JP5193670B2 - Method for producing emulsified composition for hair dyeing - Google Patents
Method for producing emulsified composition for hair dyeing Download PDFInfo
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本発明は染毛用乳化組成物の製造方法に関する。更に詳しくは本発明は、低温乳化法によって、製造直後には容器充填に好適な流動性を示し、その後に粘度が上昇して毛髪への施用時には染毛用剤としての適正な粘度を示す染毛用乳化組成物を製造する方法に関する。 The present invention relates to a method for producing an emulsified composition for hair dyeing. In more detail, the present invention shows a fluidity suitable for container filling immediately after production by the low-temperature emulsification method, and after that, the viscosity rises and exhibits an appropriate viscosity as a hair dyeing agent when applied to hair. The present invention relates to a method for producing an emulsified composition for hair.
水相と油相とを界面活性剤等の存在下で混合・撹拌して乳化組成物を製造するに当たり、旧来の標準的な高温乳化法においては、油相を油相成分の融点以上の高い温度、例えば７０〜８０℃に調整すると共に、水相も同様の高い温度に調整する。このような高温乳化法では、水相と油相の両方を加熱するエネルギーが必要であり、しかも混合後は冷却によって過剰の熱エネルギーを除去する必要があるため、エネルギーの効率利用という要求に反する。更に、混合後の冷却時間が長くなるため、乳化組成物の製造効率も悪い。 In producing an emulsified composition by mixing and stirring an aqueous phase and an oil phase in the presence of a surfactant or the like, in the conventional standard high temperature emulsification method, the oil phase is higher than the melting point of the oil phase component. While adjusting to temperature, for example, 70-80 degreeC, an aqueous phase is also adjusted to the same high temperature. In such a high temperature emulsification method, energy for heating both the aqueous phase and the oil phase is required, and after mixing, it is necessary to remove excess thermal energy by cooling, which is against the requirement of efficient use of energy. . Furthermore, since the cooling time after mixing becomes long, the production efficiency of the emulsion composition is also poor.
これに対して、近年提唱されている低温乳化法では、少なくとも水相は加温せずに、あるいは余り加温せずに用いられ、しかもこの水相により乳化と同時に冷却が行われるため、高温乳化法に比較してエネルギー効率及び製造効率が向上するという顕著なメリットがある。更に、一般的に、低温乳化法では調製直後から乳化組成物の粘度変化がなく、ロットごとに安定した品質の乳化組成物が得られることを特徴としている。 On the other hand, in the low-temperature emulsification method proposed recently, at least the aqueous phase is used without being heated, or not much heated, and cooling is performed simultaneously with the emulsification by this aqueous phase. There is a remarkable merit that energy efficiency and production efficiency are improved as compared with the emulsification method. Furthermore, in general, the low temperature emulsification method is characterized in that there is no change in the viscosity of the emulsified composition immediately after the preparation, and an emulsified composition of stable quality can be obtained for each lot.
（第１の課題）
しかし、染毛用乳化組成物の製造及び毛髪への施用に関連して、第１の課題として、乳化組成物の粘度あるいは流動性に関わる次の（ａ）、（ｂ）の性能を両立させる必要がある。しかも、低温乳化法を用いて前記の顕著なメリットを確保したもとで、これらの性能を両立させた乳化組成物を製造することは、容易ではない。
(First issue)
However, in relation to the production of an emulsified composition for hair dyeing and its application to hair, the first problem is to make the following performances (a) and (b) related to the viscosity or fluidity of the emulsified composition compatible. There is a need. In addition, it is not easy to produce an emulsified composition that achieves both of these performances while securing the above-mentioned remarkable merits using a low-temperature emulsification method.
（ａ）の性能として、乳化組成物一般に言えることではあるが、製造後の乳化組成物には十分な流動性（低粘度）が要求される。そうでなければ乳化組成物を容器に充填する際に歩留まりや充填速度の低下を招き、製造効率が悪化する。 As the performance of (a), the emulsion composition in general can be said to have a sufficient fluidity (low viscosity) after the production. Otherwise, when the emulsified composition is filled in the container, the yield and the filling speed are reduced, and the production efficiency is deteriorated.
（ｂ）の性能として、染毛用組成物に特有の事情であるが、染毛用組成物は毛髪に塗布した状態のままで数分ないし数十分間にわたり放置して使用するものであるため、その間に毛髪から垂れ落ちない程度の比較的高い粘度が要求される。即ち、製造後における適正な「後増粘」が要求される。従来、高温乳化法による乳化組成物においては後増粘の指摘が散見されるが、低温乳化法による乳化組成物については、このような報告は見られない。 The performance of (b) is a situation peculiar to the composition for hair dyeing, but the composition for hair dyeing is used by leaving it for several minutes to several tens of minutes as it is applied to the hair. Therefore, a relatively high viscosity that does not sag from the hair during that time is required. That is, an appropriate “post-thickening” after manufacture is required. Conventionally, there are some indications of post-thickening in the emulsion composition by the high temperature emulsification method, but such a report has not been found for the emulsion composition by the low temperature emulsification method.
即ち、染毛剤商品は多種の色調をシリーズにおいて取揃える必要があるため、その商品シリーズにおいて染料類の配合量が色調によって大きく異なる。そしてこれらの染料は通常は水溶性であって、塩の形態であるものも多い。一方、一般的に乳化組成物は塩などの水溶性成分の配合量により粘度が左右され易いという現象が知られている。従って、染料類以外の乳化物組成が同一でも水溶性成分としての染料類の配合量が異なるような、「同種染毛剤の多種色調に係るシリーズ商品」の相互間で粘度のバラツキが生じる。このような粘度のバラツキは特に低粘度領域において顕著に現れる。 That is, since hair dye products need to have various color tones in series, the amount of dyes in the product series varies greatly depending on the color tone. These dyes are usually water-soluble and are often in the form of salts. On the other hand, it is generally known that the viscosity of an emulsion composition is easily influenced by the amount of a water-soluble component such as a salt. Therefore, even when the emulsion composition other than the dyes is the same, there is a variation in viscosity between “series products related to various color tones of the same hair dye” in which the blending amount of the dyes as the water-soluble component is different. Such a viscosity variation is particularly noticeable in a low viscosity region.
この点に関連して、高温乳化法により調製した乳化物では後増粘が起こって高粘度になり、粘度のバラツキは相対的に小さくなるため、上記のような粘度のバラツキは余り問題にはならない。しかし従来の低温乳化法では後増粘が起こらないので、例えば文献３に示すような低温乳化法を染毛剤に適用すると、同種染毛剤の多種色調に係るシリーズ商品が色調により粘度の顕著なバラツキを伴う結果となり、製品の品質管理上に問題がある。 In this regard, in the emulsion prepared by the high temperature emulsification method, post-thickening occurs and the viscosity becomes high, and the viscosity variation becomes relatively small. Therefore, the above viscosity variation is not a problem. Don't be. However, in the conventional low-temperature emulsification method, post-thickening does not occur. For example, when the low-temperature emulsification method as shown in Document 3 is applied to a hair dye, the series products related to various color tones of the same hair dye have a remarkable viscosity due to the color tone. As a result, there is a problem in product quality control.
上記の「製品の品質管理上の問題」として、次のような具体例を挙げることができる。即ち、業務上多種色調の染毛剤を使い分ける美容師にとって、同種染毛剤の色調毎に粘度が異なると、客が求める色調によって塗布液の粘度が異なることになり、毎回塗布する際に塗布方法を注意しなければならず、使いづらい染毛剤であるとの印象を与えかねない。また、染毛用乳化組成物はチューブに充填されていることが多く、例えば色調により粘度が低いものがあると、その色調だけ流動性が高くなってしまうので、思いがけず多量に出しすぎてしまうことも想定される。 The following specific examples can be given as the above-mentioned “problems in product quality control”. That is, for hairdressers who use various color tones for business purposes, if the viscosity differs for each color tone of the same type of hair dye, the viscosity of the coating solution will differ depending on the color tone requested by the customer. Care must be taken with the method, which can give the impression that it is a hair dye that is difficult to use. Further, the emulsified composition for hair dyeing is often filled in a tube. For example, if there is a low viscosity depending on the color tone, the fluidity will be increased by that color tone, so it will be unexpectedly produced in a large amount. It is also assumed.
