JP5558034B2 - Hair care agent and hair treatment method - Google Patents
Hair care agent and hair treatment method Download PDFInfo
- Publication number
- JP5558034B2 JP5558034B2 JP2009141704A JP2009141704A JP5558034B2 JP 5558034 B2 JP5558034 B2 JP 5558034B2 JP 2009141704 A JP2009141704 A JP 2009141704A JP 2009141704 A JP2009141704 A JP 2009141704A JP 5558034 B2 JP5558034 B2 JP 5558034B2
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- JP
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- Prior art keywords
- hair
- extract
- mass
- acid
- peptide
- 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.)
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Landscapes
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Description
本発明は、シャンプー、コンディショナー等に用いられるヘアケア剤、及び当該ヘアケア剤を使用する毛髪の処理方法に関するものである。 The present invention relates to a hair care agent used in shampoos, conditioners and the like, and a hair treatment method using the hair care agent.
ブラッシング、ハンドドライヤー、熱アイロンなどによる物理的処理、及び、ヘアカラー、パーマネントウェーブなどの化学的処理は、毛髪に損傷を与える。損傷した毛髪は、損傷を受ける前に比して、毛髪の感触(例えば、はり、こし、柔らかさ)、外観(例えば、艶、まとまり)、強度(例えば、引張り強度)などの毛髪特性が悪化したものとなる。悪化した毛髪特性を改善させるためには、天然物由来のペプチド、及び/又は、カチオン基、シリル基、アシル基、若しくはエステル基を導入した変性ペプチドをヘアケア剤に配合することが知られている。 Physical treatments such as brushing, hand dryers, hot irons, and chemical treatments such as hair coloring and permanent wave damage the hair. Damaged hair has worse hair properties, such as hair feel (eg, beam, strain, softness), appearance (eg, gloss, mass), strength (eg, tensile strength) compared to before being damaged Will be. In order to improve deteriorated hair properties, it is known to incorporate a peptide derived from a natural product and / or a modified peptide into which a cationic group, a silyl group, an acyl group, or an ester group is introduced into a hair care agent. .
特許文献1には変性ペプチドの一種が開示されており、その変性ペプチドは、タンパク質のジスルフィド基(−S−S−)をカルボキシメチルジスルフィド基(−S−S−CH2COOH)に変換して得られる水溶性のものである。そして、特許文献1には、その変性ペプチドの具体的利用態様として、変性ペプチドからフィルムを形成することが開示されている。 Patent Document 1 discloses one type of modified peptide, which is obtained by converting a protein disulfide group (—S—S—) into a carboxymethyl disulfide group (—S—S—CH 2 COOH). The obtained water-soluble one. Patent Document 1 discloses forming a film from a modified peptide as a specific application mode of the modified peptide.
上述の通り、変性ペプチドをヘアケア剤に配合することは知られたところであり、毛髪特性の改善に適したヘアケア剤の開発を目的として、様々な変性ペプチドの探求が行われている。 As described above, it is known that a modified peptide is blended in a hair care agent, and various modified peptides are being searched for in order to develop a hair care agent suitable for improving hair characteristics.
本発明は、損傷した毛髪の特性改善が求められる事情に鑑み、毛髪のハリに影響を与える一要因である初期弾性率を改善することに適したヘアケア剤、及びこのヘアケア剤を使用する毛髪の処理方法の提供を目的とする。 The present invention has been made in view of the circumstances where improvement in properties of damaged hair is required, and a hair care agent suitable for improving the initial elastic modulus, which is one factor affecting hair tension, and hair using the hair care agent. The purpose is to provide a processing method.
本発明者は、鋭意検討を重ねた結果、所定の側鎖基を有するペプチドをヘアケア剤に配合し、このヘアケア剤で損傷した毛髪を処理すれば、毛髪の初期弾性率を改善できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventor has found that the initial elastic modulus of hair can be improved by blending a peptide having a predetermined side chain group into a hair care agent and treating the damaged hair with this hair care agent, The present invention has been completed.
すなわち、本発明に係るヘアケア剤は、ペプチドが配合されたヘアケア剤であって、前記ペプチドが、下記式(I)で表される基を有する基を、側鎖基として備えることを特徴とする。
−S−S−(CH2)nCOO− (I)
(式(I)中、nは1又は2である。)
That is, the hair care agent according to the present invention is a hair care agent containing a peptide, wherein the peptide includes a group having a group represented by the following formula (I) as a side chain group. .
-S-S- (CH 2) n COO- (I)
(In the formula (I), n is 1 or 2.)
当該ヘアケア剤は、上記式(I)の基を有する側鎖基を備えるペプチドが配合されていることによって、毛髪のハリに影響を与える一要因の初期弾性率を向上させ、ヘアカラー、パーマネントウェーブ等によって損傷を受けた毛髪の特性を改善することができる。なお、ここでの「ペプチド」は、2個以上のアミノ酸がペプチド結合により結合して生じる化合物の総称であって、タンパク質を含む概念である。 The hair care agent contains a peptide having a side chain group having the group of the above formula (I), thereby improving the initial elastic modulus as one factor that affects the elasticity of the hair, hair color, permanent wave It is possible to improve the properties of damaged hair. The “peptide” here is a general term for compounds formed by binding two or more amino acids by peptide bonds, and is a concept including protein.
当該ヘアケア剤に配合されるペプチドの前記側鎖基は、カルボキシメチルジスルフィド基、カルボキシメチルジスルフィド基の塩、カルボキシエチルジスルフィド基、及びカルボキシエチルジスルフィド基の塩から選択された一種又は二種以上を有することが好ましい。これらの側鎖基を有するペプチドが配合されたヘアケア剤によって、毛髪の初期弾性率を効果的に改善することができる。なお、ここでの「塩」を構成するカチオンは、カルボキシ基の水素イオンと置換しうるカチオンであって、上記効果を阻害するものでない限りは、特に限定されない。 The side chain group of the peptide blended in the hair care agent has one or more selected from carboxymethyl disulfide group, carboxymethyl disulfide group salt, carboxyethyl disulfide group, and carboxyethyl disulfide group salt. It is preferable. The initial elastic modulus of the hair can be effectively improved by the hair care agent in which the peptide having these side chain groups is blended. The cation constituting the “salt” here is not particularly limited as long as it is a cation that can be substituted with a hydrogen ion of a carboxy group and does not inhibit the above effect.
当該ヘアケア剤は、シャンプー、リンス、トリートメント、又はコンディショナーとして用いることができる。 The hair care agent can be used as a shampoo, rinse, treatment, or conditioner.
当該ヘアケア剤に配合されるペプチドの分子量は、22000以下であることが好ましい。このような低分子量のペプチドを用いることによって、大きく損傷を受けた毛髪に対しても、効果的にダメージの回復を図ることが可能となる。 It is preferable that the molecular weight of the peptide mix | blended with the said hair care agent is 22000 or less. By using such a low molecular weight peptide, it is possible to effectively recover the damage even for hair that has been greatly damaged.
当該ヘアケア剤の使用時の剤型は、液状、乳液状、クリーム状、軟膏状、ゲル状、固形状、フォーム状、又は霧状であってよい。使用者の嗜好や目的に応じて、これらの剤型でヘアケア剤を用いることが可能である。 The dosage form at the time of use of the hair care agent may be liquid, emulsion, cream, ointment, gel, solid, foam, or mist. Depending on the user's preference and purpose, it is possible to use hair care agents in these dosage forms.
また、本発明に係る毛髪の処理方法は、上記ヘアケア剤を使用することを特徴とする。 The hair treatment method according to the present invention is characterized by using the above hair care agent.
本発明に係る所定のペプチドが配合されたヘアケア剤により毛髪を処理すれば、ヘアカラー、パーマネントウェーブなどで損傷を受けた毛髪の初期弾性率を改善することができる。 If the hair is treated with a hair care agent containing the predetermined peptide according to the present invention, the initial elastic modulus of the hair damaged by hair color, permanent wave or the like can be improved.
本発明を実施形態に基づき以下に説明する。
本実施形態に係るヘアケア剤は、上記式(I)で表される基を有する基を側鎖基に有するペプチド(当該ペプチドを、以下、「CADペプチド」と称する。)が配合されたものである。上記式(I)で表される基は、解離(イオン化)してカルボキシラートアニオンとなった場合には、カルボキシラトアルキルジスルフィド基と称される。
The present invention will be described below based on embodiments.
The hair care agent according to the present embodiment is a blend of a peptide having a group having a group represented by the above formula (I) as a side chain group (hereinafter, the peptide is referred to as “CAD peptide”). is there. When the group represented by the formula (I) is dissociated (ionized) to become a carboxylate anion, it is called a carboxylatoalkyl disulfide group.
(CADペプチド)
CADペプチドは、複数のアミノ酸のペプチド結合によって形成された主鎖と、この主鎖に結合する側鎖基を有する。
(CAD peptide)
The CAD peptide has a main chain formed by peptide bonds of a plurality of amino acids and a side chain group bonded to the main chain.
CADペプチドの主鎖は、特に限定されない。この主鎖の例としては、システインを構成アミノ酸の一種としているペプチドの主鎖と同じものが挙げられる。また、システインを構成アミノ酸の一種としているペプチドの例としては、ケラチン、カゼインなどが挙げられる。なお、ケラチンは、天然物由来のペプチドの中でもシステイン比率が高いものとして知られており、かつ、CADペプチドが効率よく得られる原料となる。従って、CADペプチドの主鎖はケラチンの主鎖と同じものが好適である。 The main chain of the CAD peptide is not particularly limited. Examples of this main chain include the same main chain of peptides having cysteine as one of the constituent amino acids. Examples of peptides having cysteine as one of the constituent amino acids include keratin and casein. Keratin is known as having a high cysteine ratio among peptides derived from natural products, and is a raw material from which a CAD peptide can be efficiently obtained. Therefore, the main chain of the CAD peptide is preferably the same as the main chain of keratin.
CADペプチドの側鎖基は下記式(I)で表される基を有する基であり、この側鎖基において、ジスルフィド基はCADペプチドの主鎖側に配置する。この側鎖基は、CADペプチドに複数存在することが好ましい。
−S−S−(CH2)nCOO− (I)
(式(I)中、nは1又は2である。)
The side chain group of the CAD peptide is a group having a group represented by the following formula (I). In this side chain group, the disulfide group is arranged on the main chain side of the CAD peptide. It is preferable that a plurality of side chain groups exist in the CAD peptide.
-S-S- (CH 2) n COO- (I)
(In the formula (I), n is 1 or 2.)
上記側鎖基が有する化学構造として好適なものは、下記式(IA)で表されるカルボキシメチルジスルフィド基、下記式(IB)又は(IC)で表されるカルボキシメチルジスルフィド基の塩、下記式(IIA)で表されるカルボキシエチルジスルフィド基、及び下記式(IIB)又は(IIC)で表されるカルボキシエチルジスルフィド基の塩から選択された一種又は二種以上である。このような化学構造を有する側鎖基を備えたペプチドを配合したヘアケア剤を用いることによって、毛髪の初期弾性率を改善することができる。
−S−S−CH2COOH (IA)
−S−S−CH2COOR1 (IB)
(R1は、NH4などのアンモニウムを表す。)
−S−S−CH2COOM1 (IC)
(M1は、Na、Kなどの金属原子を表す。)
−S−S−CH2CH2COOH (IIA)
−S−S−CH2CH2COOR2 (IIB)
(R2は、NH4などのアンモニウムを表す。)
−S−S−CH2CH2COOM2 (IIC)
(M2は、Na、Kなどの金属原子を表す。)
Suitable as the chemical structure of the side chain group is a carboxymethyl disulfide group represented by the following formula (IA), a salt of the carboxymethyl disulfide group represented by the following formula (IB) or (IC), the following formula It is 1 type, or 2 or more types selected from the salt of the carboxyethyl disulfide group represented by (IIA), and the carboxyethyl disulfide group represented by the following formula (IIB) or (IIC). By using a hair care agent containing a peptide having a side chain group having such a chemical structure, the initial elastic modulus of hair can be improved.
-S-S-CH 2 COOH ( IA)
-S-S-CH 2 COOR 1 (IB)
(R 1 represents ammonium such as NH 4. )
-S-S-CH 2 COOM 1 (IC)
(M 1 represents a metal atom such as Na or K.)
-S-S-CH 2 CH 2 COOH (IIA)
-S-S-CH 2 CH 2 COOR 2 (IIB)
(R 2 represents ammonium such as NH 4. )
-S-S-CH 2 CH 2 COOM 2 (IIC)
(M 2 represents a metal atom such as Na or K.)
上記側鎖基として好ましい基は、下記式(Ia)、(Ib)、(Ic)、(IIa)、(IIb)、及び(IIc)から選択された一種又は二種以上である(下記式におけるR1、M1、R2、M2は、上記と同じである。)。
−CH2−S−S−CH2COOH (Ia)
−CH2−S−S−CH2COOR1 (Ib)
−CH2−S−S−CH2COOM1 (Ic)
−CH2−S−S−CH2CH2COOH (IIa)
−CH2−S−S−CH2CH2COOR2 (IIb)
−CH2−S−S−CH2CH2COOM2 (IIc)
A preferable group as the side chain group is one or more selected from the following formulas (Ia), (Ib), (Ic), (IIa), (IIb), and (IIc) (in the following formula R 1 , M 1 , R 2 and M 2 are the same as above.)
—CH 2 —S—S—CH 2 COOH (Ia)
—CH 2 —SS—CH 2 COOR 1 (Ib)
—CH 2 —S—S—CH 2 COOM 1 (Ic)
—CH 2 —S—S—CH 2 CH 2 COOH (IIa)
—CH 2 —SS—CH 2 CH 2 COOR 2 (IIb)
-CH 2 -S-S-CH 2 CH 2 COOM 2 (IIc)
CADペプチドを配合したヘアケア剤で毛髪を処理すれば、CADペプチドが毛髪を構成しているチオール基同士を架橋し、その結果、毛髪の初期弾性率が改善されると考えられる。この改善は毛髪にチオール基が存在するから生じるものであり、損傷を受けた毛髪におけるチオール基は増加していることから、CADペプチドを配合したヘアケア剤は、毛髪への化学的処理や物理的処理によって損傷した毛髪の処理に適する。 If the hair is treated with a hair care agent containing a CAD peptide, the CAD peptide crosslinks thiol groups constituting the hair, and as a result, the initial elastic modulus of the hair is considered to be improved. This improvement is caused by the presence of thiol groups in the hair, and since the thiol groups in damaged hair are increasing, hair care agents formulated with CAD peptides are used for chemical treatment and physical treatment on the hair. Suitable for treatment of hair damaged by treatment.
