JP2008150315A - Hair treatment - Google Patents

Hair treatment Download PDF

Info

Publication number
JP2008150315A
JP2008150315A JP2006339550A JP2006339550A JP2008150315A JP 2008150315 A JP2008150315 A JP 2008150315A JP 2006339550 A JP2006339550 A JP 2006339550A JP 2006339550 A JP2006339550 A JP 2006339550A JP 2008150315 A JP2008150315 A JP 2008150315A
Authority
JP
Japan
Prior art keywords
hair
treatment agent
hair treatment
agent
alkoxysilane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2006339550A
Other languages
Japanese (ja)
Other versions
JP5244308B2 (en
Inventor
Hiroaki Saito
裕映 斉藤
Koji Yui
幸治 湯井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to JP2006339550A priority Critical patent/JP5244308B2/en
Publication of JP2008150315A publication Critical patent/JP2008150315A/en
Application granted granted Critical
Publication of JP5244308B2 publication Critical patent/JP5244308B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair modifier usable by short-time preparation, and capable of imparting excellent tenseness and stiffness to a hair fiber, especially the hair (damaged hair, thin hair or the like) hardly having the tenseness and stiffness in a short time; and to provide a hair-modifying method. <P>SOLUTION: The hair treatment contains an alkoxysilane having a ureide group. The hair modifier comprises the hair treatment and a hair treatment for promoting hydrolysis and polymerization reaction. The hair-modifying method uses the hair modifier. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、毛髪にハリ・コシを付与する毛髪改質剤、毛髪改質方法及びこれらに用いられる毛髪処理剤に関する。   The present invention relates to a hair modifying agent that imparts firmness and firmness to hair, a hair modifying method, and a hair treatment agent used in these.

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、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、かつ毛髪内部で重合させる方法が提案されている（特許文献１〜３参照）。これらの方法によれば、毛髪直径を増加させることによって、毛髪、特に、ハリ・コシがない毛髪（損傷毛、細い毛髪等）に対し、ハリ・コシを付与することが可能であり、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、その効果はシャンプーを繰り返しても持続する。しかし、これらの方法には、毛髪へ適用する前の加水分解反応に時間が掛かり、加水分解反応の終了の見極めを行う必要があり、簡便に行うことができないという問題があった。   Conventionally, as a method for improving the physical properties, appearance, and feel of hair by infiltrating substances into the hair, a method has been proposed in which silanol compounds produced by hydrolysis of alkoxysilane are allowed to penetrate into the hair and polymerize inside the hair. (See Patent Documents 1 to 3). According to these methods, by increasing the hair diameter, it is possible to impart firmness and firmness to hair, particularly hair that has no firmness and stiffness (damaged hair, thin hair, etc.). A cohesiveness improving effect and a hair straightening effect are also obtained, and the effect persists even after repeated shampooing. However, these methods have a problem that it takes time for the hydrolysis reaction before applying to hair, and it is necessary to determine the end of the hydrolysis reaction, which cannot be easily performed.

特開2005-320314号公報JP 2005-320314 A 特開2006-160676号公報JP 2006-160676 特開2006-182715号公報JP 2006-182715 A

本発明は、短時間の準備で使用することができ、毛髪繊維、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ができる毛髪改質剤及び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。   INDUSTRIAL APPLICABILITY The present invention can be used in a short period of preparation, and can impart excellent firmness and firmness in a short time to hair fibers, particularly hair that has no firmness and firmness (damaged hair, fine hair, etc.). An object is to provide a hair modifying agent and a hair modifying method. Here, giving firmness and elasticity means improving hair elasticity.

本発明者らは、ウレイド基を有するアルコキシシランを含有する毛髪処理剤では、毛髪に処理剤を浸透させる前の加水分解のための攪拌操作が短時間で済み、これを加水分解して生成させたシラノール化合物を毛髪に塗布して浸透させ、その後、加水分解及び重合反応の促進のための毛髪処理剤を塗布して毛髪内部で重合させれば、毛髪に優れたハリ・コシを付与することができ、また、毛髪への滑らかな感触の付与や、毛髪のまとまり性の向上や、くせ毛の矯正の効果も得られることを見出した。   In the hair treatment agent containing an alkoxysilane having a ureido group, the present inventors need only a short stirring operation for hydrolysis before allowing the treatment agent to permeate into the hair. Applying a silanol compound to the hair and infiltrating it, then applying a hair treatment agent for promoting hydrolysis and polymerization reaction and polymerizing inside the hair will give the hair an excellent firmness and firmness. It has also been found that the effect of imparting a smooth feel to the hair, improving the cohesiveness of the hair, and correcting the comb hair can be obtained.

すなわち、本発明は、ウレイド基を有するアルコキシシランを含有する毛髪処理剤を提供するものである。   That is, the present invention provides a hair treatment agent containing an alkoxysilane having a ureido group.

また、本発明は、次の毛髪処理剤(Ａ)及び(Ｂ)からなる毛髪改質剤を提供するものである。
(Ａ) 前記の毛髪処理剤
(Ｂ) 加水分解及び重合反応の促進のための毛髪処理剤 The present invention also provides a hair modifier comprising the following hair treatment agents (A) and (B).
(A) said hair treatment agent
(B) Hair treatment agent for promoting hydrolysis and polymerization reaction

さらに、本発明は、前記の毛髪改質剤を用い、前記毛髪処理剤(Ａ)を毛髪に塗布した後、前記毛髪処理剤(Ｂ)を毛髪に塗布する毛髪改質方法を提供するものである。   Furthermore, the present invention provides a hair modification method in which the hair treatment agent (A) is applied to the hair after the hair treatment agent (A) is applied to the hair using the hair modification agent. is there.

