JP2004182689A - Thickening agent for hair dye, and hair dye containing the same - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、酸化剤、染料、および増粘剤とから主としてなる染毛剤の構成成分となって、水への分散性に優れた染毛剤用増粘剤、およびそれを用いた染毛剤に関する。
【０００２】
【従来の技術】
染毛剤など、水溶液として被塗布物への塗布時にたれの防止性や展着性、塗布用の器具の滑り性等が要求されるものは、増粘剤が配合されることが多い。従来より、カルボキシメチルセルロースおよび／またはその塩は、増粘剤として広く使用されている。カルボキシメチルセルロースおよび／またはその塩は、その製造工程における主溶媒成分として有機溶剤を使用する有機溶媒法、または水を使用する水媒法により製造される。水媒法は、有機溶媒法に比べてカルボキシメチルセルロースおよび／またはその塩を製造する際の付帯設備等の設備投資が少なくて済むため、従来は水媒法が好んで用いられていた。しかし、有機溶媒法によって得られるカルボキシメチルセルロースおよび／またはその塩は、水媒法によるものに比べて、原料であるモノクロル酢酸の使用量が少なくてすむことから安価に製造することができ、また、高純度品を得る場合に、水媒法では中和に多量の硫酸及びアルカリを使用するため、精製コストがかかることから、近年では有機溶媒法が好んで用いられる。
【０００３】
また、カルボキシメチルセルロースおよび／またはその塩を染毛剤用増粘剤として使用する場合には、水へ溶解させて使用する場合が多い。しかし、カルボキシメチルセルロースおよび／またはその塩は、一般的に繊維状物を含むことが多く、水への分散性が低いため、水に分散させた際に団子状のママコになりやすく、ママコとなった場合にはそれ以上の溶解が困難となる。そこで、カルボキシメチルセルロースナトリウムを造粒後に篩い分けし、繊維状物を除去することにより、ママコの発生を低減させる技術があるが、ママコの発生は十分に抑制されていなかった（特許文献１参照）。また、ママコ防止のために湿潤剤を配合したり、顆粒状にするなどの粒度を粗くする方法もあるが、他成分による水溶液の物性への影響や、造粒のコストアップの問題がある。また、粒度を粗くするとママコにはなりにくいが、溶解性が低下するという問題もあった。
【０００４】
また、染毛剤は、その構成成分として酸化剤を含むことが多く、増粘剤としてのカルボキシメチルセルロースおよび／またはその塩は、水溶液とする前の保管時などにおいて酸化剤の酸化作用により分解しやすく、経日安定性に劣り、さらに、水溶液とした際には粘度が低下し、被塗物への塗布時にたれやすいという問題があった。そこで、カルボキシメチルセルロースのアルカリ金属塩のエーテル置換度を２．０以上として、酸化剤やアルカリ剤に対して安定にする技術がある（特許文献２参照）。しかし、エーテル置換度を２．０以上にするのは、コストを低くするのが難しいという問題があった。
【０００５】
【特許文献１】
特公平５−６０４４３号公報
【特許文献２】
特開２００２−４７３４９号公報
【０００６】
【発明が解決しようとする課題】
本発明は、有機溶媒法によっても酸化剤の酸化作用により分解しにくく、経日安定性に優れ、水溶液とした際の粘度が維持でき、被塗物への塗布時にたれの防止性に優れ、かつ水へ溶解させる際の水への分散性に優れた染毛剤用増粘剤の提供を目的とする。
【０００７】
【課題を解決するための手段】
本発明者らは鋭意研究の結果、有機溶媒法によって得られるカルボキシメチルセルロースおよび／またはその塩が、特定の物性、特に特定範囲の粒径であって、特定の嵩比重及び膨潤体積を有している場合に、酸化剤の酸化作用に対する耐分解性、水溶液とした際のたれの防止性、水へ溶解させる際の水への分散性に優れることを見出し、本発明を完成するに至った。
【０００８】
本発明は、酸化剤、染料、および増粘剤とから主としてなる染毛剤の構成成分となる染毛剤用増粘剤であって、該染毛剤用増粘剤が、粒径が４６μｍ以上１７７μｍ以下である粒子の比率が５０重量％以上であり、嵩比重が６３０ｇ／ｌ以上８００ｇ／ｌ以下であり、かつ膨潤係数が２．４以下であるカルボキシメチルセルロースおよび／またはその塩から主としてなり、かつ該カルボキシメチルセルロースおよび／またはその塩が、その製造工程における主溶媒成分として有機溶剤を使用する有機溶媒法により製造されてなることを特徴とする染毛剤用増粘剤、および該染毛剤用増粘剤を、１５〜３５重量％含有することを特徴とする染毛剤に関する。
【０００９】
【発明の実施の形態】
本発明で使用するカルボキシメチルセルロースおよび／またはその塩は、粒径が４６μｍ以上１７７μｍ以下である粒子の比率が５０重量％以上であるカルボキシメチルセルロースおよびその塩である。粒径が４６μｍ未満である粒子の比率が５０重量％以上であると、即ち粒度が細かいと、水への溶解時にママコが発生しやすくなり、また、経日安定性が低下する。粒径が１７７μｍを超える粒子の比率が５０重量％以上であると、即ち粒度が粗いと、水への溶解時にママコ状にならずに分散しても溶解性が低下し、また造粒のコストも上昇する。また、染毛剤に使用する他の成分が粒度の細かい粉体であるため、移送時などに他成分と分離し、不均一となりやすく、経日安定性が低下しやすくなる可能性がある。
【００１０】
本発明で使用するカルボキシメチルセルロースおよび／またはその塩は、嵩比重が６３０ｇ／ｌ以上８００ｇ／ｌ以下である。本発明において、嵩比重Ｄはカルボキシメチルセルロースおよび／またはその塩２００ｇをメスシリンダーに入れ、１０ｃｍの高さからメスシリンダーを縦方向に１０回落下させた後、カルボキシメチルセルロースおよび／またはその塩の体積を測定し、重量及び体積より算出する。嵩比重が６３０ｇ／ｌ未満であると、繊維状物が増加するため、水への溶解時にママコ状になって分散せず、溶解性が低下する。また、酸化剤の酸化作用に対する耐分解性が低下する。嵩比重が８００ｇ／ｌを超えると、品質に問題はないものの、嵩比重が高くなりすぎてコストが増大する。また、後述のように、水を添加する場合での添加する水の配合量、あるいは水の含有量が多くなり、乾燥時間が長くなって、コストが増大する。
【００１１】
