JP4344128B2 - Perfume composition for transparent or translucent softener, and softener composition - Google Patents

Description

【００４０】
（式中Ｒ^１及びＲ^３はそれぞれ独立に、炭素数１２〜３６、好ましくは１３〜２６、特に好ましくは１３〜１８の炭化水素基であり、Ｒ^２及びＲ^４はそれぞれ独立に、炭素数１〜５、好ましくは１〜３のアルキレン基、特にエチレン基又はプロピレン基である。Ｒ^５は炭素数１〜３のアルキル基、ヒドロキシアルキル基、又はＲ^１−［Ａ−Ｒ^２］ａ−で表される基、好ましくはメチル基、エチル基、ヒドロキシエチル基であり、Ｒ^６炭素数１〜３のアルキル基又はヒドロキシアルキル基、好ましくはメチル基、エチル基、ヒドロキシエチル基である。Ａ及びＢはそれぞれ独立に、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−及び−ＮＨＣＯ−から選ばれる基、好ましくは−ＣＯＯ−又は−ＣＯＮＨ−であり、ａ及びｂはそれぞれ０又は１の数、好ましくは１である。Ｙ−は陰イオン、好ましくはハロゲンイオン、硫酸イオン又は炭素数１〜３のアルキル硫酸エステルイオンである。）
【００４１】
【化２】

【００４２】
（式中、Ｒ^７は炭素数１２〜３６、好ましくは１３〜２６、特に好ましくは１３〜１８の炭化水素基であり、Ｒ^８は炭素数１〜５、好ましくは１〜３のアルキレン基、特にエチレン基又はプロピレン基である。Ｒ^９、Ｒ^１０及びＲ^１１はそれぞれ独立に、炭素数１〜３のアルキル基又はヒドロキシアルキル基、好ましくはメチル基、エチル基又はヒドロキシエチル基である。Ｄは−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−及び−ＮＨＣＯ−から選ばれる基、好ましくは−ＣＯＯ−又は−ＣＯＮＨ−であり、ｃは０又は１の数、好ましくは１である。Ｙ−は陰イオン、好ましくはハロゲンイオン、硫酸イオン又は炭素数１〜３のアルキル硫酸エステルイオンである。）
【００４３】
本発明の（ａ１）成分としては、特に下記式（１−１）〜（１−３）で表される化合物及び下記式（２−１）〜（２−３）で表される化合物を用いることが好ましい。
【００４４】
【化３】

（式中Ｒ^１、Ｒ^３、Ｒ^５、Ｒ^６及びＹ−は、陰イオン、好ましくはハロゲンイオン、硫酸イオン又は炭素数１〜３のアルキル硫酸エステルイオンであり、、ｄ及びｅはそれぞれ２又は３の数である。）
【００４５】
化合物（１）は無機又は有機の酸で中和した塩の形態であってもよく、柔軟剤組成物に配合する前にアミノ基を酸剤により中和したものを用いることもでき、柔軟剤組成物に化合物（１）を配合した後、アミノ基を酸剤で中和してもよい。中和のための酸としては塩酸、硫酸、リン酸、グリコール酸、蓚酸、乳酸、クエン酸等のヒドロキシカルボン酸、炭素数１〜１２の脂肪酸又は炭素数１〜３のアルキル硫酸が好ましく、特に塩酸、硫酸、グリコール酸、蓚酸、乳酸、クエン酸が好ましい。中和に用いるこれらの酸は、単独で用いても複数で用いてもよい。
【００４６】
柔軟化基剤（ａ）として、化合物（１）又は化合物（２）を用いる場合には、不飽和結合を１つ有する炭化水素基においてシス体とトランス体を含有することができ、シス体／トランス体はモル比で２５／７５〜１００／０、更に５０／５０〜９５／５であることが透明にする点から好ましい。
【００４７】
（ａ）成分として、（ａ１）成分を用いる場合には、化合物（１）及び化合物（２）を併用することが柔軟効果を向上させる点から好ましく、併用する場合には化合物（１）／化合物（２）を重量比で、１／９９〜５０／５０、更に５／９５〜４０／６０、特に１０／９０〜３０／７０の割合で用いることが柔軟効果を向上させる点から好ましい。
本発明の（ａ２）成分のうち、化合物（３）としては、下記式（３−１）又は（３−２）で表される化合物から選択される１種以上が好ましく用いられる。
【００４８】
【化４】

（式中、Ｒ^７、Ｒ^９及びＲ^１０は、上述のとおりで、ｆ及びｇはそれぞれ２又は３の数である。）
【００４９】
化合物（３）は無機又は有機の酸で中和した塩の形態であってもよく、柔軟剤組成物に配合する前にアミノ基を酸剤により中和したものを用いることもでき、柔軟剤組成物に化合物（３）を配合した後、アミノ基を酸剤で中和してもよい。中和のための酸としては塩酸、硫酸、リン酸、グリコール酸、蓚酸、乳酸、クエン酸等のヒドロキシカルボン酸、炭素数１〜１２の脂肪酸又は炭素数１〜３のアルキル硫酸が好ましく、特に塩酸、硫酸、グリコール酸、蓚酸、乳酸、クエン酸が好ましい。中和に用いるこれらの酸は、単独で用いても複数で用いてもよい。
本発明の（ａ２）成分のうち、化合物（４）としては、下記式（４−１）又は（４−２）で表される化合物から選択される１種以上が好ましく用いられる。
【００５０】
【化５】