本発明によれば、ウレイド基を有する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、毛髪内部で速やかに重合させることにより毛髪直径を増加させることができる。この結果として、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・コシを付与し、しっかりとした健康的な毛髪に改質することができる。また、ウレイド基を有するアルコキシシランは加水分解が非常に速く、毛髪へ剤を浸透させる前の加水分解のための攪拌操作が著しく軽減されるため、本発明の毛髪処理剤を用いれば、毛髪の改質を短時間に行うことができ、また、従来必要であった加水分解反応の終了の見極めを行う必要がない。さらに、本発明の毛髪処理剤を用いれば、毛髪にハリ・コシ感、ボリューム感の付与効果のみならず、滑らかな感触の付与効果や毛髪のまとまり性向上効果、くせ毛の矯正効果も得られる。これら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 having a ureido group to penetrate into the hair and rapidly polymerize within the hair. As a result, it is possible to impart excellent firmness and firmness in a short period of time to hair, especially hair that does not have firmness and firmness (damaged hair, thin hair, etc.), and to modify it into firm and healthy hair. it can. In addition, alkoxysilane having a ureido group is very rapidly hydrolyzed, and the stirring operation for hydrolysis before penetrating the agent into the hair is remarkably reduced. Therefore, if the hair treatment agent of the present invention is used, The reforming can be performed in a short time, and it is not necessary to determine the completion of the hydrolysis reaction that has been conventionally required. Furthermore, when the hair treatment agent of the present invention is used, not only the effect of imparting firmness and firmness and volume feeling to the hair, but also the effect of imparting a smooth feel, the effect of improving the cohesiveness of the hair, and the effect of correcting comb hair are obtained. These effects persist 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(Ｂ)」とは、「毛髪処理剤(Ｂa)」、「毛髪処理剤(Ｂb)」のいずれをも含むものとする。 “Hair modification” in the present invention means that the hair has a firmness, firmness and coherence. In the present invention, “hair treatment agent (B)” includes both “hair treatment agent (B a )” and “hair treatment agent (B b )”.

《毛髪処理剤(Ａ)》
本発明の毛髪処理剤は、ウレイド基を有するアルコキシシランを含有するものであり、加水分解及び重合反応の促進のための毛髪処理剤(Ｂ)と組み合わせることにより、毛髪改質剤として使用される。 << Hair Treatment Agent (A) >>
The hair treatment agent of the present invention contains an alkoxysilane having a ureido group, and is used as a hair modifier by combining with a hair treatment agent (B) for promoting hydrolysis and polymerization reaction. .

〔ウレイド基を有するアルコキシシラン〕
ウレイド基を有するアルコキシシランとしては、次の一般式(1)で表されるものが好ましい。 [Alkoxysilane having a ureido group]
As the alkoxysilane having a ureido group, those represented by the following general formula (1) are preferable.

Figure 2008150315
Figure 2008150315

〔式中、Ｒ1、Ｒ3、Ｒ4及びＲ5は、水素原子又は炭素数１〜６の炭化水素基を示し、Ｒ2は、炭素数１〜６の２価の炭化水素基を示し、Ｘはハロゲン原子又は炭素数１〜６のアルコキシ基を示し、ｎは１〜３の整数を示す。〕 [Wherein R 1 , R 3 , R 4 and R 5 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R 2 represents a divalent hydrocarbon group having 1 to 6 carbon atoms. , X represents a halogen atom or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3. ]

一般式(1)において、Ｒ1、Ｒ3、Ｒ4及びＲ5としては、水素原子又は飽和若しくは不飽和の直鎖若しくは分岐鎖の炭素数１〜６の炭化水素基、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基等が挙げられる。Ｒ2としては、飽和又は不飽和の直鎖又は分岐鎖の炭素数１〜６の２価炭化水素基、具体的には、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、メチル置換テトラメチレン基、ビニレン基等が挙げられる。ｎ個のＸは、同一又は異なっていても良く、具体的には、塩素原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、t-ブトキシ基等が挙げられ、特に、加水分解反応の反応性等の点から、メトキシ基及びエトキシ基が好ましい。 In the general formula (1), R 1 , R 3 , R 4 and R 5 are each a hydrogen atom or a saturated or unsaturated linear or branched hydrocarbon group having 1 to 6 carbon atoms, specifically, Examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and the like. R 2 is a saturated or unsaturated linear or branched divalent hydrocarbon group having 1 to 6 carbon atoms, specifically, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, methyl A substituted tetramethylene group, a vinylene group, etc. are mentioned. n Xs may be the same or different, and specific examples include a chlorine atom, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. In particular, a methoxy group and an ethoxy group are preferable from the viewpoint of the reactivity of the hydrolysis reaction.

ウレイド基を有するアルコキシシランは、保管中の加水分解及び重合を回避するため、使用される直前までは水と分離して保管することが必要である。従って、毛髪処理剤(Ａ)は、ウレイド基を有するアルコキシシランを含有し、水を含有しない第１剤と、水を含有する第２剤とからなる二剤式とすることが好ましい。この第１剤と第２剤を混合して加水分解することにより、ウレイド基を有するアルコキシシランは、重合可能なシラノール化合物となる。   In order to avoid hydrolysis and polymerization during storage, the alkoxysilane having a ureido group needs to be stored separately from water until just before use. Therefore, it is preferable that the hair treatment agent (A) is a two-component type comprising an alkoxysilane having a ureido group and comprising a first agent not containing water and a second agent containing water. By mixing and hydrolyzing the first agent and the second agent, the alkoxysilane having a ureido group becomes a polymerizable silanol compound.