カルボキシメチルセルロースおよび／またはその塩は、水への親和性及び溶解力が非常に高いために、水に接触したカルボキシメチルセルロースおよび／またはその塩の粒子の表面は、溶解すると同時に水分子と結合するため、カルボキシメチルセルロースおよび／またはその塩の粒子内部への水の浸透拡散を阻害する。そのため、水への溶解時にママコとなりやすくなる。そこで、本発明におけるカルボキシメチルセルロースおよび／またはその塩は、後述の造粒工程において、粒子表面が角質化されてなることが好ましい。角質化の度合いは膨潤係数により表すことができる。粒子表面が角質化されていると、膨潤係数が小さくなり、水への分散性が優れ、ママコが発生しにくくなる。粒子表面が角質化されていないと、粒子表面が水に溶解し、粒子内部への水の浸透拡散が阻害されやすく、膨潤係数が大きくなり、ママコを発生しやすい。また、経日安定性が低下しやすくなる可能性がある。
【００１２】
本発明で使用するカルボキシメチルセルロースおよび／またはその塩は、膨潤係数が２．４以下である。本発明において、膨潤係数はカルボキシメチルセルロースおよび／またはその塩２００ｇをメスシリンダーに入れ、１０ｃｍの高さからメスシリンダーを縦方向に３０回落下させる方法により嵩比重Ｄ’を測定したカルボキシメチルセルロースおよび／またはその塩５ｇを、７０ｖｏｌ％エタノール水溶液５０ｍｌに分散させ、１０分間放置後の体積を測定し、下記式１により算出する。膨潤係数が２．４を超えると、カルボキシメチルセルロースおよび／またはその塩の粒子の表面が角質化されていないため、ママコが発生しやすくなる。また、酸化剤の酸化作用に対する耐分解性が低下する。
膨潤係数＝Ｖ／（５／Ｄ’×１０００） 式１
（但し、
Ｖ：７０ｖｏｌ％エタノール水溶液に分散させ、１０分間放置した後のカルボキシメチルセルロースおよび／またはその塩の体積（ｍｌ）
Ｄ’：７０ｖｏｌ％エタノール水溶液に分散させる前のカルボキシメチルセルロースおよび／またはその塩の嵩比重（ｇ／ｌ）
を示す。）
【００１３】
本発明で使用するカルボキシメチルセルロースおよび／またはその塩は、その製造工程における主溶媒成分として有機溶剤を使用する有機溶媒法により製造されてなる。これにより、その製造工程における主溶媒成分として水を使用する水媒法に比べ、原料の使用量を少なくすることができ、また、含有している水の量が少ないため、高純度品を製造する場合にコストを安くすることができる。上記有機溶媒としては特に限定されないが、例えば、メタノール、エタノール、イソプロパノール、ブタノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、メチルセロソルブ、エチルセロソルブ等のセロソルブ類等が挙げられ、これらは１種であっても、２種以上の混合物であってもよく、また、これらとベンゼン等の炭化水素との混合物であってもよい。
【００１４】
上記のような粒径、嵩比重、膨潤係数を有することにより、有機溶媒法によっても、酸化剤の作用により分解しにくく、経日安定性に優れ、水溶液とした際の粘度が維持でき、被塗物への塗布時にたれの防止性に優れ、かつ水へ溶解させる際の水への分散性に優れたカルボキシメチルセルロースおよび／またはその塩を得ることができる。
【００１５】
一般に、有機溶媒法により製造されるカルボキシメチルセルロースおよび／またはその塩は、次のようなアルセル化反応工程とエーテル化反応工程の２工程から主に製造される。二軸ニーダーなどのアルセル化反応装置内に、アルセル化反応のための主として有機溶媒と水酸化ナトリウム水溶液からなる混合溶液を投入した後、原料となる粉砕パルプ（セルロース）を上記混合溶液中へ供給し、適切な温度条件下でセルロースをアルセル化反応させ、アルカリセルロースとする（アルセル化工程）。このアルカリセルロースに次工程のエーテル化反応のためのエーテル化剤であるモノクロル酢酸の溶液（有機溶媒を溶媒とする）を供給・混合して、エーテル化反応装置へ排出し、アルセル化反応工程から排出されてきたアルカリセルロースとモノクロル酢酸を適切な温度条件下で反応させる（エーテル化工程）。得られたカルボキシメチルセルロースおよび／またはその塩の粗成生物は溶媒の除去、精製、乾燥、粉砕される。なお、造粒は、例えば、得られたカルボキシメチルセルロースおよび／またはその塩の粗生成物の乾燥工程の前の精製の前あるいは後に行う方法、あるいは一旦乾燥されたカルボキシメチルセルロースおよび／またはその塩を再造粒する方法により行われる。
【００１６】
さらに、本発明で使用するカルボキシメチルセルロースおよび／またはその塩は、カルボキシメチルセルロースおよびその塩を溶解または膨潤することが可能な溶媒を添加して造粒する湿式造粒法によって造粒されてなることが好ましく、溶解または膨潤することが可能な溶媒として水または水と有機溶媒との混合物を用いることがより好ましい。本発明で使用するカルボキシメチルセルロースおよび／またはその塩は、造粒工程、あるいは洗浄工程において、水（蒸気を含む）を添加して製造されるのが好ましい。即ち、造粒時に添加する水の量を所望の物性にあわせて増加させるなど調整してもよいし、洗浄段階で使用する水の量あるいは洗浄溶媒中の水濃度を調整する、あるいは、乾燥・再粉砕後に、再度水を添加して造粒するなどしてもよい。湿式造粒法により造粒されることで、本発明の染毛剤用増粘剤と酸化剤を共存させても、酸化剤の酸化作用により分解しにくく、水溶液とした際の粘度が維持でき、また、水へ溶解させる際に水への分散性が向上し、ママコとなりにくくなる。
【００１７】
本発明において、湿式造粒は、カルボキシメチルセルロースおよび／またはその塩の粗生成物の溶媒の除去後であって精製の前あるいは後の造粒時、あるいは、一旦乾燥されたカルボキシメチルセルロースおよび／またはその塩の再造粒時のいずれであってもよい。また乾燥前に湿式造粒を行い、さらに乾燥後に再度湿式造粒を行ってもよい。湿式造粒においては、カルボキシメチルセルロースおよび／またはその塩を溶解又は膨潤することが可能な溶媒として、水を用いることが好ましい。カルボキシメチルセルロースおよび／またはその塩のエーテル化反応における溶媒の乾燥前の造粒時に湿式造粒する場合には、溶媒の除去後または精製後に水を添加し、乾燥・粉砕するのが好ましく、一旦得られたカルボキシメチルセルロースおよび／またはその塩を再造粒する場合には、カルボキシメチルセルロースおよび／またはその塩に、水を配合して混練し、さらに乾燥・粉砕するのが好ましい。本発明においては、ハンドリングの面から、一旦精製されたカルボキシメチルセルロースおよび／またはその塩を湿式造粒法により再造粒するのが好ましい。
【００１８】
また、本発明における溶媒の除去は、遠心分離による脱液による方法、溶媒を蒸発させる方法等により行われることが好ましい。
【００１９】
本発明の染毛剤用増粘剤に使用するカルボキシメチルセルロースおよび／またはその塩は、エーテル化度が０．８以下であるのが好ましい。より好ましくは、カルボキシメチルセルロースおよび／またはその塩のエーテル化度が０．５〜０．８、さらに好ましくは０．５５〜０．７５であるのがよい。エーテル化度が０．８を超えると、水溶液とした場合の粘度が低下し、被塗布物への塗布時にたれの防止性が不十分となりやすい。