この第２の課題は、例えば染料以外の乳化物組成を適宜変更すれば解決可能である。しかし、場合によっては何十種類もの色調を取り揃えるケースもあり、そのような場合に、それぞれの色調ごとに適切な乳化物組成を検討するのは現実的な解決策ではない。 This second problem can be solved, for example, by appropriately changing the emulsion composition other than the dye. However, in some cases, there are cases where dozens of colors are prepared, and in such a case, it is not a practical solution to examine an appropriate emulsion composition for each color.
そこで本発明は、上記の第１の課題及び第２の課題を解決できる染毛用乳化組成物の製造方法を提供することを目的とする。本願発明者は、低温乳化法に供する染毛用乳化組成物に特定の成分を配合した場合に、恐らくはその成分と染毛用乳化組成物の必須成分である染料との経時的な相互作用によって、第１の課題及び第２の課題を解決できる適正な後増粘を発現させ得ることを見出して、本発明を完成した。 Then, an object of this invention is to provide the manufacturing method of the emulsion composition for hair dye which can solve said 1st subject and 2nd subject. The inventor of the present application, when a specific component is blended in the emulsified composition for hair dyeing to be subjected to the low temperature emulsification method, probably due to the interaction over time with the dye that is an essential component of the emulsified composition for hair dyeing. The present invention was completed by finding that an appropriate post-thickening capable of solving the first problem and the second problem can be expressed.
（第１発明）
上記課題を解決するための本願第１発明の構成は、（１）下記の（Ａ）相と（Ｂ）相とを、（Ｂ）相についてはこれに含有される直鎖状高級アルコールのうち最も融点が高い直鎖状高級アルコールの融点以上の温度に調整し、（Ａ）相については（Ｂ）相の温度よりも低い温度に調整したもとで、混合する工程を含み、
（２）上記の混合工程において、下記の（Ｄ）成分を混合前の（Ａ）相、混合前の（Ｂ）相、（Ａ）相と（Ｂ）相との混合相のうちの少なくとも１相に対して添加する、染毛用乳化組成物の製造方法である。
(First invention)
The configuration of the first invention of the present application for solving the above-mentioned problems is as follows: (1) The following (A) phase and (B) phase, and (B) phase among linear higher alcohols contained therein Adjusting the temperature to be equal to or higher than the melting point of the linear higher alcohol having the highest melting point, and for the phase (A), including a step of mixing under a temperature lower than the temperature of the phase (B),
(2) In the above mixing step, at least one of the following components (D) is mixed in the (A) phase before mixing, the (B) phase before mixing, and the mixed phase of the (A) phase and the (B) phase. It is a manufacturing method of the emulsified composition for hair dyes added with respect to a phase.
（Ａ）相：水相。 (A) Phase: Aqueous phase.
（Ｂ）相:炭素数が１６〜２２の範囲内である直鎖状高級アルコールの１種以上を含有すると共に、下記の一般式（Ｉ）で表される（Ｃ）成分を、最終的に調製された乳化組成物中における（Ｃ）成分の含有量（ｃ質量％）が（Ｄ）成分の含有量（ｄ質量％）に対してｄ／ｃ＝０．１〜５０の範囲内となるように、含有する。 (B) Phase: containing at least one linear higher alcohol having a carbon number in the range of 16 to 22, and finally, the component (C) represented by the following general formula (I): The content (c mass%) of the component (C) in the prepared emulsion composition is in the range of d / c = 0.1-50 with respect to the content (d mass%) of the component (D). So as to contain.
Ｒ−（ＯＣＨ２ＣＨ２）ｎ−ＯＨ・・・（Ｉ）
（この一般式において、Ｒは水素原子又は炭化水素を表す。但し、この炭化水素は炭素数が１〜２２の範囲内であり、飽和又は不飽和であり、直鎖状又は分岐鎖状であり、炭化水素を構成する炭素に結合した水素原子の一部が水酸基に置換されていても良い。又、ｎは２０〜２００の範囲内の整数である。）
（Ｃ）成分としてはポリエチレングリコール、ポリオキシエチレンアルキルエーテルが挙げられ、具体的にはポリエチレングリコール１０００（ＩＮＣＩ名ＰＥＧ−２０、上記の一般式におけるＲが水素原子で、ｎが２０である）、ポリエチレングリコール４０００（ＩＮＣＩ名ＰＥＧ−９０、上記の一般式におけるＲが水素原子で、ｎが９０である）、セテス−２０（上記の一般式におけるＲがＣ１６Ｈ３１で、ｎが２０である）、ベヘネス−５０（上記の一般式におけるＲがＣ２２Ｈ４５で、ｎが５０である）等が例示される。
（Ｄ）成分：酸化染料、酸性染料、塩基性染料から選ばれる少なくとも１種の染料。
R— (OCH 2 CH 2 ) n —OH (I)
(In this general formula, R represents a hydrogen atom or a hydrocarbon. However, this hydrocarbon has a carbon number in the range of 1 to 22, is saturated or unsaturated, and is linear or branched. The hydrogen atom bonded to the carbon constituting the hydrocarbon may be partially substituted with a hydroxyl group, and n is an integer in the range of 20 to 200.)
Examples of the component (C) include polyethylene glycol and polyoxyethylene alkyl ether. Specifically, polyethylene glycol 1000 (INCI name PEG-20, R in the above general formula is a hydrogen atom, and n is 20), Polyethylene glycol 4000 (INCI name PEG-90, R in the above general formula is a hydrogen atom and n is 90), ceteth-20 (R in the above general formula is C 16 H 31 and n is 20) ), Behenez-50 (R in the above general formula is C 22 H 45 , and n is 50).
Component (D): at least one dye selected from oxidation dyes, acid dyes, and basic dyes.
上記の第１発明において、（Ｃ）成分の一般式（Ｉ）中の「Ｒ」に関して、「炭化水素を構成する炭素に結合した水素原子の一部が水酸基に置換されていても良い」とは、「該当する水素原子の１個以上が水酸基に置換されていても良いが、該当する水素原子の全部が水酸基に置換されている場合を含まない」ことをいう。 In the first invention, with respect to “R” in the general formula (I) of the component (C), “a part of hydrogen atoms bonded to carbon constituting the hydrocarbon may be substituted with a hydroxyl group”. Means that “one or more of the relevant hydrogen atoms may be substituted with hydroxyl groups, but not all of the relevant hydrogen atoms are substituted with hydroxyl groups”.
第１発明によれば、（Ｂ）相はある程度高い温度に調整されるが（Ａ）相はそれよりも低い温度に調整して（Ｂ）相と混合されるので、エネルギー効率及び製造効率の向上等という低温乳化法の利点が得られる。（Ａ）相の温度が（Ｂ）相の温度より低くない場合に低温乳化法の利点を享受できないことは明確であるとしても、低温乳化法の利点が十分に得られたか否かは発明を実施する者の実施目的や価値判断に関わる問題であるため、その判定基準を一律に述べることができない。そのため、（Ｂ）相の温度に対して（Ａ）相の温度がどの程度低くあるべきかという基準を一律に規定することは困難である。しかし、一般的に言えば、（Ａ）相の温度が（Ｂ）相の温度よりも１５℃以上低く、特に２０℃以上低いことが好ましい。 According to the first invention, the phase (B) is adjusted to a somewhat high temperature, but the phase (A) is adjusted to a lower temperature and mixed with the phase (B). Advantages of the low temperature emulsification method such as improvement can be obtained. Even if it is clear that the advantages of the low temperature emulsification method cannot be enjoyed when the temperature of the phase (A) is not lower than the temperature of the phase (B), whether or not the advantages of the low temperature emulsification method are sufficiently obtained is an invention. Since it is a problem related to the implementation purpose and value judgment of the practitioner, the judgment criteria cannot be described uniformly. Therefore, it is difficult to uniformly define the standard of how much the temperature of the (A) phase should be lower than the temperature of the (B) phase. However, generally speaking, it is preferable that the temperature of the (A) phase is 15 ° C. or more lower than the temperature of the (B) phase, particularly 20 ° C. or less.
第１発明においては、上記した公知技術としての低温乳化法のメリットが確保されたもとで、以下の特徴的な効果が得られる。 In the first invention, the following characteristic effects can be obtained while the merit of the low-temperature emulsification method as the above-mentioned known technique is ensured.