ウレイド基を有するアルコキシシランの含有量は、架橋反応による反応性の点から、毛髪処理剤(Ａ)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質量％以上、特に12質量％以上が好ましく、また82質量％以下、特に58質量％以下が好ましい。また、第１剤中のウレイド基を有するアルコキシシランの含有量は、保存安定性の点から、70〜100質量％、更には80〜100質量％、特に90〜100質量％が好ましい。   The content of the alkoxysilane having a ureido group is determined in the hair treatment agent (A) from the point of reactivity due to the cross-linking reaction (in the case of the two-component type, in the total composition including the first agent and the second agent; 4 mass% or more of the same), particularly 12 mass% or more is preferable, and 82 mass% or less, particularly 58 mass% or less is preferable. In addition, the content of the alkoxysilane having a ureido group in the first agent is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass from the viewpoint of storage stability.

〔水〕
水は、本発明で使用する毛髪処理剤(Ａ)が二剤式の場合には、第１剤に配合されるウレイド基を有するアルコキシシランとは別個に、第２剤に配合され、その含有量は、毛髪を十分に膨潤させ、ウレイド基を有するアルコキシシランの加水分解物であるシラノール化合物を毛髪へ十分浸透させる観点から、毛髪処理剤(Ａ)中の20〜95質量％、特に30〜86質量％が好ましい。 〔water〕
When the hair treatment agent (A) used in the present invention is a two-component type, water is blended in the second agent separately from the alkoxysilane having a ureido group blended in the first agent, The amount is 20 to 95% by mass in the hair treatment agent (A), particularly 30 to 30% from the viewpoint of sufficiently swelling the hair and allowing the silanol compound, which is a hydrolyzate of alkoxysilane having a ureido group, to sufficiently penetrate into the hair. 86 mass% is preferable.

〔毛髪処理剤(Ａ)のpH〕
本発明で使用する処理剤(Ａ)においては、ウレイド基を有するアルコキシシランが加水分解したシラノール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(Ａ)のpH（20℃）を２〜５、特に３〜４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 (A)]
In the treatment agent (A) used in the present invention, it is necessary to delay the polymerization reaction in order to allow the silanol hydrolyzed by the alkoxysilane having a ureido group to penetrate into the hair and cause the polymerization reaction in the hair. For this purpose, it is preferable to adjust the pH (20 ° C.) of the hair treatment agent (A) to 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.

〔有機酸〕
毛髪処理剤(Ａ)には、pH調整のため、有機酸を含有させることができる。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、なかでも臭気が少ないアジピン酸が好ましい。 [Organic acid]
The hair treatment agent (A) can contain an organic acid for pH adjustment. 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), among others, odor Adipic acid with less is preferred.

有機酸は、本発明で使用する毛髪処理剤(Ａ)が二剤式の場合には、第１剤に配合されるウレイド基を有するアルコキシシランとは別個に、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(Ａ)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) used in the present invention is a two-component type, the organic acid can be blended in the second agent separately from the alkoxysilane having a ureido group blended in the first agent. From the viewpoints of solubility 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 (A) from the viewpoint of suppressing the polymerization reaction.

〔その他の成分〕
また、ウレイド基を有するアルコキシシランを毛髪処理剤(Ａ)中に均一に溶解する目的で、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。その量は、毛髪処理剤(Ａ)を毛髪に塗布した際に、毛髪を十分に膨潤させ、ウレイド基を有するアルコキシシランの加水分解物を十分に浸透させやすくするため、毛髪処理剤(Ａ)中の35質量％以下、特に20質量％以下とすることが好ましい。 [Other ingredients]
In addition, for the purpose of uniformly dissolving the alkoxysilane having a ureido group in the hair treatment agent (A), a water-soluble organic solvent such as methanol, ethanol or other lower primary alcohol having 1 to 3 carbon atoms, glycerin or the like is used. You can also. When the hair treatment agent (A) is applied to the hair, the amount of the hair treatment agent (A) is sufficient to swell the hair sufficiently to facilitate penetration of the hydrolyzate of alkoxysilane having a ureido group. The content is preferably 35% by mass or less, particularly 20% by mass or less.

毛髪処理剤(Ａ)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、浸透促進剤、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。   The hair treatment agent (A) includes other surfactants, oil agents, silicone derivatives, cationic polymers, penetration enhancers, moisturizers, viscosity modifiers, fragrances, dyes, ultraviolet absorbers, antioxidants, antibacterial agents, An antiseptic etc. can be suitably mix | blended according to the objective.

〔毛髪処理剤(Ａ)の調製〕
毛髪処理剤(Ａ)の形態は、長期間安定である点から、好適には、ウレイド基を有するアルコキシシランを含有する第１剤と、水を含有する第２剤からなるものであるが、使用直前にウレイド基を有するアルコキシシラン、水、及び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。 [Preparation of hair treatment agent (A)]
The form of the hair treatment agent (A) is preferably composed of a first agent containing an alkoxysilane having a ureido group and a second agent containing water, since it is stable for a long period of time. It may be prepared by mixing alkoxysilane having a ureido group, water, and other optional components immediately before use.

毛髪処理剤(Ａ)を、使用直前にウレイド基を有するアルコキシシラン、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、ウレイド基を有するアルコキシシランは水と混合することによって加水分解及び重合反応が開始するので、これを抑制するため、水とその他任意成分を混合した後にウレイド基を有するアルコキシシランを混合することが好ましい。   When the hair treatment agent (A) is prepared by mixing an alkoxysilane having a ureido group, water, and other optional components immediately before use, the order of mixing is not particularly limited, but the alkoxysilane having a ureido group is Since the hydrolysis and polymerization reaction starts by mixing with water, in order to suppress this, it is preferable to mix alkoxysilane having a ureido group after mixing water and other optional components.