【００２０】
なお、本発明におけるカルボキシメチルセルロースの塩は特に限定されず、例えば、ナトリウム塩、カリウム塩などのアルカリ金属塩、アンモニウム塩などが挙げられ、これらの塩の混合物であってもよい。
【００２１】
本発明の染毛剤用増粘剤は、上記カルボキシメチルセルロースおよび／またはその塩の他に、本発明の作用を阻害しない範囲で他の成分を含有していても良い。
【００２２】
本発明の染毛剤用増粘剤は、保管時などにおける酸化剤に対する耐分解性に優れるため、染毛剤用として好適に使用できる。
【００２３】
なお、本発明の染毛剤用増粘剤を染毛剤に用いる場合の染毛剤の剤型は特に限定されず、粉末剤型、クリーム剤型等が挙げられる。
【００２４】
本発明の染毛剤は、上記の染毛剤用増粘剤と酸化剤と染料とから主としてなる。酸化剤としては、一般に染毛剤用として使用されるものを使用でき、例えば過硼酸ナトリウム、過硼酸カリウム、過酸化尿素、過炭酸ナトリウム、過酸化メラミン、硫酸ナトリウム・過酸化水素付加物、ピロ燐酸ナトリウム・過酸化水素付加物等が挙げられ、これらは粉末状のものを用いることが好ましい。染料としても、一般に染毛剤用として使用されるものを使用でき、例えば、ｐ−またはｍ−あるいはｏ−フェニレンジアミン、ｐ−アミノジフェニルアミン、ｐ−またはｍ−あるいはｏ−アミノフェノール、ニトロ−ｐ−フェニレンジアミン、２−アミノ−４−ニトロフェノール、ピクラミン酸、ピクリン酸、α−ナフトール、レゾルシン、ハイドロキノン、カテコール、ピロガロール等が挙げられ、これらの塩を用いてもよい。なお、本発明においては、染毛剤としての作用を阻害しない範囲で安定剤や香料などの「医薬部外品原料規格」（１９９１年発行、薬事日報社）に記載された他の成分を含有していても良い。
【００２５】
本発明の染毛剤は、上記の染毛剤用増粘剤を１５〜３５重量％含有してなることが好ましい。染毛剤用増粘剤の含有量が１５重量％未満であると、染毛剤とした場合に経日安定性が悪くなりやすく、３５重量％を超えるとコストが高くなる。また、上記各成分の配合割合は、染毛剤に上記の染毛剤用増粘剤を１５〜３５重量％含有していれば、特に限定されない。
【００２６】
本発明の染毛剤は、粉体状で配合され保管されても、構成成分である酸化剤の酸化作用によって含有される増粘剤が分解することなく、使用時に水溶液とした場合の粘度が低下せず、たれの防止性に優れる。
【００２７】
以下に、試験例および実施例を用いて本発明をさらに詳細に説明するが、本発明はこれらによって限定されるものではない。
試験例
試験方法
（１）粒径が４６μｍ以上１７７μｍ以下である粒子の比率
実施例１〜７、比較例１〜５、参考例１の染毛剤用増粘剤について、目開き１７７μｍの篩を通過し、目開き４６μｍの篩を通過しない粒子の比率を測定した。
【００２８】
（２）嵩比重
実施例１〜７、比較例１〜５、参考例１の染毛剤用増粘剤２００ｇをメスシリンダーに入れ、１０ｃｍの高さからメスシリンダーの縦方向に１０回落下させた後、カルボキシルメチルセルロースおよびその塩の体積を測定し、重量及び体積より嵩比重Ｄ（ｇ／ｌ）を算出した。
【００２９】
（３）膨潤係数
実施例１〜７、比較例１〜５、参考例１の染毛剤用増粘剤５ｇを、ビーカー中の７０％エタノール水溶液５０ｍｌに分散させた後、メスシリンダーに移し、１０分間放置後の体積を測定し、下記式１よりカルボキシルメチルセルロースおよびその塩（以下、ＣＭＣと略記することがある）の膨潤係数を算出した。なお、膨潤係数算出のためのカルボキシルメチルセルロースおよびその塩の嵩比重Ｄ’（ｇ／ｌ）については、カルボキシルメチルセルロースおよびその塩２００ｇをメスシリンダーに入れ、１０ｃｍの高さからメスシリンダーの縦方向に３０回落下させた後、体積を測定し、重量及び体積より算出することにより得た。
膨潤係数＝Ｖ／（５／Ｄ’×１０００） 式１
（但し、
Ｖ：７０ｖｏｌ％エタノール水溶液に分散させ、１０分間放置した後のＣＭＣの体積（ｍｌ）
Ｄ’：７０ｖｏｌ％エタノール水溶液に分散させる前のＣＭＣの嵩比重（ｇ／ｌ）
を示す。）
【００３０】
（４）エーテル化度
実施例１〜７、比較例１〜５、参考例１の染毛剤用増粘剤約１ｇを精秤し、定量分析用ろ紙に包んで磁性ルツボに入れ、静かに加熱して炭化した後６００℃〜６２０℃で３時間炭化し、冷却後に５００ｍｌビーカーにルツボを移し、水２５０ｍｌを加え、さらに０．１Ｎ硫酸５０ｍｌを加え、３０分間煮沸した。これを冷却しフェノールフタレイン指示薬を加え、０．１Ｎ水酸化ナトリウム水溶液にて滴定した。同様に空試験を行い、下記式２、３、４によりカルボキシルメチルセルロースおよびその塩のエーテル化度を算出した。
Ｃ＝｛（Ｂ−Ｓ）×Ｆ／Ｇ｝−Ｅ 式２
Ｅ＝（５Ｆ−Ｓ×Ｆ’）／Ｇ 式３
エーテル化度＝１６２×Ｃ／（１００００−８０Ｃ） 式４
（但し、
Ｃ：ＣＭＣ１ｇ中の結合アルカリに消費された０．１Ｎ硫酸の使用量（ｍｌ）
Ｂ：空試験に要した０．１Ｎ水酸化ナトリウム水溶液の使用量（ｍｌ）
Ｓ：実試験に要した０．１Ｎ水酸化ナトリウム水溶液の使用量（ｍｌ）
Ｆ：０．１Ｎ硫酸の力価
Ｆ’：０．１Ｎ水酸化ナトリウム水溶液の力価
Ｇ：ＣＭＣの重量（ｇ）
Ｅ：アルカリ度
１６２：Ｃ６Ｈ７Ｏ２（ＯＨ）２（セルロースモノマー）の分子量
８０：ＣＨ２ＣＯＯＮａ−Ｈの分子量
を示す。）
【００３１】
（５）安息角
実施例１〜７、比較例１〜５、参考例１の染毛剤用増粘剤について、傾斜法により、安息角を測定した。
【００３２】
（６）染毛剤用増粘剤の水溶液の粘度
実施例１〜７、比較例１〜５、参考例１の染毛剤用増粘剤について、１重量％水溶液とした場合の粘度（ｍＰａ・ｓ）を、Ｂ型粘度計（東京計器製）を使用し、２５℃、６０ｒｐｍで測定した。
【００３３】
（７）染毛剤水溶液の混合性（分散性）
実施例１〜７、比較例１〜５、参考例１の染毛剤５ｇに、水１０ｍｌを加え、刷毛で撹拌し、下記の基準に基づいて水への混合性（分散性）の評価をした。
○：ママコの発生がなく、短時間で溶解する。
△：ママコが少し発生するが、溶解する。
×：ママコが多量に発生し、完溶しない。
【００３４】
（８）染毛剤水溶液の粘性（たれ性）
上記（７）の分散性の試験で得られた染毛剤水溶液について、下記の基準に基づいて粘性の評価をした。
○：粘性があり、刷毛からたれにくい。
×：粘性が少なく、刷毛からすぐにたれる。
【００３５】
（９）染毛剤の経日安定性
