JP4509769B2 - Hair modification method - Google Patents
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本発明は、毛髪にハリ・コシを付与する毛髪改質方法に関する。 The present invention relates to a hair modification method for imparting elasticity and firmness to hair.
従来、毛髪の内部に物質を浸透させて毛髪の物性や外観、感触を改質する方法として毛髪成分と類似したコラーゲン、ケラチン等の分解物及び誘導体を補充する方法が提案されているが、未だ十分な効果とはいえない。 Conventionally, a method of replenishing degradation products and derivatives of collagen, keratin, etc. similar to hair components has been proposed as a method for improving the physical properties, appearance, and feel of hair by infiltrating substances into the hair, but it has not yet been proposed. It is not a sufficient effect.
一方、アルカリ処理した毛髪に、アルキルトリアルコキシシランを用いて、毛髪を強化する技術が知られている（例えば、特許文献１参照）。また、有機ケイ素化合物等を用い部分的又は全体的に加水分解し、部分的又は全体的に重合させることで得られる有機ケイ素化合物を、爪、毛髪等のケラチン物質に適用することで、ケラチン物質を保護および強化するための方法も提案されている（例えば、特許文献２及び３参照）。 On the other hand, a technique for strengthening hair using alkyltrialkoxysilane on alkali-treated hair is known (see, for example, Patent Document 1). Further, by applying an organosilicon compound obtained by partial or total hydrolysis using an organosilicon compound or the like and partial or total polymerization to a keratin material such as a nail or hair, a keratin material A method for protecting and strengthening is also proposed (see, for example, Patent Documents 2 and 3).
しかしながら、これらの技術では、有機ケイ素化合物は、ケラチン表面にのみ存在するものであるため、洗浄により効果が無くなったり、ケラチン表面の感触が本来の感触でなくなったりするという問題を有する。
本発明は、毛髪繊維、特にハリ・コシがない毛髪（化学処理等で損傷した毛髪、欧米人や高齢者の細い毛髪等）に対し、短時間で優れたハリ・コシを付与することができる毛髪改質方法を提供することを目的とする。ここで、ハリ・コシを付与するとは、毛髪弾性を向上させることをいう。 The present invention can impart excellent firmness and firmness in a short time to hair fibers, particularly hair that does not have firmness and firmness (hair damaged by chemical treatment, thin hair of Westerners and elderly people, etc.). An object is to provide a hair modification method. Here, giving firmness and elasticity means improving hair elasticity.
本発明者は、アルコキシシランを加水分解する際に、有機酸を共存させることにより、加水分解で生成したシラノール化合物の重合を適度な速度に抑制しつつ毛髪に浸透させ、毛髪内部で重合させて優れたハリ・コシを付与できること、更には、毛髪にシラノールが浸透した後、酸性水溶液又はアルカリ性水溶液を塗布すれば、シラノール化合物の重合を促進し、重合にかかる時間を大幅に短縮化できることを見出した。 When the present inventors hydrolyze alkoxysilane, by allowing an organic acid to coexist, the silanol compound produced by hydrolysis is allowed to penetrate into the hair while suppressing the polymerization at an appropriate rate, and polymerized inside the hair. It has been found that excellent elasticity and elasticity can be imparted, and further, if silanol penetrates into the hair and then an acidic aqueous solution or an alkaline aqueous solution is applied, the polymerization of the silanol compound is promoted and the time required for the polymerization can be greatly shortened. It was.
本発明は、一般式(1)で表されるアルコキシシラン、有機酸及び水を配合してなる毛髪処理剤(Ａ1)を攪拌混合し、当該アルコキシシランが加水分解され一般式(2)で表されるシラノール化合物に変換された後の毛髪処理剤(Ａ2)を毛髪に塗布、浸透させ、次いで重合促進剤として、毛髪処理剤(Ａ2)に１：１の重量比で混合したときのpHを１〜４とする酸性水溶液(Ｂa)、又は毛髪処理剤(Ａ2)に１：１の重量比で混合したときのpHを８〜12とするアルカリ性水溶液(Ｂb)を毛髪に塗布する毛髪改質方法を提供するものである。 In the present invention, a hair treatment agent (A 1 ) obtained by blending an alkoxysilane represented by the general formula (1), an organic acid and water is stirred and mixed, and the alkoxysilane is hydrolyzed. When the hair treatment agent (A 2 ) after being converted into the silanol compound represented is applied to and permeated into the hair and then mixed with the hair treatment agent (A 2 ) in a weight ratio of 1: 1 as a polymerization accelerator. An acidic aqueous solution (B a ) having a pH of 1 to 4 or an alkaline aqueous solution (B b ) having a pH of 8 to 12 when mixed with a hair treatment agent (A 2 ) at a weight ratio of 1: 1 is used for hair. The present invention provides a method for modifying hair applied to a hair.
Ｒ1 pＳｉ(ＯＲ2)4-p (1)
Ｒ1 pＳｉ(ＯＨ)n(ＯＲ2)4-p-n (2)
R 1 p Si (OR 2 ) 4-p (1)
R 1 p Si (OH) n (OR 2 ) 4-pn (2)
〔式(1)及び(2)中、Ｒ1及びＲ2は、炭素数１〜６の直鎖若しくは分岐鎖のアルキル基又は炭素数２〜６の直鎖若しくは分岐鎖のアルケニル基を示す。ｐは０〜３の整数を示し、ｎは１以上（４−ｐ）以下の整数を示し、式(1)及び(2)中のｐ個のＲ1、式(1)中の（４−ｐ）個のＲ2、式(2)中の（４−ｐ−ｎ）個のＲ2は、それぞれ同一でも異なってもよい。〕 [In the formulas (1) and (2), R 1 and R 2 represent a linear or branched alkyl group having 1 to 6 carbon atoms or a linear or branched alkenyl group having 2 to 6 carbon atoms. p represents an integer of 0 to 3, n represents an integer of 1 to (4-p), and p R 1 in the formulas (1) and (2), (4- p) number of R 2, (4-p-n) pieces of R 2 in the formula (2) may be the same or different. ]
更に本発明は、次の処理剤(Ａ)と、処理剤(Ｂa)又は(Ｂb)とからなる毛髪改質剤を提供するものである。
(Ａ) 一般式(1)で表されるアルコキシシラン、第１解離指数（pKa1）が4.1〜５の範囲にある有機酸及び水を配合してなる毛髪処理剤
Furthermore, the present invention provides a hair modifier comprising the following treatment agent (A) and treatment agent (B a ) or (B b ).
(A) A hair treatment agent comprising an alkoxysilane represented by the general formula (1), an organic acid having a first dissociation index (pKa1) in the range of 4.1 to 5 and water.