（式中、Ｒ^７、Ｒ^９、Ｒ^１０及びＲ^１１は、上述のとおりで、、ｈ及びｉはそれぞれ２又は３の数である。）
【００５１】
成分（ａ）として、（ａ２）成分を用いる場合には、化合物（３）及び化合物（４）を併用することが柔軟効果を向上させる点から好ましく、併用する場合には化合物（１）／化合物（２）を重量比で、１／９９〜５０／５０、更に５／９５〜４０／６０、特に１０／９０〜３０／７０の割合で用いることが柔軟効果を向上させる点から好ましい。
【００５２】
また、（ａ）成分として、（ａ１）成分と（ａ２）成分を併用することも柔軟効果を向上させる点から好ましく、併用する場合には（ａ１）成分／（ａ２）成分を重量比で、１／９９〜２０／８０、更に５／９５〜１５／８５の割合で用いることが好ましい。
本発明の柔軟剤組成物には、（ａ）成分を全組成物に対し３〜４０重量％含有することが好ましく、更に５〜３５重量％、より更に５〜３０重量％、特に７〜２５重量％含有することが好ましい。
【００５３】
本発明の柔軟剤組成物には、透明又は半透明な柔軟剤組成物とするために、（ｂ）成分を入れることが好ましい。
（ｂ）成分としては、「溶剤ハンドブック」（講談社 １９９３年９月２０日第１３刷発行）に記載のものを用いることができる。特に、本発明では柔軟剤組成物を透明又は半透明化にするために、ｌｏｇＰが−２〜３、更に０．５〜２、特に０．５〜１．６の有機溶剤を用いることが好ましい。ここでｌｏｇＰとは、有機化合物の、水と１−オクタノールに対する親和性を示す係数である。１−オクタノール／水分配係数Ｐは、１−オクタノールと水の２液相の溶媒に微量の有機化合物が溶質として溶け込んだときの分配平衡で、それぞれの溶媒中における有機化合物の平衡濃度の比であり、底１０に対するそれらの対数ｌｏｇＰの形で示すのが一般的である。
【００５４】
多くの化合物のｌｏｇＰ値が報告され、Ｄａｙｌｉｇｈｔ ＣｈｅｍｉｃａｌＩｎｆｏｒｍａｔｉｏｎ Ｓｙｓｔｅｍｓ，Ｉｎｃ．（Ｄａｙｌｉｇｈｔ ＣＩＳ）などから入手しうるデータベースには多くの値が掲載されているので参照できる。実測のｌｏｇＰ値がない場合には、Ｄａｙｌｉｇｈｔ ＣＩＳから入手できるプログラム”ＣＬＯＧＰ”で計算すると最も便利である。このプログラムは、実測のｌｏｇＰ値がある場合にはそれと伴に、Ｈａｎｓｃｈ，Ｌｅｏのフラグメントアプローチにより算出される“計算ｌｏｇＰ（ＣｌｏｇＰ）”の値を出力する。フラグメントアプローチは化合物の化学構造に基づいており、原子の数及び化学結合のタイプを考慮している（ｃｆ．Ａ．Ｌｅｏ，Ｃｏｍｐｒｅｈｅｎｓｉｖｅ Ｍｅｄｉｃｉｎａｌ Ｃｈｅｍｉｓｔｒｙ，Ｖｏｌ．４，Ｃ．Ｈａｎｓｃｈ，Ｐ．Ｇ．Ｓａｍｍｅｎｓ，Ｊ．Ｂ．Ｔａｙｌｏｒ ａｎｄ Ｃ．Ａ．Ｒａｍｓｄｅｎ，Ｅｄｓ．，ｐ．２９５，Ｐｅｒｇａｍｏｎ Ｐｒｅｓｓ，１９９０）。
【００５５】
このＣｌｏｇＰ値は現在最も汎用的で信頼できる推定値であるので、化合物の選択に際して実測のｌｏｇＰ値の代わりに用いることができる。本発明では、ｌｏｇＰの実測値があれば実測値を用い、実測値がない場合はプログラムＣＬＯＧＰ ｖ４．０１により計算したＣｌｏｇＰ値を用いた。
【００５６】
このようなｌｏｇＰを有する有機溶剤としては下記式（５）、式（６）又は式（７）で表される化合物が好適である。
Ｒ^１２−ＯＨ （５）
（式中、Ｒ^１２は、炭素数４〜８の炭化水素基、好ましくはアルキル基、アリール基又はアリールアルキル基である。）
【００５７】
Ｒ^１３−（Ｏ−Ｒ^１４）_ｊ−Ｏ−Ｒ^１５ （６）
（式中、Ｒ^１３及びＲ^１５はそれぞれ独立に、水素原子、Ｒ^１６ＣＯ−（ここでＲ^１６は炭素数１〜３のアルキル基）又は炭素数１〜７の炭化水素基、好ましくは水素原子、アルキル基、アリール基又はアリールアルキル基であり、Ｒ^１４は炭素数２〜９の分岐鎖を有していてもよいアルキレン基である。ｊは１〜５の数である。）
【００５８】
Ｒ^１７−Ｏ−ＣＨ_２ＣＨ（Ｏ−Ｒ^１８）ＣＨ_２−Ｏ−Ｒ^１９ （７）
（式中、Ｒ^１７は炭素数３〜８のアルキル基であり、Ｒ^１８及びＲ^１９はそれぞれ独立に、水素原子又はヒドロキシ基で置換されていてもよい炭素数１〜３のアルキル基である。）
【００５９】
より具体的に好ましい化合物としては、ｎ−ブタノール、イソブタノール、２−ブタノール、ｎ−ヘキサノール、シクロヘキサノール、フェノール、ベンジルアルコール、フェネチルアルコール、２−フェノキシエタノール、２−ベンジルオキシエタノール、ジエチレングリコールモノベンジルエーテル、ジエチレングリコールモノフェニルエーテル、トリエチレングリコールモノフェニルエーテル、テトラエチレングリコールモノフェニルエーテル、２−エチルヘキサン−１，３−ジオール、ヘキサン−１，６−ジオール、ノナン−１，６−ジオール、２−メチルオクタン−１，８−ジオール、２−ブトキシエタノール、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、２−（２−メチル）プロポキシエタノール、ジエチレングリコールモノ−２−メチルプロピルエーテル、２−プロポキシ−１−プロパノール、ジプロピレングリコールモノプロピルエーテル、２−ブトキシ−１−プロパノール、ジプロピレングリコールモノブチルエーテル、２−ｔ−ブトキシ−１−プロパノール、２−フェノキシ−１−プロパノール、２−エトキシプロピル−１−アセテート、２−プロポキシプロピル−１−アセテート、１，２−ジアセトオキシプロパン、３−ジメチル−３−メトキシ−１−プロパノール、１，３−ジメチルブチルグリセリルエーテル、ペンチルグリセリルエーテル、ヘキシルグルセチルエーテル、１，２−ヘキサンジオール、１，２−ペンタンジオール、ヘキシレングリコール、１，２−ブタンジオール、１，４−シクロヘキサンジオール、１，５−ヘキサンジオールおよび／または２，４−ジメチル−２，４−ペンタンジオールを挙げることができる。
【００６０】
本発明の柔軟剤組成物には、有機溶剤（ｂ）を全組成物に対し３〜３０重量％含有することが好ましく、更に５〜２５重量％、特に１０〜２０重量％含有することが好ましい。
本発明の柔軟剤組成物には、透明又は半透明な柔軟剤組成物の審美的外観をさらに高めるために、（ｃ）成分を用いることが好ましい。
（ｃ）成分としては、光による着色剤の褪色が起こりにくい点から、ポリオキシアルキレン鎖を少なくとも１つ有する染料（以下ポリオキシアルキレン変性染料という）を用いることが好ましい。ポリオキシアルキレン変性染料は、ポリオキシアルキレン鎖と発色団を有していれば良い。
【００６１】
ポリオキシアルキレン鎖としては、式 −（ＡＯ）ｎ−
（式中、Ａは炭素数２〜４のアルキレン基、ｎはアルキレンオキサイドの平均付加モル数を示す３〜２００の数であり、ｎ個のＡは同一でも異なっていてもよい。）
で表されるポリオキシアルキレン鎖が好ましく、
式
−（Ｃ_３Ｈ_６Ｏ）ｋ−（Ｃ_２Ｈ_４Ｏ）ｍ−
（式中、ｋ、ｍはそれぞれ独立に、０〜１００の数であって、ｋ＋ｍは３〜２００の数である。また、（Ｃ_３Ｈ_６Ｏ）ｋ及び（Ｃ_２Ｈ_４Ｏ）ｍはランダムであっても、ブロックであってもよい。）
で表されるポリオキシアルキレン鎖が更に好ましい。
【００６２】
発色団としては、アゾ発色団、フタロシアニン発色団、アントラキノン発色団、アザ［１８］アヌレン発色団、フォルマザン銅錯体発色団、トリフェノジオキサジン発色団、ニトロソ発色団、ニトロ発色団、ジアリールメタン発色団、トリアリールメタン発色団、キサンテン発色団、アクリデン発色団、メチン発色団、チアゾール発色団、インダミン発色団、アジン発色団、オキサジン発色団、チアジン発色団、キノリン発色団、インジゴイド発色団、インドフェノール発色団、ラクトン発色団、アミノケトン発色団、ヒドロキシケトン発色団、スチルベン発色団等が挙げられる。ポリオキシアルキレン鎖と発色団は、例えば、窒素原子、酸素原子、硫黄原子等を介して直接的又は間接的に結合しているものが好ましい。
【００６３】
ポリオキシアルキレン変性染料の具体例としては、ポリオキシアルキレン変性アントラキノン系着色料、オキシアルキレン変性フタロシアニン系染料、シロキサン含有ポリ（オキシアルキレン）共重合体置換基を有する着色料、ポリ（オキシアルキレン）置換着色剤、ポリ（オキシアルキレン）置換着色剤、等を挙げることができる。また、ミリケン・ケミカル社製のリクィティント（Ｌｉｑｕｉｔｉｎｔ、登録商標）染料も使用できる。
【００６４】
また、（ｃ）成分としては、上記ポリオキシアルキレン変性染料のほかに、一般的に使用される色素を併用することができる。色素としては、例えば、分子内にアミノ基、スルホニル基、カルボキシル基を有する酸性染料、直接染料、塩基性染料、媒染・酸性媒染染料、アゾイック染料、硫化・硫化建染染料、建染染料、分散染料、油溶染料、反応染料、食品用色素、天然色素から選ばれる１種以上の色素が好ましい。より好ましくは、Ａｃｉｄ Ｂｌｕｅ８０、発色団にカルボニウム基を有する酸性染料、発色団にカルボニウム基を有する直接染料、塩基性染料、反応性染料、食品用色素、天然色素である。特に好ましくは、カラーインデックスでＲｅｄ、Ｂｌｕｅ、Ｙｅｌｌｏｗ、Ｖｉｏｌｅｔで分類される塩基性染料、反応性染料、媒染・酸性媒染染料、アゾイック染料、硫化・硫化建染染料、食品用色素である。
【００６５】
本発明の柔軟剤組成物にポリオキシアルキレン染料を用いる場合には、ポリオキシアルキレン染料を全組成物に対し０．１〜１００ｍｇ／ｋｇ含有することが好ましく、更に１〜７０ｍｇ／ｋｇ、特に３〜３０ｍｇ／ｋｇ含有することが好ましい。
【００６６】
本発明の柔軟剤組成物に色素を用いる場合には、色素を全組成物に対し０．１〜１００ｍｇ／ｋｇ含有することが好ましく、更に０．１〜２０ｍｇ／ｋｇ含有することが好ましい。
成分（ｄ）としては、アミノポリカルボン酸、ホスホン酸及びこれらの塩から選ばれる化合物であることが好ましい。
【００６７】
好ましいアミノポリカルボン酸は、分子中に式 −Ｎ（ＣＨ_２ＣＯＯＨ）_２で示されるイミノジ酢酸基を少なくとも１つ以上、好ましくは１又は２つ有し、且つ分子量１８０〜１０００、好ましくは２５０〜６００の化合物である。具体的にはニトリロ３酢酸、エチレンジアミン４酢酸、ジエチレントリアミン５酢酸、アスパラギンサン酸２酢酸、グルタミン酸２酢酸、グリコールエーテルジアミン四酢酸、ヒドロキシエチルイミノ二酢酸、トリエチレンテトラミン六酢酸、ジエンコル酸等を挙げることができ、特にエチレンジアミン４酢酸、ジエチレントリアミン５酢酸、アスパラギンサン酸２酢酸、グルタミン酸２酢酸が好ましい。
【００６８】
ホスホン酸としてはエタン−１，１−ジホスホン酸、エタン−１，１，２−トリホスホン酸、エタン−１−ヒドロキシ−１，１−ジホスホン酸及びその誘導体、エタンヒドロキシ−１，１，２−トリホスホン酸、エタン−１，２−ジカルボキシ−１，２−ジホスホン酸、メタンヒドロキシホスホン酸、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、トリメチレンホスホノアミン等を挙げることができ、特にエタン−１，１−ジホスホン酸、エタン−１−ヒドロキシ−１，１−ジホスホン酸、エチレンジアミンテトラ（メチレンホスホン酸）が好ましい。
【００６９】
塩としてはナトリウム塩、カリウム塩、マグネシウム塩、鉄塩、ニッケル塩、クロム塩、亜鉛塩、及びアルカノールアミン塩が好ましく、特にナトリウム塩、カリウム塩、鉄塩が好ましい。
本発明の柔軟剤組成物に配合する（ｄ）成分としては、エチレンジアミン４酢酸、及びそのナトリウム塩、カリウム塩又は鉄塩が特に好ましい。
【００７０】
本発明の柔軟剤組成物には、（ｄ）成分を全組成物に対し０．０００５〜５重量％含有することが好ましく、更に０．００１〜３重量％、特に０．００５〜０．５重量％含有することが好ましい。
さらに、光安定性の点から、（ｃ）成分と（ｄ）成分の重量比（ｃ）／（ｄ）は、１／１００００〜１０／１であることが好ましく、更に１／５０００〜１／１、特に１／１００〜１／１であることが好ましい。
【００７１】
本発明の柔軟剤組成物には、（ｅ）成分を配合することができる。
（ｅ）成分としては、炭素数１２〜３６、好ましくは１４〜２４、より好ましくは１４〜２０の飽和若しくは不飽和の脂肪酸又はその塩を用いることが好ましい。具体的にはラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸あるいはこれらの混合物が挙げられ、特にパルミチン酸、ステアリン酸、オレイン酸から選ばれる１種以上が好ましい。また、パーム油、牛脂から誘導されるアルキル組成を有する脂肪酸も好ましい。塩を用いる場合は、ナトリウム塩、カリウム塩、マグネシウム塩、アルカノールアミン塩が好ましく、特に貯蔵安定性からナトリウム塩、カリウム塩が良好である。
【００７２】
（ｅ）成分を用いる場合には、（ｅ）成分の含有量は、組成物中０．０１〜５重量％、特に０．０５〜３重量％が好ましい。また、（ｅ）成分／（ａ）成分は重量比で、１／５００〜１／５０、更に１／３００〜１／１００であることが柔軟効果の点から好ましい。
【００７３】
本発明の柔軟剤組成物には、さらに（ｆ）成分を配合することができる。
（ｆ）成分としては、炭素数１６〜３６、好ましくは１６〜２８のアルキル基又はアルケニル基と、−ＳＯ_３Ｍ基及び／又は−ＯＳＯ_３Ｍ基（Ｍ：対イオン）とを有する陰イオン（ｆ１）成分を用いることが好ましい。具体的には上記炭素数のアルキル基又はアルケニル基を有するアルキルベンゼンスルホン酸、アルキル（又はアルケニル）硫酸エステル、ポリオキシアルキレンアルキル（又はアルケニル）エーテル硫酸エステル、オレフィンスルホン酸、アルカンスルホン酸、α−スルホ脂肪酸、α−スルホ脂肪酸エステル及びこれらの塩が好ましい。
【００７４】
これらの中でも特に炭素数１６〜２８のアルキル基又はアルケニル基を有するアルキル（又はアルケニル）硫酸エステル、炭素数１６〜２８のアルキル基又はアルケニル基を有し、エチレンオキシド（以下、ＥＯと表記する）平均付加モル数が１〜６、好ましくは１〜４、特に好ましくは１〜３であるポリオキシエチレンアルキル（又はアルケニル）エーテル硫酸エステル及びこれらの塩から選ばれる一種以上を配合することが好ましい。塩としては、ナトリウム塩、カリウム塩が貯蔵安定性の点から良好である。
【００７５】
本発明では（ａ）成分として（ａ１）成分を選択する場合には、（ａ１）成分／（ｆ１）成分をモル比で好ましくは９９．５／０．５〜７０／３０、特に好ましくは９９／１〜８５／１５の割合で配合し、（ａ）成分として（ａ２）成分を選択する場合には、（ａ２）成分／（ｆ１）成分をモル比で好ましくは９５／５〜５０／５０、特に好ましくは８５／１５〜６５／３５の割合で配合することが柔軟効果の点から好ましい。
【００７６】
また、（ｆ）成分としては、貯蔵安定性の点から、さらに非イオン界面活性剤（ｆ２）を配合することが好ましい。非イオン界面活性剤（ｆ２）としては炭素数８〜２０のアルキル基又はアルケニル基を有するポリオキシエチレンアルキルエーテルが好ましく、特に下記式（８）で表される非イオン界面活性剤が好ましい。
【００７７】
Ｒ^２０−Ｆ−［（Ｒ^２１Ｏ）ｐ−Ｈ］ｑ （８）
（式中、Ｒ^２０は、炭素数１０〜１８、好ましくは１２〜１８のアルキル基又はアルケニル基であり、Ｒ^２１は炭素数２又は３のアルキレン基、好ましくはエチレン基である。ｐは２〜１００、好ましくは５〜８０、特に好ましくは１０〜６０の数を示す。Ｆは−Ｏ−、−ＣＯＮ−又は−Ｎ−であり、Ｆが−Ｏ−の場合はｑは１であり、Ｆが−ＣＯＮ−又は−Ｎ−の場合はｑは２である。）
式（８）で表される化合物の具体例として、以下の式（８−１）〜（８−４）で表される化合物を挙げることができる。
【００７８】
Ｒ^２０−Ｏ−（Ｃ_２Ｈ_４Ｏ）ｒ−Ｈ （８−１）
（式中、Ｒ^２０は前記の意味を示す。ｒは８〜１００、好ましくは１０〜６０の数である。］
【００７９】
Ｒ^２０−Ｏ−（Ｃ_２Ｈ_４Ｏ）ｓ−（Ｃ_３Ｈ_６Ｏ）ｔ−Ｈ （８−２）
［式中、Ｒ^２０は前記の意味を示す。ｓ及びｔはそれぞれ独立に２〜４０、好ましくは５〜４０の数であり、オキシエチレン基とオキシプロピレン基はランダムあるいはブロック付加体であってもよい。）
【００８０】
【化６】