第１発明によって製造された染毛用乳化組成物は、製造直後には容器充填に好適な流動性を示すので、乳化組成物の容器充填を高い歩留まりと充填速度を以て行うことができ、良好な製造効率を確保できる。このような効果を確保するための流動性（低粘度）の程度は、具体的には容器の形状及び容量や充填方法、充填速度等によって異なるため、数値的に一律に規定することは困難である。しかし、あえて一つの基準を示せば、染毛用乳化組成物は、その製造直後から２４時間〜７２時間経過あたりまでは、５，０００〜２５，０００ｍＰa・ｓ程度の低粘度を示すことが好ましい。なお、本明細書中における粘度値は、特に断りのない限り、東機産業株式会社製ＴＶ−１０Ｍ型粘度計、４号ロータ、２５℃、１２ｒｐｍ、１ｍｉｎによって測定される粘度を示す。 The emulsified composition for hair dye produced according to the first invention exhibits fluidity suitable for container filling immediately after production, so that the container filling of the emulsified composition can be performed with a high yield and filling speed, which is good. Manufacturing efficiency can be secured. Since the degree of fluidity (low viscosity) for ensuring such effects varies depending on the shape and capacity of the container, the filling method, the filling speed, etc., it is difficult to define numerically uniformly. is there. However, if one standard is shown, it is preferable that the emulsified composition for hair dyeing exhibits a low viscosity of about 5,000 to 25,000 mPa · s from the time immediately after its production until around 24 to 72 hours. . In addition, unless otherwise indicated, the viscosity value in this specification shows the viscosity measured by the Toki Sangyo Co., Ltd. TV-10M type | mold viscosity meter, 4 rotor, 25 degreeC, 12 rpm, and 1 min.
更に、この染毛用乳化組成物は、その後に粘度が上昇して毛髪への施用時には染毛用組成物としての適正な粘度を示す。そのため、毛髪に塗布した状態のままで数分ないし数十分間にわたり放置して使用しても毛髪から垂れ落ちない。即ち、適正な程度の後増粘を発現することにより前記した第１の課題を解決する。更に、このような後増粘による高粘度化により、同種染毛剤の多種色調に係るシリーズ商品間の粘度のバラツキが事実上解消され、前記した第２の課題も解決する。 Further, this emulsified composition for hair dyeing increases in viscosity thereafter, and exhibits an appropriate viscosity as a hair dyeing composition when applied to hair. Therefore, even if it is used for several minutes to several tens of minutes while being applied to the hair, it does not sag from the hair. That is, the first problem described above is solved by developing an appropriate degree of post-thickening. Furthermore, the increase in viscosity by such post-thickening substantially eliminates the variation in viscosity between series products related to the various colors of the same hair dye, and also solves the second problem described above.
以上のような後増粘の効果を確保するための粘度上昇の程度は、具体的には配合される成分によって異なるため、数値的に一律に規定することは困難である。しかし、あえて一つの基準を示せば、染毛用乳化組成物は、製造後７２時間を経過した辺りから粘度が上昇し、製造後１０日〜１４日を経過した頃以後は、２５，０００〜７５，０００ｍＰa・ｓ程度の高粘度を示すことが好ましい。なお、５０，０００ｍＰa・ｓを越える粘度については、前記した粘度測定条件において、１２ｒｐｍを６ｒｐｍに変更して測定した値を示す。 Since the degree of increase in viscosity for ensuring the effect of post-thickening as described above varies specifically depending on the components to be blended, it is difficult to define numerically uniformly. However, if one standard is shown, the viscosity of the emulsified composition for hair dye increases from about 72 hours after the production, and after about 10 to 14 days after the production, from 25,000 to It preferably exhibits a high viscosity of about 75,000 mPa · s. In addition, about the viscosity over 50,000 mPa * s, the value measured by changing 12 rpm into 6 rpm on the above-mentioned viscosity measurement conditions is shown.
第１発明によって製造された染毛用乳化組成物が、低温乳化法であるにも関わらず上記のような好適な範囲における経時的粘度変化を示す理由は、未だ十分には解明していない。しかし、（Ａ）相と（Ｂ）相との混合後、（Ｄ）成分である染料と強く水和していた水和水が徐々に非イオン性の化合物である（Ｃ）成分及び直鎖状高級アルコールと親和してゲルを形成していくことにより、１０日〜１４日経過頃までに粘度が適正範囲まで上昇するものと推定している。 The reason why the emulsified composition for hair dye produced according to the first invention shows a change in viscosity over time in the above-mentioned preferred range in spite of the low-temperature emulsification method has not been fully elucidated. However, after mixing the (A) phase and the (B) phase, the (D) component dye and the hydrated water that has been strongly hydrated are gradually nonionic compounds (C) component and linear It is presumed that the viscosity rises to an appropriate range by 10-14 days by forming a gel with affinity to the higher alcohol.
このようなゲル形成による経時的な粘度の上昇が良好に発現するためには、最終的に調製された乳化組成物中における（Ｃ）成分の含有量（ｃ質量％）と（Ｄ）成分の含有量（ｄ質量％）との比率ｄ／ｃが、ｄ／ｃ＝０．１〜５０である必要がある。ｄ／ｃが０．１未満である場合には、（Ｃ）成分の相対的な過剰のため、染毛用乳化組成物の毛髪施用時における粘度のバラツキが生じないものの、経時的な粘度上昇のレベルが高くなりすぎるため、充填時や使用時に支障がある。又、ｄ／ｃが５０を超える場合には、（Ｃ）成分の相対的な不足のため、経時的な粘度上昇のレベルが不十分となり、かつ染毛用乳化組成物の毛髪施用時における粘度のバラツキが顕著となる。ｄ／ｃは、より好ましくは０．１〜１０の範囲内である。 In order for the increase in viscosity over time due to such gel formation to be expressed well, the content (c% by mass) of component (C) and the component (D) in the finally prepared emulsion composition Ratio d / c with content (d mass%) needs to be d / c = 0.1-50. When d / c is less than 0.1, due to the relative excess of component (C), there is no variation in viscosity when the hair emulsified composition is applied to the hair, but the viscosity increases with time. Since the level of this becomes too high, there is a problem during filling and use. On the other hand, when d / c exceeds 50, the level of increase in viscosity over time is insufficient due to the relative shortage of component (C), and the viscosity of the emulsified composition for hair dyeing when applied to the hair The variation becomes remarkable. d / c is more preferably within a range of 0.1 to 10.
なお、（Ｂ）相の直鎖状高級アルコールの炭素数が１６〜２２の範囲内を外れる場合には、前記ゲル構造を経時的にうまく形成しないという点から、乳化物自体を得ることが困難である。一方、（Ｃ）成分に代えてエステル構造やポリオキシプロピレン構造を有する界面活性剤を用いた場合、前記したゲル構造を適度に生じないためと推定されるが、染毛用乳化組成物の経時的な粘度変化のパターンが好適な時期を外れ、あるいは変化する粘度の絶対値が容器充填／毛髪塗布時の好適範囲を外れる。 In addition, when carbon number of the linear higher alcohol of (B) phase remove | deviates from the inside of the range of 16-22, it is difficult to obtain the emulsion itself from the point that the said gel structure does not form well with time. It is. On the other hand, when a surfactant having an ester structure or a polyoxypropylene structure is used in place of the component (C), it is presumed that the gel structure described above is not appropriately produced. The typical viscosity change pattern deviates from the preferred time, or the absolute value of the changing viscosity deviates from the preferred range during container filling / hair application.
更に、（Ｃ）成分を表す前記の一般式（Ｉ）において、「Ｒ」の内容や「ｎ」の数値が一般式（Ｉ）で規定する範囲を外れる場合にも、前記ゲル構造を経時的にうまく形成しないという点から、望ましい経時的粘度変化を示さない。 Furthermore, in the general formula (I) representing the component (C), the content of “R” or the numerical value of “n” is not within the range defined by the general formula (I). Does not show the desired change in viscosity over time.
（第２発明）
上記課題を解決するための本願第２発明の構成は、前記第１発明に係る（Ｄ）成分が酸化染料である、染毛用乳化組成物の製造方法である。
(Second invention)
The configuration of the second invention of the present application for solving the above problem is a method for producing an emulsified composition for hair dyeing, wherein the component (D) according to the first invention is an oxidation dye.