(Ｂa) 第１解離指数（pKa1）が4.1未満の有機酸又は無機酸を含有し、かつ毛髪処理剤(Ａ)に１：１の重量比で混合したときのpHを１〜４とする重合促進剤 (B a ) The pH when the first dissociation index (pKa1) contains an organic acid or inorganic acid of less than 4.1 and is mixed with the hair treatment agent (A) at a weight ratio of 1: 1 is set to 1 to 4. Polymerization accelerator
(Ｂb) 毛髪処理剤(Ａ)に１：１の重量比で混合したときのpHを８〜12とする重合促進剤 (B b ) A polymerization accelerator for adjusting the pH to 8 to 12 when mixed with the hair treatment agent (A) at a weight ratio of 1: 1.
本発明によれば、アルコキシシランの加水分解で生成したシラノール化合物を毛髪に浸透させ、かつ毛髪内部で速やかに重合させて毛髪直径を増加することができる。その結果として、毛髪、特に、ハリ・コシがない毛髪（損傷毛、細い毛髪等）に対し、短時間で優れたハリ・コシを付与することにより、しっかりとした健康的な毛髪に改質することができる。更に、毛髪のまとまり性向上効果や、くせ毛の矯正効果も得られる。また、その効果はシャンプーを繰り返しても持続する。 According to the present invention, the diameter of the hair can be increased by allowing the silanol compound produced by hydrolysis of the alkoxysilane to penetrate into the hair and quickly polymerize within the hair. As a result, it is improved to firm and healthy hair by applying excellent elasticity and hair in a short time to hair, especially hair without damage and elasticity (damaged hair, thin hair, etc.) be able to. Furthermore, the effect of improving the cohesiveness of the hair and the effect of correcting the comb hair are also obtained. In addition, the effect persists even after repeated shampooing.
本発明における「毛髪改質」とは、毛髪をハリ・コシやまとまりのある髪質にすることをいう。また、本発明において、「毛髪処理剤(Ａ1)」とは、アルコキシシラン(1)が加水分解される前の毛髪処理剤をいい、「毛髪処理剤(Ａ2)」とは、アルコキシシラン(1)が加水分解されシラノール化合物(2)に変換された後の毛髪処理剤をいい、「毛髪処理剤(Ａ)」又は単に「毛髪処理剤」というときは、「毛髪処理剤(Ａ1)」、「毛髪処理剤(Ａ2)」のいずれをも含む。更に、本発明において、「重合促進剤(Ｂa)」とは、重合促進剤として酸性水溶液を使用する場合の当該重合促進剤をいい、「重合促進剤(Ｂb)」とは、重合促進剤としてアルカリ性水溶液を使用する場合の当該重合促進剤をいい、単に「重合促進剤」というときは、「重合促進剤(Ｂa)」、「重合促進剤(Ｂb)」のいずれを含む。 “Hair modification” in the present invention means that the hair has a firmness, firmness and coherence. In the present invention, “hair treatment agent (A 1 )” means a hair treatment agent before alkoxysilane (1) is hydrolyzed, and “hair treatment agent (A 2 )” means alkoxysilane. The hair treatment agent after (1) is hydrolyzed and converted into the silanol compound (2). When the term “hair treatment agent (A)” or simply “hair treatment agent” is used, the term “hair treatment agent (A 1 ) ”And“ hair treatment agent (A 2 ) ”. Furthermore, in the present invention, “polymerization accelerator (B a )” means the polymerization accelerator in the case of using an acidic aqueous solution as the polymerization accelerator, and “polymerization accelerator (B b )” means polymerization acceleration. The polymerization accelerator in the case of using an alkaline aqueous solution as an agent is referred to. The simple term “polymerization accelerator” includes any of “polymerization accelerator (B a )” and “polymerization accelerator (B b )”.
《毛髪処理剤》
本発明の毛髪改質方法の第一段階は、まず、アルコキシシラン(1)、有機酸及び水を構成要素とする毛髪処理剤(Ａ1)を攪拌混合し、加水分解反応によってアルコキシシランがシラノール化合物(2)に変換された後の毛髪処理剤(Ａ2)を、毛髪に塗布、浸透させることである。
《Hair treatment agent》
The first step of the hair modification method of the present invention is to first stir and mix the alkoxysilane (1), the hair treatment agent (A 1 ) containing organic acid and water as constituents, and the alkoxysilane is converted into silanol by hydrolysis reaction. The hair treatment agent (A 2 ) after being converted into the compound (2) is applied to and penetrates the hair.
〔アルコキシシラン(1)〕
一般式(1)中のＲ1及びＲ2において、アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、t-ブチル基等が挙げられ、アルケニル基としては、ビニル基、アリル基等が挙げられる。特に、Ｒ2としては、加水分解により生じる副生成物の安全性、加水分解反応の反応性等の点から、エチル基が好ましい。
[Alkoxysilane (1)]
In R 1 and R 2 in the general formula (1), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a t-butyl group. , Vinyl group, allyl group and the like. In particular, R 2 is preferably an ethyl group from the viewpoint of safety of by-products generated by hydrolysis, reactivity of hydrolysis reaction, and the like.
アルコキシシラン(1)は、本発明で使用する毛髪処理剤(Ａ1)が二剤式の場合には、水を含有しない第１剤に配合され、水を含有する第２剤と混合後、加水分解によって水溶性のシラノール化合物(2)となり、毛髪内への浸透が可能になる。生成するシラノール化合物(2)の物性、毛髪内への浸透性の点から、一般式(1)中のｐは０〜２が好ましい。アルコキシシラン(1)としては、アルキル（炭素数１〜６）トリメトキシシラン、アルキル（炭素数１〜６）トリエトキシシラン、ジアルキル（炭素数１〜６）ジエトキシシラン等が挙げられる。 When the hair treatment agent (A 1 ) used in the present invention is a two-component type, the alkoxysilane (1) is blended with the first agent not containing water and mixed with the second agent containing water, Hydrolysis results in a water-soluble silanol compound (2) that can penetrate into the hair. From the viewpoint of physical properties of the silanol compound (2) to be produced and penetrability into hair, p in the general formula (1) is preferably 0-2. Examples of the alkoxysilane (1) include alkyl (C1-6) trimethoxysilane, alkyl (C1-6) triethoxysilane, dialkyl (C1-6) diethoxysilane, and the like.