毛髪におけるチオール基同士の架橋機構を、2個の−CH2−S−S−CH2COOHを側鎖基として有するCADペプチドを例にして表せば、次の通りである。 The cross-linking mechanism between thiol groups in hair is represented as follows using a CAD peptide having two —CH 2 —SS—CH 2 COOH as side chain groups as an example.
また、毛髪におけるチオール基同士の架橋機構を、2個の−CH2−S−S−CH2CH2COOHを側鎖基として有するCADペプチドを例にして表せば、次の通りである。 Further, the cross-linking mechanism between thiol groups in the hair, if indicated the CAD peptide having two -CH 2 -S-S-CH 2 CH 2 COOH as side groups in the examples are as follows.
CADペプチドの分子量は、特に限定されないが、63000以下(63kDa以下)であると良い。CADペプチドの分子量が63000以下であることの確認は、タカラバイオ社製「Protein Molecular Weight Marker(Low)」を基準物質とし、Sodium Dodecyl Sulfate−ポリアクリルアミドゲル電気泳動(SDS−PAGE)法により確認することができる。 Although the molecular weight of CAD peptide is not specifically limited, It is good in it being 63000 or less (63 kDa or less). Confirmation that the molecular weight of the CAD peptide is 63,000 or less is confirmed by a sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) method using “Protein Molecular Weight Marker (Low)” manufactured by Takara Bio Inc. as a reference substance. be able to.
CADペプチドは、毛髪浸透性を有するものが好ましい。毛髪浸透性を有するCADペプチドの分子量は、例えば10000以下である。この毛髪浸透性を有するCADペプチドであれば、毛髪内部のチオール基同士を架橋できると考えられるため、毛髪の内部まで上記改善効果が期待され、損傷した毛髪の特性を改善することができる。なお、ここでの「毛髪浸透性」は、当該ヘアケア剤によって毛髪を処理する際に、ペプチドが毛髪の表面以外の部分にも浸透する性質を意味する。 The CAD peptide preferably has hair permeability. The molecular weight of the CAD peptide having hair permeability is, for example, 10,000 or less. This CAD peptide having hair permeability is considered to be able to crosslink thiol groups in the hair, so that the above-mentioned improvement effect is expected to the inside of the hair, and the characteristics of damaged hair can be improved. Here, “hair permeability” means the property that the peptide penetrates into portions other than the surface of the hair when the hair is treated with the hair care agent.
ヘアケア剤へのCADペプチド配合量の下限は、特に限定されないが、0.05質量%が良く、0.1質量%が好ましい。一方のCADペプチド配合量の上限も、特に限定されないが、多量の配合によるコストの上昇を抑制する観点から、15質量%が良く、10質量%が好ましく、5質量%がより好ましく、3質量%が更に好ましい。 Although the minimum of the CAD peptide compounding quantity to a hair care agent is not specifically limited, 0.05 mass% is good and 0.1 mass% is preferable. The upper limit of the amount of the CAD peptide is not particularly limited, but is preferably 15% by mass, preferably 10% by mass, more preferably 5% by mass, from the viewpoint of suppressing an increase in cost due to a large amount of formulation. Is more preferable.
(CADペプチドの製造方法)
CADペプチドを製造するための方法としては、例えば、以下に説明する製造方法(A)〜(C)が挙げられる。
(Method for producing CAD peptide)
As a method for manufacturing CAD peptide, the manufacturing method (A)-(C) demonstrated below is mentioned, for example.
[製造方法(A)]
製造方法(A)は、タンパク質のジスルフィド基をチオール基にする還元工程;及び、その還元工程でタンパク質分子に生じたチオール基と、メルカプトアルキルカルボン酸のチオール基及び/又はメルカプトアルキルカルボン酸塩のチオール基とで、上記式(I)で表される基を形成させる変性工程を備える。この製造方法(A)は、分子量が40000から63000(40kDaから63kDa)である高分子量の水溶性CADペプチドの製造に適するものである(以下、その「高分子量の水溶性CADペプチド」を「CADペプチドA」と称することがある。)。
[Production Method (A)]
The production method (A) comprises a reduction step of converting a protein disulfide group into a thiol group; and a thiol group generated in a protein molecule in the reduction step, a thiol group of mercaptoalkylcarboxylic acid, and / or a mercaptoalkylcarboxylate. A modification step of forming a group represented by the above formula (I) with a thiol group is provided. This production method (A) is suitable for production of a high molecular weight water-soluble CAD peptide having a molecular weight of 40,000 to 63,000 (40 kDa to 63 kDa) (hereinafter, the “high molecular weight water-soluble CAD peptide” is referred to as “CAD”). Sometimes referred to as "Peptide A").
還元工程では、タンパク質を含む製造原料、水及び還元剤を混合することにより、タンパク質が有するジスルフィド基(−S−S−)を2つのチオール基(−SH HS−)に還元する。 In the reduction step, the disulfide group (—S—S—) of the protein is reduced to two thiol groups (—SH HS—) by mixing the production raw material containing protein, water, and a reducing agent.
製造原料としては、ケラチンを構成タンパク質として含む羊毛(メリノ種羊毛、リンカーン種羊毛等)、人毛、獣毛、羽毛、爪などが挙げられる。中でも、安価かつ安定的に入手するために、羊毛を原料とすることが好ましい。製造原料については、殺菌、脱脂、洗浄、切断、粉砕及び乾燥を適宜に組み合わせて、予め処理すると良い。 Examples of the raw material for production include wool (merino wool, lincoln wool, etc.), human hair, animal hair, feathers, nails and the like containing keratin as a constituent protein. Among them, it is preferable to use wool as a raw material in order to obtain it inexpensively and stably. About a manufacturing raw material, it is good to process beforehand combining sterilization, degreasing, washing | cleaning, cutting | disconnection, grinding | pulverization, and drying suitably.
水の量は、特に限定されないが、例えば、製造原料1質量部に対して、20質量部以上200質量部以下であるとよい。水の量を上記範囲とすることにより、還元反応が良好に行われる。 Although the quantity of water is not specifically limited, For example, it is good in it being 20 to 200 mass parts with respect to 1 mass part of manufacturing raw materials. By setting the amount of water in the above range, the reduction reaction is favorably performed.
還元剤は、タンパク質のジスルフィド基をチオール基に変換する作用を有する。かかる還元剤としては、メルカプトアルキルカルボン酸及び/又はその塩が用いられる。また、還元剤として、メルカプトアルキルカルボン酸及び/又はその塩に加え、他の任意の化合物を用いてもよい。そのような任意の還元剤の例としては、チオ乳酸及び/又はその塩、ジチオスレイトール、2−メルカプトエタノール、グルタチオン、チオ尿素等が挙げられる。これらの任意の還元剤は、一種又は二種以上のものを使用することができる。 A reducing agent has the effect | action which converts the disulfide group of protein into a thiol group. As the reducing agent, mercaptoalkylcarboxylic acid and / or a salt thereof is used. In addition to the mercaptoalkylcarboxylic acid and / or salt thereof, any other compound may be used as the reducing agent. Examples of such an optional reducing agent include thiolactic acid and / or a salt thereof, dithiothreitol, 2-mercaptoethanol, glutathione, thiourea and the like. These optional reducing agents can be used alone or in combination of two or more.
前記メルカプトアルキルカルボン酸及び/又はその塩は、変性工程において上記式(I)で表される基を形成させる変性剤にもなる。このメルカプトアルキルカルボン酸及び/又はその塩としては、チオグリコール酸、チオグリコール酸塩、3−メルカプトプロピオン酸、及び3−メルカプトプロピオン酸塩からなる群より選択される一種又は二種以上が使用される。チオグリコール酸塩としては、例えば、チオグリコール酸ナトリウム、チオグリコール酸カリウム、チオグリコール酸リチウム、チオグリコール酸アンモニウムが挙げられる。中でも、カルボキシラトメチルジスルフィド基の形成を効率良く行える面から、チオグリコール酸ナトリウム及びチオグリコール酸カリウムが好ましく、チオグリコール酸ナトリウムがより好ましい。また、3−メルカプトプロピオン酸塩としては、例えば、3−メルカプトプロピオン酸ナトリウム、3−メルカプトプロピオン酸カリウム、3−メルカプトプロピオン酸リチウム、3−メルカプトプロピオン酸アンモニウムが挙げられる。中でも、カルボキシラトエチルジスルフィド基の形成を効率良く行える面から、3−メルカプトプロピオン酸ナトリウム及び3−メルカプトプロピオン酸カリウムが好ましく、3−メルカプトプロピオン酸ナトリウムがより好ましい。 The mercaptoalkylcarboxylic acid and / or salt thereof also serves as a modifier that forms the group represented by the above formula (I) in the modification step. As the mercaptoalkylcarboxylic acid and / or salt thereof, one or more selected from the group consisting of thioglycolic acid, thioglycolate, 3-mercaptopropionic acid, and 3-mercaptopropionic acid salt are used. The Examples of the thioglycolate include sodium thioglycolate, potassium thioglycolate, lithium thioglycolate, and ammonium thioglycolate. Of these, sodium thioglycolate and potassium thioglycolate are preferable, and sodium thioglycolate is more preferable from the viewpoint of efficiently forming a carboxylatomethyl disulfide group. Examples of 3-mercaptopropionate include sodium 3-mercaptopropionate, potassium 3-mercaptopropionate, lithium 3-mercaptopropionate, and ammonium 3-mercaptopropionate. Of these, sodium 3-mercaptopropionate and potassium 3-mercaptopropionate are preferable, and sodium 3-mercaptopropionate is more preferable from the viewpoint of efficiently forming a carboxylatoethyl disulfide group.
前記メルカプトアルキルカルボン酸及びその塩の使用量としては、製造原料1gを基準として、0.0050モル以上0.02モル以下が好ましく、0.0075モル以上0.01モル以下が特に好ましい。また、その使用量は、製造原料、水及び還元剤の合計容量を基準として、0.10mol/L以上0.40mol/L以下が好ましく、0.15mol/L以上0.25mol/L以下が特に好ましい。かかるメルカプトアルキルカルボン酸及びその塩の使用量を上記範囲とすることにより、タンパク質の還元反応の進行が良好になる。 The amount of the mercaptoalkylcarboxylic acid and its salt used is preferably 0.0050 mol or more and 0.02 mol or less, particularly preferably 0.0075 mol or more and 0.01 mol or less, based on 1 g of the production raw material. Further, the amount used is preferably 0.10 mol / L or more and 0.40 mol / L or less, particularly 0.15 mol / L or more and 0.25 mol / L or less, based on the total capacity of the production raw material, water and the reducing agent. preferable. By making the usage-amount of this mercaptoalkylcarboxylic acid and its salt into the said range, progress of a protein reduction reaction becomes favorable.
還元工程では、一種又は二種以上のアルカリ性化合物も混合することが好ましい。アルカリ性化合物とは、水に添加することで、その水をアルカリ性にすることができる化合物である。このアルカリ性化合物としては、例えば水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化バリウム、炭酸ナトリウム、炭酸カリウム、アンモニア等が挙げられ、その他にモノエタノールアミン、ジエタノールアミン、アルギニン、リジン等の塩基性アミノ酸や、重炭酸ナトリウム、重炭酸アンモニウム等も挙げられる。中でも、タンパク質の還元を効率良く行う観点から、水酸化ナトリウム及び水酸化カリウムが好ましく、水酸化ナトリウムが特に好ましい。 In the reduction step, it is preferable to mix one or more alkaline compounds. An alkaline compound is a compound that can be made alkaline by adding it to water. Examples of the alkaline compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like, and other basic compounds such as monoethanolamine, diethanolamine, arginine, and lysine. Amino acids, sodium bicarbonate, ammonium bicarbonate and the like are also included. Among these, sodium hydroxide and potassium hydroxide are preferable from the viewpoint of efficiently performing protein reduction, and sodium hydroxide is particularly preferable.
前記アルカリ性化合物の混合量は、特に限定はされないが、還元反応系のpHを下記範囲に調整するよう配合するとよい。そのpHの下限としては、9が好ましく、10が特に好ましい。一方、pHの上限としては、13が良く、12が好ましく、11が特に好ましい。pHが上記の下限以上となるように調整することで、タンパク質の還元を効率良く行うことができる。一方、pHが上記の上限以下となるように調整することで、タンパク質分子の主鎖切断を抑制することができる。 The mixing amount of the alkaline compound is not particularly limited, but it may be blended so that the pH of the reduction reaction system is adjusted to the following range. As the lower limit of the pH, 9 is preferable and 10 is particularly preferable. On the other hand, as an upper limit of pH, 13 is good, 12 is preferable, and 11 is particularly preferable. By adjusting the pH to be equal to or higher than the above lower limit, protein can be reduced efficiently. On the other hand, the main chain cleavage of the protein molecule can be suppressed by adjusting the pH to be not more than the above upper limit.
還元工程における反応系の温度下限としては、20℃が好ましく、30℃がより好ましく、40℃がさらに好ましい。一方、温度上限としては、60℃が好ましい。上記温度下限より低いと、タンパク質のジスルフィド基をチオール基に変換するための還元の時間が長くなり、十分な還元を実行できない恐れがある。一方、上記温度上限を超えると、タンパク質分子の主鎖が切断されることがある。還元反応系の設定時間は、その温度が低いほど長時間に設定され、同温度が高いほど短時間に設定される。その設定時間としては、例えば、20分以上120分以下である。 As a temperature minimum of the reaction system in a reduction process, 20 ° C is preferred, 30 ° C is more preferred, and 40 ° C is still more preferred. On the other hand, the upper temperature limit is preferably 60 ° C. When the temperature is lower than the lower limit, the reduction time for converting the disulfide group of the protein into a thiol group becomes long, and there is a possibility that sufficient reduction cannot be performed. On the other hand, when the temperature upper limit is exceeded, the main chain of the protein molecule may be cleaved. The set time of the reduction reaction system is set longer as the temperature is lower, and is set shorter as the temperature is higher. The set time is, for example, 20 minutes to 120 minutes.