（式中、Ｒ^２０は前記の意味を示す。ｕ，ｖ，ｗ及びｘはそれぞれ独立に０〜４０、好ましくは５〜４０の数であり、ｕ＋ｖ＋ｗ＋ｘは５〜６０、好ましくは５〜４０の数である。オキシエチレン基とオキシプロピレン基はランダムあるいはブロック付加体であってもよい。）
【００８１】
非イオン界面活性剤（ｆ２）を用いる場合には、非イオン界面活性剤（ｆ２）の含有量は、組成物中０．５〜１０重量％、特に１〜８重量％が、貯蔵安定性の点から好ましい。
本発明の柔軟剤組成物には、さらに（ｇ）成分を配合することができる。具体的には、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール及び／又は２，６−ジ−ｔｅｒｔ−ブチル−４−エチルフェノールを用いることが好適である。
【００８２】
本発明では（ａ）成分として（ａ１）成分を選択する場合には、（ｇ）成分を０．００１〜１重量％、特に０．００５〜０．０５重量％配合し、柔軟化基剤（ａ）成分として（ａ２）成分を選択する場合には、酸化防止剤（ｇ）を０．０００３〜０．５重量％、特に０．００７〜０．０２重量％配合することが貯蔵安定性の点から好ましい。
【００８３】
また、本発明の柔軟剤組成物は、（ｈ）成分を配合することができる。（ｈ）成分としては塩化ナトリウム及び／又は塩化カルシウムが貯蔵安定性の点から好ましく、組成物中０〜１０００ｍｇ／ｋｇ好ましくは１０〜５００ｍｇ／ｋｇ添加することが好ましい。但し、脂肪酸塩類等の界面活性剤にはナトリウム塩やカリウム塩が含まれているが、このような界面活性剤の使用によって組成物に混入する無機塩は上記制限を受けるものではない。
【００８４】
本発明の柔軟剤組成物は、（ｉ）成分を配合することができる。（ｉ）成分としては、炭素数８〜２２の飽和又は不飽和脂肪酸と多価アルコールとのエステル化合物を用いることができる。具体的に、好ましいエステル化合物としては、トリグリセライド、ジグリセライド、モノグリセライド、ペンタエリスリトールのモノ、ジ、トリエステル、ソルビタンエステル等を挙げることができ、（ｉ）成分を配合する場合には、組成物中５重量％以下含有することが好ましく、更に３重量％以下、特に１重量％以下含有することが好ましい。
【００８５】
さらに、本発明の柔軟剤組成物には、上記成分のほか、通常の柔軟剤組成物に配合される成分、例えば、シリコーン、汚れ遊離剤、殺菌剤、キレート化剤、色保護剤、保存剤、収縮防止剤、布地縮れ処理剤、染み抜き剤、腐食防止剤、酵素、水、等を、本発明の目的及び効果を損なわない質的及び量的範囲内で適宜配合することができる。
【００８６】
本発明の柔軟剤組成物は、上記成分を水で稀釈した水溶液の形態が一般的であり、使用する水は蒸留水又はイオン交換水が好ましい。貯蔵安定性の点で、水は組成物中に３０〜９５重量％、更に５０〜８５重量％含有することが好ましい。さらに、本発明の組成物は、貯蔵安定性の点から、組成物の２０℃におけるｐＨを１〜８．５、更に１〜８、特に２〜８に調整することが好ましい。
本発明の柔軟剤組成物は、上記各材料を用いて常法に従って製造することができる。
【００８７】
【実施例】
（実施例１〜１１、及び比較例１〜３：香料組成物）
表１に示す組成に従って、実施例１〜１１、及び、比較例１〜３の香料組成物を調製した。表１に示した各香料成分及び香料組成物の吸光度（４２０ｎｍ固定）を測定しＫ値を得、黄色みを評価した。
【００８８】
＜香料組成物の調製＞
香料組成物は、表１の組成に従い、香料成分（単品香料）を混合し、調製した。粉末など溶けにくい香料成分がある場合は、ウォーターバスなどを用い加熱溶解した。
【００８９】
＜評価＞
１．黄色みの測定
香料成分（単品香料）のうち、液体香料は原液を用いて黄色みの測定に供した。粉末、固体或いは粘度の高い天然物などの香料（★印のついているもの）は、無色透明のジプロピレングリコールを用い、粉末品・固体品に関しては５倍で希釈し、粘度の高い天然物などは２倍で希釈して黄色みの測定に供した。
また、香料組成物は、配合初期及び４０℃で２０日間保存後の香料組成物を測定した。
【００９０】
黄色みの評価は、４２０ｎｍにおける吸光度を測ることにより行い、得られた前記吸光度の値×１０００の値をＫ値とした。吸光度の測定は、ＳＨＩＭＡＤＺＵ社製ＵＶ−２５００（ＰＣ）によって行い、スペクトルバンド幅（スリット幅）：１．０ｎｍの条件で行った。
【００９１】
［評価基準］
（１）香料成分
測定したＫ値は以下の３つのランクに分け、黄色みを評価した。
Ａランク：Ｋ値が１０００以下の香料成分
Ｂランク：Ｋ値が１０００より大きく４０００未満の香料成分
Ｃランク：Ｋ値が４０００以上の香料成分
【００９２】
（２）香料組成物
測定したＫ値は以下の２つのランクに分け、黄色み値を評価した。
「小」：香料組成物全体のＫ値が３０００以下の香料組成物
「大」：香料組成物全体のＫ値が３０００より大きい香料組成物
得られた結果を表１に示す。
【００９３】
【表１】