アルコキシシラン(1)の含有量は、架橋反応による反応性の点から、毛髪処理剤(Ａ1)中（二剤式の場合には第１剤と第２剤を合わせた全組成中；以下同じ）の４重量％以上、特に12重量％以上が好ましく、また82重量％以下、特に58重量％以下が好ましい。また、第１剤中のアルコキシシラン(1)の含有量は、保存安定性の点から、70〜100重量％、更には80〜100重量％、特に90〜100重量％が好ましい。 The content of alkoxysilane (1) is in the hair treatment agent (A 1 ) from the point of reactivity due to the cross-linking reaction (in the case of the two-component type, in the total composition of the first agent and the second agent; 4% by weight or more, particularly 12% by weight or more, and 82% by weight or less, and particularly preferably 58% by weight or less. Further, the content of the alkoxysilane (1) in the first agent is preferably 70 to 100% by weight, more preferably 80 to 100% by weight, and particularly preferably 90 to 100% by weight from the viewpoint of storage stability.
〔有機酸〕
有機酸としては、pH調整が容易な点から、第１解離指数（pKa1）が4.1〜5.0、特に4.1〜4.7の範囲にある有機酸が好ましい。具体的には、グルタル酸（pKa＝4.13，5.01）、アジピン酸（pKa＝4.26，5.03）、酢酸（pKa＝4.56）、プロピオン酸（pKa＝4.67）等を例示することができ、なかでもシラノール化合物(2)の重合反応の制御が容易で、臭気が少ないアジピン酸が好ましい。
[Organic acid]
As the organic acid, an organic acid having a first dissociation index (pKa1) in the range of 4.1 to 5.0, particularly 4.1 to 4.7 is preferable from the viewpoint of easy pH adjustment. Specific examples include glutaric acid (pKa = 4.13, 5.01), adipic acid (pKa = 4.26, 5.03), acetic acid (pKa = 4.56), propionic acid (pKa = 4.67), and silanol among others. Adipic acid that can easily control the polymerization reaction of the compound (2) and has less odor is preferred.
有機酸は、本発明で使用する毛髪処理剤(Ａ1)が二剤式の場合には、第１剤に配合されるアルコキシシラン(1)とは別個に第２剤に配合することが溶解性、保存安定性の点から好ましい。有機酸の含有量は、重合反応の抑制の点から、毛髪処理剤中の0.001〜５重量％、特に0.001〜１重量％が好ましい。 When the hair treatment agent (A 1 ) used in the present invention is a two-component type, the organic acid can be dissolved in the second agent separately from the alkoxysilane (1) compounded in the first agent. From the viewpoint of stability and storage stability. The content of the organic acid is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1% by weight in the hair treatment agent from the viewpoint of suppressing the polymerization reaction.
〔水〕
水は、本発明で使用する毛髪処理剤(Ａ1)が二剤式の場合には、第１剤に配合されるアルコキシシラン(1)とは別個に、第２剤に配合され、その含有量は、毛髪を十分に膨潤させ、加水分解で生成するシラノール化合物(2)を毛髪へ十分浸透させる観点から、毛髪処理剤中の20〜95重量％、特に30〜86重量％が好ましい。
〔water〕
When the hair treatment agent (A 1 ) used in the present invention is a two-component type, water is blended in the second agent separately from the alkoxysilane (1) blended in the first agent, and its content The amount is preferably 20 to 95% by weight, particularly 30 to 86% by weight in the hair treatment agent, from the viewpoint of sufficiently swelling the hair and allowing the silanol compound (2) produced by hydrolysis to sufficiently penetrate into the hair.
〔毛髪処理剤のpH〕
本発明で使用する毛髪処理剤においては、アルコキシシラン(1)を加水分解させ、シラノール化合物(2)を生成させる必要があり、またシラノール化合物(2)を毛髪内に浸透させて毛髪内で重合反応をさせるために、重合反応を遅らせる必要がある。このために毛髪処理剤(Ａ2)のpH（20℃）が２〜５、特に３〜４となるように調整するのが好ましい。なお、二剤式の場合には第２剤のpH（20℃）を上記範囲に調整するのが好ましい。
[PH of hair treatment agent]
In the hair treatment agent used in the present invention, it is necessary to hydrolyze the alkoxysilane (1) to form the silanol compound (2), and the silanol compound (2) penetrates into the hair and polymerizes in the hair. In order to react, it is necessary to delay the polymerization reaction. Therefore, it is preferable to adjust the hair treatment agent (A 2 ) so that the pH (20 ° C.) is 2 to 5, particularly 3 to 4. In the case of the two-agent type, it is preferable to adjust the pH (20 ° C.) of the second agent to the above range.
〔その他の成分〕
また、シラノール化合物(2)を溶解する目的で、メタノール、エタノール等の炭素数１〜３の低級１級アルコール、グリセリン等の水溶性有機溶剤を使用することもできるが、その量が多すぎると、毛髪処理剤(Ａ2)を毛髪に塗布した際に、毛髪が十分に膨潤せず、シラノール化合物(2)が十分に浸透し難くなる。そのため、水溶性有機溶剤の使用量は、毛髪処理剤中の35重量％以下、特に20重量％以下とすることが好ましい。なお、これ以外に、アルコキシシラン(1)の加水分解後の毛髪処理剤(Ａ2)には、副生物としてのＲ2ＯＨが含有されることになる。
[Other ingredients]
In addition, for the purpose of dissolving the silanol compound (2), a water-soluble organic solvent such as methanol or ethanol having 1 to 3 carbon atoms such as lower primary alcohol or glycerin can be used. When the hair treatment agent (A 2 ) is applied to the hair, the hair is not sufficiently swollen and the silanol compound (2) is not sufficiently penetrated. Therefore, the amount of water-soluble organic solvent used is preferably 35% by weight or less, particularly 20% by weight or less in the hair treatment agent. In addition, R 2 OH as a by-product is contained in the hair treatment agent (A 2 ) after hydrolysis of the alkoxysilane (1).
毛髪処理剤には、その他、界面活性剤、油剤、シリコーン誘導体、カチオン性ポリマー、保湿剤、粘度調整剤、香料、色素、紫外線吸収剤、酸化防止剤、抗菌剤、防腐剤等を、目的に応じて適宜配合することができる。 Other hair treatment agents include surfactants, oils, silicone derivatives, cationic polymers, humectants, viscosity modifiers, fragrances, pigments, UV absorbers, antioxidants, antibacterial agents, preservatives, etc. It can mix | blend suitably according to it.