本発明に係る染毛用乳化組成物の製造方法は、第２発明のように、酸化染料を含む酸化染毛用組成物の製造に対して、特に好ましく適用される。 The method for producing an emulsified composition for hair dyeing according to the present invention is particularly preferably applied to the production of a composition for hair dyeing containing an oxidative dye as in the second invention.
なお、染料が酸化染料である場合は、通常は本発明の染毛用乳化組成物が第１剤とされ、この第１剤が使用時において一定の組成の第２剤と所定の比率で混合調製される。しかし、第１剤が第１発明で述べたような十分な高粘度領域に増粘しているため、第２剤との混合調製後も粘度の低下は実用上無視できる程度であり、毛髪への施用のための適正な粘度範囲を外れない。 When the dye is an oxidative dye, the emulsified composition for hair dyeing of the present invention is usually the first agent, and this first agent is mixed at a predetermined ratio with the second agent having a constant composition at the time of use. Prepared. However, since the first agent is thickened in a sufficiently high viscosity region as described in the first invention, the decrease in viscosity is negligible even after mixing and preparation with the second agent. Does not deviate from the proper viscosity range for application.
本発明によって、適正な後増粘により容器充填時と毛髪塗布時にそれぞれ好適な範囲の粘度を示す染毛用乳化組成物が得られ、かつ、染料類の配合量が異なるシリーズ商品を構成する染毛用乳化組成物間での粘度のバラツキを防止することができる。 According to the present invention, it is possible to obtain an emulsified composition for hair dyeing that exhibits a suitable range of viscosities at the time of filling the container and applying the hair by appropriate post-thickening, and that constitutes a series product having different amounts of dyes. Variations in viscosity between the emulsified compositions for hair can be prevented.
次に、本発明を実施するための形態を、その最良の形態を含めて説明する。 Next, modes for carrying out the present invention will be described including the best mode.
〔染毛用乳化組成物の製造方法〕
本発明に係る染毛用乳化組成物の製造方法においては、（１）下記の（Ａ）相と（Ｂ）相とを、（Ｂ）相についてはこれに含有される直鎖状高級アルコールのうち最も融点が高い直鎖状高級アルコールの融点以上の温度に調整し、（Ａ）相については（Ｂ）相の温度よりも低い温度、好ましくは１５℃以上低い温度、より好ましくは２０℃以上低い温度に調整したもとで、混合する工程を含む。従って、本発明に係る染毛用乳化組成物の製造方法は低温乳化法の一種である。
[Method for producing emulsified composition for hair dyeing]
In the method for producing an emulsified composition for hair dyeing according to the present invention, (1) the following (A) phase and (B) phase, and (B) phase of the linear higher alcohol contained therein Of these, the temperature is adjusted to a temperature equal to or higher than the melting point of the linear higher alcohol having the highest melting point, and the temperature of the (A) phase is lower than the temperature of the (B) phase, preferably 15 ° C or more, more preferably 20 ° C or more. The process of mixing is performed while adjusting to a low temperature. Therefore, the method for producing an emulsified composition for hair dyeing according to the present invention is a kind of low temperature emulsification method.
（Ａ）相：水相。 (A) Phase: Aqueous phase.
（Ｂ）相:炭素数が１６〜２２の範囲内である直鎖状高級アルコールの１種以上を含有すると共に、下記の一般式（Ｉ）で表される（Ｃ）成分を、最終的に調製された乳化組成物中における（Ｃ）成分の含有量（ｃ質量％）が（Ｄ）成分の含有量（ｄ質量％）に対してｄ／ｃ＝０．１〜５０の範囲内となるように、含有する。 (B) Phase: containing at least one linear higher alcohol having a carbon number in the range of 16 to 22, and finally, the component (C) represented by the following general formula (I): The content (c mass%) of the component (C) in the prepared emulsion composition is in the range of d / c = 0.1-50 with respect to the content (d mass%) of the component (D). So as to contain.
Ｒ−（ＯＣＨ２ＣＨ２）ｎ−ＯＨ・・・（Ｉ）
（この一般式において、Ｒは水素原子又は炭化水素を表す。但し、この炭化水素は炭素数が１〜２２の範囲内であり、飽和又は不飽和であり、直鎖状又は分岐鎖状であり、炭化水素を構成する炭素に結合した水素原子の一部が水酸基に置換されていても良い。又、ｎは２０〜２００の範囲内の整数である。）
又、本発明に係る染毛用乳化組成物の製造方法においては、以上の混合工程において、（Ｄ）成分：酸化染料、酸性染料、塩基性染料から選ばれる少なくとも１種の染料を、混合前の（Ａ）相、混合前の（Ｂ）相、あるいは、（Ａ）相と（Ｂ）相との混合相のうちの少なくとも１相に対して添加する。
R— (OCH 2 CH 2 ) n —OH (I)
(In this general formula, R represents a hydrogen atom or a hydrocarbon. However, this hydrocarbon has a carbon number in the range of 1 to 22, is saturated or unsaturated, and is linear or branched. The hydrogen atom bonded to the carbon constituting the hydrocarbon may be partially substituted with a hydroxyl group, and n is an integer in the range of 20 to 200.)
In the method for producing an emulsified composition for hair dyeing according to the present invention, in the above mixing step, at least one dye selected from component (D): oxidation dye, acid dye, basic dye is added before mixing. The (A) phase, the (B) phase before mixing, or the mixed phase of the (A) phase and the (B) phase are added to at least one phase.
（Ａ）相と（Ｂ）相との混合・乳化の方法及び使用する装置は特段に限定されない。即ち、低温乳化のための温度調整が可能なように構成された一般的な乳化装置を任意に選択して使用すれば良い。混合・撹拌の方式としても、例えば、パルセーター攪拌、プロペラ攪拌、ホモミキサー攪拌、ラインミキサー攪拌、コンビミキサー攪拌等の任意の方法で行うことができる。高い攪拌強度を得たい場合には、ホモミキサー攪拌、ラインミキサー攪拌が望ましい。また、国際公開２００１−５６６８７号パンフレットに開示されたような低温乳化により適した構造を有する乳化装置を選択することも望ましい。 The method of mixing and emulsifying the (A) phase and the (B) phase and the apparatus to be used are not particularly limited. That is, a general emulsification apparatus configured to be capable of adjusting the temperature for low-temperature emulsification may be arbitrarily selected and used. As a mixing / stirring method, for example, pulsator stirring, propeller stirring, homomixer stirring, line mixer stirring, combination mixer stirring and the like can be performed. In order to obtain high stirring strength, homomixer stirring and line mixer stirring are desirable. It is also desirable to select an emulsifying device having a structure suitable for low-temperature emulsification as disclosed in WO 2001-56687 pamphlet.
乳化装置の具体的な使用形態として、まず（Ａ）相と（Ｂ）相とのいずれか一方の相を撹拌槽に収容しておき、これに対して他一方の相を投入して混合・撹拌するという形態が多い。後述の実施例、比較例においては、撹拌槽に収容した（Ｂ）相に対して（Ａ）相を投入して混合・撹拌している。しかしその逆に、撹拌槽に収容した（Ａ）相に対して（Ｂ）相を投入して混合・撹拌することも、もちろん可能である。 As a specific form of use of the emulsifying device, first, either one of the (A) phase and the (B) phase is accommodated in a stirring tank, and the other phase is added to this for mixing and mixing. There are many forms of stirring. In the examples and comparative examples described later, the (A) phase is added to the (B) phase accommodated in the stirring vessel and mixed and stirred. However, on the contrary, it is of course possible to add the (B) phase to the (A) phase accommodated in the stirring tank and mix and stir.
混合・乳化の処理条件、即ち撹拌の剪断速度、処理時間等も特段に限定されず、必要に応じて適宜に設計すれば良い。上記のように（Ａ）相と（Ｂ）相との混合相に（Ｃ）成分や（Ｄ）成分を添加する場合には、（Ｃ）成分や（Ｄ）成分の添加後にも十分に混合・乳化処理を行うことが好ましい。 The processing conditions for mixing / emulsification, that is, the shear rate of stirring, the processing time, and the like are not particularly limited, and may be appropriately designed as necessary. When the (C) component and (D) component are added to the mixed phase of the (A) phase and the (B) phase as described above, sufficient mixing is performed even after the addition of the (C) component and (D) component. -It is preferable to perform an emulsification treatment.