変性工程では、還元工程で得られた液に酸化剤及び酸を混合することにより、タンパク質に上記式(I)で表される基を導入し、CADペプチドを生成させる。なお、酸の混合は、酸化剤の混合前及び酸化剤の混合後のいずれであっても良い。 In the denaturation step, an oxidant and an acid are mixed with the liquid obtained in the reduction step, thereby introducing the group represented by the above formula (I) into the protein and generating a CAD peptide. The acid may be mixed before the oxidant is mixed or after the oxidant is mixed.
酸化剤は、タンパク質への上記式(I)で表される基の導入を促進するために使用するものである。一種又は二種以上の酸化剤を使用すると良く、酸化剤の水溶液及び/又はガス状の酸化剤を使用すると良い。 The oxidizing agent is used for promoting the introduction of the group represented by the above formula (I) into the protein. One or more oxidizing agents may be used, and an aqueous oxidizing agent solution and / or a gaseous oxidizing agent may be used.
酸化剤としては、例えば、臭素酸ナトリウム、臭素酸カリウム、過ホウ酸ナトリウム、過酸化水素等が挙げられる。また、ガス状の酸化剤としては、酸素などが挙げられる。ガス状酸化剤を使用するときには、バブリングによりタンパク質含有液に供給すると良い。 Examples of the oxidizing agent include sodium bromate, potassium bromate, sodium perborate, hydrogen peroxide, and the like. Moreover, oxygen etc. are mentioned as a gaseous oxidizing agent. When a gaseous oxidant is used, it may be supplied to the protein-containing solution by bubbling.
非ガス状の酸化剤の使用量は、特に限定されないが、製造原料1gを基準として、0.001モル以上0.02モル以下が好ましく、酸化剤が混合される液の容量を基準として、0.02mol/L以上1mol/L以下が好ましい。酸化剤の使用量が上記上限よりも多いと、副生成物であるシスチンモノオキシド、シスチンジオキシド、システイン酸が生成するおそれがある。一方、酸化剤の使用量が上記下限よりも少ないと、上記式(I)で表される基の導入が不十分となるおそれがある。非ガス状酸化剤の混合では、液中の酸化剤濃度が局所的に高くなることを避けるため、1mol/L以上5mol/L以下程度の酸化剤水溶液を、例えば30分から6時間かけて徐々に混合すると良い。 The amount of the non-gaseous oxidant used is not particularly limited, but is preferably 0.001 mol or more and 0.02 mol or less based on 1 g of the manufacturing raw material, and is 0 based on the volume of the liquid in which the oxidant is mixed. 0.02 mol / L or more and 1 mol / L or less is preferable. When the amount of the oxidizing agent used is larger than the above upper limit, by-products such as cystine monooxide, cystine dioxide and cysteic acid may be produced. On the other hand, when the amount of the oxidizing agent used is less than the above lower limit, the introduction of the group represented by the formula (I) may be insufficient. In the mixing of the non-gaseous oxidant, in order to avoid locally increasing the oxidant concentration in the liquid, an oxidant aqueous solution of about 1 mol / L or more and 5 mol / L or less is gradually added over, for example, 30 minutes to 6 hours. Mix well.
酸化剤を混合する際の温度は、特に限定されないが、例えば還元工程での温度以下に設定される。 Although the temperature at the time of mixing an oxidizing agent is not specifically limited, For example, it sets to below the temperature in a reduction process.
酸は、変性工程における反応系のpHを低下させ、タンパク質に上記式(I)で表される基を十分に導入させるために使用される。この酸は、一種又は二種以上のものが使用される。 The acid is used for lowering the pH of the reaction system in the denaturation step and sufficiently introducing the group represented by the above formula (I) into the protein. One or two or more of these acids are used.
酸としては、例えば、クエン酸、乳酸、コハク酸、酢酸等の有機酸;塩酸等の無機酸が挙げられる。酢酸を用いれば、CADペプチドからの特異臭が問題になることがあるが、クエン酸等を用いれば、その特異臭を抑制することができる。 Examples of the acid include organic acids such as citric acid, lactic acid, succinic acid, and acetic acid; and inorganic acids such as hydrochloric acid. If acetic acid is used, the specific odor from CAD peptide may be a problem, but if citric acid or the like is used, the specific odor can be suppressed.
酸の混合量としては、特に限定されないが、変性工程における反応系のpHを下記範囲に調整するよう配合するとよい。最終的なpHとしては、5以上9以下が好ましく、6以上8以下が特に好ましい。このようにケラチン混合液の最終的なpHを前記範囲に調整することで、タンパク質への上記式(I)で表される基の導入を促進できると同時に、タンパク質のチオール基同士によるジスルフィド基生成を抑制できる。なお、反応系におけるpHが局所的に低下すると、タンパク質のチオール基同士がジスルフィド基になるおそれが大きくなるため、反応系に酸を徐々に混合することが好ましい。 The mixing amount of the acid is not particularly limited, but it may be blended so that the pH of the reaction system in the modification step is adjusted to the following range. The final pH is preferably from 5 to 9, and particularly preferably from 6 to 8. In this way, by adjusting the final pH of the keratin mixture to the above range, introduction of the group represented by the above formula (I) into the protein can be promoted, and at the same time, disulfide group generation by thiol groups of the protein can occur. Can be suppressed. In addition, when pH in a reaction system falls locally, since there exists a possibility that the thiol group of protein may become a disulfide group, it is preferable to mix an acid into a reaction system gradually.
酸を混合するときの反応系における温度としては、10℃以上60℃以下が好ましく、20℃以上40℃以下が特に好ましい。この温度範囲に制御することで、副生成物であるシスチンモノオキシド等の生成を抑制できる。酸の混合が終了した後の放置時間は、例えば1〜48時間である。この放置時間であれば、上記式(I)で表される基の導入が十分となる。 The temperature in the reaction system when mixing the acid is preferably 10 ° C. or more and 60 ° C. or less, and particularly preferably 20 ° C. or more and 40 ° C. or less. By controlling within this temperature range, the production of by-products such as cystine monooxide can be suppressed. The standing time after the acid mixing is completed is, for example, 1 to 48 hours. With this standing time, the introduction of the group represented by the above formula (I) is sufficient.
変性工程を経ることで、タンパク質に上記式(I)で表される基が導入される。例えば、製造原料として羊毛を使用し、還元剤としてチオグリコール酸を使用した場合、上記式(I)で表される基の一種であるカルボキシメチルジスルフィド基がタンパク質分子に導入される機構は、次の通りである。 Through the denaturation step, the group represented by the above formula (I) is introduced into the protein. For example, when wool is used as a production raw material and thioglycolic acid is used as a reducing agent, the mechanism by which a carboxymethyl disulfide group, which is one of the groups represented by the above formula (I), is introduced into a protein molecule is as follows. It is as follows.
また、製造原料として羊毛を使用し、還元剤として3−メルカプトプロピオン酸を使用した場合、上記式(I)で表される基の一種であるカルボキシエチルジスルフィド基がタンパク質分子に導入される機構は、次の通りである。 In addition, when wool is used as a production raw material and 3-mercaptopropionic acid is used as a reducing agent, the mechanism by which a carboxyethyl disulfide group, which is one of the groups represented by the above formula (I), is introduced into a protein molecule is It is as follows.
変性工程での処理により上記式(I)で表される基が導入されたタンパク質は、水に溶解するタンパク質と水に不溶のタンパク質とを含む。前者の水溶性タンパク質がCADペプチドAであり、後者の不溶性タンパク質を除去する必要がある場合には、濾過、遠心分離、圧搾分離、沈降分離、浮上分離等の公知の固液分離手段を採用することができる。CADペプチドA水溶液については、必要に応じてイオン交換や電気透析等による脱塩等を行うと良い。また、固形状のCADペプチドAを得たい場合には、(1)CADペプチドA溶液の凍結乾燥、(2)CADペプチドA溶液の噴霧乾燥、(3)塩酸等の酸をCADペプチドA溶液に添加して、この溶液のpHを2.5から4.0程度に低下させることにより生じたCADペプチドA沈殿物の回収などの方法を採用することができる。回収した固形状のCADペプチドAについては、水や酸性水溶液による洗浄、乾燥等を、必要に応じて行うと良い。 The protein into which the group represented by the formula (I) is introduced by the treatment in the denaturation step includes a protein that is soluble in water and a protein that is insoluble in water. When the former water-soluble protein is CAD peptide A and the latter insoluble protein needs to be removed, known solid-liquid separation means such as filtration, centrifugation, squeezing separation, sedimentation separation, and flotation separation are employed. be able to. About CAD peptide A aqueous solution, it is good to perform desalting etc. by ion exchange, electrodialysis, etc. as needed. In order to obtain solid CAD peptide A, (1) freeze drying of CAD peptide A solution, (2) spray drying of CAD peptide A solution, and (3) acid such as hydrochloric acid is added to CAD peptide A solution. A method such as recovery of CAD peptide A precipitate generated by adding and lowering the pH of the solution from about 2.5 to about 4.0 can be employed. About the collect | recovered solid CAD peptide A, it is good to perform washing | cleaning by water, acidic aqueous solution, drying, etc. as needed.
[製造方法(B)]
製造方法(B)は、還元工程、変性工程、及び加水分解工程を備える。製造方法(B)における還元工程及び変性工程は、製造方法(A)における還元工程及び変性工程と同じである。加水分解工程を備える製造方法(B)は、分子量が40000以下(40kDa以下)の水溶性CADペプチドの製造に適するものである(以下、「分子量40000以下の水溶性CADペプチド」を「CADペプチドB」と称することがある。)。
[Production Method (B)]
The production method (B) includes a reduction process, a modification process, and a hydrolysis process. The reduction process and the modification process in the production method (B) are the same as the reduction process and the modification process in the production method (A). The production method (B) including a hydrolysis step is suitable for the production of a water-soluble CAD peptide having a molecular weight of 40000 or less (40 kDa or less) (hereinafter referred to as “water-soluble CAD peptide having a molecular weight of 40000 or less”). ").
加水分解工程では、変性工程での処理で得られた上記式(I)で表される基が導入されたタンパク質を、加水分解する。公知の加水分解方法としては、(b1)酵素による加水分解、(b2)酸による加水分解及び(b3)アルカリによる加水分解が挙げられる。加水分解方法(b3)では、タンパク質に導入した上記式(I)で表される基のβ脱離反応が進行する恐れがあるので、加水分解方法(b1)〜(b3)のうち、酵素又は酸による加水分解が特に好ましい。 In the hydrolysis step, the protein introduced with the group represented by the above formula (I) obtained by the treatment in the denaturation step is hydrolyzed. Known hydrolysis methods include (b1) enzymatic hydrolysis, (b2) acid hydrolysis, and (b3) alkali hydrolysis. In the hydrolysis method (b3), since the β elimination reaction of the group represented by the above formula (I) introduced into the protein may proceed, among the hydrolysis methods (b1) to (b3), an enzyme or Hydrolysis with acid is particularly preferred.
(b1)酵素による加水分解
酵素としては、例えば、ペプシン、プロテアーゼA、プロテアーゼBなどの酸性タンパク質分解酵素;パパイン、プロメライン、サーモライシン、プロナーゼ、トリプシン、キモトリプシンなどの中性タンパク質分解酵素等が挙げられる。また、市販されているタンパク質分解酵素としては、大和化学工業社製の「プロテライザーA」が酵素による加水分解において好適に使用される。加水分解時のpHは、酸性タンパク質分解酵素の場合には1以上3以下に調整すると良く、中性タンパク質分解酵素の場合には5以上9以下に調整するすると良い。加水分解時の反応温度は30℃以上60℃以下が良く、反応時間は10分以上24時間以内が良い。加水分解を停止させるには、温度を70℃以上にして酵素を失活させると良い。
(B1) Hydrolysis by enzymes Examples of enzymes include acidic proteolytic enzymes such as pepsin, protease A, and protease B; neutral proteolytic enzymes such as papain, promelain, thermolysin, pronase, trypsin, and chymotrypsin. . Moreover, as a commercially available proteolytic enzyme, “Proteizer A” manufactured by Daiwa Chemical Industry Co., Ltd. is preferably used in the hydrolysis with an enzyme. The pH at the time of hydrolysis is preferably adjusted to 1 or more and 3 or less in the case of acidic proteolytic enzymes, and is adjusted to 5 or more and 9 or less in the case of neutral proteolytic enzymes. The reaction temperature during hydrolysis is preferably 30 ° C. or more and 60 ° C. or less, and the reaction time is preferably 10 minutes or more and 24 hours or less. In order to stop the hydrolysis, it is preferable to deactivate the enzyme at a temperature of 70 ° C. or higher.
(b2)酸による加水分解
塩酸、硫酸、リン酸、硝酸、臭化水素酸等の無機酸;及び蟻酸、シュウ酸等の有機酸から適宜選択した酸を使用して、加水分解を行う。この加水分解の条件は、例えば、pH4以下、反応温度40℃以上100℃以下、反応時間2時間以上24時間以内である。
(B2) Hydrolysis with acid Hydrolysis is performed using an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrobromic acid; and an acid appropriately selected from organic acids such as formic acid and oxalic acid. The hydrolysis conditions are, for example, pH 4 or less, reaction temperature 40 ° C. or more and 100 ° C. or less, and reaction time 2 hours or more and 24 hours or less.
(b3)アルカリによる加水分解
水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化バリウム、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、ケイ酸ナトリウム、ホウ酸ナトリウム等のアルカリを使用して、加水分解を行う。この加水分解の条件は、例えば、反応系の全質量に対して、アルカリ1質量%以上20質量%以下、反応温度15℃以上100℃以下、反応時間30分以上24時間以内である。
(B3) Hydrolysis with alkali Hydrolysis is performed using alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate, sodium borate, etc. Do. The hydrolysis conditions are, for example, alkali 1% by mass to 20% by mass, reaction temperature 15 ° C. to 100 ° C., and reaction time 30 minutes to 24 hours with respect to the total mass of the reaction system.
加水分解工程での処理後、水溶性のタンパク質であるCADペプチドBと水に不溶のタンパク質を分離する必要があるときは、公知の固液分離手段で分離すると良い。また、固形状のCADペプチドBを得たい場合には、(1)CADペプチドB溶液の凍結乾燥、(2)CADペプチドB溶液の噴霧乾燥などの方法を採用することができる。回収した固形状のCADペプチドBについては、水や酸性水溶液による洗浄、乾燥等を、必要に応じて行うと良い。 When it is necessary to separate CAD peptide B, which is a water-soluble protein, from water-insoluble protein after the treatment in the hydrolysis step, it may be separated by a known solid-liquid separation means. In order to obtain solid CAD peptide B, methods such as (1) freeze-drying of CAD peptide B solution and (2) spray drying of CAD peptide B solution can be employed. About the collect | recovered solid CAD peptide B, it is good to perform washing | cleaning with water, acidic aqueous solution, drying, etc. as needed.