〔毛髪処理剤(Ａ1)の形態〕
毛髪処理剤(Ａ1)の形態は、長期間安定である点から、好適には、アルコキシシラン(1)を含有する第１剤と、有機酸及び水を含有する第２剤からなるものであるが、使用直前にアルコキシシラン(1)、有機酸及び水、並びにその他任意成分を混合することによって調製されたものであってもよい。
[Form of hair treatment agent (A 1 )]
The form of the hair treatment agent (A 1 ) is preferably composed of a first agent containing alkoxysilane (1) and a second agent containing organic acid and water from the viewpoint of being stable for a long period of time. However, it may be prepared by mixing alkoxysilane (1), organic acid and water, and other optional components immediately before use.
毛髪処理剤を、使用直前にアルコキシシラン(1)、有機酸及び水、並びにその他任意成分を混合することによって調製する場合、混合する順序は、特に限定されないが、加水分解によって生成したシラノール化合物(2)は、即座に重合反応を開始するので、これを抑制するため、有機酸と水を混合した後にアルコキシシラン(1)を混合することが好ましい。 When the hair treatment agent is prepared by mixing alkoxysilane (1), organic acid and water, and other optional components immediately before use, the order of mixing is not particularly limited, but the silanol compound produced by hydrolysis ( In 2), since the polymerization reaction starts immediately, in order to suppress this, it is preferable to mix the alkoxysilane (1) after mixing the organic acid and water.
二剤式毛髪処理剤(Ａ1)の第１剤及び第２剤を使用直前に混合することにより、又はアルコキシシラン(1)、有機酸及び水、並びにその他任意成分を混合することにより、アルコキシシラン(1)は、加水分解によって水溶性のシラノール化合物(2)となり、毛髪内への浸透が可能になる。シラノール化合物(2)の物性、毛髪内への浸透性の点から、一般式(2)中のｐは０〜２が好ましく、ｎは２〜４が好ましく、（４−ｐ−ｎ）は０が好ましい。また、シラノール化合物(2)の分子量は、毛髪内への浸透のし易さから、300以下、特に90〜200が好ましい。 By mixing the first and second agents of the two-part hair treatment agent (A 1 ) immediately before use, or by mixing alkoxysilane (1), organic acid and water, and other optional components Silane (1) becomes a water-soluble silanol compound (2) by hydrolysis and can penetrate into hair. From the viewpoint of the physical properties of the silanol compound (2) and the penetrability into hair, p in the general formula (2) is preferably 0 to 2, n is preferably 2 to 4, and (4-pn) is 0. Is preferred. Further, the molecular weight of the silanol compound (2) is preferably 300 or less, particularly preferably 90 to 200, from the viewpoint of easy penetration into hair.
《重合促進剤》
本発明の毛髪改質方法の第二段階は、シラノール化合物(2)が毛髪に浸透した後、重合促進剤として酸性水溶液(Ｂa)又はアルカリ性水溶液(Ｂb)を毛髪に塗布して、シラノール化合物の重合を促進することである。特に、前記毛髪処理剤に配合される有機酸のpKaが4.1〜５の場合は毛髪に浸透したシラノール化合物が安定で重合しにくいため、重合促進剤を用いて重合することは、効果向上と時間短縮に効果的である。
<Polymerization accelerator>
In the second step of the hair modification method of the present invention, after the silanol compound (2) has penetrated into the hair, an acidic aqueous solution (B a ) or an alkaline aqueous solution (B b ) is applied to the hair as a polymerization accelerator. It is to accelerate the polymerization of the compound. In particular, when the pKa of the organic acid blended in the hair treatment agent is 4.1 to 5, the silanol compound that has penetrated into the hair is stable and difficult to polymerize. Effective for shortening.
〔酸性水溶液〕
重合促進剤(Ｂa)を使用する場合、すなわち毛髪に浸透したシラノール化合物の重合促進に酸性水溶液を使用する場合、酸としては、重縮合の反応速度の点から、pKaが4.1未満、特に3.7以下であるものが好ましい。なお、ここでいうpKaは、二酸以上の場合には、第１解離指数（pKa1）をいう。このうち有機酸としては、シュウ酸（pKa＝1.04，3.82）、マレイン酸（pKa＝1.75，5.83）、アスパラギン酸（pKa＝1.93，3.70）、サリチル酸（pKa＝2.81）、酒石酸（pKa＝2.82，3.96）、フマル酸（pKa＝2.85，4.10）、クエン酸（pKa＝2.90，4.34）、リンゴ酸（pKa＝3.24，4.71）、コハク酸（pKa＝4.00，5.24）、蟻酸（pKa＝3.55）、乳酸（pKa＝3.66）等が、無機酸としては、リン酸（pKa＝2.15）、塩酸（pKa＝-8）等が挙げられる。なかでも、リンゴ酸、乳酸、塩酸、リン酸が好ましい。
[Acid aqueous solution]
When the polymerization accelerator (B a ) is used, that is, when an acidic aqueous solution is used to accelerate the polymerization of the silanol compound that has penetrated into the hair, the acid has a pKa of less than 4.1, particularly 3.7 from the viewpoint of the reaction rate of polycondensation. The following are preferred. In addition, pKa here means a 1st dissociation index | exponent (pKa1) in the case of a diacid or more. Among these, oxalic acid (pKa = 1.04, 3.82), maleic acid (pKa = 1.75, 5.83), aspartic acid (pKa = 1.93, 3.70), salicylic acid (pKa = 2.81), tartaric acid (pKa = 2.82) 3.96), fumaric acid (pKa = 2.85, 4.10), citric acid (pKa = 2.90, 4.34), malic acid (pKa = 3.24, 4.71), succinic acid (pKa = 4.00, 5.24), formic acid (pKa = 3.55), Examples of inorganic acids include lactic acid (pKa = 2.66) and phosphoric acid (pKa = 2.15), hydrochloric acid (pKa = -8), and the like. Of these, malic acid, lactic acid, hydrochloric acid, and phosphoric acid are preferable.
酸性水溶液(Ｂa)は、重縮合の反応速度の点から、毛髪処理剤(Ａ)〔好ましくは毛髪処理剤(Ａ2)〕に１：１の重量比で混合したときのpHを１〜４とするものを使用し、好ましくは当該pHを1.5〜3.5、特に２〜3.3とするものを使用する。また、酸性水溶液(Ｂa)は、上記pH範囲の緩衝系としてもよい。 The acidic aqueous solution (B a ) has a pH of 1 to 1 when mixed with the hair treatment agent (A) [preferably the hair treatment agent (A 2 )] at a weight ratio of 1: 1 from the viewpoint of the polycondensation reaction rate. 4 is used, and preferably the pH is 1.5 to 3.5, particularly 2 to 3.3. The acidic aqueous solution (B a ) may be a buffer system having the above pH range.