〔（Ａ）相〕
（Ａ）相は、水を媒体とするいわゆる水相であり、水のみからなることもあり得るが、（Ｄ）成分を含めて任意の成分が分散又は溶解していても良い。
[(A) phase]
The (A) phase is a so-called aqueous phase using water as a medium, and may consist of water alone, but any component including the component (D) may be dispersed or dissolved.
（Ａ）相には、例えば、任意の水溶性成分やポリマー等の水膨潤性分散物、Ｏ／Ｗ型エマルジョン等の水分散性成分等を混合することができる。これらの成分は、調整温度において、（Ａ）相中で溶解又は均一に分散していることが好ましい。 In the (A) phase, for example, an arbitrary water-soluble component, a water-swellable dispersion such as a polymer, a water-dispersible component such as an O / W emulsion can be mixed. These components are preferably dissolved or uniformly dispersed in the phase (A) at the adjusted temperature.
〔（Ｂ）相〕
（Ｂ）相は、炭素数が１６〜２２の範囲内である直鎖状高級アルコールの１種以上と、前記一般式（Ｉ）で表される（Ｃ）成分とを少なくとも含有する、油相である。
[(B) phase]
The (B) phase is an oil phase containing at least one kind of linear higher alcohol having 16 to 22 carbon atoms and the component (C) represented by the general formula (I). It is.
直鎖状高級アルコールには、炭素鎖が飽和のものも不飽和のものも含まれる。炭素数が１６〜２２の範囲内である直鎖状高級アルコールとしては、セタノール、ステアリルアルコール、セトステアリルアルコール、アラキルアルコール、ベヘニルアルコール、オレイルアルコール、リノレイルアルコール等を例示することができ、特にセタノール、ステアリルアルコール、ベヘニルアルコール、セトステアリルアルコール等が好ましい。これらの高級アルコールは、１種又は２種以上を組み合わせて用いることができる。 Linear higher alcohols include those with saturated and unsaturated carbon chains. Examples of linear higher alcohols having 16 to 22 carbon atoms include cetanol, stearyl alcohol, cetostearyl alcohol, aralkyl alcohol, behenyl alcohol, oleyl alcohol, linoleyl alcohol and the like, and in particular cetanol. Stearyl alcohol, behenyl alcohol, cetostearyl alcohol and the like are preferable. These higher alcohols can be used alone or in combination of two or more.
（Ｂ）相における１種または２種以上の直鎖状高級アルコールの合計含有量は限定されないが、最終的に調製された染毛用乳化組成物中の２〜２０質量％となるように、特に好ましくは５〜１５質量％となるように配合される。直鎖状高級アルコールの合計含有量が上記の範囲を下回ると乳化物の粘度が十分確保されないという面で不満足になる恐れがあり、逆に、上記の範囲を上回ると乳化物の粘度が高くなりすぎ、充填時や使用時に支障があるという面で不満足になる恐れがある。 (B) The total content of one or more linear higher alcohols in the phase is not limited, but 2 to 20% by mass in the finally prepared emulsion composition for hair dyeing, Especially preferably, it mix | blends so that it may become 5-15 mass%. If the total content of the linear higher alcohol is below the above range, the emulsion may not be sufficiently secured, and if it exceeds the above range, the viscosity of the emulsion increases. It may be unsatisfactory in terms of problems during filling and use.
（Ｃ）成分は前記一般式（Ｉ）で表される成分であり、一般式中の「Ｒ」が炭化水素である場合の炭素数は１２〜２２の範囲内、より好ましくは１６〜２２の範囲内であり、一般式中の整数「ｎ」の数値は２０〜２００の範囲内、より好ましくは２０〜１５０の範囲内である。 The component (C) is a component represented by the general formula (I), and the carbon number in the case where “R” in the general formula is a hydrocarbon is in the range of 12-22, more preferably 16-22. Within the range, the numerical value of the integer “n” in the general formula is in the range of 20 to 200, more preferably in the range of 20 to 150.
前記した理由から、（Ｃ）成分の含有量（ｃ質量％）は、（Ａ）相と（Ｂ）相との混合時において、染料の含有量（ｄ質量％）に対してｄ／ｃ＝０．１〜５０の範囲内となるように調整される。更に、（Ｃ）成分の含有量（ｃ質量％）の絶対値は必ずしも限定されないが、一般的には、最終的に調製された乳化組成物中における１〜１０質量％程度であることが好ましい。 For the reason described above, the content (c mass%) of the component (C) is d / c = d with respect to the dye content (d mass%) at the time of mixing the (A) phase and the (B) phase. It adjusts so that it may become in the range of 0.1-50. Furthermore, the absolute value of the content of component (C) (c mass%) is not necessarily limited, but generally it is preferably about 1 to 10 mass% in the finally prepared emulsion composition. .
（Ｂ）相には、上記の直鎖状高級アルコール、（Ｃ）成分の他に、任意の油性成分や多価アルコール、界面活性剤などを混合することができる。これらの成分は、（Ｂ）相の混合前調整温度において融解または他の成分に溶解することが好ましく、又、調整温度において直鎖状高級アルコールと相溶性を有することが好ましい。 In the (B) phase, in addition to the above linear higher alcohol and the component (C), an arbitrary oil component, polyhydric alcohol, surfactant and the like can be mixed. These components are preferably melted or dissolved in other components at the pre-mixing adjustment temperature of the phase (B), and preferably compatible with the linear higher alcohol at the adjustment temperature.
〔（Ａ）相、（Ｂ）相におけるその他の成分〕
（Ａ）相及び／又は（Ｂ）相には、上記した各成分の他にも、必要に応じて、かつ、本発明の効果を損なわない範囲で、染毛用乳化組成物に通常使用されている任意の成分を含有させることが出来る。これらの成分としては、ポリオキシエチレンラウリルエーテル硫酸ナトリウムなどのアニオン界面活性剤、塩化ベヘニルトリメチルアンモニウムなどのカチオン界面活性剤、両性界面活性剤、セテス−１０（ポリオキシエチレン（１０）セチルエーテル）、セテス−１５（ポリオキシエチレン（１５）セチルエーテル）、ステアレス−５（ポリオキシエチレン（５）ステアリルエーテル）、ポリオキシエチレン硬化ひまし油等の（Ｃ）成分に該当しない非イオン界面活性剤、（Ａ）成分及び（Ｃ）成分以外の油分、シリコーン類、プロピレングリコールなどの多価アルコール、紫外線吸収剤、防腐剤、保湿剤、ポリマー類、アミノ酸誘導体、糖誘導体、香料、水、低級アルコール、ベンジルアルコールなどの芳香族アルコール、増粘剤、色剤、金属イオン封鎖剤、アンモニア水やモノエタノールアミン、乳酸などのｐＨ調整剤、亜硫酸ナトリウムやＬ−アスコルビン酸などの酸化防止剤、薬剤等が挙げられ、これら成分は本発明の効果を損なわない限り、（Ａ）相と（Ｂ）相との混合相に添加されることを妨げない。
[Other components in phase (A) and phase (B)]
In addition to the above-described components, the (A) phase and / or the (B) phase are usually used in an emulsion composition for hair dyeing as necessary and within a range not impairing the effects of the present invention. Any component can be included. These components include anionic surfactants such as sodium polyoxyethylene lauryl ether sulfate, cationic surfactants such as behenyltrimethylammonium chloride, amphoteric surfactants, ceteth-10 (polyoxyethylene (10) cetyl ether), Nonionic surfactants that do not fall under component (C) such as ceteth-15 (polyoxyethylene (15) cetyl ether), steareth-5 (polyoxyethylene (5) stearyl ether), polyoxyethylene hydrogenated castor oil, (A ) Component and oils other than component (C), silicones, polyhydric alcohols such as propylene glycol, ultraviolet absorbers, preservatives, humectants, polymers, amino acid derivatives, sugar derivatives, fragrances, water, lower alcohols, benzyl alcohol Aromatic alcohol, thickener, colorant, etc. Examples include sequestering agents, pH adjusters such as ammonia water, monoethanolamine, and lactic acid, antioxidants such as sodium sulfite and L-ascorbic acid, drugs, and the like, unless these components impair the effects of the present invention. Addition to the mixed phase of (A) phase and (B) phase is not prevented.