二剤式毛髪処理剤(Ａ)の第１剤及び第２剤を使用直前に混合することにより、又はウレイド基を有するアルコキシシラン、水、及びその他任意成分を混合することにより、ウレイド基を有するアルコキシシランは加水分解してシラノール化合物となり、毛髪内へ浸透し易くなる。ウレイド基を有するアルコキシシラン及び加水分解物（シラノール化合物）の物性、毛髪内への浸透性の点から、当該アルコキシシランとして一般式(1)中、ｎが２〜３であるものを使用するのが好ましい。   It has a ureido group by mixing the first agent and the second agent of the two-part hair treatment agent (A) immediately before use, or by mixing alkoxysilane having ureido group, water, and other optional components. Alkoxysilane is hydrolyzed to become a silanol compound and easily penetrates into the hair. From the viewpoint of the physical properties of the alkoxysilane having a ureido group and the hydrolyzate (silanol compound) and the penetrability into the hair, the alkoxysilane having a general formula (1) where n is 2 to 3 is used. Is preferred.

《毛髪処理剤(Ｂ)》
毛髪処理剤(Ｂ)は、ウレイド基を有するアルコキシシランが加水分解したシラノール化合物の毛髪内での重合を促進させるものであるとともに、加水分解を促進させることもでき、一部加水分解されることなく毛髪内に浸透した場合にも、毛髪内で完全にシラノール化合物に加水分解させ、重合させる役割を有する。毛髪処理剤(Ｂ)を用いて加水分解及び重合させることにより、ハリ・コシ付与効果を向上し、また処理時間を短縮することができる。 << Hair Treatment Agent (B) >>
The hair treatment agent (B) promotes polymerization in the hair of a silanol compound hydrolyzed by an alkoxysilane having a ureido group, can also promote hydrolysis, and is partially hydrolyzed. Even when it penetrates into the hair, it has a role of completely hydrolyzing and polymerizing the silanol compound in the hair. By hydrolyzing and polymerizing using the hair treatment agent (B), the effect of imparting firmness and stiffness can be improved and the treatment time can be shortened.

毛髪処理剤(Ｂ)としては、次の(Ｂa)及び(Ｂb)のいずれかを用いることができる。 As the hair treatment agent (B), any of the following (B a ) and (B b ) can be used.

・毛髪処理剤(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の質量比で混合した場合の混合物のpHを１〜４とする毛髪処理剤（酸性水溶液） Hair treatment agent (B a ): a mixture of organic acid or inorganic acid having a first dissociation index (pKa1) of less than 4.1 and mixed with the hair treatment agent (A) at a mass ratio of 1: 1 Hair treatment agent with pH 1 to 4 (acidic aqueous solution)

・毛髪処理剤(Ｂb)：単独でのpHが８〜12であり、毛髪処理剤(Ａ)に１：１の質量比で混合した場合の混合物のpHを８〜12とする毛髪処理剤（アルカリ性水溶液） Hair treatment agent (B b ): A hair treatment agent having a pH of 8 to 12 alone and a pH of the mixture of 8 to 12 when mixed with the hair treatment agent (A) at a mass ratio of 1: 1. (Alkaline aqueous solution)

〔毛髪処理剤(Ｂa)：酸性水溶液〕
毛髪処理剤(Ｂa)を使用する場合、すなわちウレイド基を有するアルコキシシランの加水分解及びその後の重合反応の促進に酸性水溶液を使用する場合、有機酸又は無機酸は、重縮合の反応速度の点から、pKaが4.1未満のものを用いるが、特に3.7以下であるものが好ましく、pKaが１以上、更には２以上、特に３以上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、乳酸が好ましい。 [Hair treatment agent (B a ): acidic aqueous solution]
When the hair treatment agent (B a ) is used, that is, when an acidic aqueous solution is used for the hydrolysis of the alkoxysilane having a ureido group and the subsequent polymerization reaction, the organic acid or inorganic acid has a reaction rate of polycondensation. In view of the above, those having a pKa of less than 4.1 are used, but those having a pKa of 3.7 or less are particularly preferred, and those having a pKa of 1 or more, more preferably 2 or more, particularly 3 or more 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 and lactic acid are preferred.

毛髪処理剤(Ｂa)は、重縮合の反応速度の点から、毛髪処理剤(Ａ)に１：１の質量比で混合した場合の混合物のpHを１〜４とするものを使用し、好ましくは当該pHを２〜４、特に2.5〜3.8とするものを使用する。また、毛髪処理剤(Ｂa)は、上記pH範囲の緩衝系としてもよい。 The hair treatment agent (B a ) is one having a pH of 1 to 4 when the hair treatment agent (A) is mixed at a mass ratio of 1: 1 from the viewpoint of the polycondensation reaction rate, Preferably, the pH is 2 to 4, particularly 2.5 to 3.8. The hair treatment agent (B a ) may be a buffer system in the above pH range.

〔毛髪処理剤(Ｂb)：アルカリ性水溶液〕
毛髪処理剤(Ｂb)を使用する場合、すなわちウレイド基を有するアルコキシシランの加水分解及びその後の重合反応の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。 [Hair treatment agent (B b ): alkaline aqueous solution]
When the hair treatment agent (B b ) is used, that is, when an alkaline aqueous solution is used to promote hydrolysis of the alkoxysilane having a ureido group and the subsequent polymerization reaction, the alkali includes carbonates such as sodium bicarbonate and calcium carbonate. Salts; hydroxides such as sodium hydroxide and potassium hydroxide; alkanolamines such as monoethanolamine and 2-amino-2-methyl-1-propanol can be used.