【００９４】
実施例の香料組成物は、Ｋ値が１０００以下の香料を４０重量％以上配合し、更に４０００以上の香料を１０重量％以下配合している。その結果、香料組成物全体のクレット値は３０００以下に抑えることが達成されている。
一方、比較例の香料組成物では、Ｋ値が１０００以下の香料を４０重量％未満配合し、更に４０００以上の香料を１０重量％より多く配合している。その結果、香料組成物全体のＫ値は３０００以下に抑えることが達成できていない。
【００９５】
（実施例１１〜１９、比較例１１〜１３：柔軟剤組成物）
表２に示す組成に従って、実施例１〜９の香料組成物を表２の香料組成物（ｊ）として用いて実施例１１〜１９の柔軟剤組成物を、及び、比較例１〜３の香料組成物を表２の香料組成物（ｊ）として用いて比較例１１〜１３の柔軟剤組成物を調製した。実施例１１〜１９、及び比較例１１〜１３の柔軟剤組成物において、香料組成物（ｊ）は各々０．５重量％配合した。得られた各柔軟剤組成物を用いて、香料組成物が柔軟剤の外観に及ぼす影響、さらに保存安定性試験及び耐光性試験を行い、各試験後の柔軟剤組成物のＫ値の変化、及び匂いの変化、さらに残香性を評価した。
【００９６】
＜柔軟剤組成物の調製＞
柔軟剤組成物の出来上がり質量が２００ｇになるのに必要な量の９５％相当量のイオン交換水を３００ｍｌビーカーに入れ、ウォーターバスで６０℃に昇温した。攪拌しながら（３００ｒ／ｍｉｎ）、所要量の（ｂ）成分、（ｅ）成分を溶解させた。次に所要量の（ａ）成分と（ｄ）成分を予め混合した混合品（４０℃）を添加した。
【００９７】
そのまま５分攪拌後、順次、（ｃ）成分、（ｆ）成分から（ｈ）成分を添加し、５分攪拌後、３５％塩酸水溶液と４８％水酸化ナトリウム水溶液で目標のｐＨに調整し、出来上がり質量にするのに必要な量の６０℃のイオン交換水を添加した。その後１０分間攪拌し、５℃の水を入れたウォーターバスにビーカーを移し、攪拌しながら２０℃にまで冷却した。なお、表２に示したｐＨは、冷却後（２０℃）のｐＨである。
【００９８】
【表２】

【００９９】
＜評価＞
（保存安定性試験）
調製した柔軟剤組成物を、４０℃で２０日間保存を行い、保存安定性試験後の試料とした。
（耐光性試験）
調製した柔軟剤組成物に、スガ試験機社製 キセノンロングライフフェードメーター ＦＡＬ−７Ｘ−Ｌ−Ｂ型を用いて、積算で１００００ｋＪ／ｍ^２紫外線を照射し、耐光性試験後の試料とした。
【０１００】
１．香料組成物が柔軟剤組成物の外観に及ぼす影響
柔軟剤組成物のＫ値を上記香料組成物の黄色み評価と同様に測定し、香料組成物が柔軟剤組成物の外観に及ぼす影響を評価した。
［評価基準］
柔軟剤組成物のＫ値が３０００以下の場合を、香料組成物が柔軟剤組成物の外観に及ぼす影響「なし」と評価し、３０００より大きい場合を影響「あり」と評価した。
【０１０１】
２．保存安定性試験、及び耐光性試験後の柔軟剤組成物のＫ値の変化
Ｋ値の変化は、調製（配合）直後のサンプルと保存後のサンプルのＫ値の変化率が１０％未満の場合、変化「なし」と評価し、調製（配合）直後サンプルと保存後のサンプルのＫ値の変化率が１０％以上の場合、変化「あり」と評価した。
【０１０２】
３．保存安定性試験、及び耐光性試験後の柔軟剤組成物の匂いの変化
匂いの変化は、１０人の専門パネラーによって、調製（配合）直後のサンプルと保存後のサンプルを評価し、変化があるとしたパネラーは０点、変化がないとしたパネラーは＋１点とし、１０人の評価点数の合計点でランク分けした。パネラーの評価点の合計点が７点以上の場合、変化「なし」と評価し、合計点が７点未満の場合、変化「あり」と評価した。
【０１０３】
４．残香性
市販の木綿タオル２ｋｇ、アクリルジャージ１ｋｇを３．５°ＤＨ硬水にて市販洗剤アタック（花王（株）、登録商標）にて５回繰り返し洗濯（３０Ｌ洗濯機）をし、繊維についた繊維処理剤を除去した後、表２に示した柔軟剤組成物を１０ｍｌ投入し、２５℃で３分間攪拌し処理した。
上記方法で処理した布を室内で風乾後、２５℃、６５％ＲＨの恒温恒湿室で２４時間放置した。これらの布を専門パネラー１０人で残香性の評価を行った。
実施例１の柔軟剤組成物で処理した布と各サンプルを比較して、同等或いはそれ以上の残香が感じられたとしたパネラーは１点、それよりも弱いと感じられるとしたパネラーは０点とし、１０人の評価点数の合計点でランク分けした。
【０１０４】
［評価基準］
パネラの評価点の合計点が７点以上の場合、残香性「あり」と評価し、合計点が７点未満の場合、残香性「なし」と評価した。
評価の結果は、表３に示したとおりである。
【０１０５】
【表３】