〔アルカリ性水溶液〕
重合促進剤(Ｂb)を使用する場合、すなわち毛髪に浸透したシラノール化合物の重合促進にアルカリ性水溶液を使用する場合、アルカリとしては、炭酸水素ナトリウム、炭酸カルシウム等の炭酸塩；水酸化ナトリウム、水酸化カリウム等の水酸化物；モノエタノールアミン、2-アミノ-2-メチル-1-プロパノール等のアルカノールアミンなどを使用することができる。アルカリ性水溶液(Ｂb)は、重縮合の反応速度の点から、毛髪処理剤(Ａ)〔好ましくは毛髪処理剤(Ａ2)〕に１：１の重量比で混合したときのpHを８〜12.0とするものを使用し、好ましくは当該pHを8.5〜12、特に９〜10とするものを使用する。
(Alkaline aqueous solution)
When the polymerization accelerator (B b ) is used, that is, when an alkaline aqueous solution is used to accelerate the polymerization of the silanol compound that has penetrated into the hair, the alkali includes carbonates such as sodium hydrogen carbonate and calcium carbonate; sodium hydroxide, water Hydroxides such as potassium oxide; alkanolamines such as monoethanolamine and 2-amino-2-methyl-1-propanol can be used. The alkaline aqueous solution (B b ) has a pH of 8 to 8 when mixed with the hair treatment agent (A) [preferably the hair treatment agent (A 2 )] at a weight ratio of 1: 1 from the viewpoint of the reaction rate of polycondensation. Those having a pH of 12.0 are used, preferably those having a pH of 8.5 to 12, particularly 9 to 10.
〔その他の成分〕
重合促進剤には、その他、界面活性剤、油剤、シリコーン誘導体、カチオン性ポリマー、保湿剤、粘度調整剤、香料、色素、紫外線吸収剤、酸化防止剤、抗菌剤、防腐剤等を、目的に応じて適宜配合することができる。また、油剤と界面活性剤を用いて乳化物にしても良い。
[Other ingredients]
Other polymerization accelerators include surfactants, oils, silicone derivatives, cationic polymers, humectants, viscosity modifiers, fragrances, dyes, UV absorbers, antioxidants, antibacterial agents, preservatives, etc. It can mix | blend suitably according to it. Moreover, you may make it an emulsion using an oil agent and surfactant.
《毛髪改質方法》
本発明の毛髪改質方法において、毛髪処理剤による毛髪の処理は、毛髪処理剤(Ａ1)が二剤式である場合は第１剤及び第２剤を使用直前に混合後、毛髪処理剤(Ａ1)が一剤式である場合はアルコキシシラン(1)、有機酸及び水、並びにその他任意成分を使用直前に混合後、振とう攪拌して、目視で混合溶液が均一な１相になったことを確認した後に、得られた混合物、すなわち毛髪処理剤(Ａ2)を毛髪に塗布するのが好ましい。二剤式である場合の第１剤と第２剤の混合割合（第１剤／第２剤の重量比）は、好ましくは80／20〜１／99、更に好ましくは60／40〜20／80である。混合直後はお互いに相溶しない状態であったのが、振とう攪拌を継続するうちに均一な１相となることで、アルコキシシラン(1)が加水分解し、シラノール化合物(2)が生成したことを確認することができる。
《Hair modification method》
In the hair modification method of the present invention, when the hair treatment agent (A 1 ) is a two-component type, the hair treatment agent is mixed with the first agent and the second agent immediately before use. When (A 1 ) is a one-component system, alkoxysilane (1), organic acid and water, and other optional components are mixed immediately before use, and then shaken and stirred to make the mixed solution uniform in one phase visually. After confirming that it has become, it is preferable to apply the obtained mixture, that is, the hair treatment agent (A 2 ) to the hair. The mixing ratio of the first agent and the second agent (weight ratio of the first agent / second agent) in the case of the two- agent type is preferably 80/20 to 1/99, more preferably 60/40 to 20 / 80. Immediately after mixing, they were incompatible with each other, but by continuing to be shaken and stirred, it became a uniform single phase, so that alkoxysilane (1) was hydrolyzed and silanol compound (2) was produced. I can confirm that.
得られた毛髪処理剤(Ａ2)を放置すれば、シラノール化合物(2)の重合反応が進むので、30分以内、特に15分以内に、得られた毛髪処理剤(Ａ2)を毛髪に塗布することが好ましい。これにより、シラノール化合物(2)を毛髪内に浸透させることができる。塗布する毛髪は、濡れていてもよく、乾いていてもよい。乾燥した毛髪１ｇに対して、前記毛髪処理剤(Ａ2)を、0.5ｇ〜３ｇ塗布することが好ましい。塗布する対象は、人の頭髪であってもよく、かつら等の毛髪であってもよい。 If the obtained hair treatment agent (A 2 ) is allowed to stand, the polymerization reaction of the silanol compound (2) proceeds, so within 30 minutes, particularly within 15 minutes, the obtained hair treatment agent (A 2 ) is applied to the hair. It is preferable to apply. This allows the silanol compound (2) to penetrate into the hair. The hair to be applied may be wet or dry. It is preferable to apply 0.5 g to 3 g of the hair treatment agent (A 2 ) to 1 g of dried hair. The target to be applied may be human hair or hair such as a wig.
シラノール化合物(2)を毛髪に十分に浸透させるために、毛髪に塗布しておく時間は、10〜90分、特に20〜60分が好ましい。塗布後一定時間放置することで、シラノール化合物(2)の浸透及び重合反応を進める。この際、毛髪の乾燥を防ぐためにラップ等で包んでもよく、また毛髪の塗布部を40〜90℃、好ましくは40〜60℃に加温してもよい。 In order to allow the silanol compound (2) to sufficiently penetrate into the hair, the time for applying to the hair is preferably 10 to 90 minutes, particularly preferably 20 to 60 minutes. By allowing it to stand for a certain period of time after coating, the penetration and polymerization reaction of the silanol compound (2) proceeds. At this time, the hair may be wrapped with a wrap or the like to prevent the hair from drying, and the hair application part may be heated to 40 to 90 ° C., preferably 40 to 60 ° C.
毛髪処理剤(Ａ2)による処理後、そのまま重合促進剤を毛髪に塗布してもよいが、重合促進剤の無駄な希釈を避けるために、毛髪表面に付着している毛髪処理剤をタオル等で拭き取るなどして除去した後に、重合促進剤を塗布することが好ましい。 After the treatment with the hair treatment agent (A 2 ), the polymerization accelerator may be applied to the hair as it is. However, in order to avoid unnecessary dilution of the polymerization accelerator, the hair treatment agent attached to the hair surface is removed with a towel or the like. It is preferable to apply a polymerization accelerator after removing by wiping with, for example.