実施例１〜７、比較例１〜５、参考例１の染毛剤５ｇをサンプル瓶に入れて密封し、５０℃で１ヶ月間、暗所にて保管した。１ヶ月後、上記（７）の分散性の試験と同様に水を加え、上記（７）〜（８）と同様の評価を行い、下記の基準に基いて、経日安定性の評価をした。
○：粘性の変化がほとんどない。
△：粘性が少しなくなっている。
×：粘性がなくなっている。
【００３６】
２．試験結果
表１に染毛剤用増粘剤に関する上記（１）〜（６）の試験結果を、表２に染毛剤に関する上記（７）〜（９）の試験結果を示す。
【００３７】
【実施例】
実施例１
まず、主溶媒成分としてイソプロピルアルコール（以下、ＩＰＡと略記する。）を使用する有機溶媒法によりカルボキシメチルセルロースおよびその塩を製造した。即ち、撹拌装置付きの３Ｌセパラブルフラスコに、ＩＰＡ１６１０ｇと水１２８ｇ、原料となる粉砕パルプ（セルロース）７０ｇを投入して撹拌した。３０℃の温度条件下で、水酸化ナトリウム２９ｇと水２８ｇとの水溶液を添加し、３０〜３５℃で６０分間撹拌混合して、アルカリセルロースを得た（アルセル化工程）。これに、モノクロル酢酸（以下、ＭＣＡと略記する。）２７ｇをＩＰＡ２２ｇに溶解したＩＰＡ溶液を供給・混合して、７０℃の温度で６０分間反応させた。反応終了後、３Ｌセパラブルフラスコから得られた反応物を取り出し、遠心分離機により脱液し、湿綿状のカルボキシメチルセルロースナトリウム塩（以下、ＣＭＣ−Ｎａと略記する。）を得た（エーテル化工程）。得られた湿綿状のＣＭＣ−Ｎａを８０重量％メチルアルコール水溶液で洗浄し、過酸化水素で粘度を調整後、脱液、乾燥、粉砕し、精製されたＣＭＣ−Ｎａを得た。
【００３８】
精製されたＣＭＣ−Ｎａ８０ｇを撹拌しながら、水１００ｇを噴霧添加し、ＣＭＣ−Ｎａの造粒物を得た（湿式造粒）。造粒物の水分が１０％以下となるように、乾燥機において、８０℃で１時間乾燥させ、ハンマー式ミルで粉砕後、目開き１７７μｍの篩により篩い分け、粒径１７７μｍ以下の染毛剤用増粘剤を得た。なお、粒径が１７７μｍを超えた粉砕後の造粒物については、粉砕、篩い分けを繰り返し、染毛剤用増粘剤とした。
【００３９】
次に、得られた染毛剤用増粘剤を、表３に示した配合量となるように混合し、染毛剤を得た。
【００４０】
実施例２
精製されたＣＭＣ−Ｎａとして、ダイセル化学工業社製の＜１１９０＞を用いた以外は、実施例１と同様にして湿式造粒以後の工程を行い、染毛剤用増粘剤及び染毛剤を得た。
【００４１】
実施例３
精製されたＣＭＣ−Ｎａとして、ダイセル化学工業社製の＜１１７０＞を用いた以外は、実施例１と同様にして湿式造粒以後の工程を行い、染毛剤用増粘剤及び染毛剤を得た。
【００４２】
実施例４
水酸化ナトリウムを２９ｇ、ＭＣＡを２４ｇ用い、湿式造粒における添加水量を９０ｇとした以外は実施例１と同様にして、染毛剤用増粘剤及び染毛剤を得た。
【００４３】
実施例５
精製されたＣＭＣ−Ｎａとして、ダイセル化学工業社製の＜１１８０＞を用いた以外は、実施例１と同様にして湿式造粒以後の工程を行い、染毛剤用増粘剤及び染毛剤を得た。
【００４４】
実施例６
精製されたＣＭＣ−Ｎａとして、ダイセル化学工業社製の＜１１７０＞を用い、湿式造粒において添加水量を１１５ｇとした以外は、実施例１と同様にして湿式造粒以後の工程を行い、染毛剤用増粘剤及び染毛剤を得た。
【００４５】
実施例７
実施例１と同様にして、湿綿状のＣＭＣ−Ｎａを得た後、これに水１５０ｇを徐々に添加し、ＣＭＣ−Ｎａの湿綿状の造粒物を得た。これを８０重量％メチルアルコール水溶液で洗浄し、過酸化水素で粘度を調製した後、脱液、乾燥し、染毛剤用増粘剤を得た。また、実施例１と同様にして染毛剤を得た。
【００４６】
比較例１
精製されたＣＭＣ−Ｎａとして、ダイセル化学工業社製の＜１１７０＞をそのまま染毛剤用増粘剤として使用し、実施例１と同様にして染毛剤を得た。
【００４７】
比較例２
湿式造粒において、水５０ｇを噴霧添加した以外は、実施例１と同様にして、染毛剤用増粘剤及び染毛剤を得た。
【００４８】
比較例３
精製されたＣＭＣ−Ｎａとして、ダイセル化学工業社製の＜１１７０＞を用い、湿式造粒において、水８０ｇを添加し、目開き７４μｍの篩を用いて篩い分けをした以外は実施例１と同様にして、染毛剤用増粘剤及び染毛剤を得た。
【００４９】
比較例４
精製されたＣＭＣ−Ｎａとして、ダイセル化学工業社製の＜１１４０＞を用いた以外は、実施例１と同様にして湿式造粒以後の工程を行い、染毛剤用増粘剤及び染毛剤を得た。
【００５０】
比較例５
精製されたＣＭＣ−Ｎａとして、ダイセル化学工業社製の＜１１７０＞１００ｇに、メチルアルコール１５ｇを添加後、さらに水７ｇを添加し、そのまま目開き１７７μｍの篩で篩分け、繊維状のＣＭＣ−Ｎａを除去し、染毛剤用増粘剤を得た。また、実施例１と同様にして、染毛剤を得た。
【００５１】
参考例１
精製されたＣＭＣ−Ｎａとして、ダイセル化学工業社製の＜１２８０＞を用いた以外は、実施例１と同様にして湿式造粒以後の工程を行い、染毛剤用増粘剤及び染毛剤を得た。
【００５２】
【表１】
【表２】
【表３】
硫酸ｐ−フェニレンジアミン ３重量部、硫酸ｐ−アミノフェノール ０．５重量部、硫酸ｍ−アミノフェノール １重量部、硫酸ｐ−ニトロ−ｏ−フェニレンジアミン ０．５重量部）
【００５５】
表１、２より明らかなように、比較例１の染毛剤は、繊維状物が多いため、ママコが発生して混合性が悪くなり、経日安定性も悪かった。比較例２の染毛剤は、造粒が不十分であるため経日安定性が悪かった。比較例３の染毛剤は、粒度が細かすぎるためママコが発生し、混合性が悪かった。比較例４の染毛剤は、粘度が低いため粘性（たれ性）が悪かった。比較例５の染毛剤は、繊維状物の除去が不十分であるため、経日安定性が悪かった。
【００５６】
【発明の効果】
本発明により、酸化剤の酸化作用により分解しにくく、経日安定性に優れ、水溶液とした際の粘度が維持でき、被塗物への塗布時のたれの防止性に優れ、かつ水へ溶解させる際の水への分散性に優れたカルボキシメチルセルロースおよび／またはその塩を、有機溶媒法によって得ることができる。これにより、水溶液として用いる際の作業性やコストなどの経済性に優れた、染毛剤用として好適に使用できる染毛剤用増粘剤を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a hair dye thickener excellent in dispersibility in water, which is a constituent of a hair dye mainly comprising an oxidizing agent, a dye, and a thickener, and a hair dye using the same. Agent.