〔（Ｄ）成分〕
（Ｄ）成分たる染料は、混合前の（Ａ）相、混合前の（Ｂ）相、又は（Ａ）相と（Ｂ）相との混合相のうちの少なくとも１相に添加される成分であるが、あえて言えば、染料の耐熱性等の点から、（Ａ）相、あるいは（Ａ）相と（Ｂ）相との混合相に、より好ましく添加される。
[Component (D)]
The (D) component dye is a component added to at least one of the (A) phase before mixing, the (B) phase before mixing, or the mixed phase of the (A) phase and (B) phase. In other words, it is more preferably added to the (A) phase or the mixed phase of the (A) phase and the (B) phase from the viewpoint of the heat resistance of the dye.
染料は酸化染料、酸性染料、塩基性染料から選ばれるが、通常、それらの内のいずれか一つのカテゴリーから選ばれる１種又は２種以上の染料である。 The dye is selected from an oxidation dye, an acid dye, and a basic dye, and is usually one or two or more dyes selected from any one of them.
染料が酸化染料から選ばれる場合、染毛用乳化組成物は酸化染毛剤の構成要素であり、通常は酸化染毛剤の第１剤を構成して、少なくとも酸化剤を含有する酸化染毛剤第２剤と組み合わせて使用される。染料が酸性染料又は塩基性染料から選ばれる場合、染毛用乳化組成物は通常は１剤式の染毛料を構成する。 When the dye is selected from oxidative dyes, the emulsified composition for hair dyeing is a component of the oxidative hair dye, and usually constitutes the first agent of the oxidative hair dye and contains at least an oxidant. Used in combination with the second agent. When the dye is selected from an acid dye or a basic dye, the emulsified composition for hair dye usually constitutes a one-component hair dye.
染料の含有量は特段に限定されないが、例えば、酸化染料の場合は最終的に調製された染毛用乳化組成物中の０．０１〜１０質量％となるように、酸性染料の場合は最終的に調製された染毛用乳化組成物中の０．０５〜３質量％となるように、塩基性染料の場合は最終的に調製された染毛用乳化組成物中の０．０５〜３質量％となるように、配合することができる。 The content of the dye is not particularly limited. For example, in the case of an oxidation dye, the final content is 0.01 to 10% by mass in the case of an acid dye so that the final amount is 0.01 to 10% by mass. In the case of a basic dye, 0.05 to 3 in the finally prepared hair dyeing emulsified composition so that it becomes 0.05 to 3% by mass in the emulsified hair dye prepared composition. It can mix | blend so that it may become the mass%.
酸化染料は主要中間体からなり、あるいは主要中間体とカプラーからなる。主要中間体としては、例えばオルト−又はパラ−のフェニレンジアミン類やアミノフェノール類等が例示され、より具体的にはｐ−フェニレンジアミン、トルエン−２，５−ジアミン、Ｎ，Ｎ−ビス（β−ヒドロキシエチル）−ｐ−フェニレンジアミン、２−β−ヒドロキシエチル−ｐ−フェニレンジアミン、Ｎ−β−ヒドロキシエチル−Ｎ−エチル−ｐ−フェニレンジアミン、Ｎ−フェニル−ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルアミン、ｐ−アミノフェノール、ｏ−アミノフェノール、ｐ−メチルアミノフェノール、ｏ−クロル−ｐ−フェニレンジアミンおよび２，４−ジアミノフェノール等が例示される。カプラーとしては、例えばメタ−のジアミン類、アミノフェノール類又はジフェノール類等が例示され、より具体的にはレゾルシン、カテコール、ピロガロール、フロログルシン、没食子酸、ハイドロキノン、５−アミノ−ｏ−クレゾール、ｍ−アミノフェノール、５−（２−ヒドロキシエチルアミノ）−２−メチルフェノール、ｍ−フェニレンジアミン、２，４−ジアミノフェノキシエタノール、トルエン−３，４−ジアミン、α−ナフトール、２，６−ジアミノピリジン、ジフェニルアミン、３，３’−イミノジフェニール、１，５−ジヒドロキシナフタレンおよびタンニン酸等が例示される。 Oxidative dyes consist of major intermediates or consist of major intermediates and couplers. Examples of the main intermediate include ortho- or para-phenylenediamines and aminophenols. More specifically, p-phenylenediamine, toluene-2,5-diamine, N, N-bis (β -Hydroxyethyl) -p-phenylenediamine, 2-β-hydroxyethyl-p-phenylenediamine, N-β-hydroxyethyl-N-ethyl-p-phenylenediamine, N-phenyl-p-phenylenediamine, 4,4 Examples include '-diaminodiphenylamine, p-aminophenol, o-aminophenol, p-methylaminophenol, o-chloro-p-phenylenediamine, and 2,4-diaminophenol. Examples of couplers include meta-diamines, aminophenols or diphenols, and more specifically, resorcin, catechol, pyrogallol, phloroglucin, gallic acid, hydroquinone, 5-amino-o-cresol, m -Aminophenol, 5- (2-hydroxyethylamino) -2-methylphenol, m-phenylenediamine, 2,4-diaminophenoxyethanol, toluene-3,4-diamine, α-naphthol, 2,6-diaminopyridine, Examples include diphenylamine, 3,3′-iminodiphenyl, 1,5-dihydroxynaphthalene and tannic acid.
酸性染料としては、赤色２号、赤色３号、赤色１０２号、赤色１０４号の（１）、赤色１０５号の（１）、赤色１０６号、赤色２２７号、赤色２３０号の（１）、黄色４号、黄色５号、黄色２０２号の（１）、黄色２０２号の（２）、黄色２０３号、だいだい色２０５号、だいだい色２０７号、だいだい色４０２号、緑色３号、緑色２０４号、緑色４０１号、紫色４０１号、青色１号、青色２号、青色２０２号、かっ色２０１号、黒色４０１号等が例示される。 As acid dyes, Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 227, Red No. 230 (1), Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Daigo Color No. 205, Daigo Color No. 207, Daigo Color No. 402, Green No. 3, Green No. 204, Examples include green 401, purple 401, blue 1, blue 2, blue 202, brown 201, black 401 and the like.
塩基性染料としては、Basic Blue 3、Basic Blue 6、Basic Blue 7、Basic Blue 9、Basic Blue 26、Basic Blue 41、Basic Blue 47、Basic Blue 99、Basic Brown 4、Basic Brown 16、Basic Brown 17、Basic Green 1、Basic Green 4、Basic Orange 1、Basic Orange 2、Basic Orange 31、Basic Red 1、Basic Red 2、Basic Red 22、Basic Red 46、Basic Red 51、Basic Red 76、Basic Red 118、Basic Violet 1、Basic Violet 3、Basic Violet 4、Basic Violet 10、Basic Violet 11:1、Basic Violet 14、Basic Violet 16、Basic Yellow 11、Basic Yellow 28、Basic Yellow 57、Basic Yellow 87等が例示される。 Basic dyes include Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Orange 31, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet Examples include 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 11: 1, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 57, Basic Yellow 87, and the like.
〔第１実施例群〕
（酸化染毛剤第１剤の組成）
表１〜表４の実施例１〜２１及び表５〜表８の比較例１〜２１に示す組成の、染毛用乳化組成物である酸化染毛剤第１剤を後述の方法により調製した。これらの各表に示す酸化染毛剤第１剤の組成は、（Ｂ）相を構成する成分である「Ｂ相構成成分」、（Ａ）相を構成する成分である「Ａ相構成成分」、（Ａ）相と（Ｂ）相との混合相に投入する成分である「ＡＢ混合相投入成分」ごとに分けて表示した。表５〜表８の「混合相」とは「ＡＢ混合相投入成分」であることを意味する。「Ｂ相構成成分」中の直鎖状高級アルコールについては融点(ｍ.ｐ.)を付記した。表中の各成分について示す数値は、酸化染毛剤第１剤の全量に対する質量％の数値である。
[First Example Group]
(Composition of oxidation hair dye first agent)
Oxidative hair dye 1st agent which is the emulsion composition for hair dyeing of the composition shown in Examples 1-21 of Table 1-Table 4 and Comparative Examples 1-21 of Table 5-Table 8 was prepared by the below-mentioned method. . The composition of the first agent of the oxidative hair dye shown in each of these tables is “B phase constituent component” which is a component constituting the (B) phase, “A phase constituent component” which is the component constituting the (A) phase. The “AB mixed phase input component”, which is a component input to the mixed phase of the (A) phase and the (B) phase, is displayed separately. “Mixed phase” in Tables 5 to 8 means “AB mixed phase input component”. The melting point (mp) is added to the linear higher alcohol in the “B phase constituent”. The numerical value shown about each component in a table | surface is a numerical value of the mass% with respect to the whole quantity of oxidative hair dye 1st agent.