毛髪処理剤(Ｂb)は、重縮合の反応速度の点から、単独でのpHが８〜12であるが、当該pHは8.5〜12、特に９〜10であるのが好ましい。毛髪処理剤(Ｂb)は、毛髪処理剤(Ａ)に１：１の質量比で混合した場合の混合物のpHを８〜12とするが、当該pHを8.5〜12、特に９〜10とするものが好ましい。また、毛髪処理剤(Ｂb)は、上記pH範囲の緩衝系としてもよい。 The hair treatment agent (B b ) has a pH of 8 to 12 alone from the viewpoint of the reaction rate of polycondensation, but the pH is preferably 8.5 to 12, particularly 9 to 10. The hair treatment agent (B b ) has a pH of 8 to 12 when mixed with the hair treatment agent (A) at a mass ratio of 1: 1, and the pH is 8.5 to 12, particularly 9 to 10. Those that do are preferred. The hair treatment agent (B b ) may be a buffer system in the above pH range.

〔その他の成分〕
毛髪処理剤(Ｂ)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、浸透促進剤、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よい。 [Other ingredients]
The hair treatment agent (B) includes other surfactants, oil agents, silicone derivatives, cationic polymers, penetration enhancers, moisturizers, viscosity modifiers, fragrances, pigments, ultraviolet absorbers, antioxidants, antibacterial agents, An antiseptic etc. can be suitably mix | blended according to the objective. Moreover, you may make it an emulsion using an oil agent and surfactant.

《毛髪改質方法》
以上説明した毛髪改質剤を用いた毛髪の改質は、毛髪処理剤(Ａ)を毛髪に塗布した後、毛髪処理剤(Ｂ)を毛髪に塗布することにより行われる。 《Hair modification method》
The hair modification using the hair modifying agent described above is performed by applying the hair treatment agent (A) to the hair and then applying the hair treatment agent (B) to the hair.

本発明の毛髪改質方法において、毛髪処理剤(Ａ)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、又はウレイド基を有するアルコキシシラン、水、並びにその他任意成分を使用直前に混合後、毛髪に塗布する。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剤の質量比）は、好ましくは80／20〜１／99、更に好ましくは60／40〜20／80である。   In the hair modification method of the present invention, when the hair treatment agent (A) is a two-component type, after mixing the first agent and the second agent immediately before use, or alkoxysilane having a ureido group, water, and other optional The ingredients are mixed immediately before use and then applied to the hair. The mixing ratio of the first agent and the second agent (mass 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.

混合された毛髪処理剤(Ａ)を放置すれば、ウレイド基を有するアルコキシシランの加水分解及び重合反応が進むので、30分以内、特に15分以内に、混合された毛髪処理剤(Ａ)を毛髪に塗布することが好ましい。これにより、ウレイド基を有するアルコキシシランの加水分解物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(Ａ)を、0.5〜３ｇ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 mixed hair treatment agent (A) is allowed to stand, hydrolysis and polymerization reaction of alkoxysilane having a ureido group proceeds, so within 30 minutes, particularly within 15 minutes, the mixed hair treatment agent (A) is It is preferably applied to the hair. Thereby, the hydrolyzate of the alkoxysilane which has a ureido group can be osmose | permeated in hair. The hair to be applied may be wet or dry. It is preferable to apply 0.5 to 3 g of the hair treatment agent (A) to 1 g of dried hair. The target to be applied may be human hair or hair such as a wig.

ウレイド基を有するアルコキシシランの加水分解物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、ウレイド基を有するアルコキシシランの加水分解物の浸透、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 for the hydrolyzate of alkoxysilane having a ureido group 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 to stand for a certain period of time after coating, the penetration of the hydrolyzate of alkoxysilane having a ureido group and the polymerization reaction are advanced. 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(Ａ)による処理後、そのまま毛髪処理剤(Ｂ)を毛髪に塗布してもよいが、毛髪処理剤(Ｂ)の効果を高める点から、毛髪表面に付着している毛髪処理剤(Ａ)をタオル等で拭き取るなどして除去した後に、毛髪処理剤(Ｂ)を塗布することが好ましい。この場合において、拭き取り後に毛髪表面に残っている毛髪処理剤(Ａ)の質量に対する毛髪処理剤(Ｂ)の塗布量〔毛髪処理剤(Ｂ)／毛髪処理剤(Ａ)〕の値を２〜50にするのが好ましく、より好ましくは４〜30、最も好ましくは６〜10である。   After the treatment with the hair treatment agent (A), the hair treatment agent (B) may be applied to the hair as it is, but the hair treatment agent adhered to the hair surface from the point of enhancing the effect of the hair treatment agent (B). It is preferable to apply the hair treatment agent (B) after removing (A) by wiping with a towel or the like. In this case, the value of the amount of the hair treatment agent (B) applied to the mass of the hair treatment agent (A) remaining on the hair surface after wiping [hair treatment agent (B) / hair treatment agent (A)] is 2 to 2. It is preferably 50, more preferably 4 to 30, and most preferably 6 to 10.

毛髪処理剤(Ｂ)の塗布後、ウレイド基を有するアルコキシシランの加水分解及びシラノール化合物の重合を進めるために放置しておく時間は、１〜60分が好ましく、より好ましくは5〜40分、最も好ましくは10〜20分である。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 application of the hair treatment agent (B), the time allowed to stand to proceed with hydrolysis of the alkoxysilane having a ureido group and polymerization of the silanol compound is preferably 1 to 60 minutes, more preferably 5 to 40 minutes, Most preferably, it is 10 to 20 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.