[0002]
[Prior art]
Thickeners are often added to hair dyes and the like that require anti-sagging property and spreadability when applied to an object to be coated as an aqueous solution, and slipperiness of an application tool. Conventionally, carboxymethylcellulose and / or its salts have been widely used as thickeners. Carboxymethylcellulose and / or a salt thereof are produced by an organic solvent method using an organic solvent as a main solvent component in the production process, or an aqueous medium method using water. The aqueous medium method has conventionally been favorably used because the aqueous medium method requires less capital investment such as ancillary equipment for producing carboxymethyl cellulose and / or a salt thereof than the organic solvent method. However, carboxymethylcellulose and / or a salt thereof obtained by the organic solvent method can be produced at a low cost because monochloroacetic acid as a raw material can be used in a smaller amount than that obtained by the aqueous medium method. In order to obtain a high-purity product, a large amount of sulfuric acid and alkali are used for neutralization in the aqueous medium method, so that purification costs are high. Therefore, in recent years, the organic solvent method is preferably used.
[0003]
When carboxymethylcellulose and / or a salt thereof are used as a thickener for a hair dye, they are often dissolved in water before use. However, carboxymethylcellulose and / or a salt thereof generally contains a fibrous substance in many cases and has low dispersibility in water. If so, further dissolution becomes difficult. Thus, there is a technique for reducing the occurrence of momako by sieving sodium carboxymethylcellulose after granulation and removing fibrous materials, but the occurrence of momako has not been sufficiently suppressed (see Patent Document 1). . In addition, there is a method of adding a wetting agent to prevent mamako or making the particle size coarse, such as granulation. However, there is a problem in that other components affect the physical properties of the aqueous solution and increase the cost of granulation. In addition, when the particle size is made coarse, it is difficult to form mamako, but there is a problem that the solubility is reduced.
[0004]
Hair dyes often contain an oxidizing agent as a component thereof, and carboxymethylcellulose and / or a salt thereof as a thickening agent are decomposed by the oxidizing action of the oxidizing agent during storage before being made into an aqueous solution. However, there is a problem that the viscosity is low when used as an aqueous solution, and the resin tends to sag when applied to an object to be coated. Therefore, there is a technique of setting the degree of ether substitution of an alkali metal salt of carboxymethylcellulose to 2.0 or more to stabilize against an oxidizing agent or an alkaline agent (see Patent Document 2). However, setting the degree of ether substitution to 2.0 or more has a problem that it is difficult to reduce the cost.
[0005]
[Patent Document 1]
Japanese Patent Publication No. 5-60443
[Patent Document 2]
JP-A-2002-47349
[0006]
[Problems to be solved by the invention]
The present invention is hardly decomposed due to the oxidizing action of the oxidizing agent even by the organic solvent method, is excellent in stability over time, can maintain the viscosity when used as an aqueous solution, and is excellent in preventing sagging during application to an object to be coated, Another object of the present invention is to provide a thickening agent for a hair dye which is excellent in dispersibility in water when dissolved in water.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies and found that carboxymethylcellulose and / or a salt thereof obtained by the organic solvent method have specific physical properties, particularly a specific range of particle size, specific bulk specific gravity and swelling volume. In this case, the present inventors have found that the composition has excellent decomposition resistance to the oxidizing action of the oxidizing agent, prevention of dripping when formed into an aqueous solution, and excellent dispersibility in water when dissolved in water, thereby completing the present invention.
[0008]
The present invention is a thickening agent for a hair dye which is a component of a hair dye mainly comprising an oxidizing agent, a dye, and a thickening agent, wherein the thickening agent for a hair dye has a particle size of 46 μm. It is mainly composed of carboxymethylcellulose having a ratio of particles of not less than 177 μm or less and not less than 50% by weight, a bulk specific gravity of not less than 630 g / l and not more than 800 g / l, and a swelling coefficient of not more than 2.4 and / or a salt thereof. And the carboxymethyl cellulose and / or a salt thereof is produced by an organic solvent method using an organic solvent as a main solvent component in the production process, and a hair dye thickener, and the hair dye. The present invention relates to a hair dye containing 15 to 35% by weight of a thickening agent.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Carboxymethylcellulose and / or a salt thereof used in the present invention are carboxymethylcellulose and a salt thereof in which the ratio of particles having a particle size of 46 μm to 177 μm is 50% by weight or more. If the ratio of the particles having a particle size of less than 46 μm is 50% by weight or more, that is, if the particle size is small, mamako is likely to be generated when dissolved in water, and the stability over time is reduced. If the ratio of particles having a particle size exceeding 177 μm is 50% by weight or more, that is, if the particle size is coarse, the solubility is reduced even if the particles are dispersed without dissolving in water, and the cost of granulation is reduced. Also rises. In addition, since the other components used in the hair dye are fine powder, the components may be separated from other components at the time of transfer or the like, become nonuniform, and the stability over time may be easily reduced.
[0010]
The carboxymethyl cellulose and / or a salt thereof used in the present invention has a bulk specific gravity of 630 g / l or more and 800 g / l or less. In the present invention, the bulk specific gravity D is obtained by placing 200 g of carboxymethylcellulose and / or a salt thereof in a measuring cylinder, dropping the measuring cylinder 10 times in a vertical direction from a height of 10 cm, and then measuring the volume of carboxymethylcellulose and / or a salt thereof. Measure and calculate from weight and volume. If the bulk specific gravity is less than 630 g / l, the amount of fibrous material increases, so that it dissolves in water and does not disperse, resulting in reduced solubility. Also, the decomposition resistance to the oxidizing action of the oxidizing agent is reduced. If the bulk specific gravity exceeds 800 g / l, there is no problem with the quality, but the bulk specific gravity becomes too high and the cost increases. In addition, as described later, when water is added, the amount of water to be added or the content of water is increased, so that the drying time is increased and the cost is increased.