[製造方法(C)]
製造方法(C)は、製造方法(A)と同様の還元工程及び変性工程で得られた水に不溶のタンパク質を、加水分解工程で処理する方法である。製造方法(C)における加水分解工程は、製造方法(B)における加水分解工程と同じである。また、固形状のCADペプチドを得る手段は、製造方法(B)の手段を採用すると良い。
[Production Method (C)]
The production method (C) is a method in which a water-insoluble protein obtained in the same reduction step and denaturation step as in the production method (A) is treated in the hydrolysis step. The hydrolysis step in the production method (C) is the same as the hydrolysis step in the production method (B). Moreover, as a means for obtaining a solid CAD peptide, the means of the production method (B) may be employed.
製造方法(C)は、分子量が22000以下(22kDa以下)の水溶性CADペプチドの製造に適するものである(以下、「分子量22000以下の水溶性CADペプチド」を「CADペプチドC」と称することがある。)。つまり、羊毛の構成タンパク質であるケラチンは、分子量45000から63000のミクロフィブリル及び分子量10000から22000のマトリックスを含んでおり、製造方法(C)における加水分解工程の主たる加水分解対象はミクロフィブリルよりも硫黄含量が多いマトリックス由来のタンパク質であるから、製造方法(C)は硫黄含量が多いCADペプチドCの製造に適する。 The production method (C) is suitable for the production of a water-soluble CAD peptide having a molecular weight of 22000 or less (22 kDa or less) (hereinafter, “water-soluble CAD peptide having a molecular weight of 22000 or less” may be referred to as “CAD peptide C”). is there.). That is, keratin, which is a constituent protein of wool, contains microfibrils having a molecular weight of 45000 to 63000 and a matrix having a molecular weight of 10,000 to 22000, and the main hydrolysis target in the hydrolysis step in the production method (C) is sulfur rather than microfibrils. Since it is a matrix-derived protein with a high content, the production method (C) is suitable for the production of CAD peptide C with a high sulfur content.
(ヘアケア剤)
本実施形態における「ヘアケア剤」とは、毛髪の手入れや手当てを行うための処理剤である。例えば、シャンプー、リンス、コンディショナー、トリートメント(例えば、洗い流さないトリートメント、洗い流すトリートメント、整髪兼用トリートメント、多剤式トリートメントの一構成剤、パーマの前処理のためのトリートメント、パーマの後処理のためのトリートメント、カラーリングの前処理のためのトリートメント、カラーリングの後処理のためのトリートメント、ブリーチの前処理のためのトリートメント、ブリーチの後処理のためのトリートメント)が、かかるヘアケア剤に該当する。
(Hair care agent)
The “hair care agent” in the present embodiment is a treatment agent for performing care and care for hair. For example, shampoos, rinses, conditioners, treatments (e.g. non-washing treatments, flushing treatments, combined hair treatments, a multi-drug treatment, pre-treatment for perms, post-treatments for perms, Treatments for pre-treatment of coloring, treatments for post-treatment of coloring, treatments for pre-treatment of bleach, and treatments for post-treatment of bleach) fall under such hair care agents.
ヘアケア剤の使用時の剤型は、特に限定されず、例えば、液状、乳液状、クリーム状、軟膏状、ゲル状、固形状、フォーム状(泡状)、霧状が挙げられる。 The dosage form at the time of use of a hair care agent is not specifically limited, For example, liquid form, emulsion, cream form, ointment form, gel form, solid form, foam form (foam form), and mist form are mentioned.
ヘアケア剤の一成分としてCADペプチドが配合されている限り、本実施形態のヘアケア剤に該当する。例えば、公知のヘアケア剤の追加配合成分としてCADペプチドを配合したヘアケア剤、公知のヘアケア剤の配合成分の代替成分としてCADペプチドを配合したヘアケア剤は、本実施形態のヘアケア剤に該当する。 As long as CAD peptide is mix | blended as one component of a hair care agent, it corresponds to the hair care agent of this embodiment. For example, a hair care agent in which a CAD peptide is blended as an additional blending component of a known hair care agent, and a hair care agent in which a CAD peptide is blended as an alternative component of the blending component of a known hair care agent correspond to the hair care agent of this embodiment.
適宜に選定した公知のヘアケア剤原料を、CADペプチドの他に配合される本実施形態に係るヘアケア剤原料として採用することができる。その公知のヘアケア剤原料は、例えば、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、ノニオン界面活性剤、アルコール、多価アルコール、糖類、油脂、エステル油、脂肪酸、エーテル、炭化水素、ロウ、シリコーン、合成高分子化合物、半合成高分子化合物、天然高分子化合物、タンパク、アミノ酸、動植物抽出物、微生物由来物、無機化合物、香料、防腐剤、金属イオン封鎖剤、紫外線吸収剤、色素などである。 An appropriately selected known hair care agent raw material can be employed as the hair care agent raw material according to the present embodiment blended in addition to the CAD peptide. The known hair care raw materials include, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, alcohols, polyhydric alcohols, sugars, fats and oils, ester oils, fatty acids, ethers, hydrocarbons, Wax, silicone, synthetic polymer compound, semi-synthetic polymer compound, natural polymer compound, protein, amino acid, animal and plant extract, microorganism-derived material, inorganic compound, fragrance, preservative, sequestering agent, UV absorber, dye Etc.
前記アニオン界面活性剤の例としては、
ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ヤシ油脂肪酸等の脂肪酸のナトリウム塩、カリウム塩、アミン塩等の脂肪酸石鹸;
ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンラウリルエーテル硫酸アンモニム、ポリオキシエチレンラウリルエーテル硫酸トリエタノールアミン、ポリオキシエチレンアルキル(C12−13)エーテル硫酸ナトリウム、ポリオキシエチレンアルキル(C12−13)エーテル硫酸アンモニウム、ポリオキシエチレンアルキル(C12−13)エーテル硫酸トリエタノールアミン等のポリオキシエチレンアルキルエーテル硫酸塩;
ラウリル硫酸ナトリウム、ラウリル硫酸アンモニム、ラウリル硫酸トリエタノールアミン等のアルキル硫酸塩;
オレフィンスルホン酸塩;
ヤシ油脂肪酸エチルエステルスルホン酸塩;
ドデシルベンゼンスルホン酸塩、パラトルエンスルホン酸塩等のアルキルベンゼンスルホン酸塩;
ポリオキシエチレンアルキルエーテル酢酸ナトリウム(ポリオキシエチレントリデシルエーテル酢酸ナトリウム、ポリオキシエチレンラウリルエーテル酢酸ナトリウム、ポリオキシエチレンヤシ油脂肪酸酢酸ナトリウム等)等のポリオキシエチレンアルキルエーテルカルボン酸塩;
ジアルキルスルホコハク酸、ポリオキシアルキレンアルキルスルホコハク酸塩、スルホコハク酸ジオクチルナトリウム、スルホコハク酸ラウリル二ナトリウム、ポリオキシエチレンスルホコハク酸ラウリル二ナトリウム、ポリオキシエチレンアルキル(C12−13)スルホコハク酸二ナトリウム、ポリオキシエチレンアルキル(C12−14)スルホコハク酸二ナトリウム、スルホコハク酸ポリオキシエチレンラウロイルエタノールアミド二ナトリウム等のアルキルスルホコハク酸塩;
ポリオキシエチレンヤシ油脂肪酸モノエタノールアミド硫酸ナトリウム等のポリオキシエチレン脂肪酸アミドエーテル硫酸塩;
ヤシ油脂肪酸メチルタウリンナトリウム、ラウロイルメチルタウリンナトリウム、ミリストイルメチルタウリンナトリウム、パルミトイルメチルタウリンナトリウム、ステアロイルメチルタウリンナトリウム、ヤシ油脂肪酸タウリンナトリウム、ラウリン酸タウリンナトリウム、アシルメチルタウリン等のタウリン塩;
ヤシ油脂肪酸サルコシンナトリウム、ラウロイルサルコシンナトリウム、ヤシ油脂肪酸サルコシンカリウム、ラウロイルサルコシンカリウム、ヤシ油脂肪酸サルコシントリエタノールアミン、ラウロイルサルコシントリエタノールアミン等のサルコシン塩;
ラウリルリン酸、オレイルリン酸、ポリオキシエチレンラウリルエーテルリン酸、ポリオキシエチレンアルキル(C12−15)エーテルリン酸、ポリオキシエチレンセチルエーテルリン酸、ポリオキシエチレンステアリルエーテルリン酸、ジポリオキシエチレンアルキルエーテルリン酸、トリポリオキシエチレンアルキルエーテルリン酸、ポリオキシエチレンオレイルエーテルリン酸、ポリオキシエチレンヤシ油脂肪酸モノエタノールアミドリン酸塩等のナトリウム、カリウム、アンモニウム、トリエタノールアミン等の塩であるリン酸塩;
N−アシル−L−アスパラギン酸塩、N−アシルグルタミン酸塩(N−ヤシ油脂肪酸アシルグルタミン酸塩、N−ラウロイルグルタミン酸塩、N−ミリストイルグルタミン酸塩、N−パルミトイルグルタミン酸塩、N−ステアロイルグルタミン酸塩、N−オレオイルグルタミン酸塩等)、N−アシルメチルアラニン塩(N−ヤシ油脂肪酸メチルアラニン塩、N−ラウロイルメチルアラニン塩、N−ミリストイルメチルアラニン塩)、N−アシルサルコシン酸塩(N−ヤシ油脂肪酸サルコシン塩、N−ラウロイルサルコシン塩、N−ミリストイルサルコシン塩、N−オレオイルサルコシン塩等)、N−アシルシルクアミノ酸塩(N−ラウロイルシルクアミノ酸塩等)等のアミノ酸誘導体の塩;が挙げられる。
Examples of the anionic surfactant include
Fatty acid soaps such as sodium salts, potassium salts, amine salts of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, coconut oil fatty acid;
Sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl ether triethanolamine sulfate, polyoxyethylene alkyl (C12-13) sodium ether sulfate, polyoxyethylene alkyl (C12-13) ether ammonium sulfate Polyoxyethylene alkyl ether sulfates such as polyoxyethylene alkyl (C12-13) ether sulfate triethanolamine;
Alkyl sulfates such as sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate;
Olefin sulfonates;
Coconut oil fatty acid ethyl ester sulfonate;
Alkyl benzene sulfonates such as dodecyl benzene sulfonate and para-toluene sulfonate;
Polyoxyethylene alkyl ether carboxylates such as sodium polyoxyethylene alkyl ether acetate (sodium polyoxyethylene tridecyl ether acetate, sodium polyoxyethylene lauryl ether acetate, sodium polyoxyethylene coconut oil fatty acid acetate, etc.);
Dialkyl sulfosuccinic acid, polyoxyalkylene alkyl sulfosuccinate, dioctyl sodium sulfosuccinate, disodium lauryl sulfosuccinate, disodium lauryl polyoxyethylene sulfosuccinate, polyoxyethylene alkyl (C12-13) disodium sulfosuccinate, polyoxyethylene alkyl (C12-14) alkylsulfosuccinates such as disodium sulfosuccinate and disodium polyoxyethylene lauroylethanolamide sulfosuccinate;
Polyoxyethylene fatty acid amide ether sulfate such as polyoxyethylene coconut oil fatty acid sodium monoethanolamide sulfate;
Taurine salts such as coconut oil fatty acid methyl taurine sodium, lauroyl methyl taurine sodium, myristoyl methyl taurine sodium, palmitoyl methyl taurine sodium, stearoyl methyl taurine sodium, coconut oil fatty acid taurine sodium, lauric acid taurine sodium, acylmethyl taurine;
Sarcosine salts such as coconut oil fatty acid sarcosine sodium, lauroyl sarcosine sodium, coconut oil fatty acid sarcosine potassium, lauroyl sarcosine potassium, coconut oil fatty acid sarcosine triethanolamine, lauroyl sarcosine triethanolamine;
Lauryl phosphate, oleyl phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene alkyl (C12-15) ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene stearyl ether phosphate, dipolyoxyethylene alkyl ether Phosphate that is a salt of sodium, potassium, ammonium, triethanolamine, etc. such as phosphoric acid, tripolyoxyethylene alkyl ether phosphoric acid, polyoxyethylene oleyl ether phosphoric acid, polyoxyethylene coconut oil fatty acid monoethanolamide phosphate ;
N-acyl-L-aspartate, N-acyl glutamate (N-coconut oil fatty acid acyl glutamate, N-lauroyl glutamate, N-myristoyl glutamate, N-palmitoyl glutamate, N-stearoyl glutamate, N -Oleoyl glutamate, etc.), N-acylmethylalanine salt (N-coconut oil fatty acid methylalanine salt, N-lauroylmethylalanine salt, N-myristoylmethylalanine salt), N-acylsarcosine salt (N-coconut oil) Salts of amino acid derivatives such as fatty acid sarcosine salts, N-lauroyl sarcosine salts, N-myristoyl sarcosine salts, N-oleoyl sarcosine salts), N-acyl silk amino acid salts (N-lauroyl silk amino acid salts, etc.); .
前記カチオン界面活性剤の例としては、アンモニウム塩が挙げられ、当該アンモニウム塩としては、例えば、臭化セチルトリメチルアンモニウム、臭化ステアリルトリメチルアンモニウム、塩化ステアリルトリメチルアンモニウム等のトリメチルアンモニウム塩;
塩化ジメチルジステアリルアンモニウム、塩化ジココイルジメチルアンモニウム、エチル硫酸ラノリン脂肪酸アミノプロピルエチルジメチルアンモニウム等のジメチルアンモニウム塩;が挙げられる。また、前記カチオン界面活性剤の他の例としては、塩化ベンザルコニウム、ラウリルアミンオキサイドが挙げられる。
Examples of the cationic surfactant include ammonium salts. Examples of the ammonium salt include trimethylammonium salts such as cetyltrimethylammonium bromide, stearyltrimethylammonium bromide, stearyltrimethylammonium chloride;
And dimethylammonium salts such as dimethyldistearylammonium chloride, dicocoyldimethylammonium chloride, and ethyl sulfate lanolin fatty acid aminopropylethyldimethylammonium. Other examples of the cationic surfactant include benzalkonium chloride and laurylamine oxide.