重合促進剤の塗布後、シラノール化合物(2)の重合を進めるために放置しておく時間は、１〜60分、特に20〜40分程度が好ましい。この際、毛髪の乾燥を防ぐためにラップ等で包んでもよく、また塗布部を40〜90℃、好ましくは40〜60℃に加温してもよい。その後はシャンプー等で洗浄し、適宜乾燥すればよい。 After the application of the polymerization accelerator, the time for leaving the silanol compound (2) to proceed for polymerization is preferably 1 to 60 minutes, particularly preferably about 20 to 40 minutes. At this time, the hair may be wrapped with a wrap or the like to prevent the hair from drying, and the coated part may be heated to 40 to 90 ° C, preferably 40 to 60 ° C. Thereafter, it may be washed with shampoo or the like and dried appropriately.
試験例１（実施例１〜17及び比較例１〜３）
シラノール化合物が脱水縮合して分子量が増えると、溶液に不溶になるため白濁する。従って溶液が白濁する時間を調べることにより、重合に要する時間を見積もることができる。そこで、表１に示す毛髪処理剤50ｇと表２に示す重合促進剤50ｇをガラス容器に入れ、室温（25℃）で攪拌しながら溶液が白濁する時間を調べた。
Test Example 1 (Examples 1 to 17 and Comparative Examples 1 to 3)
When the silanol compound is dehydrated and condensed to increase the molecular weight, it becomes insoluble in the solution and becomes cloudy. Therefore, the time required for polymerization can be estimated by examining the time during which the solution becomes cloudy. Therefore, 50 g of the hair treatment agent shown in Table 1 and 50 g of the polymerization accelerator shown in Table 2 were put in a glass container, and the time during which the solution became cloudy was examined while stirring at room temperature (25 ° C.).
実施例18〜21及び比較例４
以下の実施例及び比較例では、表３に示す毛髪処理剤及び重合促進剤を使用した。
Examples 18 to 21 and Comparative Example 4
In the following examples and comparative examples, the hair treatment agents and polymerization accelerators shown in Table 3 were used.
また、以下の実施例及び比較例での毛髪へのケイ素化合物の収着量の評価は、以下の方法でケイ素元素の収着量を測定することにより行った。 Moreover, evaluation of the sorption amount of the silicon compound to the hair in the following Examples and Comparative Examples was performed by measuring the sorption amount of the silicon element by the following method.
毛髪へのケイ素化合物の収着量評価には「ICP（誘導結合プラズマ）発光分析装置（堀場製作所，JY238ULTRACE）」を用いた。ケイ素化合物の収着量は、灰化／アルカリ溶融／ICP法を用いて測定したケイ素元素の量に基づき、ケイ素元素収着量として求めた。
試料0.1ｇを白金坩堝に採取し、ヒーターで煙が出なくなるまで炭化後、550℃の電気炉に２時間入れ灰化させる。冷却後、残った灰分上にアルカリ融剤（Ｎａ2ＣＯ3：Ｈ3ＢＯ3＝５：２）１ｇを加え、950℃電気炉30分でアルカリ溶融し、冷却後、６Ｎ塩酸４mLで溶解して純水で50mLにメスアップしたものを試料溶液とした。吸収波長251.612nm、積分時間３秒で３回測定し、その平均値から、検量線を使用してケイ素元素量を求めた。毛髪へのケイ素元素収着量の計算法は次のとおりである。
An ICP (inductively coupled plasma) emission spectrometer (Horiba, JY238ULTRACE) was used to evaluate the amount of silicon compound sorbed on the hair. The sorption amount of the silicon compound was determined as the sorption amount of silicon element based on the amount of silicon element measured using ashing / alkaline melting / ICP method.
0.1 g of sample is collected in a platinum crucible, carbonized until no smoke is produced with a heater, and then placed in an electric furnace at 550 ° C. for 2 hours for ashing. After cooling, add 1 g of alkaline flux (Na 2 CO 3 : H 3 BO 3 = 5: 2) on the remaining ash, melt in alkali at 950 ° C. for 30 minutes, cool and dissolve in 4 mL of 6N hydrochloric acid. The sample solution was made up to 50 mL with pure water. Measurement was performed three times at an absorption wavelength of 251.512 nm and an integration time of 3 seconds, and the amount of silicon element was determined from the average value using a calibration curve. The calculation method of the silicon element sorption amount to the hair is as follows.
ケイ素元素収着量（％）＝〔ケイ素元素量（mg）／毛髪重量（ｇ）〕×0.1 Silicon element sorption amount (%) = [silicon element amount (mg) / hair weight (g)] × 0.1
実施例18
化学処理履歴のない毛束３ｇに毛髪処理剤ａを３ｇ塗布した後、30分間剤が乾燥しないようにラップで包み、室温（25℃）で放置した。毛髪処理剤ａをタオルで拭き取り、重合促進剤ａを３ｇ均一に塗布した後、30分間剤が乾燥しないようにラップで包み、放置した。その後シリコーンを含有しないシャンプーで洗い流し、十分に乾燥した後、毛髪に付着及び浸透したケイ素の収着量を定量した。毛髪のケイ素収着量の測定にはICP（誘導プラズマ）発光分析装置を用いた。処理した毛髪に収着したケイ素の量は0.4重量％であった。なお、毛髪処理剤ａと重合促進剤ａを１：１の重量比で混合したときのpHは、2.1である。
Example 18
After 3 g of hair treatment agent a was applied to 3 g of hair bundle without chemical treatment history, it was wrapped in a wrap so that the agent did not dry for 30 minutes and allowed to stand at room temperature (25 ° C.). The hair treatment agent a was wiped off with a towel and 3 g of the polymerization accelerator a was uniformly applied, and then wrapped in a wrap so that the agent did not dry for 30 minutes and left to stand. Thereafter, it was washed away with a shampoo containing no silicone, and after sufficiently drying, the amount of silicon adsorbed and penetrated to the hair was quantified. An ICP (induction plasma) emission spectrometer was used to measure the silicon sorption amount of the hair. The amount of silicon sorbed to the treated hair was 0.4% by weight. The pH when the hair treatment agent a and the polymerization accelerator a are mixed at a weight ratio of 1: 1 is 2.1.