[0011]
Since carboxymethylcellulose and / or its salt have a very high affinity and solubility for water, the surface of carboxymethylcellulose and / or its salt particles in contact with water dissolves and binds to water molecules at the same time. , Carboxymethylcellulose and / or salts thereof, which inhibit the penetration and diffusion of water into the interior of the particles. Therefore, when dissolved in water, it tends to become mamako. Therefore, it is preferable that the carboxymethylcellulose and / or a salt thereof in the present invention has a keratinized particle surface in a granulation step described below. The degree of keratinization can be represented by a swelling coefficient. When the particle surface is keratinized, the swelling coefficient is reduced, the dispersibility in water is excellent, and the occurrence of mamako is difficult. If the surface of the particles is not keratinized, the surface of the particles is dissolved in water, penetration and diffusion of water into the inside of the particles are easily inhibited, the swelling coefficient is increased, and mamako is easily generated. In addition, chronological stability may be likely to decrease.
[0012]
The swelling coefficient of carboxymethylcellulose and / or a salt thereof used in the present invention is 2.4 or less. In the present invention, the swelling coefficient is carboxymethylcellulose and / or whose bulk specific gravity D ′ is measured by placing 200 g of carboxymethylcellulose and / or a salt thereof in a measuring cylinder and dropping the measuring cylinder 30 times vertically from a height of 10 cm. 5 g of the salt is dispersed in 50 ml of 70 vol% ethanol aqueous solution, and the volume after standing for 10 minutes is measured, and calculated by the following formula 1. If the swelling coefficient exceeds 2.4, the surface of the particles of carboxymethylcellulose and / or a salt thereof is not keratinized, so that mamako is likely to occur. Also, the decomposition resistance to the oxidizing action of the oxidizing agent is reduced.
Swelling coefficient = V / (5 / D ′ × 1000) Equation 1
(However,
V: The volume (ml) of carboxymethylcellulose and / or its salt after being dispersed in a 70 vol% ethanol aqueous solution and left for 10 minutes.
D ': Bulk specific gravity (g / l) of carboxymethylcellulose and / or its salt before being dispersed in a 70 vol% ethanol aqueous solution
Is shown. )
[0013]
The carboxymethyl cellulose and / or a salt thereof used in the present invention is produced by an organic solvent method using an organic solvent as a main solvent component in the production process. As a result, the amount of raw materials used can be reduced compared to the aqueous medium method in which water is used as the main solvent component in the production process, and the amount of water contained is small, so that high-purity products can be produced. Cost can be reduced. The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropanol and butanol, ketones such as acetone and methyl ethyl ketone, and cellosolves such as methyl cellosolve and ethyl cellosolve. Or a mixture of two or more thereof, or a mixture of these with a hydrocarbon such as benzene.
[0014]
By having the above-mentioned particle size, bulk specific gravity, and swelling coefficient, it is hard to be decomposed by the action of an oxidizing agent even by the organic solvent method, has excellent stability over time, and can maintain the viscosity when used as an aqueous solution. It is possible to obtain carboxymethylcellulose and / or a salt thereof that are excellent in preventing sagging during application to a coating material and excellent in dispersibility in water when dissolved in water.
[0015]
Generally, carboxymethylcellulose and / or a salt thereof produced by an organic solvent method are mainly produced from the following two steps of an arsellation reaction step and an etherification reaction step. A mixed solution mainly composed of an organic solvent and an aqueous solution of sodium hydroxide is charged into an alcerization reaction device such as a biaxial kneader, and then ground pulp (cellulose) as a raw material is supplied into the above mixed solution. Then, the cellulose is subjected to an arsellation reaction under appropriate temperature conditions to obtain alkali cellulose (arsellation step). A solution of monochloroacetic acid (using an organic solvent as a solvent), which is an etherifying agent for the etherification reaction in the next step, is supplied to and mixed with the alkali cellulose, discharged to the etherification reaction apparatus, and the alkalinized cellulose is reacted. The discharged alkali cellulose and monochloroacetic acid are reacted under an appropriate temperature condition (etherification step). The obtained crude product of carboxymethylcellulose and / or its salt is subjected to solvent removal, purification, drying and pulverization. The granulation is performed, for example, by a method performed before or after purification before the drying step of the obtained crude product of carboxymethylcellulose and / or its salt, or by re-using carboxymethylcellulose and / or its salt once dried. It is performed by a granulating method.
[0016]
Further, the carboxymethylcellulose and / or a salt thereof used in the present invention may be granulated by a wet granulation method in which a solvent capable of dissolving or swelling carboxymethylcellulose and a salt thereof is added and granulated. More preferably, water or a mixture of water and an organic solvent is used as the solvent capable of dissolving or swelling. The carboxymethylcellulose and / or a salt thereof used in the present invention is preferably produced by adding water (including steam) in a granulation step or a washing step. That is, the amount of water added at the time of granulation may be adjusted to increase according to desired physical properties, or the amount of water used in the washing step or the concentration of water in the washing solvent may be adjusted, or After re-grinding, granulation may be performed by adding water again. By being granulated by the wet granulation method, even when the thickener for a hair dye of the present invention and an oxidizing agent coexist, it is hardly decomposed by the oxidizing action of the oxidizing agent, and the viscosity of the aqueous solution can be maintained. In addition, when dissolved in water, the dispersibility in water is improved, and it is difficult to form a mamako.
[0017]
In the present invention, wet granulation is carried out after the removal of the solvent of the crude product of carboxymethylcellulose and / or its salt, before or after purification, or during the granulation of carboxymethylcellulose and / or its once dried carboxymethylcellulose. Any time during re-granulation of the salt may be used. Further, wet granulation may be performed before drying, and wet granulation may be performed again after drying. In wet granulation, it is preferable to use water as a solvent capable of dissolving or swelling carboxymethylcellulose and / or a salt thereof. In the case of performing wet granulation at the time of granulation of the solvent in the etherification reaction of carboxymethylcellulose and / or its salt before drying, it is preferable to add water after removal of the solvent or after purification, and then dry and pulverize. When re-granulating the obtained carboxymethylcellulose and / or its salt, it is preferable to mix water with carboxymethylcellulose and / or its salt, knead the mixture, and further dry and pulverize it. In the present invention, from the viewpoint of handling, it is preferable to re-granulate carboxymethyl cellulose and / or a salt thereof once purified by a wet granulation method.
[0018]
Further, the removal of the solvent in the present invention is preferably performed by a method of liquid removal by centrifugation, a method of evaporating the solvent, or the like.
[0019]
Carboxymethylcellulose and / or a salt thereof used in the hair dye thickener of the present invention preferably has a degree of etherification of 0.8 or less. More preferably, the degree of etherification of carboxymethylcellulose and / or a salt thereof is 0.5 to 0.8, more preferably 0.55 to 0.75. When the degree of etherification exceeds 0.8, the viscosity in the case of an aqueous solution decreases, and the prevention of sagging during application to an object to be coated tends to be insufficient.
[0020]
The salt of carboxymethyl cellulose in the present invention is not particularly limited, and includes, for example, alkali metal salts such as sodium salt and potassium salt, ammonium salt, and the like, and may be a mixture of these salts.