【０１０６】
実施例１〜９の香料組成物を賦香した実施例１１〜１９の柔軟剤組成物では、香料による黄変により透明柔軟剤の外観を損ねない透明柔軟剤組成物が達成されている。またこの柔軟剤組成物は残香性も損なうことなく、熱による保存安定性、光による耐光性試験でも変化の少ないサンプルであることが確認された。
【０１０７】
比較例１〜３の香料組成物を配合した比較例１１〜１３の柔軟剤組成物の外観は、明らかに我々の設計したレベル以下であった。またシッフベースを多く含む香料は実施例に比べ匂いの安定性が劣り、またテルペン系アルコールが多く配合されている比較例では光に対する安定性が悪いことが確認された。
【０１０８】
これらのことより、本発明品は、透明又は半透明系柔軟剤組成物の外観を損ねることなく、熱・光に対して安定で、残香性も兼ね備えたバランスの良い香料組成物、及び柔軟剤組成物であることが明らかにされた。
【０１０９】
【発明の効果】
本発明に係る柔軟剤用香料組成物においては、香料成分（単品香料）を黄色みの度合いを示すＫ値でランク分けをして、そのうち、Ｋ値が１０００以下の香料を香料組成物全体の４０重量％以上とし、且つ、香料組成物全体の黄色みの度合いをＫ値が３０００以下とすることにより、黄色みが低くて、柔軟剤の所望の色を損ねるような着色をせず、且つ残香性が高く、香料組成物の安定性が良く匂いの劣化が少ない香料組成物が得られる。従って、本発明に係る香料組成物は、特に透明柔軟剤の透明な外観を強調して商品価値を高めるために透明な容器に充填する場合であっても、光により外観が損なわれず、設計通りの香調が維持できる。
【０１１０】
本発明に係る柔軟剤組成物は、前記本発明に係る香料組成物を含有するため、残香性が高く、匂いの劣化が少なく、且つ香料組成物により外観を損なわれない透明又は半透明柔軟剤組成物である。[0001]
BACKGROUND OF THE INVENTION
The present invention provides a perfume composition for a transparent or translucent softener that has a low yellowness, does not impair the desired color, has a residual fragrance, and has a low odor deterioration, and has a residual fragrance and a low odor deterioration. The present invention relates to a transparent or translucent softener composition.
[0002]
[Prior art]
In recent years, transparent or translucent softeners have been developed from an aesthetic point of view (Patent Documents 1 and 2).
[0003]
In transparent or translucent softeners, the color of the softener itself is very important compared to conventional opaque softeners because of its aesthetic appearance. However, there is a problem that when exposed to light, the color changes and the appearance is impaired, and particularly when a transparent container is filled in order to emphasize the transparent appearance, it becomes a significant problem. Conventionally, attempts have been made to solve the problem by adding an antioxidant or an ultraviolet absorber, or by using an opaque container, but this is not sufficient.
[0004]
On the other hand, a fragrance is generally used as a softening agent. The fragrance used in the softener is required to have a fragrance. However, fragrances with high fragrance are generally dark in color, and when these fragrances are added, the color of the softener is discolored and the appearance is impaired. There is a problem. In addition, there are some fragrances that fade or odor change when exposed to light, and these discoloration and odor changes cause the softening agent to change color and deteriorate the appearance, and the designed fragrance cannot be maintained. There is. However, so far, there has not been much study on a perfume that does not impair the desired color of the softening agent, has a high residual fragrance, and has little odor degradation.
[0005]
[Patent Document 1]
Japanese Patent Laid-Open No. 7-3650
[0006]
[Patent Document 2]
JP-T-2001-524616
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a fragrance composition for a transparent or translucent softener that has a low yellowness, does not impair the desired color, has a high residual fragrance, and has little odor degradation, and a softness containing the fragrance composition It is to provide an agent composition.
[0008]
[Means for Solving the Problems]
The inventors rank the degree of yellowness of the fragrance ingredient itself by the value of absorbance at 1000 nm × 1000 (hereinafter referred to as K value) to define the content of the ranked fragrance ingredient, and It has been found that the above-mentioned problems can be solved by the above-mentioned fragrance composition that defines the degree of yellowness of the composition itself, and that the above-mentioned problems can be solved by a softener composition using such a fragrance composition.
[0009]
That is, the present invention Benzyl acetate, allyl amyl glycolate, γ-undecalactone, n-octanol, lyial, 1- (2-t-butylcyclohexyloxy) -2-butanol, phenylethyl alcohol, hexamethylhexahydrocyclopentabenzopyran, iso From camphorcyclohexanol, methyl dihydrojasmonate, tricyclodecenyl propionate, hexylcinnamic aldehyde, cyclopentadecanolide, porenate, musk ketone, limonene, methyl b-naphthyl ketone, α-isomethyl ionone, citronellol, and geraniol One or more selected from the group consisting of A fragrance composition containing 40% by weight or more of a fragrance component, Transparent or translucent with a light transmittance of 30% or more at a wavelength of 660 nm when a quartz cell having an optical path length of 10 mm is used and ion-exchanged water is added to the control side cell Perfume composition for softener, and A compound having at least one hydrocarbon group having 12 to 36 carbon atoms and at least one tertiary amino group or acid salt or quaternary ammonium group thereof; and Contains the fragrance composition When a quartz cell having an optical path length of 10 mm is used and ion exchange water is added to the control side cell, the light transmittance at a wavelength of 660 nm is 30% or more. A transparent or translucent softener composition is provided.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the K value is a value used as a yellowish index, and is measured using a spectrophotometer (for example, manufactured by SHIMADZU).
[0011]
A fragrance | flavor component may be colored already by the deterioration after preparation or after preparation. When preparing a fragrance composition by mixing one or two or more fragrance components, the yellow color of the fragrance composition is increased by the color of such a fragrance itself, and the color tone of the fragrance composition as intended. May not be obtained.
[0012]
Since the color of the fragrance often exhibits yellowishness, the yellowness of the fragrance composition and the fragrance components constituting the fragrance composition can be evaluated using absorbance at 420 nm as an index. In the present invention, a value obtained by multiplying the measured value of absorbance by 1000 times is used for ease of viewing the evaluation value. The larger this value, the stronger the yellowness of the specimen, and the more difficult it is to adjust the color of the transparent or translucent softener that is the product.
[0013]
In the present invention, the fragrance component is a concept including, for example, a single synthetic fragrance, a natural fragrance, a fragrance made of a mixture of a single synthetic fragrance and a natural fragrance, and the like.
Moreover, content in a fragrance | flavor composition means the value with respect to the whole composition which consists only of fragrance | flavor components, and is not the value with respect to the fragrance | flavor composition which added additives, such as a solvent.
[0014]
Furthermore, in the present invention, translucency means that when a quartz cell having an optical path length of 10 mm is used as a measurement cell and ion-exchanged water is added to the control side cell, the light transmittance at a wavelength of 660 nm is 30% or more and 95%. The term “transparent” means that the transmittance is 95% or more.
[0015]
The fragrance composition for transparent or translucent softener according to the present invention is a fragrance composition containing 40% by weight or more of a fragrance component having a K value of 1000 or less, and the K value of the fragrance composition is 3000 or less. .
[0016]
In the fragrance composition according to the present invention, the fragrance components are ranked according to the K value indicating the degree of yellowness, of which the fragrance having a K value of 1000 or less is 40% by weight or more of the entire fragrance composition, and By setting the degree of yellowness of the entire fragrance composition to a K value of 3000 or less, the desired color of the softener is not impaired, the remaining fragrance property is high, the stability of the fragrance composition is good, and the odor is less deteriorated. A fragrance composition for transparent or translucent softener is obtained. Accordingly, the fragrance composition for transparent or translucent softeners according to the present invention, even when filled into a transparent container to enhance the commercial value by emphasizing the transparent appearance of the transparent softener, Appearance is not spoiled and the designed scent can be maintained.
[0017]
Examples of perfume ingredients having a K value of 1000 or less include acetophenone, acetyleugenol, acetylisoeugenol ★ (★: perfume such as powder, solid or high-viscosity natural product), α-damascon, decanal, γ-un Decalactone, ethyl 3-methyl-3-phenylglycidate, γ-nonalactone, n-hexanal, n-octanal, n-nonanal, allyl amyl glycolate, allyl hexanoate, allyl heptanoate, allyl ionone, allyl phenoxyacetate, 1- (2-t-butylcyclohexyloxy) -2-butanol, ambretlide, amylcinnamic aldehyde, amyl salicylate, anethole, anis alcohol, anisaldehyde, α-pinene, α-terpinene, α-terpineol, bacdanol, 2-no Methyl phosphate, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl benzoate, benzyl cinnamate ★, include benzyl propionate.
[0018]
Examples of the fragrance component having a K value of 1000 or less include benzyl salicylate, borneol, β-pinene, caron ★, camphor ★, cedrol ★, cedryl acetate ★, cedrol methyl ether, 4-acetyldimethyl-t-butylindane. ★, cinnamyl acetate, cis-3-hexenol, cis-3-hexenyl acetate, cis-3-hexenyl salicylate, cis-jasmon, citral, citronellol, citronellyl acetate, citronellyl formate, citronellonitrile, coumarin ★, cyclamenaldehyde, salicylic acid Cyclohexyl, α, α-dimethylphenylethyl alcohol, dimethylbenzyl carvinyl acetate, dimethylbenzyl carvinyl isobutyrate, dimethylbenzyl carvinyl butyrate, δ-damascone, decenol, decylacetic acid Diethyl malonate, dihydrojasmonate, dihydromyrcenol, N- methyl anthranilate methyl, 2,6-dimethyl heptanol, dipentene, diphenyl oxide, 4-tricyclo cyclododecylidene isopropylidene butanal include estragole.
[0019]
Examples of perfume ingredients having a K value of 1000 or less include, for example, ethyl linalool, ethyl maltol *, methyl phenylglycidate, ethyl safranate, ethyl salicylate, ethyl vanillin *, ethylene brushate, eugenol, p-ethyldimethylhydro Synamic aldehyde, Ethyl acetoacetate Ethylene glycol ketal, Fruate, Geraniol, Geranyl acetate, Geranyl cyclopentanone, Helional, Heliotropin ★, Heliotropylacetone ★, Hexyl acetate, Hexylcinnamic aldehyde, Hexyl salicylate, Hydratropic aldehyde, Hydroxycitronellal, Indole ★, α-Yonone, β-Yonone, Iso-e-super, Amyl isoacetate, Isoboroneol ★, Bornyl isoacetate, Isocycl Rocitral, isodamascon, isomenthone, coabon, 3,4,5,6,6-pentamethyl-2-heptanol, δ-decalactone, γ-decalactone, δ-undecalactone, δ-dodecalactone, γ-dodecalactone .
[0020]
Examples of the fragrance component having a K value of 1000 or less include, for example, δ-nonalactone, 1-carvone, cis-3-hexenylmethyl carbonate, lyial, limonene, linalool, linalyl acetate, 1-menthol *, 1-menton, and rilal. ★, Magnolan ★, Maltol ★, p-Isopropylcyclohexyl methanol, Methyl dihydrojasmonate, Methyl anisate, Methyl anthranilate, Methyl benzoate, Methyl b-naphthyl ketone ★, Methyl cinnamate, α-Isomethylionone, Methyl isoeugenol , Methyl octynecarboxylate, methyl salicylate, methyl atrate *, mugor, ethylene dodecanedioate, musk ketone *, mylacaldehyde, nerol, nerolidol, β-naphthol ethyl ether ★, β-naphtho Methyl ether *, neryl acetate, nopyru acetate, p-pentylcyclohexanone, cresol, p-cresyl acetate, hexamethylhexahydrocyclopentabenzopyran *, cyclopentadecanolide *, phenoxyethyl alcohol, phenylacetaldehyde dimethyl acetal, phenyl acetate Examples include ethyl, phenylethyl alcohol, phenylethyl phenylacetate, phenylethyl pivalate, phenylethyl propionate, and porenate.
[0021]
Examples of the perfume ingredients having a K value of 1000 or less include prenyl acetate, raspberry ketone *, rubofix, rose oxide, rosephenone *, isocamphylcyclohexanol *, 5-methyl-3-heptanone oxime, styrylyl acetate, Terpineol, terpinolene, terpinyl acetate, tetrahydrogeraniol, tetrahydrolinalol, tetrahydromumol, thymol *, 2,2,6-trimethylcyclohexyl-3-hexanol *, tricyclodecenyl acetate, tricyclodecenyl propionate, trimethyl Undecenal, Tripral, 4-Methyl-3-decen-5-ol, Vanillin *, 2,2,5,5-Tetramethyl-4-isopropyl-1,3-dioxane, Bernaldehyde, Anise oil, Basilo Le, coriander oil, elemi resinoid ★, like peppermint, lavandin oil, lavender oil, lemon oil, lime oil, nutmeg oil, oak moss absolute, orange essence oil, orange oil
[0022]
Examples of perfume ingredients having a K value of 1000 or less include, for example, patchouli oil, pepper oil white, peppermint oil, pettigren oil, terpeneless, pine oil, rosemary oil, stylus oil, tonka beans resinoid ★, ligstral, 2 -Ethyl methylbutyrate, lime oxide, 3-methyl-5-phenylpentanol, rubafuran, ambroxane, sandalmysol core, styryl propionate, ot-butylcyclohexyl acetate.
[0023]
Among the fragrance components having a K value of 1000 or less, as components having high residual fragrance, α-damascone, γ-undecalactone, ambroxan, anethole, anisaldehyde, cinnamyl acetate, δ-damascone, p-ethyldimethylhydro Examples thereof include cinnamic aldehyde, fruitate, iso-e super, γ-decalactone, musk ketone, β-naphthol methyl ether, raspberry ketone, rubafuran, thymol, tricyclodecenyl acetate, and tricyclodecenyl propionate.
[0024]
The content of the fragrance component having a K value of 3000 or less in the entire fragrance composition is 40% by weight or more, preferably 60% by weight or more, and more preferably 80% from the point that the K value of the entire fragrance composition is 3000 or less. % Or more is particularly preferable.
[0025]
In order to reduce the yellowness of the fragrance composition, it is desired to use a fragrance component having a low yellowness. On the other hand, the fragrance composition for softeners is required to have a residual fragrance. However, usually, a small amount of a fragrance component having a high residual fragrance is often yellowish. That is, since there are relatively few fragrance components having low yellowness and high residual fragrance properties, it is often difficult to scent as desired using only fragrance components having low yellowness.
[0026]
Therefore, in the present invention, in order to reduce yellowing, a fragrance component having a K value of 1000 or less is blended in a proportion of 40% by weight or more, and the K value is mainly used for the purpose of imparting a residual fragrance as needed. By blending 1000 or more fragrance components with the upper limit being 60% by weight, high residual fragrance can be imparted to the fragrance composition in addition to low yellowness.
[0027]
Since the K value is not necessarily directly proportional to the blending amount of the fragrance component, if the fragrance component having a K value of 1000 or less is blended in the proportion of 40% by weight or more in the fragrance composition, the entire fragrance composition The K value can be suppressed to 3000 or less.
Examples of perfume ingredients having a K value of 1000 or more and less than 4000 include cedolyl acetate, cinnamyl cinnamate *, geranyl nitrile, guayl acetate, isobutyl quinoline, jasmolactone, perilaldehyde, almose oil, cedar wood oil, and guaiac. Examples include wood oil *, palmarosa oil, reartrix resinoid, laral Schiff base.
[0028]
Of the fragrance components having a K value of 1000 or more, Rabudacore, Rabdanum Absolute, Acetyl Cedrene, Aldehide C-12 MNA Schiff Base, 2-methyl-3- (p-methoxyphenyl)- Examples thereof include propanal Schiff base, Ligstral Schiff base, Lilyar Schiff base, 3,5,5-trimethylhexanal Schiff base, vetiberyl acetate, and geranyl nitrile.
[0029]
A fragrance component having a large K value has an effect of strongly yellowing the entire fragrance composition even when used in a small amount. Therefore, the fragrance component having a K value of 4000 or more preferably contains 10% by weight or less from the viewpoint of securing a low yellowishness with the K value of the entire fragrance composition being 3000 or less, and further 8% by weight or less. It is particularly preferable to contain 6% by weight or less.
[0030]
As perfume ingredients having a K value of 4000 or more, for example, Olivenham Resinoid ★, Opoponax Oil ★, Opoponax Resinoid ★, Orange Bitter Oil, Orange Flower Absolute Spain, Orange Flower Water Absolute, Orange Pella, Patchouli Oil, Sandalwood Oil Examples include Mysore, Stylax Resinoid *, Torimos Absolute *, Vetiver Oil *, Ylang Ylang, and Acetyl Cedrene.
[0031]
Schiff base fragrances with a K value of 4000 or more include aldehyde C-12 MNA Schiff base ★, aldehyde C-9 Schiff base ★, 2-methyl-3- (methoxyphenyl) -propanal Schiff base ★, cyclamenaldehyde Schiff base ★, Helio Examples include Narschiff base *, Ligstral Schiff base *, Lilyar Schiff base *, 3,5,5-trimethylhexanal Schiff base *, and Lyral Schiff base *.
[0032]
In addition, when using the above Schiff base fragrance, the K value of the entire fragrance composition is 3000 or less, the stability of the fragrance composition is good, and the coloring and odor deterioration is reduced to 0.5 wt% or less. It is preferably contained, more preferably 0.3% by weight or less, particularly preferably 0.2% by weight or less.
[0033]
Examples of terpene and sesquiterpene alcohols having a double bond include linalool, geraniol, nerol, citronellol, myrcenol, lavandulol, dihydromyrcenol, aloocimenol, terpineol, isopulegol, farnesol, nerolidol, bisabolol, etc. It is done.
[0034]
When using a terpene-based and sesquiterpene-based alcohol having a double bond, it is preferably contained in an amount of 10% by weight or less, and more preferably 8% by weight from the viewpoint of improving the stability of the fragrance composition and reducing the deterioration of odor. % Or less, preferably 5% by weight or less.
In combination with the fragrance composition of the present invention, for example, solvent dipropylene glycol, propylene glycol, isopropyl myristate, diethyl phthalate and the like can be appropriately blended within a range not impairing the effects of the present invention.
[0035]
The fragrance composition of the present invention has a low yellowness, does not impair the desired color, has a residual fragrance, and has little deterioration in odor. Therefore, a softener, a liquid cleaning agent (for example, a cleaning agent for clothing, a cleaning agent for residential use) Agent, kitchen cleaning agent, body cleaning agent), skin lotion, and perfume composition for hair cosmetics. Among these, it is preferable as a fragrance composition for a softener because it has a low yellowness, does not impair the desired color, has high residual fragrance properties, and has little deterioration in odor. In particular, it is preferable as a fragrance composition for transparent softeners, and can be used stably against light even when it is filled in a transparent container in order to emphasize a transparent appearance.
[0036]
Next, the softener composition according to the present invention will be described.
The softener composition according to the present invention is a transparent or translucent softener composition containing the fragrance composition according to the present invention.
Since the softener composition according to the present invention contains the fragrance composition according to the present invention, it is a transparent or translucent softener that has high residual fragrance, little odor degradation, and whose appearance is not impaired by the fragrance composition. It is a composition.
[0037]
In the softener composition of the present invention, in addition to the fragrance composition according to the present invention, the component (a) component (b) component (c) component (d) component (e The component (f), the component (g), the component (h), the component (i) can be appropriately selected and combined.
[0038]
Preferably, a softener composition having high transparency can be obtained by using the following.
As the component (a) of the softening agent composition of the present invention, a compound having one or more hydrocarbon groups having 12 to 36 carbon atoms and one or more tertiary amino groups or acid salts thereof or quaternary ammonium groups thereof. It is. Two or three long-chain hydrocarbon groups selected from a compound represented by the following formula (1) (hereinafter referred to as compound (1)) and a compound represented by formula (2) (hereinafter referred to as compound (2)) Compound (hereinafter referred to as component (a1)), a compound represented by formula (3) below (hereinafter referred to as compound (3)), and a compound represented by formula (4) (hereinafter referred to as compound (4)). It is preferable to use a compound having one selected long-chain hydrocarbon group (hereinafter referred to as component (a2)).
[0039]
[Chemical 1]

