nitroso dyes, triphenylmethane dyes,
Examples include xanthene dyes, quinoline dyes, anthraquinone dyes, and indigoid dyes. The content (amount) of the acidic dye is usually 0.01 to 20% by weight based on the total amount of the composition. Examples of acids used for pH adjustment in the present invention include, but are not limited to, organic acids such as tartaric acid, acetic acid, citric acid, and oxalic acid, and inorganic acids such as phosphoric acid and hydrochloric acid. The acid content (blended amount) is the amount necessary to adjust the PH of the composition to 1.2 to 4.0. The content of water used in the present invention is 10.0 to 97% by weight based on the total amount of the composition. Furthermore, the hair dye of the present invention may contain preservatives, chelating agents, fragrances, etc. in addition to the above-mentioned essential components, as long as they do not impair system stability or PH value. (Effects of the Invention) As described above, the hair dye of the present invention can dye hair uniformly in a short time, shorten the dyeing time, and improve color fastness. Its effects are remarkable and its commercial value is extremely high. (Example) The present invention will be explained in more detail with reference to Examples below. In addition, parts shown in Examples means parts by weight, and % means weight %. The test methods for hair dyeing completion time (dyeing speed), hair dyeing condition, and color fastness shown in Examples are as follows. (1) Dyeing completion time (dyeing speed) 2g of hair strands (white hair strands) are added to the sample dye solution (30
℃) to impregnate the hair with the dye solution, the hair is left in a heated greenhouse at 30℃, taken out at predetermined intervals, washed with water, and air-dried. Color measurement is performed on this dyed hair bundle using a high-speed color difference meter (manufactured by Murakami Shikizai Co., Ltd.), and the X, Y, and Z values of the dyed hair bundle are converted to Hunter's Lab color system, and the dyeing is performed. The color difference from the previous white hair bundle was measured, and the time when the color difference became almost constant (the inflection point of the color difference) was defined as the hair dyeing completion time. The smaller the displayed value (the shorter the dyeing completion time (minutes)), the faster the hair dyeing speed. (2) Dyeing condition The hue of the dyed hair was observed with the naked eye by three specialized inspectors, and the leveling condition (presence of uneven dyeing) and coloring condition (whether the color was developing normally) were examined. (3) Dyeing fastness (washing fastness) The dyed hair obtained in the dyeing completion time test in (1) above was treated with 5% sodium lauryl sulfate.
% aqueous solution (30°C), washed by hand 10 times, washed with water, and air-dried. After repeating this 20 times, the fading rate after the hair washing test was determined using the following formula. Fading rate (%) = (1-color difference between hair after hair washing test and gray hair/color difference between hair before hair washing test and gray hair)
×100 A fading rate of up to 20% was rated as "good," a rate of 21 to less than 50% was rated as "poor," and a rate of 50% or more was rated as "severely poor." Example 1 0.5 parts of xanthan gum, 1.0 parts of hydroxyethyl cellulose, and 71 parts of water were uniformly dissolved, and in this solution were added 22 parts of benzyl alcohol, 1.0 parts of acid dye Purple No. 401 (C.I No. 60730), and citric acid. 4.5 parts were added and stirred and mixed uniformly to prepare a blue hair dye. The pH of the obtained hair dye was 3.3. Using this hair dye, various tests such as dyeability and color fastness were evaluated. As a result, it took 5 minutes to complete the hair dyeing, the dyeing speed was extremely fast, and the hair was uniformly dyed blue (normal tone). Even after the fastness test, it remains dark and maintains its normal color tone.
The color fastness was good. Comparative Example 1 A comparative hair dye was prepared in the same manner as in Example 1, except that hydroxyethyl cellulose was not used. Using this hair dye, various tests such as dyeability and color fastness were evaluated. As a result, it took 10 minutes to complete the hair dyeing, the dyeing speed was fast, and the hair was uniformly dyed blue (normal tone). Even after the fastness test, it exhibited a deep color and maintained a normal color tone, and the color fastness was good. Comparative Example 2 A comparative hair dye was prepared in the same manner as in Example 1, except that xanthan gum was not used. As a result of conducting the above-mentioned tests using this hair dye, it was found that hair dyeing took 30 minutes and the dyeing speed was slow. Although the hair was dyed almost uniformly and blue, a brown color was observed after the fastness test, and the fastness was poor. Also, long-term storage of this hair dye (35℃, 6 months)
The dyeability and fastness were further significantly reduced. Example 2 The same procedure as in Example 1 was carried out except that the total amount of benzyl alcohol and water was kept constant and the ratio was varied as shown in Table 1. The results are shown in Table 1.