（酸化染毛剤第１剤の調製方法）
乳化装置としてプライミクス株式会社製のＴ．Ｋ．アジホモミクサー２Ｍ−０３型を使用し、各実施例、各比較例とも３００ｇずつの酸化染毛剤第１剤を調製した。
(Preparation method of oxidation hair dye 1st agent)
As an emulsifying device, T.M. K. Adihomomicr 2M-03 type was used, and each Example and each Comparative Example prepared 300 g of the first oxidation hair dye.
具体的には、まず、(Ｂ)相が表中の「混合時のＢ相の温度（℃）」の欄に示す温度になるように設定し、（Ｂ）相の各成分が完溶するのを確認したうえで、ホモミキサー３，０００ｒ．ｐ．ｍ．、パドルミキサー９０ｒ．ｐ．ｍ．、減圧０．０３ＭＰａの条件で、ミキサーを回転させながら投入口より（Ａ）相を添加した。この（Ａ）相は、表中の「混合時のＡ相の温度（℃）」の欄に示す温度に調整したものである。 Specifically, first, the (B) phase is set to a temperature shown in the column of “B phase temperature during mixing (° C.)” in the table, and each component of the (B) phase is completely dissolved. Of the homomixer 3,000 r. p. m. Paddle mixer 90r. p. m. The phase (A) was added from the inlet while rotating the mixer under the reduced pressure of 0.03 MPa. This (A) phase is adjusted to the temperature shown in the column of “temperature of A phase during mixing (° C.)” in the table.
（Ａ）相を添加した後、上記の条件で２分間の乳化終了後、減圧０．０４ＭＰａに調節し、パドルミキサー１５ｒ．ｐ．ｍ．の条件で攪拌しながら２５℃になるまで冷却し、投入口より２５℃に調整した「ＡＢ混合相投入成分」を添加し、更にホモミキサー５００ｒ．ｐ．ｍ．、パドルミキサー９０ｒ．ｐ．ｍ．の条件で１分間の撹拌・混合を行い、組成物を得た。なお、表７の比較例１１では以上の操作によって乳化することができなかったので、後述する各種の評価を行っていない。 (A) After adding the phase, after completion of emulsification for 2 minutes under the above conditions, the pressure was adjusted to 0.04 MPa, and the paddle mixer 15r. p. m. The mixture was cooled to 25 ° C. with stirring under the conditions described above, “AB mixed phase charging component” adjusted to 25 ° C. was added from the charging port, and homomixer 500 r. p. m. Paddle mixer 90r. p. m. The composition was obtained by stirring and mixing for 1 minute under the above conditions. In Comparative Example 11 of Table 7, since the emulsification could not be performed by the above operation, various evaluations described later were not performed.
（酸化染毛剤第１剤の粘度の評価）
上記の冷却操作によって２５℃まで冷却した時点で、各実施例、各比較例に係る酸化染毛剤第１剤の粘度を、「第１発明」に関して前記した条件により測定した。それらの測定結果を表中の「第１剤の粘度（調製直後、ｍＰａ・ｓ）」の欄に示す。また、これらの各実施例、各比較例に係る酸化染毛剤第１剤を２５℃の恒温室に２週間静置した後にも、前記条件により粘度を測定した。それらの測定結果を表中の「第１剤の粘度（調製２週間後、ｍＰａ・ｓ）」の欄に示す。
(Evaluation of viscosity of oxidation hair dye first agent)
At the time of cooling to 25 ° C. by the above cooling operation, the viscosity of the first agent of the oxidative hair dye according to each example and each comparative example was measured under the conditions described above with respect to the “first invention”. The measurement results are shown in the column of “viscosity of first agent (immediately after preparation, mPa · s)” in the table. In addition, the viscosity was measured under the above conditions after the oxidative hair dye first agent according to each of these Examples and Comparative Examples was allowed to stand in a thermostatic chamber at 25 ° C. for 2 weeks. The measurement results are shown in the column of “viscosity of first agent (after 2 weeks of preparation, mPa · s)” in the table.
（酸化染毛剤第１剤の第２剤との混合性の評価）
表９に示す乳化組成物である酸化染毛剤第２剤（使用時粘度：前記粘度測定条件において、４号ロータを３号ロータに変更して測定した値で３０００ｍＰａ・ｓ）を常法により調製し、上記の各実施例、各比較例に係る酸化染毛剤第１剤に対してそれぞれ質量混合比が１：１になるように、第１剤及び第２剤を各４０ｇずつ染毛用カップに量り取り、染毛用ハケにて混合することにより、第２剤との混合性を評価した。その評価結果を表中の「第２剤との混合性」の欄に示す。表８に示す比較例１８、２１では「混合不可」と表記したように、第１剤の粘度が高すぎたため混ざり合わなかった。そのため、これらの比較例では、後述の「混合液の垂れ落ち」、「染毛色調」を評価していない。
(Evaluation of mixing properties of the first agent of the oxidative hair dye with the second agent)
Oxidative hair dye 2nd agent which is an emulsified composition shown in Table 9 (viscosity in use: 3000 mPa · s as measured by changing the No. 4 rotor to the No. 3 rotor in the above viscosity measurement conditions) by a conventional method 40 g each of the first agent and the second agent so that the mass mixing ratio is 1: 1 with respect to the first agent of the oxidative hair dye according to each of the above Examples and Comparative Examples. The mixture with the second agent was evaluated by weighing into a cup and mixing with a hair dye brush. The evaluation results are shown in the column of “Mixability with the second agent” in the table. In Comparative Examples 18 and 21 shown in Table 8, as described as “unmixable”, the viscosity of the first agent was too high, so it did not mix. For this reason, in these comparative examples, “mixed liquid dripping” and “hair dye color tone” described later are not evaluated.
（混合液の垂れ落ちの評価）
上記の混合性の評価で調製した各実施例、各比較例に係る酸化染毛剤第１剤と表９に示す酸化染毛剤第２剤との混合液を、それぞれ長さ１５ｃｍの毛束に常用される程度の一定量塗布した後、それらの毛束を３７℃の恒温槽内に吊り下げ、３０分放置後の混合液の垂れ落ちの有無を評価した。その評価結果を表中の「混合液の垂れ落ち」の欄に示す。「問題なし」との表記は、垂れ落ちが全くなかったことを意味する。
(Evaluation of dripping of liquid mixture)
A hair bundle of 15 cm in length, each of a mixture of the first hair dye agent according to each of the examples and comparative examples prepared in the evaluation of the mixing property and the second hair dye agent shown in Table 9 Then, the hair bundles were hung in a constant temperature bath at 37 ° C., and the presence or absence of dripping of the mixed solution after being allowed to stand for 30 minutes was evaluated. The evaluation results are shown in the column of “Liquid dripping” in the table. The expression “no problem” means that there was no dripping.
（染毛色調の評価）
上記の混合性の評価で調製した各実施例、各比較例に係る酸化染毛剤第１剤と表９に示す酸化染毛剤第２剤との混合液を、それぞれ白色山羊毛に塗布し、３０分放置した後に洗浄し、乾燥させた後に山羊毛の色調を標準光源下にて評価した。その評価結果を表中の「染毛色調」の欄に示す。
(Evaluation of hair color)
Each mixed solution of the first hair dye agent according to each of the examples and comparative examples prepared in the evaluation of the mixing property and the second hair dye agent shown in Table 9 was applied to white goat hair. After being allowed to stand for 30 minutes, washed and dried, the color of goat hair was evaluated under a standard light source. The evaluation results are shown in the column of “Dye color” in the table.