[0040]
(Where R ¹ And R ³ Are each independently a hydrocarbon group having 12 to 36 carbon atoms, preferably 13 to 26 carbon atoms, particularly preferably 13 to 18 carbon atoms, and R ² And R ⁴ Are each independently an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, particularly an ethylene group or a propylene group. R ⁵ Is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or R ¹ -[AR ² A-, preferably a methyl group, an ethyl group or a hydroxyethyl group, R ⁶ An alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, preferably a methyl group, an ethyl group, or a hydroxyethyl group. A and B are each independently a group selected from —COO—, —OCO—, —CONH— and —NHCO—, preferably —COO— or —CONH—, and a and b are each a number of 0 or 1 , Preferably 1. Y- is an anion, preferably a halogen ion, a sulfate ion or an alkyl sulfate ester ion having 1 to 3 carbon atoms. )
[0041]
[Chemical formula 2]

[0042]
(Wherein R ⁷ Is a hydrocarbon group having 12 to 36 carbon atoms, preferably 13 to 26, particularly preferably 13 to 18 carbon atoms, R ⁸ Is an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, particularly an ethylene group or a propylene group. R ⁹ , R ¹⁰ And R ¹¹ Are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably a methyl group, an ethyl group or a hydroxyethyl group. D is a group selected from -COO-, -OCO-, -CONH- and -NHCO-, preferably -COO- or -CONH-, and c is a number of 0 or 1, preferably 1. Y- is an anion, preferably a halogen ion, a sulfate ion or an alkyl sulfate ester ion having 1 to 3 carbon atoms. )
[0043]
As the component (a1) of the present invention, compounds represented by the following formulas (1-1) to (1-3) and compounds represented by the following formulas (2-1) to (2-3) are used. It is preferable.
[0044]
[Chemical 3]

(Where R ¹ , R ³ , R ⁵ , R ⁶ And Y- are anions, preferably halogen ions, sulfate ions or alkylsulfate ions having 1 to 3 carbon atoms, and d and e are 2 or 3, respectively. )
[0045]
The compound (1) may be in the form of a salt neutralized with an inorganic or organic acid, and may be obtained by neutralizing an amino group with an acid agent before blending into the softener composition. After compound (1) is blended in the composition, the amino group may be neutralized with an acid agent. As the acid for neutralization, hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, succinic acid, lactic acid, citric acid, and other hydroxycarboxylic acids, fatty acids having 1 to 12 carbon atoms, or alkyl sulfuric acids having 1 to 3 carbon atoms are particularly preferable. Hydrochloric acid, sulfuric acid, glycolic acid, succinic acid, lactic acid, and citric acid are preferred. These acids used for neutralization may be used alone or in combination.
[0046]
When the compound (1) or the compound (2) is used as the softening base (a), the hydrocarbon group having one unsaturated bond can contain a cis isomer and a trans isomer, The trans isomer is preferably 25/75 to 100/0 and more preferably 50/50 to 95/5 in terms of molar ratio.
[0047]
When the component (a1) is used as the component (a), it is preferable to use the compound (1) and the compound (2) together from the viewpoint of improving the softening effect, and when used in combination, the compound (1) / compound (2) is preferably used in a weight ratio of 1/99 to 50/50, more preferably 5/95 to 40/60, and particularly preferably 10/90 to 30/70 from the viewpoint of improving the flexibility effect.
Among the components (a2) of the present invention, as the compound (3), one or more selected from compounds represented by the following formula (3-1) or (3-2) are preferably used.
[0048]
[Formula 4]