[0021]
The thickener for a hair dye of the present invention may contain other components in addition to the carboxymethylcellulose and / or a salt thereof as long as the action of the present invention is not inhibited.
[0022]
The thickener for hair dyes of the present invention has excellent resistance to decomposition against oxidizing agents during storage and the like, and therefore can be suitably used for hair dyes.
[0023]
When the thickener for a hair dye of the present invention is used as a hair dye, the dosage form of the hair dye is not particularly limited, and examples thereof include a powder type and a cream type.
[0024]
The hair dye of the present invention mainly comprises the above thickener for hair dye, oxidizing agent and dye. As the oxidizing agent, those generally used for hair dyes can be used, for example, sodium perborate, potassium perborate, urea peroxide, sodium percarbonate, melamine peroxide, sodium sulfate / hydrogen peroxide adduct, pyro Sodium phosphate / hydrogen peroxide adducts and the like are preferable, and these are preferably used in powder form. As the dye, those generally used for hair dyes can be used. For example, p- or m- or o-phenylenediamine, p-aminodiphenylamine, p- or m- or o-aminophenol, nitro-p -Phenylenediamine, 2-amino-4-nitrophenol, picramic acid, picric acid, α-naphthol, resorcin, hydroquinone, catechol, pyrogallol, and the like, and salts thereof may be used. In the present invention, other ingredients described in "Quasi-drug raw material standards" (published in 1991, Yakuji Nippo Co., Ltd.) such as stabilizers and fragrances are contained as long as the action as a hair dye is not impaired. May be.
[0025]
The hair dye of the present invention preferably contains 15 to 35% by weight of the above hair dye thickener. When the content of the thickener for hair dye is less than 15% by weight, the stability over time tends to deteriorate when the hair dye is used, and when it exceeds 35% by weight, the cost increases. The mixing ratio of each component is not particularly limited as long as the hair dye contains the thickener for hair dye in an amount of 15 to 35% by weight.
[0026]
The hair dye of the present invention has a viscosity when used as an aqueous solution at the time of use, without the thickener contained therein being decomposed due to the oxidizing action of the oxidizing agent as a constituent even when stored and stored in powder form. It does not decrease and is excellent in sagging prevention.
[0027]
Hereinafter, the present invention will be described in more detail with reference to Test Examples and Examples, but the present invention is not limited thereto.
Test example
Test method
(1) Ratio of particles having a particle size of 46 μm or more and 177 μm or less
For the thickeners for hair dyes of Examples 1 to 7, Comparative Examples 1 to 5, and Reference Example 1, the ratio of particles passing through a sieve having an opening of 177 µm and not passing through a sieve having an opening of 46 µm was measured.
[0028]
(2) Bulk specific gravity
200 g of the thickener for hair dyes of Examples 1 to 7 and Comparative Examples 1 to 5 and Reference Example 1 were put into a measuring cylinder and dropped from the height of 10 cm in the longitudinal direction of the measuring cylinder 10 times. And the volume of the salt were measured, and the bulk specific gravity D (g / l) was calculated from the weight and the volume.
[0029]
(3) Swelling coefficient
After dispersing 5 g of the thickener for hair dyes of Examples 1 to 7, Comparative Examples 1 to 5, and Reference Example 1 in 50 ml of a 70% aqueous ethanol solution in a beaker, the dispersion was transferred to a measuring cylinder and left for 10 minutes. The volume was measured, and the swelling coefficient of carboxymethylcellulose and its salt (hereinafter may be abbreviated as CMC) was calculated from the following formula 1. The bulk specific gravity D '(g / l) of carboxymethylcellulose and its salt for calculating the swelling coefficient is as follows: 200 g of carboxymethylcellulose and its salt are put in a measuring cylinder, and the height of 10 cm is set at 30 cm in the longitudinal direction of the measuring cylinder. After being dropped several times, the volume was measured, and it was obtained by calculating from the weight and the volume.
Swelling coefficient = V / (5 / D ′ × 1000) Equation 1
(However,
V: Volume (ml) of CMC after dispersing in 70 vol% ethanol aqueous solution and leaving for 10 minutes
D ': Bulk specific gravity (g / l) of CMC before being dispersed in 70 vol% ethanol aqueous solution
Is shown. )
[0030]
(4) Degree of etherification
About 1 g of the thickener for hair dyes of Examples 1 to 7, Comparative Examples 1 to 5, and Reference Example 1 was precisely weighed, wrapped in a filter paper for quantitative analysis, placed in a magnetic crucible, and gently heated and carbonized. The mixture was carbonized at 600 ° C. to 620 ° C. for 3 hours. After cooling, the crucible was transferred to a 500 ml beaker, 250 ml of water was added, 50 ml of 0.1N sulfuric acid was added, and the mixture was boiled for 30 minutes. This was cooled, a phenolphthalein indicator was added, and the mixture was titrated with a 0.1N aqueous sodium hydroxide solution. Similarly, a blank test was performed, and the degree of etherification of carboxymethylcellulose and its salt was calculated by the following formulas 2, 3, and 4.
C = {(B−S) × F / G} −E Equation 2
E = (5F−S × F ′) / G Equation 3
Degree of etherification = 162 × C / (10000-80C) Formula 4
(However,
C: Usage amount (ml) of 0.1 N sulfuric acid consumed by bound alkali in 1 g of CMC
B: Used amount (ml) of 0.1N sodium hydroxide aqueous solution required for blank test
S: Amount (ml) of 0.1N aqueous sodium hydroxide solution required for the actual test
F: titer of 0.1N sulfuric acid
F ': titer of 0.1N aqueous sodium hydroxide solution
G: Weight of CMC (g)
E: alkalinity
162: C 6 H 7 O 2 (OH) 2 (Cellulose monomer) molecular weight
80: CH 2 Molecular weight of COONa-H
Is shown. )
[0031]
(5) Angle of repose
The angles of repose of the thickeners for hair dyes of Examples 1 to 7, Comparative Examples 1 to 5, and Reference Example 1 were measured by a tilt method.
[0032]
(6) Viscosity of aqueous solution of thickener for hair dye
With respect to the thickeners for hair dyes of Examples 1 to 7, Comparative Examples 1 to 5, and Reference Example 1, the viscosity (mPa · s) in a 1% by weight aqueous solution was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Was measured at 25 ° C. and 60 rpm.
[0033]
(7) Mixing (dispersibility) of hair dye aqueous solution
To 5 g of the hair dyes of Examples 1 to 7, Comparative Examples 1 to 5, and Reference Example 1, 10 ml of water was added, and the mixture was stirred with a brush, and evaluated for miscibility (dispersibility) with water based on the following criteria. did.
：: Dissolves in a short time without generation of momako.
Δ: Mamako is slightly generated, but is dissolved.
X: Mamako is generated in large quantities and does not completely dissolve.
[0034]
(8) Viscosity (dripiness) of hair dye aqueous solution
The viscosity of the aqueous solution of hair dye obtained in the dispersibility test of (7) was evaluated based on the following criteria.
：: Viscous and difficult to drip from brush.
X: Less viscous and immediately dries from the brush.