前記両性界面活性剤の例としては、
2−ココイル−2−イミダゾリニウムヒドロキサイド−1−カルボキシエチロキシ2ナトリウム塩等のイミダゾリン系両性界面活性剤;
イミダゾリニウムベタイン、アルキルベタイン、アミドベタイン、スルホベタイン等のベタイン系界面活性剤;
アシルメチルタウリン等が挙げられる。
Examples of the amphoteric surfactant include
Imidazoline-based amphoteric surfactants such as 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt;
Betaine surfactants such as imidazolinium betaine, alkyl betaine, amide betaine, sulfobetaine;
And acylmethyl taurine.
ノニオン界面活性剤の例としては、
ソルビタンモノステアレート、セスキオレイン酸ソルビタン等のソルビタン脂肪酸エステル;
モノステアリン酸グリセリン等のグリセリン脂肪酸;
グリセリンモノステアレート、グリセリンモノイソステアレート、グリセリントリイソステアレート等のグリセリン脂肪酸エステル;
モノステアリン酸プロピレングリコール等のプロピレングリコール脂肪酸エステル;
硬化ヒマシ油誘導体;
グリセリンアルキルエーテル;
POEソルビタンモノオレエート、モノステアリン酸ポリオキエチレンソルビタン等のPOEソルビタン脂肪酸エステル;
POEグリセリンモノイソステアレート等のPOEグリセリン脂肪酸エステル;
ポリエチレングリコールモノオレート、POEジステアレート等のPOE脂肪酸エステル;
POEラウリルエーテル、POEセチルエーテル、POEオレイルエーテル、POEステアリルエーテル、POE2−オクチルドデシルエーテル等のPOEアルキルエーテル;
POEノニルフェニルエーテル等のPOEアルキルフェニルエーテル;
プルロニック型;
POE・POP2−デシルテトラデシルエーテル等のPOE・POPアルキルエーテル;
テトロニック型;
POEヒマシ油、及びPOEヒマシ油誘導体;
POE硬化ヒマシ油、及びPOE硬化ヒマシ油誘導体;
その他、ショ糖脂肪酸エステル、アルキルグルコシド、デシルグルコシド、ヤシ油脂肪酸モノエタノールアミド、ヤシ油脂肪酸ジエタノールアミド、テトラオレイン酸POEソルビット等が挙げられる。なお、上記化合物中、「POE」とは「ポリオキシエチレン」を意味し、「POP」とは「ポリオキシプロピレン」を意味する。
Examples of nonionic surfactants include
Sorbitan fatty acid esters such as sorbitan monostearate and sorbitan sesquioleate;
Glycerin fatty acids such as glyceryl monostearate;
Glycerol fatty acid esters such as glycerol monostearate, glycerol monoisostearate, glycerol triisostearate;
Propylene glycol fatty acid esters such as propylene glycol monostearate;
Hardened castor oil derivative;
Glycerin alkyl ether;
POE sorbitan fatty acid esters such as POE sorbitan monooleate and polyoxyethylene sorbitan monostearate;
POE glycerol fatty acid esters such as POE glycerol monoisostearate;
POE fatty acid esters such as polyethylene glycol monooleate and POE distearate;
POE alkyl ethers such as POE lauryl ether, POE cetyl ether, POE oleyl ether, POE stearyl ether, POE2-octyldodecyl ether;
POE alkyl phenyl ethers such as POE nonyl phenyl ether;
Pluronic type;
POE · POP alkyl ethers such as POE · POP2-decyltetradecyl ether;
Tetronic type;
POE castor oil and POE castor oil derivatives;
POE hydrogenated castor oil and POE hydrogenated castor oil derivative;
Other examples include sucrose fatty acid esters, alkyl glucosides, decyl glucosides, coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, tetraoleic acid POE sorbitol, and the like. In the above compounds, “POE” means “polyoxyethylene”, and “POP” means “polyoxypropylene”.
前記アルコールの例としては、
エタノール、プロパノール、イソプロパノール等の炭素数6以下の低級一価アルコール;
セチルアルコール、ステアリルアルコール、イソステアリルアルコール、ベヘニルアルコール、オクチルドデカノール、ミリスチルアルコール等の高級一価アルコールが挙げられる。
Examples of the alcohol include
Lower monohydric alcohols having 6 or less carbon atoms, such as ethanol, propanol, and isopropanol;
Higher monohydric alcohols such as cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol and the like can be mentioned.
前記多価アルコールの例としては、
エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、グリセリン、ジグリセリン、1,3−ブチレングリコール、エリスリトール、イソプレングリコール、1,2−ペンタンジオール、2,4−ヘキサンジオール、1,2−ヘキサンジオール、1,2−オクタンジオール等が挙げられる。
As an example of the polyhydric alcohol,
Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, diglycerin, 1,3-butylene glycol, erythritol, isoprene glycol, 1,2-pentanediol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octanediol and the like can be mentioned.
前記糖類の例としては、
ソルビトール、トレハロース、ブドウ糖、ショ糖、キシリトール、マルチトール等が挙げられる。また、前記油脂の例としては、マカデミアナッツ油、アボガド油、トウモロコシ油、オリーブ油、ナタネ油、ゴマ油、ヒマシ油、サフラワー油、綿実油、ホホバ油、ヤシ油、パーム油、硬化ヤシ油、硬化油、硬化ヒマシ油、シア脂等が挙げられる。
Examples of the saccharide include
Examples include sorbitol, trehalose, glucose, sucrose, xylitol, maltitol and the like. Examples of the oils and fats include macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, palm oil, palm oil, hardened palm oil, hardened oil, Examples include hardened castor oil and shea fat.
前記エステル油の例としては、
エイコセン酸カプリリル、エチルヘキサン酸セチル、オクタン酸アルキル、イソノナン酸イソトリデシル、パルミチン酸イソプロピル、ミリスチン酸イソプロピル、イソノナン酸オクチル、イソノナン酸イソトリデシル、トリオレイン酸PEG−3グリセリル、トリイソステアリン酸PEG−3グリセリル、ミリスチン酸PPG−3ベンジル、ラウロイルグルタミン酸ジオクチルドデシル、トリオレイン酸PEG−5グリセリル、トリイソステアリン酸PEG−5グリセリル、トリイソステアリン酸PEG−5グリセリル、コハク酸ジオクチル、ラノリン脂肪酸コレステリル、ジペンタエリトリット脂肪酸エステル等を挙げることができる。
Examples of the ester oil include
Capryryl eicosenoate, cetyl ethylhexanoate, alkyl octanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl myristate, octyl isononanoate, isotridecyl isononanoate, PEG-3 glyceryl trioleate, PEG-3 glyceryl triisostearate, myristine PPG-3 benzyl acid, dioctyldodecyl lauroyl glutamate, PEG-5 glyceryl trioleate, PEG-5 glyceryl triisostearate, PEG-5 glyceryl triisostearate, dioctyl succinate, lanolin fatty acid cholesteryl, dipentaerythritol fatty acid ester, etc. Can be mentioned.
前記脂肪酸の例としては、
オレイン酸、イソステアリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ウンデシレン酸などの高級脂肪酸等が挙げられる。
Examples of the fatty acids include
And higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and undecylenic acid.
前記エーテルの例としては、
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等が挙げられる。
Examples of the ether include
Examples include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
前記炭化水素の例としては、
流動パラフィン、スクワラン、プリスタン、オゾケライト、パラフィン、セレシン、ワセリン、マイクロクリスタリンワックス等が挙げられる。
Examples of the hydrocarbon include
Examples thereof include liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, and microcrystalline wax.
前記ロウの例としては、
ミツロウ、モクロウ、キャンデリラロウ、カルナウバロウ、イボタロウ、ラノリン、水素添加還元ラノリン、ホホバロウ等が挙げられる。
Examples of the wax include
Examples include beeswax, mole, candelilla wax, carnauba wax, ibota wax, lanolin, hydrogenated reduced lanolin, jojoba wax and the like.
前記シリコーンの例としては、
ジメチコノール、メチルフェニルポリシロキサン、デカメチルトリシロキサン、メチルポリシロキサン、架橋型メチルポリシロキサン、高重合ジメチルポリシロキサン、デカメチルシクロペンタシロキサン、ポリオキシエチレン・メチルポリシロキサン共重合体、ジメチルシロキサン・メチルステアロキシシロキサン共重合体、アミノ変性シリコーン(アミノエチルアミノプロピルシロキサン・ジメチルシロキサン共重合体、アミノエチルアミノプロピルメチルシロキサン・ジメチルシロキサン共重合体、高重合ジメチルシロキサン・メチル(アミノプロピル)シロキサン共重合体等)、トリメチルシロキシケイ酸、メチルハイドロジェンポリシロキサン等が挙げられる。
Examples of the silicone include
Dimethiconol, methylphenylpolysiloxane, decamethyltrisiloxane, methylpolysiloxane, cross-linked methylpolysiloxane, highly polymerized dimethylpolysiloxane, decamethylcyclopentasiloxane, polyoxyethylene / methylpolysiloxane copolymer, dimethylsiloxane / methylstea Roxysiloxane copolymer, amino-modified silicone (aminoethylaminopropylsiloxane / dimethylsiloxane copolymer, aminoethylaminopropylmethylsiloxane / dimethylsiloxane copolymer, highly polymerized dimethylsiloxane / methyl (aminopropyl) siloxane copolymer, etc. ), Trimethylsiloxysilicic acid, methyl hydrogen polysiloxane and the like.
前記合成高分子化合物の例としては、
カルボキシビニルポリマー、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリル酸、メタクリロイルエチルベタイン・メタクリル酸エステル共重合体等を挙げることができる。
前記半合成高分子化合物の例としては、
メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース、可溶性デンプン等が挙げられる。
また、前記天然高分子の例としては、
アルギン酸ナトリウム、キサンタンガム、硅酸アルミニウム、マルメロ種子抽出物、トラガントガム、デンプン等が挙げられる。
Examples of the synthetic polymer compound include
Examples thereof include carboxyvinyl polymer, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, methacryloylethylbetaine / methacrylic acid ester copolymer, and the like.
Examples of the semi-synthetic polymer compound include
Examples include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and soluble starch.
Examples of the natural polymer include
Examples include sodium alginate, xanthan gum, aluminum oxalate, quince seed extract, tragacanth gum, starch and the like.
前記タンパクの例としては、
加水分解ダイズタンパク、(ジヒドロキシメチルシリルプロポキシ)ヒドロキシプロピル加水分解ダイズタンパク、(ジヒドロキシメチルシリルプロポキシ)ヒドロキシプロピル加水分解ゴマタンパク、加水分解ライスタンパク等が挙げられる。
Examples of the protein include
Examples include hydrolyzed soy protein, (dihydroxymethylsilylpropoxy) hydroxypropyl hydrolyzed soy protein, (dihydroxymethylsilylpropoxy) hydroxypropyl hydrolyzed sesame protein, hydrolyzed rice protein, and the like.
前記アミノ酸類の例としては、
グリシン、アラニン、バリン、ロイシン、イソロイシン、フェニルアラニン、トリプトファン、シスチン、システイン、メチオニン、プロリン、ヒドロキシプロリン、アスパラギン酸、グルタミン酸、アルギニン、ヒスチジン、リジン及びその誘導体等を挙げることができる。
Examples of the amino acids include
Examples thereof include glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, cystine, cysteine, methionine, proline, hydroxyproline, aspartic acid, glutamic acid, arginine, histidine, lysine and derivatives thereof.