(Wherein R ⁷ , R ⁹ And R ¹⁰ Is as described above, and f and g are each a number of 2 or 3. )
[0049]
The compound (3) may be in the form of a salt neutralized with an inorganic or organic acid, and can be obtained by neutralizing an amino group with an acid agent before blending into the softener composition. After compound (3) is added to the composition, the amino group may be neutralized with an acid agent. As the acid for neutralization, hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, succinic acid, lactic acid, citric acid, and other hydroxycarboxylic acids, fatty acids having 1 to 12 carbon atoms, or alkyl sulfuric acids having 1 to 3 carbon atoms are particularly preferable. Hydrochloric acid, sulfuric acid, glycolic acid, succinic acid, lactic acid, and citric acid are preferred. These acids used for neutralization may be used alone or in combination.
Among the components (a2) of the present invention, as the compound (4), one or more selected from compounds represented by the following formula (4-1) or (4-2) are preferably used.
[0050]
[Chemical formula 5]

(Wherein R ⁷ , R ⁹ , R ¹⁰ And R ¹¹ Is as described above, and h and i are each a number of 2 or 3. )
[0051]
When the component (a2) is used as the component (a), it is preferable to use the compound (3) and the compound (4) together from the viewpoint of improving the softening effect, and when used in combination, the compound (1) / compound (2) is preferably used in a weight ratio of 1/99 to 50/50, more preferably 5/95 to 40/60, and particularly preferably 10/90 to 30/70 from the viewpoint of improving the flexibility effect.
[0052]
As the component (a), it is also preferable to use the component (a1) and the component (a2) in combination from the viewpoint of improving the softening effect. When the component is used in combination, the component (a1) / (a2) is used in a weight ratio. It is preferable to use at a ratio of 1/99 to 20/80, more preferably 5/95 to 15/85.
The softener composition of the present invention preferably contains 3 to 40% by weight of the component (a), more preferably 5 to 35% by weight, still more 5 to 30% by weight, particularly 7 to 25%. It is preferable to contain by weight.
[0053]
In order to obtain a transparent or translucent softener composition in the softener composition of the present invention, the component (b) is preferably added.
As the component (b), those described in "Solvent Handbook" (Kodansha, September 20, 1993, 13th edition) can be used. In particular, in the present invention, in order to make the softener composition transparent or translucent, it is preferable to use an organic solvent having a log P of −2 to 3, more preferably 0.5 to 2, particularly 0.5 to 1.6. . Here, logP is a coefficient indicating the affinity of an organic compound for water and 1-octanol. The 1-octanol / water partition coefficient P is a distribution equilibrium when a trace amount of an organic compound is dissolved as a solute in a two-phase solvent of 1-octanol and water, and is a ratio of the equilibrium concentration of the organic compound in each solvent. They are typically shown in the form of their logarithmic log P with respect to the base 10.
[0054]
Log P values for many compounds have been reported and are described in Daylight Chemical Information Systems, Inc. Many values are listed in a database available from (Daylight CIS) or the like, and can be referred to. If there is no measured log P value, it is most convenient to calculate with the program “CLOGP” available from Daylight CIS. This program outputs the value of “calculated logP (ClogP)” calculated by Hansch, Leo's fragment approach when there is an actually measured logP value. The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bond (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, JB Taylor and CA Ramsden, Eds., P. 295, Pergamon Press, 1990).
[0055]
Since this ClogP value is currently the most general and reliable estimate, it can be used in place of the actual logP value when selecting a compound. In the present invention, if there is a measured value of logP, the measured value is used, and if there is no measured value, the ClogP value calculated by the program CLOGP v4.01 is used.
[0056]
As the organic solvent having such log P, a compound represented by the following formula (5), formula (6) or formula (7) is suitable.
R ¹² -OH (5)
(Wherein R ¹² Is a hydrocarbon group having 4 to 8 carbon atoms, preferably an alkyl group, an aryl group or an arylalkyl group. )
[0057]
R ¹³ -(O-R ¹⁴ ) _j -O-R ¹⁵ (6)
(Wherein R ¹³ And R ¹⁵ Each independently represents a hydrogen atom, R ¹⁶ CO- (where R ¹⁶ Is an alkyl group having 1 to 3 carbon atoms) or a hydrocarbon group having 1 to 7 carbon atoms, preferably a hydrogen atom, an alkyl group, an aryl group or an arylalkyl group, and R ¹⁴ Is an alkylene group which may have a branched chain having 2 to 9 carbon atoms. j is a number from 1 to 5. )
[0058]
R ¹⁷ -O-CH ₂ CH (O-R ¹⁸ ) CH ₂ -O-R ¹⁹ (7)
(Wherein R ¹⁷ Is an alkyl group having 3 to 8 carbon atoms, and R ¹⁸ And R ¹⁹ Are each independently an alkyl group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom or a hydroxy group. )
[0059]
More specifically preferred compounds include n-butanol, isobutanol, 2-butanol, n-hexanol, cyclohexanol, phenol, benzyl alcohol, phenethyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, diethylene glycol monobenzyl ether, Diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, 2-ethylhexane-1,3-diol, hexane-1,6-diol, nonane-1,6-diol, 2-methyloctane -1,8-diol, 2-butoxyethanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 2- (2-methyl) propo Siethanol, diethylene glycol mono-2-methylpropyl ether, 2-propoxy-1-propanol, dipropylene glycol monopropyl ether, 2-butoxy-1-propanol, dipropylene glycol monobutyl ether, 2-t-butoxy-1-propanol 2-phenoxy-1-propanol, 2-ethoxypropyl-1-acetate, 2-propoxypropyl-1-acetate, 1,2-diacetoxypropane, 3-dimethyl-3-methoxy-1-propanol, 1, 3-dimethylbutyl glyceryl ether, pentyl glyceryl ether, hexyl glyceryl ether, 1,2-hexanediol, 1,2-pentanediol, hexylene glycol, 1,2-butanediol, 1,4-cyclohexane Can be mentioned ol, 1,5-hexanediol and / or 2,4-dimethyl-2,4-pentanediol.
[0060]
The softener composition of the present invention preferably contains 3 to 30% by weight, more preferably 5 to 25% by weight, and particularly preferably 10 to 20% by weight of the organic solvent (b) based on the total composition. .
In order to further enhance the aesthetic appearance of the transparent or translucent softener composition, it is preferable to use the component (c) in the softener composition of the present invention.
As the component (c), it is preferable to use a dye having at least one polyoxyalkylene chain (hereinafter referred to as a polyoxyalkylene-modified dye) from the viewpoint that the colorant is not easily faded by light. The polyoxyalkylene-modified dye may have a polyoxyalkylene chain and a chromophore.
[0061]
As the polyoxyalkylene chain, the formula-(AO) n-
(In the formula, A is an alkylene group having 2 to 4 carbon atoms, n is a number of 3 to 200 indicating the average number of added moles of alkylene oxide, and n A's may be the same or different.)
A polyoxyalkylene chain represented by
formula
-(C ₃ H ₆ O) k- (C ₂ H ₄ O) m-
(In the formula, k and m are each independently a number from 0 to 100, and k + m is a number from 3 to 200. Also, (C ₃ H ₆ O) k and (C ₂ H ₄ O) m may be random or a block. )
The polyoxyalkylene chain represented by is more preferable.
[0062]
As chromophores, azo chromophore, phthalocyanine chromophore, anthraquinone chromophore, aza [18] annulene chromophore, formazan copper complex chromophore, triphenodioxazine chromophore, nitroso chromophore, nitro chromophore, diarylmethane chromophore, Triarylmethane chromophore, xanthene chromophore, acridene chromophore, methine chromophore, thiazole chromophore, indamine chromophore, azine chromophore, oxazine chromophore, thiazine chromophore, quinoline chromophore, indigoid chromophore, indophenol chromophore Lactone chromophore, aminoketone chromophore, hydroxyketone chromophore, stilbene chromophore and the like. The polyoxyalkylene chain and the chromophore are preferably bonded directly or indirectly via, for example, a nitrogen atom, oxygen atom, sulfur atom or the like.
[0063]
Specific examples of polyoxyalkylene-modified dyes include polyoxyalkylene-modified anthraquinone colorants, oxyalkylene-modified phthalocyanine dyes, colorants having a siloxane-containing poly (oxyalkylene) copolymer substituent, poly (oxyalkylene) substitution Coloring agents, poly (oxyalkylene) substituted coloring agents, and the like can be mentioned. Also, Liquidint (registered trademark) dyes manufactured by Milliken Chemical Co. can be used.
[0064]
As the component (c), in addition to the polyoxyalkylene-modified dye, commonly used pigments can be used in combination. Examples of dyes include acidic dyes having amino groups, sulfonyl groups, and carboxyl groups in the molecule, direct dyes, basic dyes, mordant / acid mordant dyes, azoic dyes, sulfurized / sulfurized vat dyes, vat dyes, and dispersions. One or more dyes selected from dyes, oil-soluble dyes, reactive dyes, food dyes, and natural dyes are preferred. More preferably, Acid Blue 80, an acid dye having a carbonium group in the chromophore, a direct dye having a carbonium group in the chromophore, a basic dye, a reactive dye, a food color, and a natural color. Particularly preferred are basic dyes, reactive dyes, mordanting / acidic mordanting dyes, azoic dyes, sulfurizing / sulfurizing vat dyes, and food colorings classified as Red, Blue, Yellow, and Violet by color index.
[0065]
When a polyoxyalkylene dye is used in the softener composition of the present invention, the polyoxyalkylene dye is preferably contained in an amount of 0.1 to 100 mg / kg, more preferably 1 to 70 mg / kg, especially 3 It is preferable to contain -30 mg / kg.
[0066]
When using a pigment | dye for the softening agent composition of this invention, it is preferable to contain 0.1-100 mg / kg of pigment | dye with respect to the whole composition, and also it is preferable to contain 0.1-20 mg / kg.
Component (d) is preferably a compound selected from aminopolycarboxylic acids, phosphonic acids, and salts thereof.
[0067]
Preferred aminopolycarboxylic acids have the formula —N (CH ₂ COOH) ₂ It is a compound having at least one, preferably 1 or 2, iminodiacetic acid groups, and having a molecular weight of 180 to 1000, preferably 250 to 600. Specific examples include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aspartic acid diacetic acid, glutamic acid diacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetramine hexaacetic acid, and diencoric acid. In particular, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aspartic acid diacetic acid, and glutamic acid diacetic acid are preferred.
[0068]
Examples of phosphonic acid include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid. Acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), trimethylenephosphonoamine, etc. In particular, ethane-1,1-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, and ethylenediaminetetra (methylenephosphonic acid) are preferable.
[0069]
As the salt, sodium salt, potassium salt, magnesium salt, iron salt, nickel salt, chromium salt, zinc salt and alkanolamine salt are preferable, and sodium salt, potassium salt and iron salt are particularly preferable.
As the component (d) to be blended in the softener composition of the present invention, ethylenediaminetetraacetic acid and its sodium salt, potassium salt or iron salt are particularly preferable.
[0070]
In the softener composition of the present invention, the component (d) is preferably contained in an amount of 0.0005 to 5% by weight, more preferably 0.001 to 3% by weight, particularly 0.005 to 0.5%, based on the total composition. It is preferable to contain by weight.
Furthermore, from the viewpoint of light stability, the weight ratio (c) / (d) of the component (c) to the component (d) is preferably 1/10000 to 10/1, and more preferably 1/5000 to 1 / 1, particularly 1/100 to 1/1.
[0071]
(E) component can be mix | blended with the softening agent composition of this invention.
As the component (e), it is preferable to use a saturated or unsaturated fatty acid having 12 to 36 carbon atoms, preferably 14 to 24, more preferably 14 to 20, or a salt thereof. Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and mixtures thereof, and one or more selected from palmitic acid, stearic acid, and oleic acid are particularly preferable. Moreover, the fatty acid which has the alkyl composition induced | guided | derived from palm oil and beef tallow is also preferable. In the case of using a salt, sodium salt, potassium salt, magnesium salt, and alkanolamine salt are preferable, and sodium salt and potassium salt are particularly preferable in view of storage stability.
[0072]
When the component (e) is used, the content of the component (e) is preferably 0.01 to 5% by weight, particularly 0.05 to 3% by weight in the composition. The component (e) / component (a) is preferably 1/500 to 1/50, more preferably 1/300 to 1/100 in terms of weight ratio, from the viewpoint of flexibility.
[0073]
The softening agent composition of the present invention can further contain component (f).
As the component (f), an alkyl or alkenyl group having 16 to 36 carbon atoms, preferably 16 to 28 carbon atoms, and -SO ₃ M group and / or -OSO ₃ It is preferable to use an anion (f1) component having an M group (M: counter ion). Specifically, alkylbenzene sulfonic acid having an alkyl group or alkenyl group having the above carbon number, alkyl (or alkenyl) sulfate, polyoxyalkylene alkyl (or alkenyl) ether sulfate, olefin sulfonic acid, alkane sulfonic acid, α-sulfo Fatty acids, α-sulfo fatty acid esters and salts thereof are preferred.
[0074]
Among these, an alkyl (or alkenyl) sulfate having an alkyl group or alkenyl group having 16 to 28 carbon atoms, an alkyl group or alkenyl group having 16 to 28 carbon atoms, and an average of ethylene oxide (hereinafter referred to as EO) average It is preferable to blend one or more selected from polyoxyethylene alkyl (or alkenyl) ether sulfates having 1 to 6, preferably 1 to 4, particularly preferably 1 to 3, and their salts. As the salt, sodium salt and potassium salt are preferable from the viewpoint of storage stability.
[0075]
In the present invention, when the component (a1) is selected as the component (a), the component (a1) / component (f1) is preferably 99.5 / 0.5 to 70/30, particularly preferably 99 in terms of molar ratio. / 1 to 85/15, and when component (a2) is selected as component (a), component (a2) / component (f1) is preferably in a molar ratio of 95/5 to 50/50. In particular, it is preferable from the viewpoint of a softening effect to mix | blend in the ratio of 85 / 15-65 / 35.
[0076]
In addition, as the component (f), it is preferable to further blend a nonionic surfactant (f2) from the viewpoint of storage stability. As the nonionic surfactant (f2), polyoxyethylene alkyl ether having an alkyl group or alkenyl group having 8 to 20 carbon atoms is preferable, and a nonionic surfactant represented by the following formula (8) is particularly preferable.
[0077]
R ²⁰ -F-[(R ²¹ O) pH] q (8)
(Wherein R ²⁰ Is an alkyl or alkenyl group having 10 to 18 carbon atoms, preferably 12 to 18 carbon atoms, and R ²¹ Is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. p represents a number of 2 to 100, preferably 5 to 80, particularly preferably 10 to 60. F is —O—, —CON— or —N—, q is 1 when F is —O—, and q is 2 when F is —CON— or —N—. )
Specific examples of the compound represented by the formula (8) include compounds represented by the following formulas (8-1) to (8-4).
[0078]
R ²⁰ -O- (C ₂ H ₄ O) r-H (8-1)
(Wherein R ²⁰ Indicates the above meaning. r is a number of 8 to 100, preferably 10 to 60. ]
[0079]
R ²⁰ -O- (C ₂ H ₄ O) s- (C ₃ H ₆ O) t-H (8-2)
[Wherein R ²⁰ Indicates the above meaning. s and t are each independently a number of 2 to 40, preferably 5 to 40, and the oxyethylene group and the oxypropylene group may be random or block adducts. )
[0080]
[Chemical 6]