実施例19
化学処理履歴のない毛束３ｇに毛髪処理剤ａを３ｇ塗布した後、30分間剤が乾燥しないようにラップで包み、室温（25℃）で放置した。毛髪処理剤ａをタオルで拭き取り、重合促進剤ａを３ｇ均一に塗布した後、30分間剤が乾燥しないようにラップで包み、放置した。その後シリコーンを含有しないシャンプーで洗い流し、十分に乾燥した。上記毛髪処理剤塗布からシャンプーまでの処理を３回繰り返した後、毛髪に付着及び浸透したケイ素の収着量を定量した。毛髪のケイ素収着量の測定にはICP（誘導プラズマ）発光分析装置を用いた。処理した毛髪に収着したケイ素の量は1.6重量％であり、繰り返して処理を行うことによりケイ素の収着量が向上した。なお、毛髪処理剤ａと重合促進剤ａを１：１の重量比で混合したときのpHは、2.1である。
Example 19
After 3 g of hair treatment agent a was applied to 3 g of hair bundle without chemical treatment history, it was wrapped in a wrap so that the agent did not dry for 30 minutes and allowed to stand at room temperature (25 ° C.). The hair treatment agent a was wiped off with a towel and 3 g of the polymerization accelerator a was uniformly applied, and then wrapped in a wrap so that the agent did not dry for 30 minutes and left to stand. Thereafter, it was washed away with a shampoo containing no silicone and sufficiently dried. After repeating the treatment from application of the hair treatment agent to shampoo three times, the amount of silicon adsorbed and penetrated to the hair was quantified. An ICP (induction plasma) emission spectrometer was used to measure the silicon sorption amount of the hair. The amount of silicon sorbed to the treated hair was 1.6% by weight, and the amount of silicon sorption was improved by repeated treatment. The pH when the hair treatment agent a and the polymerization accelerator a are mixed at a weight ratio of 1: 1 is 2.1.
実施例20
化学処理履歴のない毛束３ｇに毛髪処理剤ｂを３ｇ塗布した後、30分間剤が乾燥しないようにラップで包み、室温（25℃）で放置した。毛髪処理剤ｂをタオルで拭き取り、重合促進剤ｂを３ｇ均一に塗布した後、30分間剤が乾燥しないようにラップで包み、放置した。その後シリコーンを含有しないシャンプーで洗い流し、十分に乾燥した後、毛髪に付着及び浸透したケイ素の収着量を定量した。毛髪のケイ素収着量の測定にはICP（誘導プラズマ）発光分析装置を用いた。処理した毛髪に収着したケイ素の量は1.20重量％であり、毛髪処理剤に含まれるケイ素化合物の含有量を増やすことによりケイ素の収着量が向上した。なお、毛髪処理剤ｂと重合促進剤ｂを１：１の重量比で混合したときのpHは、3.1である。
Example 20
After 3 g of hair treatment agent b was applied to 3 g of hair bundle without chemical treatment history, it was wrapped in wrap so that the agent did not dry for 30 minutes and allowed to stand at room temperature (25 ° C.). The hair treatment agent b was wiped off with a towel and 3 g of the polymerization accelerator b was uniformly applied, and then wrapped in a wrap so that the agent did not dry for 30 minutes and allowed to stand. Thereafter, it was washed away with a shampoo containing no silicone, and after sufficiently drying, the amount of silicon adsorbed and penetrated to the hair was quantified. An ICP (induction plasma) emission spectrometer was used to measure the silicon sorption amount of the hair. The amount of silicon sorbed on the treated hair was 1.20% by weight, and the silicon sorption amount was improved by increasing the content of the silicon compound contained in the hair treatment agent. The pH when the hair treatment agent b and the polymerization accelerator b are mixed at a weight ratio of 1: 1 is 3.1.
実施例21
ヘアカラー、ヘアストレートパーマ履歴のあるロングヘアーの女性の髪を真ん中から二つにクシで分け、片側の髪に毛髪処理剤ｃを均一に塗布した後、処理部分をラップで覆い、頭部加温器（ローラーボール）で48℃に加温しながら30分間放置した。毛髪処理剤ｃをタオルで拭き取り、重合促進剤ｂを均一に塗布した後、室温（25℃）で15分間放置した。その後シリコーンを含有しないシャンプーで洗い流し、十分に乾燥した後、処理した髪と、処理していない髪の外観及び感触を評価した。また、毛髪に付着及び浸透したケイ素の収着量も定量した。毛髪のケイ素収着量の測定にはICP（誘導プラズマ）発光分析装置を用いた。処理した毛髪は、処理していない毛髪と比較して明らかに弾力性が向上し、かつハネ毛、浮き毛が抑制され、まとまりのある外観になった。処理した毛髪に収着したケイ素の量は2.09重量％であり、毛髪処理剤を塗布した後に加温することにより、ケイ素の収着量が向上した。なお、毛髪処理剤ｃと重合促進剤ｂを１：１の重量比で混合したときのpHは、3.1である。
Example 21
Divide the hair of a long-haired woman with a history of hair color and hair straight perm into two from the middle, apply hair treatment agent c evenly on one side of the hair, cover the treated area with wrap, The mixture was allowed to stand for 30 minutes while being heated to 48 ° C with a warmer (roller ball). The hair treatment agent c was wiped off with a towel and the polymerization accelerator b was uniformly applied, and then allowed to stand at room temperature (25 ° C.) for 15 minutes. After washing with a shampoo containing no silicone and drying sufficiently, the appearance and feel of the treated and untreated hair were evaluated. The amount of silicon sorbed and penetrated into the hair was also quantified. An ICP (induction plasma) emission spectrometer was used to measure the silicon sorption amount of the hair. The treated hair was clearly improved in elasticity as compared to the untreated hair, and the hairs and floating hairs were suppressed, resulting in a coherent appearance. The amount of silicon sorbed on the treated hair was 2.09% by weight, and the sorption amount of silicon was improved by heating after applying the hair treatment agent. The pH when the hair treatment agent c and the polymerization accelerator b are mixed at a weight ratio of 1: 1 is 3.1.
比較例４
化学処理履歴のない毛束３ｇに毛髪処理剤ａを３ｇ塗布した後、30分間剤が乾燥しないようにラップで包み、室温（25℃）で放置した。シリコーンを含有しないシャンプーで洗い流し、十分に乾燥した後、毛髪に付着及び浸透したケイ素の収着量を定量した。毛髪のケイ素収着量の測定にはICP（誘導プラズマ）発光分析装置を用いた。処理した毛髪に収着したケイ素の量は0.19重量％であった。
Comparative Example 4
After 3 g of hair treatment agent a was applied to 3 g of hair bundle without chemical treatment history, it was wrapped in a wrap so that the agent did not dry for 30 minutes and allowed to stand at room temperature (25 ° C.). After rinsing with a shampoo containing no silicone and sufficiently drying, the amount of silicon adsorbed and penetrated to the hair was quantified. An ICP (induction plasma) emission spectrometer was used to measure the silicon sorption amount of the hair. The amount of silicon sorbed to the treated hair was 0.19% by weight.