前記動植物抽出物及び微生物由来物の例としては、
アスコルビン酸及びそのアルカリ金属塩又はアルカリ土類金属塩、L−アスコルビン酸アルキルエステル、L−アスコルビン酸リン酸エステル及びその塩、L−アスコルビン酸−2−硫酸エステル及びその塩、L−アスコルビン酸グルコシド等のアスコルビン酸誘導体;
アルコキシサリチル酸及びその塩;
ハイドロキノン配糖体及びその誘導体;
コウジ酸及びその誘導体;
その他、エラグ酸、カミツレエキス、アルテアエキス、カンゾウエキス、ソウハクヒエキス、ラズベリーエキス、リンゴフラボノイド、フスマエキス、ビタミンE及びその誘導体、ヒノキチオール、プラセンタエキス、ルシノール、カモミラET、グルタチオン、チョウジエキス、茶抽出物、アスタキサンチン、牛胎盤エキス、トラネキサム酸及びその誘導体、レゾルシンの誘導体、アズレン、γ−ヒドロキシ酪酸、アシタバエキス、アボガドエキス、アマチャエキス、アルニカエキス、アロエエキス、アンズエキス、アンズ核エキス、イチョウエキス、ウイキョウエキス、ウコンエキス、ウーロン茶エキス、エイジツエキス、エチナシ葉エキス、オウゴンエキス、オウバクエキス、オウレンエキス、オオムギエキス、オトギリソウエキス、オドリコソウエキス、オランダカラシエキス、オレンジエキス、海水乾燥物、海藻エキス、加水分解エラスチン、加水分解コムギ末、加水分解シルク、カモミラエキス、カロットエキス、カワラヨモギエキス、甘草エキス、油溶性甘草エキス、カルカデエキス、カキョクエキス、キウイエキス、キナエキス、キューカンバーエキス、グアノシン、クチナシエキス、クマザサエキス、クララエキス、クルミエキス、グレープフルーツエキス、クレマティスエキス、クロレラエキス、クワエキス、ゲンチアナエキス、紅茶エキス、酵母エキス、ゴボウエキス、コメヌカ発酵エキス、コメ胚芽油、コンフリーエキス、コケモモエキス、サイシンエキス、サイコエキス、サイタイ抽出液、サルビアエキス、サボンソウエキス、ササエキス、サンザシエキス、サンショウエキス、シイタケエキス、ジオウエキス、シコンエキス、シソエキス、シナノキエキス、シモツケソウエキス、シャクヤクエキス、ショウブ根エキス、シラカバエキス、スギナエキス、セイヨウキズタエキス、セイヨウサンザシエキス、セイヨウニワトコエキス、セイヨウノコギリソウエキス、セイヨウハッカエキス、セージエキス、ゼニアオイエキス、センキュウエキス、センブリエキス、ダイズエキス、タイソウエキス、タイムエキス、茶エキス、チガヤエキス、チンピエキス、トウキエキス、トウキンセンカエキス、トウニンエキス、トウヒエキス、ドクダミエキス、トマトエキス、納豆エキス、ニンジンエキス、ニンニクエキス、ノバラエキス、ハイビスカスエキス、バクモンドウエキス、パセリエキス、ハマメリスエキス、パリエタリアエキス、ヒキオコシエキス、ビサボロール、ビワエキス、フキタンポポエキス、フキノトウエキス、ブクリョウエキス、ブッチャーブルームエキス、ブドウエキス、プロポリス、ヘチマエキス、ベニバナエキス、ペパーミントエキス、ボダイジュエキス、ボタンエキス、ホップエキス、マツエキス、マロニエエキス、ミズバショウエキス、ムクロジエキス、メリッサエキス、モモエキス、ヤグルマギクエキス、ユーカリエキス、ユキノシタエキス、ユズエキス、ヨクイニンエキス、ヨモギエキス、ラベンダーエキス、リンゴエキス、レタスエキス、レモンエキス、レンゲソウエキス、ローズエキス、ローズマリーエキス、ローマカミツレエキス、ローヤルゼリーエキス、蜂蜜等が挙げられる。
Examples of the animal and plant extracts and microorganism-derived extracts are:
Ascorbic acid and its alkali metal salt or alkaline earth metal salt, L-ascorbic acid alkyl ester, L-ascorbic acid phosphate and its salt, L-ascorbic acid-2-sulfate and its salt, L-ascorbic acid glucoside Ascorbic acid derivatives such as;
Alkoxysalicylic acid and its salts;
Hydroquinone glycosides and derivatives thereof;
Kojic acid and its derivatives;
Others, ellagic acid, chamomile extract, altea extract, licorice extract, scorpion extract, raspberry extract, apple flavonoid, bran extract, vitamin E and its derivatives, hinokitiol, placenta extract, lucinol, chamomile ET, glutathione, clove extract, tea extract, Astaxanthin, bovine placenta extract, tranexamic acid and its derivatives, derivatives of resorcin, azulene, γ-hydroxybutyric acid, ashitaba extract, avocado extract, achacha extract, arnica extract, aloe extract, apricot extract, ginkgo biloba extract, ginkgo biloba extract , Turmeric extract, Oolong tea extract, Ages extract, Echinacea leaf extract, Ogon extract, Oat extract, Auren extract, Barley extract, Hypericum extract, Licorice extract, Dutch mustard extract, orange extract, seawater dried product, seaweed extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, chamomile extract, carrot extract, Chinese mugwort extract, licorice extract, oil-soluble licorice extract, calcade extract Extract Fermented extract, Rice germ oil, Comfrey extract, Cowberry extract, Saishin extract, Psycho extract, Saitai extract, Salvia extract, Soap extract, Sasa extract, Hawthorn , Salamander extract, Shiitake extract, Giant extract, Shikon extract, Perilla extract, Linden extract, Shimotake extract, Peonies extract, Pepper root extract, Birch extract, Horsetail extract, Kizuta extract, Hawthorn extract, Elderflower extract, Yarrowworm extract, Mint extract, sage extract, mallow extract, nematode extract, senbu extract, soybean extract, taisu extract, thyme extract, tea extract, chigaya extract, chimpi extract, clove extract, cassava extract, tonin extract, spruce extract, dokudami extract, tomato extract, natto Extract, carrot extract, garlic extract, wild rose extract, hibiscus extract, bacmond extract, parsley extract, hammamels Kiss, Parietalia extract, toad extract, bisabolol, loquat extract, dandelion extract, fuquito extract, butterfly extract, butcher bloom extract, grape extract, propolis, loofah extract, safflower extract, peppermint extract, body extract, button extract, hop extract, pine extract , Maronnier extract, Citrus extract, Mukuroji extract, Melissa extract, Peach extract, Cornflower extract, Eucalyptus extract, Yukinoshita extract, Yuzu extract, Yakuinin extract, Artemisia extract, Lavender extract, Apple extract, Lettuce extract, Lemon extract, Forsythia extract, Rose extract, Examples include rosemary extract, Roman chamomile extract, royal jelly extract, and honey.
前記無機化合物の例としては、
酸化チタン、酸化ジルコニウム、酸化亜鉛、酸化セリウム、酸化マグネシウム等の金属酸化物;
硫酸バリウム、硫酸カルシウム、硫酸マグネシウム等の硫酸金属塩;
炭酸カルシウム、炭酸マグネシウム等の炭酸金属塩;
ケイ酸、及び、無水ケイ酸、ケイ酸アルミニウム、ケイ酸マグネシウム、ケイ酸アルミニウムマグネシウム、ケイ酸カルシウム、ケイ酸バリウム、ケイ酸ストロンチウム等のケイ酸誘導体;
その他、タングステン酸金属塩、ヒドロキシアパタイト、バーミキュライト、ハイジライト、ベントナイト、モンモリロナイト、ヘクトライト、ゼオライト、セラミックスパウダー、第二リン酸カルシウム、アルミナ、水酸化アルミニウム、窒化ボロン、シリカ等が挙げられる。
Examples of the inorganic compound include
Metal oxides such as titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide;
Metal sulfates such as barium sulfate, calcium sulfate, magnesium sulfate;
Metal carbonates such as calcium carbonate and magnesium carbonate;
Silicic acid and silicic acid derivatives such as anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate;
In addition, tungstic acid metal salt, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, silica and the like can be mentioned.
前記防腐剤の例としては、
安息香酸、安息香酸ナトリウム、サリチル酸、パラオキシ安息香酸メチル、パラオキシ安息香酸プロピル、パラオキシ安息香酸ベンゼン、フェノキシエタノール、ヒノキチオール等が挙げられる。
Examples of the preservative include
Examples include benzoic acid, sodium benzoate, salicylic acid, methyl paraoxybenzoate, propyl paraoxybenzoate, benzene paraoxybenzoate, phenoxyethanol, and hinokitiol.
前記金属イオン封鎖剤の例としては、
アラニン(前記アミノ酸類にも分類)、エデト酸、エデト酸二ナトリウム、ジエチレントリアミン五酢酸等が挙げられる。
Examples of the sequestering agent include:
Examples include alanine (also classified as the aforementioned amino acids), edetic acid, edetate disodium, diethylenetriaminepentaacetic acid, and the like.
本発明のヘアケア剤を用いた毛髪の処理方法は、典型的には、当該ヘアケア剤を毛髪に塗布する工程、及びこのヘアケア剤を塗布した毛髪に対して水洗処理を行う工程を含む。また、このような毛髪処理の前後において、公知の前処理及び後処理を毛髪に対して行ってもよい。 The method for treating hair using the hair care agent of the present invention typically includes a step of applying the hair care agent to the hair, and a step of washing the hair coated with the hair care agent with water. Moreover, you may perform well-known pre-processing and post-processing with respect to hair before and after such a hair treatment.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明の趣旨を逸脱することがない限り、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless departing from the gist of the present invention.
[実施例1]
CADペプチドAの3質量%水溶液を、実施例1のヘアケア剤として調製した。
[Example 1]
A 3% by mass aqueous solution of CAD peptide A was prepared as the hair care agent of Example 1.
実施例1で使用したCADペプチドAは、以下の還元工程及び変性工程に従って製造したCADペプチドA水溶液から回収したものである。 CAD peptide A used in Example 1 was recovered from an aqueous CAD peptide A solution produced according to the following reduction and denaturation steps.
(還元工程)
中性洗剤で洗浄、乾燥させたメリノ種羊毛を、約5mmに切断した。この羊毛5g、30質量%チオグリコール酸ナトリウム水溶液15.4g及び6mol/L水酸化ナトリウム水溶液8.5gを混合し、さらにイオン交換水を混合して全量150ml、pH11の混合液を調製した。この混合液を、45℃、1時間の条件で攪拌した。次いで、さらに水を混合して全量を200mlとし、45℃、2時間の条件で放置し、その後、液温が常温になるまで自然冷却した。
(Reduction process)
Merino wool, washed with neutral detergent and dried, was cut to about 5 mm. 5 g of this wool, 15.4 g of a 30% by mass sodium thioglycolate aqueous solution and 8.5 g of a 6 mol / L sodium hydroxide aqueous solution were mixed, and ion-exchanged water was further mixed to prepare a mixture of 150 ml in total volume and pH 11. The mixture was stirred at 45 ° C. for 1 hour. Subsequently, water was further mixed to make a total volume of 200 ml, left under conditions of 45 ° C. for 2 hours, and then naturally cooled until the liquid temperature reached room temperature.
(変性工程)
還元工程後の混合液を攪拌しながら、当該混合液に、臭素酸ナトリウムを2.05g配合した水溶液25gを約60分かけて混合した。その後、混合液の攪拌を終始継続し、この混合液に、クエン酸を7.08g配合した水溶液100gを約85分かけて混合し、CADペプチドA水溶液を得た。クエン酸混合後のpHは7であった。
(Modification process)
While stirring the mixed solution after the reduction step, 25 g of an aqueous solution containing 2.05 g of sodium bromate was mixed with the mixed solution over about 60 minutes. Thereafter, stirring of the mixed solution was continued throughout, and 100 g of an aqueous solution containing 7.08 g of citric acid was mixed with the mixed solution over about 85 minutes to obtain a CAD peptide A aqueous solution. The pH after mixing with citric acid was 7.
変性工程での処理によって得られたCADペプチドA水溶液から、固体部をろ過分離した。その後、36質量%塩酸水溶液を添加してCADペプチドA水溶液のpHを3.8にすることにより、CADペプチドAの沈殿を生じさせた。この沈殿を回収、水洗し、固形状のCADペプチドAを得た。 The solid part was separated by filtration from the CAD peptide A aqueous solution obtained by the treatment in the denaturing step. Thereafter, precipitation of CAD peptide A was caused by adding 36 mass% hydrochloric acid aqueous solution to bring the pH of CAD peptide A aqueous solution to 3.8. This precipitate was recovered and washed with water to obtain a solid CAD peptide A.
CADペプチドAの分子量を、タカラバイオ社製「Protein Molecular Weight Marker(Low)」を基準物質とし、Sodium Dodecyl Sulfate−ポリアクリルアミドゲル電気泳動(SDS−PAGE)法により確認した。その結果、CADペプチドAの分子量は、40000から63000(40kDaから63kDa)の範囲内のものであると確認された。 The molecular weight of CAD peptide A was confirmed by a sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) method using “Protein Molecular Weight Marker (Low)” manufactured by Takara Bio Inc. as a reference substance. As a result, the molecular weight of CAD peptide A was confirmed to be in the range of 40,000 to 63,000 (40 kDa to 63 kDa).
[実施例2]
CADペプチドCの3質量%水溶液を、実施例2のヘアケア剤として調製した。
[Example 2]
A 3% by mass aqueous solution of CAD peptide C was prepared as the hair care agent of Example 2.
実施例2で使用したCADペプチドCは、実施例1で使用したCADペプチドAの水溶液からろ過分離した固体部を加水分解したものである。その加水分解の手順は、次の通り行った。ろ過分離した固体部100質量部、タンパク質分解酵素(大和化学社製「プロテライザーA」)1質量部、pHが8.0〜8.5となるように適量の炭酸水素ナトリウム及び水を混合し、50℃の水中で加水分解反応を20分間進行させた。その後、80℃、5分の条件でタンパク質分解酵素を失活させた。その失活後、ろ過によりCADペプチドCの水溶液を得た。上記同様のSDS−PAGE法により実施例2のCADペプチドの分子量を確認したところ、分子量が22000を超えるCADペプチドを確認することができなかった。つまり、実施例2のCADペプチドの分子量は、22000以下(22kDa以下)の範囲内のものであることが確認された。 CAD peptide C used in Example 2 is a product obtained by hydrolyzing the solid portion filtered and separated from the aqueous solution of CAD peptide A used in Example 1. The hydrolysis procedure was as follows. 100 parts by mass of the solid part separated by filtration, 1 part by mass of a proteolytic enzyme (“Proteerizer A” manufactured by Daiwa Chemical Co., Ltd.), and an appropriate amount of sodium bicarbonate and water were mixed so that the pH would be 8.0 to 8.5. The hydrolysis reaction was allowed to proceed for 20 minutes in water at 50 ° C. Thereafter, the proteolytic enzyme was inactivated at 80 ° C. for 5 minutes. After the deactivation, an aqueous solution of CAD peptide C was obtained by filtration. When the molecular weight of the CAD peptide of Example 2 was confirmed by the same SDS-PAGE method, a CAD peptide having a molecular weight exceeding 22,000 could not be confirmed. That is, it was confirmed that the molecular weight of the CAD peptide of Example 2 was within the range of 22000 or less (22 kDa or less).
[参考例1]
加水分解ケラチンを17質量%含有するミルボン社製「ノワロードプロ・ハイケラチン」を、参考例1のヘアケア剤として用意した。
[Reference Example 1]
“Now Road Pro Hikeratin” manufactured by Milbon, containing 17% by mass of hydrolyzed keratin, was prepared as a hair care agent of Reference Example 1.
[試験例1]
実施例1、実施例2又は参考例1のヘアケア剤を使用し、下記に従って毛髪処理を行った。
[Test Example 1]
Using the hair care agent of Example 1, Example 2 or Reference Example 1, hair treatment was performed according to the following.
緩波状の黒髪を、シャンプー(ミルボン社製「ディーセス・アウフェ・ベースアクアA」)で洗浄し、温風乾燥させた後、温度25℃、湿度50%の雰囲気中に一晩放置した。この黒髪を毛髪試料とし、実施例1、実施例2又は参考例1のヘアケア剤に毛髪試料を5分間浸漬し、水洗後、温風乾燥させた。 The slow-waved black hair was washed with shampoo ("Deceths Aufé Base Aqua A" manufactured by Milbon), dried with warm air, and then left overnight in an atmosphere at a temperature of 25 ° C and a humidity of 50%. Using this black hair as a hair sample, the hair sample was immersed in the hair care agent of Example 1, Example 2 or Reference Example 5 for 5 minutes, washed with water, and then dried with warm air.