【表】実施例３キサンタンガム0.5部、ヒドロキシエチルセル
ロース0.5部とエデト酸ニナトリウム0.5部及び水
80部を均一に溶解し、この溶液の中にフエネチル
アルコール10.3部、酸性染料の橙色205号（C.INo.
15510）0.9部、酸性染料の紫色401号（C.INo.
60730）0.3部、コハク酸７部を添加して、均一に
攪拌混合して赤褐色系の染毛剤を調製した。得られた染毛剤のPHは3.1であつた。この染毛剤を使用して染着性、染色堅牢性など
の諸試験について評価した。その結果、染毛完了
時間は５分で、染着速度は極めて早く、毛髪は赤
褐色（正常の色調）に均一に染色されていた。堅
牢性試験後も濃色を呈し、かつ正常の色調を保
ち、染色堅牢性は良好であつた。実施例４キサンタンガム1.0部、ヒドロキシエチルセル
ロース0.55部及び水75.2部を均一に溶解し、この
溶液の中にアニスアルコール19.7部、酸性染料の
褐色201号（C.INo.20170）0.4部、酸性染料の黄色
４号（C.INo.19140）0.3部、酸性染料の黒色401号
（C.INo.20470）を0.05部、リン酸2.5部及び香料0.3
部を添加して均一に攪拌混合して本発明の黒色系
の染毛剤を調整した。得られた染毛剤のPHは約
2.1であつた。この染毛剤を使用して染着性、染色堅牢性など
の諸試験について評価した。その結果、染毛完了
時間は５分で、染着速度は極めて早く、毛髪は黒
色（正常の色調）に均一に染色されていた。堅牢
性試験後も濃色を呈し、かつ正常の色調を保ち、
染色堅牢性は良好であつた。比較例３キサンタンガムの代りにカルボキシメチルセル
ロースを使用する他は、実施例１と同様に行なつ
て比較の染毛剤を調整した。この染毛剤を使用して前記の諸試験を行なつた
結果、染毛完了時間は40分で染着速度は遅かつ
た。毛髪は略々均一に、かつ青色に染色されてい
たが、堅牢性試験後の褐色は著るしく、堅牢性は
不良であつた。比較例４ベンジルアルコールの代りにエタノールを使用
する他は、実施例１と同様に行なつて比較の染毛
剤を調整した。この染毛剤を使用して前記の諸試験を行なつた
結果、染毛完了時間は50分で染着速度は遅かつ
た。毛髪は略々均一に、かつ青色に染色されてい
たが、堅牢性試験後の褪色は著るしく、堅牢性は
著るしく不良であつた。比較例５ベンジルアルコールの代りにスチレングリコー
ルを使用する他は、実施例１と同様に行なつて、
比較の染毛剤を調整した。この染毛剤を使用して前記の諸試験を行なつた
結果、染毛完了時間は30分で染着速度は遅かつ
た。毛髪は略々均一に、かつ青色に染色されてい
たが、堅牢性試験後に褪色を認め、堅牢性は不良
であつた。[Table] Example 3 0.5 part of xanthan gum, 0.5 part of hydroxyethyl cellulose, 0.5 part of edetate disodium, and water
In this solution, 10.3 parts of phenethyl alcohol and acid dye Orange No. 205 (C.I No.
15510) 0.9 parts, acid dye purple No. 401 (C.INo.
60730) and 7 parts of succinic acid were added and mixed uniformly with stirring to prepare a reddish-brown hair dye. The pH of the obtained hair dye was 3.1. Using this hair dye, various tests such as dyeability and color fastness were evaluated. As a result, it took 5 minutes to complete the hair dyeing, the dyeing speed was extremely fast, and the hair was uniformly dyed reddish brown (normal tone). Even after the fastness test, it exhibited a deep color and maintained a normal color tone, and the color fastness was good. Example 4 1.0 parts of xanthan gum, 0.55 parts of hydroxyethyl cellulose and 75.2 parts of water were uniformly dissolved, and in this solution were added 19.7 parts of anise alcohol, 0.4 parts of acid dye Brown No. 201 (C.I No. 20170), and 0.4 parts of acid dye Brown 201 (C.I No. 20170). 0.3 parts of Yellow No. 4 (C.I No. 19140), 0.05 parts of acid dye Black No. 401 (C.I No. 20470), 2.5 parts of phosphoric acid, and 0.3 parts of fragrance.
A black hair dye of the present invention was prepared by adding 1.0 parts and stirring and mixing uniformly. The pH of the resulting hair dye is approximately
It was 2.1. Using this hair dye, various tests such as dyeability and color fastness were evaluated. As a result, it took 5 minutes to complete the hair dyeing, the dyeing speed was extremely fast, and the hair was uniformly dyed black (normal tone). Even after the fastness test, it remains dark and maintains its normal color tone.
The color fastness was good. Comparative Example 3 A comparative hair dye was prepared in the same manner as in Example 1, except that carboxymethyl cellulose was used instead of xanthan gum. As a result of conducting the above-mentioned tests using this hair dye, the completion time of hair dyeing was 40 minutes, and the dyeing speed was slow. The hair was dyed almost uniformly and blue, but after the fastness test, the brown color was significant and the fastness was poor. Comparative Example 4 A comparative hair dye was prepared in the same manner as in Example 1, except that ethanol was used instead of benzyl alcohol. As a result of conducting the above-mentioned tests using this hair dye, it was found that the completion time of hair dyeing was 50 minutes and the dyeing speed was slow. Although the hair was dyed almost uniformly and blue, the color faded significantly after the fastness test, and the fastness was extremely poor. Comparative Example 5 The same procedure as Example 1 was carried out except that styrene glycol was used instead of benzyl alcohol.
A comparative hair dye was prepared. As a result of conducting the above-mentioned tests using this hair dye, it was found that hair dyeing took 30 minutes to complete and the dyeing speed was slow. Although the hair was dyed almost uniformly and blue, fading was observed after the fastness test, and the fastness was poor.

Claims

[Claims] 1. The following general formula (In the formula, R ₁ is a hydrogen atom, methyl group or methoxy group, R ₂ is a −CH ₂ OH group, −CH ₂ CH ₂ OH group, [Formula] −CH ₂ CH ₂ CH ₂ OH group, [Formula] [Formula] [Formula] -CH=CH.CH ₂ OH group or -OCH ₂ CH ₂ OH group. 0.1 to 3.0% by weight, 0.01 to 20% by weight of acid dye, and 10.0 to 97% by weight of water, and the weight ratio of the aromatic alcohol to water is 3/97 to 80/20. and the final PH
A hair dye characterized in that the ratio is 1.2 to 4.0.