なお、混合された毛髪処理剤(Ａ)を毛髪に塗布した後、塗布部を加温し、その後毛髪処理剤(Ｂ)を塗布し、再度塗布部を加温することが好ましい。   In addition, after apply | coating the mixed hair treatment agent (A) to hair, it is preferable to heat an application part, apply | coat a hair treatment agent (B) after that, and heat an application part again.

実施例１及び比較例１ 毛髪処理剤(Ａ)
ウレイドプロピルトリアルコキシシラン〔前記式(1)におけるＲ2がトリメチレン基であり、Ｒ3、Ｒ4及びＲ5が水素原子であり、Ｘがメトキシ基及びエトキシ基であり、ｎ＝３である化合物、以下同様〕のメタノール溶液（GEシリコーン社製 SILQUEST A-1160 メトキシエトキシ混合物）をロータリーエバポレーターによって減圧濃縮して油状物を得た。アジピン酸0.75gを精製水59.27gに溶解したものに、この油状物を40g加え、容器を一定時間手で振って均一に混合させ、表１に示す組成からなる実施例１の毛髪処理剤(Ａ)を調製した。
また、ウレイドプロピルトリアルコキシシランの代わりにメチルトリエトキシシラン（信越シリコーン社製 LS-1890）を用い、混合をマグネチックスターラーにより行ったほかは同様の方法を行い、比較例１の毛髪処理剤(Ａ)を調製した。
これらの毛髪処理剤(Ａ)の加水分解処理に要した混合時間を表１に示す。 Example 1 and Comparative Example 1 Hair Treatment (A)
Ureidopropyltrialkoxysilane [compound in which R 2 in formula (1) is a trimethylene group, R 3 , R 4 and R 5 are hydrogen atoms, X is a methoxy group and an ethoxy group, and n = 3 , The same applies hereinafter) methanol solution (SILQUEST A-1160 methoxyethoxy mixture manufactured by GE Silicone) was concentrated under reduced pressure using a rotary evaporator to obtain an oily substance. 40 g of this oily substance was added to a solution of 0.75 g of adipic acid in 59.27 g of purified water, and the container was shaken by hand for a certain period of time to uniformly mix the hair treatment agent of Example 1 having the composition shown in Table 1 ( A) was prepared.
The hair treatment agent of Comparative Example 1 was prepared in the same manner except that methyltriethoxysilane (LS-1890 manufactured by Shin-Etsu Silicone Co., Ltd.) was used instead of ureidopropyltrialkoxysilane and mixing was performed with a magnetic stirrer. A) was prepared.
Table 1 shows the mixing time required for the hydrolysis treatment of these hair treatment agents (A).

Figure 2008150315
Figure 2008150315

表１に示すとおり、実施例１の毛髪処理剤(Ａ)は、加水分解処理に要する時間が比較例１の毛髪処理剤(Ａ)に比して短かった。   As shown in Table 1, the time required for the hydrolysis treatment of the hair treatment agent (A) of Example 1 was shorter than that of the hair treatment agent (A) of Comparative Example 1.

実施例２〜３及び比較例２〜３ 毛髪改質剤
表２に示す毛髪処理剤(Ａ)及び毛髪処理剤(Ｂ)からなる毛髪改質剤（実施例２〜３及び比較例２〜３）について、使用後の毛髪のケイ素元素含有量及び毛髪の感触を以下のように調べた。なお、実施例１及び比較例１の毛髪処理剤(Ａ)は、ウレイドプロピルトリアルコキシシラン又はメチルトリエトキシシランを加えてからそれぞれ１分、30分混合したものを用いた。また、表２中の(Ｂa)及び(Ｂb)は、それぞれ表３〜４に示す組成からなる重合促進剤(Ｂa)及び(Ｂb)を示す。 Examples 2 to 3 and Comparative Examples 2 to 3 Hair modifiers Hair modifiers comprising the hair treatment agent (A) and the hair treatment agent (B) shown in Table 2 (Examples 2 to 3 and Comparative Examples 2 to 3) ), The silicon element content of the hair after use and the feel of the hair were examined as follows. The hair treatment agents (A) of Example 1 and Comparative Example 1 were mixed for 1 minute and 30 minutes, respectively, after adding ureidopropyltrialkoxysilane or methyltriethoxysilane. In Table 2, (B a ) and (B b ) represent polymerization accelerators (B a ) and (B b ) having the compositions shown in Tables 3 to 4, respectively.

〔毛髪の処理〕
化学処理履歴のないコーカシアンの毛髪で作製した毛束（European Natural 25〜30cm Hair Color No.9/0、Kerling International Haarfabrik GmbH社より入手）５ｇに毛髪処理剤(Ａ)を10ｇ塗布した後、剤が乾燥しないようにラップで包み、恒温機（50℃）で30分間放置した。毛髪処理剤(Ａ)をタオルで拭き取り、毛髪処理剤(Ｂ)を５ｇ均一に塗布した後、剤が乾燥しないようにラップで包み、恒温機（50℃）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、処理毛を得た。 [Hair treatment]
After applying 10g of hair treatment agent (A) to 5g of hair bundle made of Caucasian hair without chemical treatment history (European Natural 25-30cm Hair Color No.9 / 0, obtained from Kerling International Haarfabrik GmbH) Wrapped in a wrap so as not to dry, and left in a constant temperature machine (50 ° C.) for 30 minutes. The hair treatment agent (A) was wiped off with a towel and 5 g of the hair treatment agent (B) was uniformly applied, and then wrapped in a wrap so that the agent did not dry, and left for 15 minutes in a constant temperature machine (50 ° C.). Thereafter, it was washed away with a shampoo containing no silicone and sufficiently dried to obtain treated hair.