上記処理済みの毛髪試料について、単位断面積当たりの初期弾性率と破断強度を測定した。この試験例では、3本の毛髪試料に関する測定値の平均値を初期弾性率、破断強度とした。測定機はオリエンテック社製「TENSILON UTM−II−20」を使用した。測定条件は、測定前に毛髪試料を水に24時間浸漬、測定時に毛髪試料を水中浸漬、温度25℃、引張り速度2mm/分、毛髪試料の引張り間隔20mmとした。 About the said processed hair sample, the initial stage elastic modulus and breaking strength per unit cross-sectional area were measured. In this test example, the average value of the measured values for the three hair samples was taken as the initial elastic modulus and breaking strength. The measuring machine used was "TENSILON UTM-II-20" manufactured by Orientec. Measurement conditions were such that the hair sample was immersed in water for 24 hours before the measurement, the hair sample was immersed in water at the time of measurement, the temperature was 25 ° C., the pulling speed was 2 mm / min, and the tension interval of the hair sample was 20 mm.
試験例1の結果を表1に示す。表1における「未処理」とは、ヘアケア剤で処理されていない緩波状の黒髪について、初期弾性率及び破断強度を測定した例を示す。表1に示す通り、実施例1及び実施例2の初期弾性率及び破断強度の値は、参考例及び未処理の値より高いことを確認できる。 The results of Test Example 1 are shown in Table 1. “Untreated” in Table 1 indicates an example in which the initial elastic modulus and the breaking strength were measured for slow-waved black hair that was not treated with a hair care agent. As shown in Table 1, it can be confirmed that the values of the initial elastic modulus and the breaking strength of Examples 1 and 2 are higher than those of the Reference Examples and untreated values.
[試験例2]
後記の損傷を大きく受けた毛髪を毛髪試料とし、実施例1又は実施例2のヘアケア剤に毛髪試料を10分間浸漬し、水洗後、温風乾燥させた。その後、毛髪試料各5本の初期弾性率及び破断強度を試験例1と同様に測定し、平均値を求めた。また、同じく損傷を大きく受けた毛髪を毛髪試料とし、ヘアケア剤による処理を行わずに、初期弾性率及び破断強度を測定した(上記試験例1と同様に「未処理」と称する)。
[Test Example 2]
The hair damaged greatly as described later was used as a hair sample, the hair sample was immersed in the hair care agent of Example 1 or Example 10 for 10 minutes, washed with water, and then dried with warm air. Thereafter, the initial elastic modulus and breaking strength of each of the five hair samples were measured in the same manner as in Test Example 1, and the average value was obtained. Similarly, the damaged hair was used as a hair sample, and the initial elastic modulus and breaking strength were measured without performing treatment with a hair care agent (referred to as “untreated” as in Test Example 1).
試験例2での毛髪試料は、直毛黒髪を次の通り処理したものである。直毛黒髪を、ブリーチ処理、パーマ処理、カラー処理、洗髪処理、カラー処理、洗髪処理、パーマ処理、カラー処理、洗髪処理、カラー処理、洗髪処理、乾燥処理の手順で処理した。 The hair sample in Test Example 2 is obtained by treating straight black hair as follows. Straight hair black hair was processed by the procedures of bleaching, perm treatment, color treatment, hair washing treatment, color treatment, hair washing treatment, perm treatment, color treatment, hair washing treatment, color treatment, hair washing treatment, and drying treatment.
上記ブリーチ処理では、ミルボン社製「プロマティス フレーブ−アド」の第1剤と第2剤を1質量部:2質量部程度の割合で混合し、これを毛髪に塗布した。塗布量は、毛髪質量の2倍とした。塗布後の毛髪をフィルムで覆い、15分経過後にシャンプーで洗い、温風で乾燥させた。 In the bleaching treatment, the first agent and the second agent of “Promatis Flave-Ad” manufactured by Milbon were mixed in a ratio of about 1 part by mass: 2 parts by mass, and this was applied to the hair. The coating amount was twice the hair mass. The coated hair was covered with a film, washed with shampoo after 15 minutes, and dried with warm air.
上記パーマ処理では、直径12mmのパーマ用ロッドに巻き付けた毛髪を、ミルボン社製「プレジュームC/T」の第1剤に10分間浸漬し、水洗後、「プレジュームC/T」の第2剤に10分間浸漬し、水洗した。その後、毛髪を温風で乾燥させた。 In the perm treatment, hair wound around a perm rod with a diameter of 12 mm is dipped in the first agent of “Pre-Cum C / T” manufactured by Milbon for 10 minutes, washed with water, and then second of “Pre-Cum C / T”. It was immersed in the agent for 10 minutes and washed with water. Thereafter, the hair was dried with warm air.
上記カラー処理では、ミルボン社製「オルディーブ」の第1剤と第2剤を1質量部:1質量部程度の割合で混合し、これを毛髪に塗布した。塗布量は、毛髪質量の10倍とし、塗布後、10分間放置した。 In the color treatment, the first and second agents of “Oldive” manufactured by Milbon were mixed at a ratio of about 1 part by mass to about 1 part by mass, and this was applied to the hair. The coating amount was 10 times the mass of the hair, and was allowed to stand for 10 minutes after coating.
上記洗髪処理では、毛髪のシャンプー、トリートメント及び温風乾燥を1サイクルとし、この60サイクルを行った。シャンプーでは、試料毛髪質量の5倍量のシャンプー(ユニリーバ社製「ラックス・スーパーリッチシャイン」)を毛髪に塗布し、3分間放置した後に水洗した。トリートメントでは、試料毛髪質量の5倍量のトリートメント(ユニリーバ社製「ラックス・スーパーリッチシャイン」)を毛髪に塗布し、3分間放置した後に水洗した。 In the hair washing treatment, hair shampooing, treatment, and warm air drying were defined as one cycle, and these 60 cycles were performed. In the shampoo, shampoo (“Lux Super Rich Shine” manufactured by Unilever Co., Ltd.) 5 times the mass of the sample hair was applied to the hair, allowed to stand for 3 minutes and then washed with water. In the treatment, 5 times the sample hair mass (Unilever “Luxe Super Rich Shine”) was applied to the hair, allowed to stand for 3 minutes and then washed with water.
試験例2の結果を表2に示す。表2に示す通り、未処理の場合と比較して、実施例1及び実施例2共に初期弾性率が向上していることを確認できる。また、実施例1の破断強度は、未処理よりも低下しているが、実施例2の破断強度は、未処理よりも向上していたことを確認できる。つまり、分子量22000以下のCADペプチドCを配合した実施例2のヘアケア剤によれば、大きく損傷した毛髪特性にも対応し得る。 The results of Test Example 2 are shown in Table 2. As shown in Table 2, it can be confirmed that the initial elastic modulus is improved in both Example 1 and Example 2 as compared with the case of no treatment. Moreover, although the breaking strength of Example 1 is falling rather than untreated, it can confirm that the breaking strength of Example 2 was improving rather than untreated. That is, according to the hair care agent of Example 2 in which the CAD peptide C having a molecular weight of 22000 or less is blended, it can cope with hair properties that are greatly damaged.
[実施例3〜4、比較例1及び参考例2〜3]
塩化ステアリルトリメチルアンモニウム0.8質量%、イソプロパノール0.2質量%、セタノール3質量%、ベヘニルアルコール0.8質量%、プロピレングリコール0.02質量%、ジプロピレングリコール2質量%、軟質ラノリン脂肪酸コレステリル0.4質量%、シア脂2質量%、ヒドロキシエチルセルロース0.06質量%、タマリンドシードガム0.2質量%、ジメチコノール1質量%、デカメチルシクロペンタシロキサン16質量%、メチルポリシロキサン2質量%、架橋型メチルポリシロキサン0.2質量%、アミノ変性シリコーン2質量%、高重合ジメチルシロキサン・メチル(アミノプロピル)シロキサン共重合体0.1質量%、コカミドプロピルジメチルアンモニオヒドロキシプロピルオキシプロピルシロキサン・メチルポリシロキサン共重合体酢酸塩0.5質量%、アクリルアミド・2−(アクリロイルオキシ)エチルトリメチルアンモニウムクロリド共重合物0.03質量%、酸化防止剤0.05質量%、防腐剤0.2質量%及び香料0.2質量%を水に配合することによって調製した未洗トリートメント(洗い流さないタイプのトリートメント)用のクリーム1を用意した(比較例1)。また、アルギニンを用いてpHを8.72に調整したCADペプチドAの4質量%水溶液を、上記のクリーム1に、各々5質量%及び1質量%の割合で配合することによって、CADペプチドAの割合が0.2質量%であるクリーム2(実施例3)、及び同割合が0.04質量%であるクリーム3(実施例4)を調製した。一方、ケラチン5質量%水溶液(クローダジャパン株式会社製の「ケラテックIFP−HMW」)を、クリーム1に、各々4質量%及び0.8質量%の割合で配合することによって、ケラチンの割合が0.2質量%であるクリーム4(参考例2)、及び同割合が0.04質量%であるクリーム5(参考例3)を調製した。
[Examples 3-4, Comparative Example 1 and Reference Examples 2-3]
Stearyltrimethylammonium chloride 0.8% by mass, isopropanol 0.2% by mass, cetanol 3% by mass, behenyl alcohol 0.8% by mass, propylene glycol 0.02% by mass, dipropylene glycol 2% by mass, soft lanolin fatty acid cholesteryl 4% by mass, 2% by mass of shea fat, 0.06% by mass of hydroxyethylcellulose, 0.2% by mass of tamarind seed gum, 1% by mass of dimethiconol, 16% by mass of decamethylcyclopentasiloxane, 2% by mass of methylpolysiloxane, cross-linked type 0.2% by weight of methylpolysiloxane, 2% by weight of amino-modified silicone, 0.1% by weight of highly polymerized dimethylsiloxane / methyl (aminopropyl) siloxane copolymer, cocamidopropyldimethylammoniohydroxypropyloxypropylsiloxane Polypolysiloxane copolymer acetate 0.5% by mass, acrylamide-2- (acryloyloxy) ethyltrimethylammonium chloride copolymer 0.03% by mass, antioxidant 0.05% by mass, preservative 0.2% by mass % And fragrance 0.2% by mass were prepared in a cream 1 for a non-washed treatment (a type of treatment that was not washed away) prepared by blending in water (Comparative Example 1). In addition, by blending 4% by mass aqueous solution of CAD peptide A adjusted to pH 8.72 with arginine in the above cream 1 at a ratio of 5% by mass and 1% by mass, respectively, Cream 2 (Example 3) having a ratio of 0.2% by mass and Cream 3 (Example 4) having the same ratio of 0.04% by mass were prepared. On the other hand, a 5% by weight aqueous solution of keratin (“Keratec IFP-HMW” manufactured by Croda Japan Co., Ltd.) is blended in Cream 1 at a ratio of 4% by weight and 0.8% by weight, respectively, so that the ratio of keratin is 0. Cream 4 (Reference Example 2) having a content of 2% by mass and Cream 5 (Reference Example 3) having the same ratio of 0.04% by mass were prepared.
[試験例3]
上記のクリーム1〜5(実施例3〜4、比較例1及び参考例2〜3)の各々を人頭毛髪に塗布した後、厚み感の順位についての官能評価を実施した(厚み感が最も良かったものを1位、最も劣っていたものを5位とした)。また、ウィッグの毛髪にも塗布し、同様の評価を行った。
[Test Example 3]
After applying each of the above creams 1 to 5 (Examples 3 to 4, Comparative Example 1 and Reference Examples 2 to 3) to human hair, a sensory evaluation was performed on the order of thickness feeling (thickness feeling was the most). The best one was ranked first and the worst one was ranked fifth). Moreover, it applied to the hair of the wig and the same evaluation was performed.
ここでの「厚み感」とは、毛髪の表面に何らかの物質がコーティングされているような感触を意味する。各クリームによる処理後の厚み感の官能評価の結果を表3に示す。表3の結果から、CADペプチドAもケラチンも配合しなかった比較例1のクリームや、ケラチンを配合した参考例1及び2のクリームと比べて、CADペプチドAを配合した実施例3及び実施例4のクリームは、厚み感が大きくなることが分かった。 Here, the “thickness” means a feeling that a certain substance is coated on the surface of the hair. The results of sensory evaluation of the feeling of thickness after treatment with each cream are shown in Table 3. From the results in Table 3, Example 3 and Example in which CAD peptide A was blended compared to the cream in Comparative Example 1 in which neither CAD peptide A nor keratin was blended or the cream in Reference Examples 1 and 2 in which keratin was blended were used. The cream of No. 4 was found to have a greater sense of thickness.
[実施例5及び参考例4]
アルギニンを用いてpHを8.72に調整したCADペプチドAの4質量%水溶液を、水で希釈して1質量%水溶液とした(実施例5;この水溶液を「ミスト1」と称する)。また、ケラチン5質量%水溶液(クローダジャパン株式会社製の「ケラテックIFP−HMW」)を、水で希釈して1質量%水溶液とした(参考例4;この水溶液を「ミスト2」と称する)。
[Example 5 and Reference Example 4]
A 4% by mass aqueous solution of CAD peptide A adjusted to pH 8.72 with arginine was diluted with water to give a 1% by mass aqueous solution (Example 5; this aqueous solution is referred to as “mist 1”). In addition, a 5% by mass aqueous solution of keratin (“Keratech IFP-HMW” manufactured by Croda Japan Co., Ltd.) was diluted with water to give a 1% by mass aqueous solution (Reference Example 4; this aqueous solution is referred to as “mist 2”).
[試験例4]
上記のミスト1及び2(実施例5及び参考例4)の各々を人頭毛髪に噴霧した後、ハリ・コシ感の程度を官能評価した。
[Test Example 4]
Each of the mists 1 and 2 (Example 5 and Reference Example 4) was sprayed on human hair, and then the degree of firmness and firmness was subjected to sensory evaluation.
各ミストによる処理後のハリ・コシ感の官能評価の結果を、表4に示す。表4の結果から、ケラチンを配合した参考例4のミストと比べて、CADペプチドAを配合した実施例5のミストにおいては、ハリ・コシ感が大きくなることが分かった。 Table 4 shows the results of sensory evaluation of elasticity and firmness after the treatment with each mist. From the results of Table 4, it was found that the firmness and firmness of the mist of Example 5 containing CAD peptide A was greater than that of Reference Example 4 containing keratin.