[0035]
(9) Daily stability of hair dye
5 g of the hair dyes of Examples 1 to 7, Comparative Examples 1 to 5, and Reference Example 1 were put in a sample bottle, sealed, and stored at 50 ° C for one month in a dark place. One month later, water was added in the same manner as in the dispersibility test described in (7) above, and the same evaluation as in (7) to (8) was performed. .
：: Little change in viscosity.
Δ: The viscosity is slightly reduced.
X: The viscosity has disappeared.
[0036]
2. Test results
Table 1 shows the test results of the above (1) to (6) for the thickener for hair dyes, and Table 2 shows the test results of the above (7) to (9) for the hair dyes.
[0037]
【Example】
Example 1
First, carboxymethyl cellulose and a salt thereof were produced by an organic solvent method using isopropyl alcohol (hereinafter abbreviated as IPA) as a main solvent component. That is, 1610 g of IPA, 128 g of water, and 70 g of ground pulp (cellulose) as a raw material were charged into a 3 L separable flask equipped with a stirrer and stirred. Under a temperature condition of 30 ° C., an aqueous solution of 29 g of sodium hydroxide and 28 g of water was added, and the mixture was stirred and mixed at 30 to 35 ° C. for 60 minutes to obtain an alkali cellulose (alcerization step). To this, an IPA solution in which 27 g of monochloroacetic acid (hereinafter abbreviated as MCA) was dissolved in 22 g of IPA was supplied and mixed, and reacted at a temperature of 70 ° C. for 60 minutes. After the completion of the reaction, the reaction product obtained from the 3 L separable flask was taken out and drained by a centrifugal separator to obtain a flocculent sodium carboxymethyl cellulose (hereinafter abbreviated as CMC-Na) (etherification). Process). The obtained wet cotton-like CMC-Na was washed with an 80% by weight aqueous solution of methyl alcohol, and after adjusting the viscosity with hydrogen peroxide, deliquored, dried and pulverized to obtain purified CMC-Na.
[0038]
While stirring 80 g of the purified CMC-Na, 100 g of water was added by spraying to obtain a granulated CMC-Na (wet granulation). In a dryer, dried at 80 ° C. for 1 hour, pulverized by a hammer mill, and sieved with a sieve having an opening of 177 μm so that the water content of the granulated product becomes 10% or less. A thickener was obtained. In addition, about the granulated material after grinding | pulverization whose particle diameter exceeded 177 micrometers, grinding and sieving were repeated and it was set as the thickener for hair dyes.
[0039]
Next, the obtained thickener for a hair dye was mixed so as to have a compounding amount shown in Table 3 to obtain a hair dye.
[0040]
Example 2
Except that <1190> manufactured by Daicel Chemical Industries, Ltd. was used as the purified CMC-Na, the steps after wet granulation were performed in the same manner as in Example 1, and a thickener for hair dye and a hair dye Got.
[0041]
Example 3
Except for using <1170> manufactured by Daicel Chemical Industries, Ltd. as the purified CMC-Na, the steps after wet granulation were performed in the same manner as in Example 1, and a thickener for hair dye and a hair dye Got.
[0042]
Example 4
A thickener for hair dye and a hair dye were obtained in the same manner as in Example 1 except that 29 g of sodium hydroxide and 24 g of MCA were used, and the amount of water added in wet granulation was 90 g.
[0043]
Example 5
Except that <1180> manufactured by Daicel Chemical Industries, Ltd. was used as the purified CMC-Na, the steps after wet granulation were performed in the same manner as in Example 1, and a thickener for hair dye and a hair dye Got.
[0044]
Example 6
<1170> manufactured by Daicel Chemical Industries, Ltd. was used as the purified CMC-Na, and the steps after wet granulation were performed in the same manner as in Example 1 except that the amount of water added was 115 g in the wet granulation. A thickener for hair and a hair dye were obtained.
[0045]
Example 7
After obtaining wet cotton-like CMC-Na in the same manner as in Example 1, 150 g of water was gradually added thereto to obtain wet cotton-like granules of CMC-Na. This was washed with an 80% by weight aqueous solution of methyl alcohol, and the viscosity was adjusted with hydrogen peroxide, followed by deliquoring and drying to obtain a thickener for a hair dye. Further, a hair dye was obtained in the same manner as in Example 1.
[0046]
Comparative Example 1
As purified CMC-Na, <1170> manufactured by Daicel Chemical Industries, Ltd. was used as it was as a thickener for a hair dye, and a hair dye was obtained in the same manner as in Example 1.
[0047]
Comparative Example 2
In wet granulation, a thickener for hair dye and a hair dye were obtained in the same manner as in Example 1 except that 50 g of water was added by spraying.
[0048]
Comparative Example 3
The same as Example 1 except that <1170> manufactured by Daicel Chemical Industries, Ltd. was used as the purified CMC-Na, and in wet granulation, 80 g of water was added and sieved using a sieve having an opening of 74 μm. Thus, a thickener for hair dye and a hair dye were obtained.
[0049]
Comparative Example 4
Except that <1140> manufactured by Daicel Chemical Industries, Ltd. was used as the purified CMC-Na, the steps after wet granulation were performed in the same manner as in Example 1, and a thickener for hair dye and a hair dye Got.
[0050]
Comparative Example 5
As purified CMC-Na, 15 g of methyl alcohol was added to 100 g of <1170> manufactured by Daicel Chemical Industries, Ltd., 7 g of water was further added, and the mixture was sieved with a sieve having openings of 177 μm to obtain fibrous CMC-Na. Was removed to obtain a thickener for a hair dye. A hair dye was obtained in the same manner as in Example 1.
[0051]
Reference Example 1
Except that <1280> manufactured by Daicel Chemical Industries, Ltd. was used as the purified CMC-Na, the steps after wet granulation were performed in the same manner as in Example 1 to increase the viscosity of the hair dye and the hair dye. Got.
[0052]
[Table 1]
[Table 2]
[Table 3]
3 parts by weight of p-phenylenediamine sulfate, 0.5 part by weight of p-aminophenol sulfate, 1 part by weight of m-aminophenol sulfate, 0.5 part by weight of p-nitro-o-phenylenediamine sulfate)
[0055]
As is clear from Tables 1 and 2, the hair dye of Comparative Example 1 had a large amount of fibrous substances, so that mamako was generated and the mixing property was poor, and the stability over time was also poor. The hair dye of Comparative Example 2 had poor stability over time due to insufficient granulation. The hair dye of Comparative Example 3 had too small a particle size, so that mamako was generated and the mixing property was poor. The hair dye of Comparative Example 4 had low viscosity (dripiness) due to low viscosity. The hair dye of Comparative Example 5 was inferior in the removal of fibrous substances, and therefore had poor stability over time.
[0056]
【The invention's effect】
According to the present invention, it is hardly decomposed due to the oxidizing action of the oxidizing agent, has excellent stability over time, can maintain the viscosity of an aqueous solution, is excellent in preventing sagging during application to a substrate, and is soluble in water. Carboxymethylcellulose and / or a salt thereof having excellent dispersibility in water at the time of the production can be obtained by an organic solvent method. This makes it possible to provide a thickening agent for hair dyes that is excellent in economics such as workability and cost when used as an aqueous solution and can be suitably used for hair dyes.
Claims (4)
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