〔毛髪のケイ素元素の含有量の定量〕
得られた処理毛に付着及び浸透したケイ素元素の量を定量した。定量は「ICP（誘導結合プラズマ）発光分析装置（堀場製作所，JY238ULTRACE）」を用いて以下のように行った。
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時間入れ灰化させた。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の含有量を以下の計算式を用いて求めた。 [Quantification of content of silicon element in hair]
The amount of silicon element adhering to and penetrating the resulting treated hair was quantified. Quantification was performed using an “ICP (inductively coupled plasma) emission spectrometer (Horiba, JY238ULTRACE)” as follows.
A 0.1 g sample was collected in a platinum crucible, carbonized until no smoke was generated 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 content of silicon element was determined from the average value using a calibration curve using the following formula.

ケイ素元素の含有量（質量％）＝〔ケイ素元素質量（mg）／毛髪質量（ｇ）〕×0.1   Content of silicon element (mass%) = [mass element silicon (mg) / hair mass (g)] × 0.1

また、毛髪処理剤(Ａ)と毛髪処理剤(Ｂ)とを１：１の質量比で混合し、得られた混合物の20℃におけるpHを測定した。このように求めたpHとケイ素元素の含有量を表２に示す。   Further, the hair treatment agent (A) and the hair treatment agent (B) were mixed at a mass ratio of 1: 1, and the pH of the obtained mixture at 20 ° C. was measured. Table 2 shows the pH and silicon element content thus determined.

Figure 2008150315
Figure 2008150315

Figure 2008150315
Figure 2008150315

Figure 2008150315
Figure 2008150315

表２に示すとおり、実施例２及び３の毛髪改質剤を用いることにより、毛髪へのケイ素の収着が認められた。   As shown in Table 2, by using the hair modifiers of Examples 2 and 3, sorption of silicon to the hair was observed.

〔感触の評価〕
毛髪改質剤で処理して得た処理毛、及び毛髪改質剤による処理を行っていない未処理毛の「滑らかな感触」、「ハリ・コシ感」、「ボリューム感」、「髪のまとまり感」及び「浮き毛、はね毛の少なさ」について、10名のパネラーにより、下記基準に従い５段階評価で官能評価を行った。評価の平均値を算出し、平均値が4.5以上の場合を非常に良好（◎）、3.5以上4.5未満の場合を良好（○）、2.5以上3.5未満の場合を普通（△）、2.5未満の場合を不良（×）と判定した。算出した平均値及び判定結果を表５に示す。 [Evaluation of feel]
"Smooth feel", "harshness", "volume", "hairiness" of treated hair obtained by treatment with hair modifier and untreated hair not treated with hair modifier The “feel” and “little float and splash hair” were sensory-evaluated by 10 panelists according to the following criteria in a five-step evaluation. The average value of the evaluation is calculated. When the average value is 4.5 or more, it is very good (◎), when it is 3.5 or more and less than 4.5 (○), when it is 2.5 or more and less than 3.5, it is normal (△), less than 2.5 The case was determined to be defective (x). Table 5 shows the calculated average values and determination results.

（評価基準）
５；良い
４；やや良い
３；普通
２；やや悪い
１；悪い (Evaluation criteria)
5; Good 4; Slightly good 3; Normal 2; Slightly bad 1; Bad

Figure 2008150315
Figure 2008150315

表５に示すとおり、実施例２及び３の毛髪改質剤を用いることにより、比較例２及び３の毛髪改質剤では得られないような滑らかな感触、ハリ・コシ感、ボリューム感、髪のまとまり感が得られ、浮き毛・はね毛も抑制できた。   As shown in Table 5, by using the hair modifiers of Examples 2 and 3, a smooth feel, firmness, volume, hair, which cannot be obtained with the hair modifiers of Comparative Examples 2 and 3 A feeling of unity was obtained, and floating hair and splashing hair were also suppressed.

Claims (9)