（保存安定性の評価）
上記の「酸化染毛剤第１剤の調製方法」の欄で調製した各実施例、各比較例に係る酸化染毛剤第１剤を、それぞれ第１サンプルと第２サンプルの２試料ずつ４号規格瓶に充填した。そして、第１サンプルの４号規格瓶は５０℃の恒温槽にて、第２サンプルの４号規格瓶は２５℃の恒温槽にてそれぞれ１ヶ月間保存した後、両者のサンプルの乳化状態を目視にて比較することにより、保存安定性を評価した。その評価結果を表中の「乳化組成物の保存安定性」の欄に示す。「問題なし」との評価は「第１サンプル、第２サンプルの乳化状態が共に良好であった」ことを意味し、「やや悪い」との評価は「第２サンプルの乳化状態は良好であるが、それに比較して第１サンプルではやや相分離が起きていた」ことを意味する。
(Evaluation of storage stability)
For each of the Examples and Comparative Examples prepared in the column “Preparation Method of Oxidative Hair Dye First Agent” above, the first sample of the oxidative hair dye according to each Comparative Example is divided into two samples, one sample and one second sample. No. standard bottle was filled. The first sample No. 4 standard bottle is stored in a thermostatic bath at 50 ° C., and the second sample No. 4 standard bottle is stored in a 25 ° C. constant temperature bath for 1 month, respectively. Storage stability was evaluated by visual comparison. The evaluation results are shown in the column of “Storage stability of emulsion composition” in the table. An evaluation of “no problem” means “the emulsification state of the first sample and the second sample was both good”, and an evaluation of “somewhat bad” is “the emulsification state of the second sample is good” However, in comparison with the first sample, phase separation was slightly occurring ”.
〔第２実施例群〕
表１０に示す実施例２２、２３に係る組成の、染毛用乳化組成物である１剤式の染毛料を調製した。表１０における染毛料の各成分の表記の要領は第１実施例群の場合と同様である。
[Second Example Group]
One-component hair dyes, which are emulsified compositions for hair dyeing, according to Examples 22 and 23 shown in Table 10, were prepared. The point of description of each component of the hair dye in Table 10 is the same as in the case of the first embodiment group.
実施例２２、２３に係る染毛料の調製方法は第１実施例群に係る酸化染毛剤第１剤の場合と同様である。 The method for preparing the hair dye according to Examples 22 and 23 is the same as that of the first agent for the oxidative hair dye according to the first example group.
実施例２２、２３に係る染毛料についても、第１実施例群に係る酸化染毛剤第１剤の場合と同様に粘度の評価を行った。又、これらの染毛料は１剤式であるから第１実施例群のような「混合性の評価」は行っていないが、調製した染毛料を用いて、第１実施例群の場合と同様の要領で、「垂れ落ちの評価」、「染毛色調の評価」、「保存安定性の評価」をそれぞれ行い、それらの評価結果を表１０の該当欄に示した。 For the hair dyes according to Examples 22 and 23, the viscosity was evaluated in the same manner as in the case of the first agent for the oxidative hair dye according to the first example group. In addition, since these hair dyes are of a single agent type, “evaluation of mixing” as in the first example group is not performed, but using the prepared hair dyes, the same as in the first example group. In this manner, “Evaluation of dripping”, “Evaluation of hair color tone”, and “Evaluation of storage stability” were performed, and the evaluation results are shown in the corresponding columns of Table 10.
本発明によれば、適正な後増粘により容器充填時と毛髪塗布時にそれぞれ好適な範囲の粘度を示す染毛用乳化組成物が得られ、かつ、染料類の配合量が異なるシリーズ商品を構成する染毛用乳化組成物間での粘度のバラツキを防止することができる。 According to the present invention, it is possible to obtain an emulsified composition for hair dyeing having a suitable range of viscosities at the time of filling the container and applying the hair by appropriate post-thickening, and constituting series products with different amounts of dyes. It is possible to prevent variation in viscosity between the emulsion compositions for hair dyeing.
Claims (2)
（２）上記の混合工程において、下記の（Ｄ）成分を混合前の（Ａ）相、混合前の（Ｂ）相、（Ａ）相と（Ｂ）相との混合相のうちの少なくとも１相に対して添加する、
ことを特徴とする染毛用乳化組成物の製造方法。
（Ａ）相：水相。
（Ｂ）相:炭素数が１６〜２２の範囲内である直鎖状高級アルコールの１種以上を含有すると共に、下記の一般式（Ｉ）で表される（Ｃ）成分を、最終的に調製された乳化組成物中における（Ｃ）成分の含有量（ｃ質量％）が（Ｄ）成分の含有量（ｄ質量％）に対してｄ／ｃ＝０．１〜５０の範囲内となるように、含有する。
Ｒ−（ＯＣＨ２ＣＨ２）ｎ−ＯＨ・・・（Ｉ）
（この一般式において、Ｒは水素原子又は炭化水素を表す。但し、この炭化水素は炭素数が１〜２２の範囲内であり、飽和又は不飽和であり、直鎖状又は分岐鎖状であり、炭化水素を構成する炭素に結合した水素原子の一部が水酸基に置換されていても良い。又、ｎは２０〜２００の範囲内の整数である。）
（Ｄ）成分：酸化染料、酸性染料、塩基性染料から選ばれる少なくとも１種の染料。 (1) The following (A) phase and (B) phase, and for the (B) phase, at a temperature higher than the melting point of the linear higher alcohol having the highest melting point among the linear higher alcohols contained therein. And adjusting the phase (A) to a temperature lower than the temperature of the phase (B) and mixing,
(2) In the above mixing step, at least one of the following components (D) is mixed in the (A) phase before mixing, the (B) phase before mixing, and the mixed phase of the (A) phase and the (B) phase. Add to the phase,
The manufacturing method of the emulsion composition for hair dyeing characterized by the above-mentioned.
(A) Phase: Aqueous phase.
(B) Phase: containing at least one linear higher alcohol having a carbon number in the range of 16 to 22, and finally, the component (C) represented by the following general formula (I): The content (c mass%) of the component (C) in the prepared emulsion composition is in the range of d / c = 0.1-50 with respect to the content (d mass%) of the component (D). So as to contain.
R— (OCH 2 CH 2 ) n —OH (I)
(In this general formula, R represents a hydrogen atom or a hydrocarbon. However, this hydrocarbon has a carbon number in the range of 1 to 22, is saturated or unsaturated, and is linear or branched. The hydrogen atom bonded to the carbon constituting the hydrocarbon may be partially substituted with a hydroxyl group, and n is an integer in the range of 20 to 200.)
Component (D): at least one dye selected from oxidation dyes, acid dyes, and basic dyes.
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| JP6214124B2 (en) * | 2011-03-02 | 2017-10-18 | ホーユー株式会社 | Hair cosmetic composition |
| JP6046352B2 (en) * | 2012-01-26 | 2016-12-14 | ホーユー株式会社 | Hair dye composition |
| JP6381893B2 (en) * | 2013-10-31 | 2018-08-29 | ホーユー株式会社 | Hair cosmetic composition |
| JP7348615B2 (en) * | 2016-07-22 | 2023-09-21 | ホーユー株式会社 | Oxidized hair dye first agent and method for stabilizing color tone of oxidized hair dye composition |
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| JP2775590B2 (en) * | 1994-05-21 | 1998-07-16 | ホーユー株式会社 | Acid hair dye |
| DE19829647A1 (en) * | 1998-07-02 | 2000-01-13 | Wella Ag | Process for the preparation of aqueous emulsions or suspensions |
| DE10219523A1 (en) * | 2002-05-02 | 2003-11-13 | Wella Ag | Process for the technical production of hair or skin cosmetic products using equipment with microstructure units |
| JP2004107247A (en) * | 2002-09-18 | 2004-04-08 | Nikko Chemical Co Ltd | Hair conditioning agent which can simultaneously dye and condition hair |
| JP2004189717A (en) * | 2002-11-27 | 2004-07-08 | Shiseido Co Ltd | Hair dye composition |
| JP4022184B2 (en) * | 2003-08-07 | 2007-12-12 | ホーユー株式会社 | Hair dye composition |
| JP4014163B2 (en) * | 2003-08-07 | 2007-11-28 | ホーユー株式会社 | Hair dye composition |
| EP1832273B1 (en) * | 2006-03-09 | 2020-02-26 | Noxell Corporation | Thickened hair colourant and bleaching compositions |
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