Claims (7)
Ｒ1 pＳｉ(ＯＲ2)4-p (1)
〔式中、Ｒ1及びＲ2は、炭素数１〜６の直鎖若しくは分岐鎖のアルキル基又は炭素数２〜６の直鎖若しくは分岐鎖のアルケニル基を示し、ｐ個のＲ1及び（４−ｐ）個のＲ2は同一でも異なってもよい。ｐは０〜２の整数を示す。〕
で表されるアルコキシシラン、有機酸及び水を構成要素とする毛髪処理剤(Ａ1)を使用直前に攪拌混合し、混合溶液が均一な１相になることで、当該アルコキシシランが加水分解され次の一般式(2)
Ｒ1 pＳｉ(ＯＨ)n(ＯＲ2)4-p-n (2)
〔式中、Ｒ1、Ｒ2及びｐは前記と同じ意味を示し、ｎは１以上（４−ｐ）以下の整数を示す。ｐ個のＲ1及び（４−ｐ−ｎ）個のＲ2は同一でも異なってもよい。〕
で表される分子量300以下のシラノール化合物に変換されたことを確認し、その後30分以内に、当該確認後の毛髪処理剤(Ａ2)を毛髪に塗布し、10〜90分間放置することによって、当該シラノール化合物を毛髪内に浸透させ、次いで重合促進剤として、毛髪処理剤(Ａ2)に１：１の重量比で混合したときのpHを１〜４とする酸性水溶液(Ｂa)、又は毛髪処理剤(Ａ2)に１：１の重量比で混合したときのpHを８〜12とするアルカリ性水溶液(Ｂb)を毛髪に塗布して、シラノール化合物を毛髪内部で重合させる毛髪改質方法。 The following general formula (1)
R 1 p Si (OR 2 ) 4-p (1)
[Wherein, R 1 and R 2 represent a linear or branched alkyl group having 1 to 6 carbon atoms or a linear or branched alkenyl group having 2 to 6 carbon atoms, and p R 1 and ( 4-p) R 2 may be the same or different. p is an integer of 0-2. ]
The hair treatment agent (A 1 ) containing the alkoxysilane, organic acid and water represented by the formula is stirred and mixed immediately before use, so that the mixed solution becomes a uniform one phase, so that the alkoxysilane is hydrolyzed. The following general formula (2)
R 1 p Si (OH) n (OR 2 ) 4-pn (2)
[Wherein R 1 , R 2 and p represent the same meaning as described above, and n represents an integer of 1 or more and (4-p) or less. p R 1 and (4-p−n) R 2 may be the same or different. ]
By confirming that it has been converted to a silanol compound having a molecular weight of 300 or less represented by the formula , and then applying the hair treatment agent (A 2 ) after the confirmation to the hair within 30 minutes and leaving it for 10 to 90 minutes , the silanol compound is permeated into the hair, then as the polymerization accelerator, the hair treatment agent (a 2) to 1: acidic aqueous solution of pH when mixed in a weight ratio between 1 to 4 (B a), Alternatively, an alkaline aqueous solution (B b ) having a pH of 8 to 12 when mixed in a weight ratio of 1: 1 with the hair treatment agent (A 2 ) is applied to the hair, and the hair modification is carried out to polymerize the silanol compound inside the hair. Quality method.
Priority Applications (7)
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| JP2004379418A JP4509769B2 (en) | 2004-12-28 | 2004-12-28 | Hair modification method |
| PCT/JP2005/006775 WO2005097050A1 (en) | 2004-04-07 | 2005-04-06 | Hair-treating agent and methods of treating hair |
| KR1020067019109A KR20060134988A (en) | 2004-04-07 | 2005-04-06 | Hair-treating agent and methods of treating hair |
| US11/578,146 US20070218028A1 (en) | 2004-04-07 | 2005-04-06 | Hair-Treating Agent And Methods Of Treating Hair |
| EP05728472.1A EP1736139B1 (en) | 2004-04-07 | 2005-04-06 | Hair processing compositions and methods for processing hair |
| CN2005800107718A CN1937996B (en) | 2004-04-07 | 2005-04-06 | Hair-treating agent and methods of treating hair |
| US12/819,752 US8420064B2 (en) | 2004-04-07 | 2010-06-21 | Hair-treating agent and methods of treating hair |
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| JP5235050B2 (en) * | 2006-08-11 | 2013-07-10 | 花王株式会社 | Hair modifier |
| JP5244308B2 (en) * | 2006-12-18 | 2013-07-24 | 花王株式会社 | Hair treatment agent |
| JP5238276B2 (en) * | 2008-02-07 | 2013-07-17 | 花王株式会社 | Hair treatment agent |
| FR2930439B1 (en) * | 2008-04-25 | 2012-09-21 | Oreal | USE OF A COSMETIC COMPOSITION COMPRISING AT LEAST ONE ORGANIC COMPOUND OF SILICON IN ASSOCIATION WITH A KERATIN FIBER CARE AND / OR WASH COMPOSITION |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02160836A (en) * | 1988-08-18 | 1990-06-20 | Fraunhofer Ges | Method and composition for preparing |
| JPH06263875A (en) * | 1993-09-27 | 1994-09-20 | Toshiba Silicone Co Ltd | Production of fine polyorganosililsequioxane particle |
| JP2001002989A (en) * | 1999-06-21 | 2001-01-09 | Jsr Corp | Composition for forming film, formation of film and low- density film |
| JP2003510261A (en) * | 1999-09-27 | 2003-03-18 | ロレアル | Cosmetic compositions based on organosilicon compounds containing at least one non-basic, solubilizing functional group |
| WO2004012691A1 (en) * | 2002-07-25 | 2004-02-12 | Itn Nanovation Gmbh | Use of silanes in cosmetic agents and methods for treating hair |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02160836A (en) * | 1988-08-18 | 1990-06-20 | Fraunhofer Ges | Method and composition for preparing |
| JPH06263875A (en) * | 1993-09-27 | 1994-09-20 | Toshiba Silicone Co Ltd | Production of fine polyorganosililsequioxane particle |
| JP2001002989A (en) * | 1999-06-21 | 2001-01-09 | Jsr Corp | Composition for forming film, formation of film and low- density film |
| JP2003510261A (en) * | 1999-09-27 | 2003-03-18 | ロレアル | Cosmetic compositions based on organosilicon compounds containing at least one non-basic, solubilizing functional group |
| WO2004012691A1 (en) * | 2002-07-25 | 2004-02-12 | Itn Nanovation Gmbh | Use of silanes in cosmetic agents and methods for treating hair |
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