ウレイド基を有するアルコキシシランを含有する毛髪処理剤。   A hair treatment agent containing an alkoxysilane having a ureido group. ウレイド基を有するアルコキシシランが、次の一般式(1)
Figure 2008150315
 〔式中、Ｒ1、Ｒ3、Ｒ4及びＲ5は、水素原子又は炭素数１〜６の炭化水素基を示し、Ｒ2は、炭素数１〜６の２価の炭化水素基を示し、Ｘはハロゲン原子又は炭素数１〜６のアルコキシ基を示し、ｎは１〜３の整数を示す。〕
で表されるものである請求項１記載の毛髪処理剤。 An alkoxysilane having a ureido group is represented by the following general formula (1):
Figure 2008150315
 [Wherein R 1 , R 3 , R 4 and R 5 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R 2 represents a divalent hydrocarbon group having 1 to 6 carbon atoms. , X represents a halogen atom or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3. ]
The hair treatment agent according to claim 1, which is represented by: 次の毛髪処理剤(Ａ)及び(Ｂ)からなる毛髪改質剤。
(Ａ) 請求項１又は２記載の毛髪処理剤
(Ｂ) 加水分解及び重合反応の促進のための毛髪処理剤 A hair modifier comprising the following hair treatment agents (A) and (B).
(A) The hair treatment agent according to claim 1 or 2
(B) Hair treatment agent for promoting hydrolysis and polymerization reaction 毛髪処理剤(Ｂ)が、次の毛髪処理剤(Ｂa)である請求項３記載の毛髪改質剤。
(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の質量比で混合した場合の混合物のpHを１〜４とする毛髪処理剤 The hair modifying agent according to claim 3, wherein the hair treating agent (B) is the following hair treating agent (B a ).
(B a ) The pH of the mixture when the first dissociation index (pKa1) is less than 4.1 and mixed with the hair treatment agent (A) at a mass ratio of 1: 1 is 1-4. Hair treatment agent 毛髪処理剤(Ｂ)が、次の毛髪処理剤(Ｂb)である請求項３記載の毛髪改質剤。
(Ｂb) 単独でのpHが８〜12であり、毛髪処理剤(Ａ)に１：１の質量比で混合した場合の混合物のpHを８〜12とする毛髪処理剤 The hair modifying agent according to claim 3, wherein the hair treating agent (B) is the following hair treating agent (B b ).
(B b ) A hair treatment agent having a pH of 8 to 12 alone and a pH of the mixture of 8 to 12 when mixed with the hair treatment agent (A) at a mass ratio of 1: 1. 毛髪処理剤(Ａ)が、ウレイド基を有するアルコキシシランを含有する第１剤と、水を含有する第２剤から構成されるものである請求項３〜５のいずれかに記載の毛髪改質剤。   The hair modification agent according to any one of claims 3 to 5, wherein the hair treatment agent (A) is composed of a first agent containing an alkoxysilane having a ureido group and a second agent containing water. Agent. 請求項３〜６のいずれかに記載の毛髪改質剤を用い、毛髪処理剤(Ａ)を毛髪に塗布した後、毛髪処理剤(Ｂ)を毛髪に塗布する毛髪改質方法。   A hair modification method comprising applying the hair treatment agent (B) to the hair after applying the hair treatment agent (A) to the hair using the hair modification agent according to any one of claims 3 to 6. 毛髪処理剤(Ａ)を毛髪に塗布した後、塗布部を加温する請求項７記載の毛髪改質方法。   The hair modification method according to claim 7, wherein the application part is heated after the hair treatment agent (A) is applied to the hair. 毛髪処理剤(Ｂ)を毛髪に塗布した後、塗布部を加温する請求項７又は８記載の毛髪改質方法。   The hair modification method according to claim 7 or 8, wherein after the hair treatment agent (B) is applied to the hair, the applied portion is heated.
JP2006339550A 2006-12-18 2006-12-18 Hair treatment agent Active JP5244308B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006339550A JP5244308B2 (en) 2006-12-18 2006-12-18 Hair treatment agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2006339550A JP5244308B2 (en) 2006-12-18 2006-12-18 Hair treatment agent

Publications (2)

Publication Number Publication Date
JP2008150315A true JP2008150315A (en) 2008-07-03
JP5244308B2 JP5244308B2 (en) 2013-07-24

Family

ID=39652890

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2006339550A Active JP5244308B2 (en) 2006-12-18 2006-12-18 Hair treatment agent

Country Status (1)

Country Link
JP (1) JP5244308B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012516313A (en) * 2009-01-30 2012-07-19 ロレアル Cosmetic composition comprising an aqueous dispersion of polysiloxane / polyurea and silane, cosmetic treatment process, and kit therefor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS617A (en) * 1984-04-12 1986-01-06 レブロン　インコ−ポレ−テツド Hair tonic and permanent waving composition
JP2005320314A (en) * 2004-04-07 2005-11-17 Kao Corp Hair cosmetic
JP2006160676A (en) * 2004-12-08 2006-06-22 Kao Corp Hair cosmetic
JP2006182715A (en) * 2004-12-28 2006-07-13 Kao Corp Method for modifying hair

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS617A (en) * 1984-04-12 1986-01-06 レブロン　インコ−ポレ−テツド Hair tonic and permanent waving composition
JP2005320314A (en) * 2004-04-07 2005-11-17 Kao Corp Hair cosmetic
JP2006160676A (en) * 2004-12-08 2006-06-22 Kao Corp Hair cosmetic
JP2006182715A (en) * 2004-12-28 2006-07-13 Kao Corp Method for modifying hair

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012516313A (en) * 2009-01-30 2012-07-19 ロレアル Cosmetic composition comprising an aqueous dispersion of polysiloxane / polyurea and silane, cosmetic treatment process, and kit therefor

Also Published As

Publication number Publication date
JP5244308B2 (en) 2013-07-24

Similar Documents

Publication Publication Date Title
EP1736139B1 (en) Hair processing compositions and methods for processing hair
WO2004000251A1 (en) Composition for hair treatment
JP5235050B2 (en) Hair modifier
JP2013253067A (en) Treating agent for hair deformation
JP5244308B2 (en) Hair treatment agent
JP2007254419A (en) Dental whitener
JP4804770B2 (en) Hair conditioning agent and method of use thereof
JP5238276B2 (en) Hair treatment agent
JP2009067711A (en) Treatment agent for hair deformation
JP4509769B2 (en) Hair modification method
JP4883964B2 (en) Hair cosmetics
JP4509760B2 (en) Hair cosmetics
JP4509729B2 (en) Hair cosmetics
JP4836576B2 (en) Hair treatment method
JP4989058B2 (en) Hair cosmetics
JP5931482B2 (en) Deodorant for hair deformation treatment
JP2012087074A (en) Hair treating agent
JP4522764B2 (en) Hair cosmetics
JP2007099693A (en) Hair treating method
JP2008001676A (en) Hair treatment agent
JP2010150225A (en) Composition for removing solid product formed on surface of tooth
JP2010120880A (en) Oral composition
TW201625211A (en) Composition for use in oral cavity
JP5260845B2 (en) Teeth whitening method
JP3847708B2 (en) Solid bleach for textiles

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20091124

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20110927

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20111025

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20111215

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20120911

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20121105

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20130108

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20130215

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20130402

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20130408

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20160412

Year of fee payment: 3

R151 Written notification of patent or utility model registration

Ref document number: 5244308

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R151

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20160412

Year of fee payment: 3

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250