[実施例6、7及び参考例5]
トリートメント用クリーム6(実施例6)を、CADペプチドA2質量%、臭化セチルトリメチルアンモニウム2質量%、エタノール1質量%、セタノール3質量%及びステアリルアルコール2質量%を水に配合することによって調製した。また、トリートメント用クリーム7(参考例5)を、臭化セチルトリメチルアンモニウム2質量%、塩化ステアリルトリメチルアンモニウム0.05質量%、塩化ジココイルジメチルアンモニウム0.08質量%、ポリオキシエチレンセチルエーテル(20E.O.)0.01質量%、エタノール1質量%、セタノール6質量%、高重合ジメチルシロキサン2質量%、アミノエチルアミノプロピルシロキサン・ジメチルシロキサン共重合体1質量%、エチル硫酸ラノリン脂肪酸アミノプロピルエチルジメチルアンモニウム(2)0.01質量%、アミノ酸0.2質量%、防腐剤0.3質量%及び香料0.3質量%を水に配合することによって調製した。さらに、前記クリーム6を第1剤とし、前記クリーム7を第2剤とする2剤式トリートメントを用意した(実施例7)。
[Examples 6 and 7 and Reference Example 5]
Treatment cream 6 (Example 6) was prepared by blending 2% by weight CAD peptide A, 2% by weight cetyltrimethylammonium bromide, 1% by weight ethanol, 3% by weight cetanol and 2% by weight stearyl alcohol in water. . Further, treatment cream 7 (Reference Example 5) was prepared by adding 2% by mass of cetyltrimethylammonium bromide, 0.05% by mass of stearyltrimethylammonium chloride, 0.08% by mass of dicocoyldimethylammonium chloride, polyoxyethylene cetyl ether (20E O.) 0.01% by mass, ethanol 1% by mass, cetanol 6% by mass, highly polymerized dimethylsiloxane 2% by mass, aminoethylaminopropylsiloxane / dimethylsiloxane copolymer 1% by mass, ethyl lanolin sulfate fatty acid aminopropylethyl Prepared by blending 0.01% by weight of dimethylammonium (2), 0.2% by weight of amino acid, 0.3% by weight of preservative and 0.3% by weight of perfume into water. Further, a two-component treatment was prepared in which the cream 6 was the first agent and the cream 7 was the second agent (Example 7).
[試験例5]
実施例6の上記クリーム6については、クリーム6を評価用毛束に塗布し、毛束全体に馴染ませた後、水洗し温風乾燥させた。一方、参考例5の上記クリーム7については、クリーム7を評価用毛束に塗布し、毛束全体に馴染ませた後、水洗し温風乾燥させた。また、実施例7の上記クリーム6及び7からなる2剤式トリートメントについては、クリーム6(第1剤)とクリーム7(第2剤)とを、この順で評価用毛束に塗布し、毛束全体に馴染ませた後、水洗し温風乾燥させた。そして、これらの処理後の毛束の厚みの程度について、官能評価した。
[Test Example 5]
About the said cream 6 of Example 6, after applying the cream 6 to the hair bundle for evaluation and making it adjust to the whole hair bundle, it washed with water and dried with warm air. On the other hand, about the said cream 7 of the reference example 5, after apply | coating the cream 7 to the hair bundle for evaluation and making it adjust to the whole hair bundle, it washed with water and dried with warm air. For the two-component treatment consisting of the creams 6 and 7 in Example 7, apply cream 6 (first agent) and cream 7 (second agent) to the evaluation hair bundle in this order, After making it adjust to the whole bundle, it washed with water and dried with warm air. And sensory evaluation was performed about the grade of the thickness of the hair | bristle bundle after these processes.
各トリートメントによる処理後の厚み感の官能評価の結果を、表5に示す。表5の通り、実施例6及び7においては、強い厚み感が得られた。 Table 5 shows the results of sensory evaluation of the feeling of thickness after treatment by each treatment. As shown in Table 5, in Examples 6 and 7, a strong thickness feeling was obtained.
[実施例8〜13、比較例2〜3及び参考例6〜11]
シャンプーA(比較例2)及びシャンプー1〜6(実施例8〜10及び参考例6〜8)を、次の通り調製した。シャンプーA(比較例2)の調製は、ポリオキシエチレンラウリルエーテル硫酸ナトリウム5質量%、ラウリル硫酸トリエタノールアミン4質量%、ポリオキシエチレンラウリルエーテル酢酸ナトリウム2質量%、ラウロイルメチル−β−アラニンナトリウム0.9質量%、ラウリン酸アミドプロピルベタイン4質量%、ヤシ油脂肪酸ジエタノールアミド3質量%、ヤシ油脂肪酸モノエタノールアミド0.1質量%、1,3−ブチレングリコール0.2質量%、塩化o−[2−ヒドロキシ−3−(トリメチルアンモニオ)プロピル]ヒドロキシエチルセルロース0.4質量%、キレート剤0.3質量%、防腐剤0.3質量%、酸化防止剤0.1質量%及び香料0.2質量%を水に配合することにより行った。CADペプチドAの割合が0.2質量%であるシャンプー1(実施例8)の調製、同割合が0.12質量%であるシャンプー2(実施例9)の調製、及び同割合が0.04質量%であるシャンプー3(実施例10)の調製は、シャンプーA(比較例2)の配合原料に加えて上記CADペプチドA4質量%水溶液を水に配合することにより行った。また、ケラチンの割合が0.2質量%であるシャンプー4(参考例6)の調製、同割合が0.12質量%であるシャンプー5(参考例7)の調製、及び同割合が0.04質量%であるシャンプー6(参考例8)の調製は、シャンプーA(比較例2)の配合原料にケラチン5質量%含有水溶液(クローダジャパン株式会社製の「ケラテックIFP−HMW」)を加えて水に配合することにより行った。
[Examples 8 to 13, Comparative Examples 2 to 3, and Reference Examples 6 to 11]
Shampoo A (Comparative Example 2) and shampoos 1 to 6 (Examples 8 to 10 and Reference Examples 6 to 8) were prepared as follows. Preparation of shampoo A (Comparative Example 2) was prepared by 5% by weight of sodium polyoxyethylene lauryl ether sulfate, 4% by weight of triethanolamine lauryl sulfate, 2% by weight of sodium polyoxyethylene lauryl ether acetate, sodium lauroylmethyl-β-alanine 0 .9% by mass, lauric acid amidopropyl betaine 4% by mass, coconut oil fatty acid diethanolamide 3% by mass, coconut oil fatty acid monoethanolamide 0.1% by mass, 1,3-butylene glycol 0.2% by mass, o-chloride [2-Hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose 0.4% by weight, chelating agent 0.3% by weight, preservative 0.3% by weight, antioxidant 0.1% by weight and perfume 0. It was carried out by blending 2% by mass with water. Preparation of shampoo 1 (Example 8) in which the proportion of CAD peptide A is 0.2% by mass, preparation of shampoo 2 (Example 9) in which the proportion is 0.12% by mass, and the proportion is 0.04 Preparation of the shampoo 3 (Example 10) which is mass% was performed by blending the CAD peptide A 4 mass% aqueous solution with water in addition to the blending raw material of shampoo A (Comparative Example 2). In addition, preparation of shampoo 4 (Reference Example 6) having a keratin ratio of 0.2% by mass, preparation of shampoo 5 (Reference Example 7) having the same ratio of 0.12% by mass, and the same ratio of 0.04%. Preparation of shampoo 6 (Reference Example 8), which is mass%, is carried out by adding an aqueous solution containing 5% by mass of keratin (“Keratech IFP-HMW” manufactured by Croda Japan Co., Ltd.) to the blended raw material of shampoo A (Comparative Example 2). It was carried out by blending.
トリートメントA(比較例3)及びトリートメント1〜6(実施例11〜13及び参考例9〜11)を、次の通り調製した。トリートメントA(比較例3)の調製は、臭化セチルトリメチルアンモニウム2質量%、塩化アルキルトリメチルアンモニウム3質量%、エタノール0.8質量%、イソプロパノール0.7質量%、セタノール5質量%、ステアリルアルコール2質量%、濃グリセリン4質量%、ポリオキシエチレンステアリルエーテル0.5質量%、2−エチルヘキサン酸セチル1質量%、ジペンタエリトリット脂肪酸エステル0.8質量%、スクワラン0.3質量%、高重合メチルポリシロキサン0.3質量%、ジメチルシロキサン・メチルステアロキシシロキサン共重合体0.2質量%、防腐剤0.2質量%及び香料0.3質量%を水に配合することにより行った。CADペプチドAの割合が0.2質量%であるトリートメント1(実施例11)の調製、同割合が0.12質量%であるトリートメント2(実施例12)の調製、及び同割合が0.04質量%であるトリートメント3(実施例13)の調製は、トリートメントA(比較例3)の配合原料に加えて上記CADペプチドA4質量%水溶液を水に配合することにより行った。また、ケラチンの割合が0.2質量%であるトリートメント4(参考例9)の調製、同割合が0.12質量%であるトリートメント5(参考例10)の調製、及び同割合が0.04質量%であるトリートメント6(参考例11)の調製は、トリートメントA(比較例3)の配合原料に加えてケラチン5質量%含有水溶液(クローダジャパン株式会社製の「ケラテックIFP−HMW」)を加えて水に配合することにより行った。 Treatment A (Comparative Example 3) and Treatments 1-6 (Examples 11-13 and Reference Examples 9-11) were prepared as follows. Preparation of Treatment A (Comparative Example 3) was performed using 2% by mass of cetyltrimethylammonium bromide, 3% by mass of alkyltrimethylammonium chloride, 0.8% by mass of ethanol, 0.7% by mass of isopropanol, 5% by mass of cetanol, and stearyl alcohol 2 Mass%, concentrated glycerin 4 mass%, polyoxyethylene stearyl ether 0.5 mass%, cetyl 2-ethylhexanoate 1 mass%, dipentaerythritol fatty acid ester 0.8 mass%, squalane 0.3 mass%, high It was carried out by blending 0.3% by mass of polymerized methylpolysiloxane, 0.2% by mass of dimethylsiloxane / methylstearoxysiloxane copolymer, 0.2% by mass of preservative and 0.3% by mass of perfume into water. Preparation of Treatment 1 (Example 11) in which the proportion of CAD peptide A is 0.2% by mass, Preparation of Treatment 2 (Example 12) in which the proportion is 0.12% by mass, and the same ratio is 0.04 Preparation of Treatment 3 (Example 13) in mass% was carried out by blending the above CAD peptide A 4 mass% aqueous solution with water in addition to the ingredients of Treatment A (Comparative Example 3). Also, the preparation of Treatment 4 (Reference Example 9) having a keratin ratio of 0.2% by mass, the preparation of Treatment 5 (Reference Example 10) having the same ratio of 0.12% by mass, and the same ratio of 0.04%. Preparation of Treatment 6 (Reference Example 11), which is mass%, is performed by adding an aqueous solution containing 5% by mass of keratin (“Keratech IFP-HMW” manufactured by Croda Japan Co., Ltd.) in addition to the ingredients of Treatment A (Comparative Example 3). And blended in water.
[試験例6]
ブリーチ処理した毛髪3gを纏めて1つの毛束としたものを複数用意し、これを評価用毛束とした。以下の表6(a)に示すシャンプー(実施例8〜10、参考例6〜8及び比較例2)及びトリートメントA(比較例3)の組み合わせ、並びに、シャンプーA(比較例2)及び以下の表6(b)に示すトリートメント(実施例11〜13、参考例9〜11及び比較例3)の組み合わせを用いて、各毛束に対して、シャンプーの塗布及び水洗、並びにトリートメントの塗布及び水洗を行った後、温風乾燥させた。そして、これらの処理後の毛束の厚み感、なめらかさ及び柔らかさの程度について、比較例2又は比較例3を基準として官能評価した。
[Test Example 6]
A plurality of hair bundles obtained by combining 3 g of the bleached hair were prepared and used as evaluation hair bundles. Combinations of shampoos (Examples 8 to 10, Reference Examples 6 to 8 and Comparative Example 2) and Treatment A (Comparative Example 3) shown in Table 6 (a) below, and Shampoo A (Comparative Example 2) and Using a combination of treatments (Examples 11 to 13, Reference Examples 9 to 11 and Comparative Example 3) shown in Table 6 (b), shampoo application and water washing, and treatment application and water washing for each hair bundle Then, it was dried with warm air. And the sensory evaluation was performed on the basis of Comparative Example 2 or Comparative Example 3 with respect to the sense of thickness, smoothness and softness of the hair bundle after these treatments.
各シャンプー及びトリートメントによる処理後の厚み感、なめらかさ及び柔らかさの官能評価の結果を、表6(a)及び(b)に示す(表中の評価「−」は、評価をしなかったことを示す。)。 Tables 6 (a) and 6 (b) show the results of sensory evaluation of the sense of thickness, smoothness and softness after the treatment with each shampoo and treatment (the evaluation "-" in the table was not evaluated) Is shown.)
以上のように、本発明のヘアケア剤は、損傷を受けた毛髪の初期弾性率を効果的に向上させることができるため、業務用又は家庭用の毛髪処理に好適に使用される。
As described above, since the hair care agent of the present invention can effectively improve the initial elastic modulus of damaged hair, it is preferably used for hair treatment for business use or home use.
Claims (3)
前記ペプチドとして、マトリックス由来のものを含み、下記還元工程、変性工程及び加水分解工程を経て得られるものが配合されたことを特徴とするヘアケア剤。
−S−S−(CH2)nCOO− (I)
(式(I)中、nは1又は2である。)
還元工程:ケラチンを含むタンパク質のジスルフィド基をチオール基にする工程
変性工程:前記還元工程でタンパク質分子に生じたチオール基と、メルカプトアルキルカルボン酸のチオール基及び/又はメルカプトアルキルカルボン酸塩のチオール基とで、上記式(I)で表される基を形成させる工程
加水分解工程:前記変性工程で得られた水に不溶のタンパク質を加水分解する工程 A hair care agent containing a peptide having a group having a group represented by the following formula (I) as a side chain group,
A hair care agent comprising a peptide derived from a matrix as the peptide and obtained through the following reduction step, denaturation step and hydrolysis step.
-S-S- (CH 2) nCOO- (I)
(In the formula (I), n is 1 or 2.)
Reduction step: Step of converting keratin-containing protein disulfide group to thiol group Modification step: Thiol group generated in protein molecule in the reduction step, thiol group of mercaptoalkylcarboxylic acid and / or thiol group of mercaptoalkylcarboxylate And a step of forming a group represented by the above formula (I) Hydrolysis step: a step of hydrolyzing a protein insoluble in water obtained in the denaturation step
The hair care agent according to claim 1 or 2, wherein a peptide having a molecular weight of 22000 or less is blended as the peptide.
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