(Wherein R ²⁰ Indicates the above meaning. u, v, w and x are each independently a number of 0 to 40, preferably 5 to 40, and u + v + w + x is a number of 5 to 60, preferably 5 to 40. The oxyethylene group and the oxypropylene group may be random or block adducts. )
[0081]
When the nonionic surfactant (f2) is used, the content of the nonionic surfactant (f2) is 0.5 to 10% by weight, particularly 1 to 8% by weight in the composition, which is storage stable. It is preferable from the point.
(G) component can be further mix | blended with the softening agent composition of this invention. Specifically, it is preferable to use 2,6-di-tert-butyl-4-methylphenol and / or 2,6-di-tert-butyl-4-ethylphenol.
[0082]
In the present invention, when the component (a1) is selected as the component (a), the component (g) is blended in an amount of 0.001 to 1% by weight, particularly 0.005 to 0.05% by weight. When component (a2) is selected as component a), it is storage stable to blend 0.0003 to 0.5% by weight, particularly 0.007 to 0.02% by weight of antioxidant (g). It is preferable from the point.
[0083]
Moreover, the softening agent composition of this invention can mix | blend (h) component. As the component (h), sodium chloride and / or calcium chloride is preferable from the viewpoint of storage stability, and 0 to 1000 mg / kg, preferably 10 to 500 mg / kg is preferably added to the composition. However, although surfactants such as fatty acid salts include sodium salts and potassium salts, the inorganic salts mixed into the composition by using such surfactants are not limited to the above.
[0084]
The softening agent composition of this invention can mix | blend (i) component. (I) As a component, the ester compound of a C8-C22 saturated or unsaturated fatty acid and a polyhydric alcohol can be used. Specifically, preferred ester compounds include triglycerides, diglycerides, monoglycerides, mono-, di-, triesters, and sorbitan esters of pentaerythritol. When the component (i) is blended, 5 The content is preferably not more than wt%, more preferably not more than 3 wt%, particularly preferably not more than 1 wt%.
[0085]
Furthermore, in addition to the above components, the softener composition of the present invention includes components blended in ordinary softener compositions such as silicone, soil release agents, bactericides, chelating agents, color protection agents, preservatives. Further, a shrinkage inhibitor, a fabric shrinkage treatment agent, a stain remover, a corrosion inhibitor, an enzyme, water, and the like can be appropriately blended within a qualitative and quantitative range that does not impair the object and effect of the present invention.
[0086]
The softener composition of the present invention is generally in the form of an aqueous solution in which the above components are diluted with water, and the water used is preferably distilled water or ion-exchanged water. From the viewpoint of storage stability, water is preferably contained in the composition in an amount of 30 to 95% by weight, more preferably 50 to 85% by weight. Furthermore, in the composition of the present invention, it is preferable to adjust the pH at 20 ° C. of the composition to 1 to 8.5, further 1 to 8, particularly 2 to 8 from the viewpoint of storage stability.
The softening agent composition of this invention can be manufactured in accordance with a conventional method using each said material.
[0087]
【Example】
(Examples 1-11 and Comparative Examples 1-3: Fragrance composition)
According to the composition shown in Table 1, the fragrance | flavor composition of Examples 1-11 and Comparative Examples 1-3 was prepared. The absorbance (420 nm fixed) of each fragrance component and fragrance composition shown in Table 1 was measured to obtain a K value, and yellowness was evaluated.
[0088]
<Preparation of perfume composition>
The fragrance composition was prepared by mixing fragrance ingredients (single fragrance) according to the composition of Table 1. If there was a fragrance component that was difficult to dissolve, such as powder, it was dissolved by heating using a water bath or the like.
[0089]
<Evaluation>
1. Yellowness measurement
Among the perfume ingredients (single product perfume), the liquid perfume was subjected to yellowness measurement using the stock solution. Perfumes such as powders, solids or high-viscosity natural products (marked with ★) use colorless and transparent dipropylene glycol. For powders and solids, dilute 5 times to obtain natural products with high viscosity. Was diluted by a factor of 2 and subjected to yellowness measurement.
Moreover, the fragrance | flavor composition measured the fragrance | flavor composition after a compounding initial stage and storage at 40 degreeC for 20 days.
[0090]
The yellowness was evaluated by measuring the absorbance at 420 nm, and the obtained absorbance value × 1000 was defined as the K value. Absorbance was measured with UV-2500 (PC) manufactured by SHIMADZU, under the condition of spectral bandwidth (slit width): 1.0 nm.
[0091]
[Evaluation criteria]
(1) Fragrance ingredient
The measured K value was divided into the following three ranks and yellowness was evaluated.
Rank A: Perfume ingredients with a K value of 1000 or less
Rank B: Perfume ingredients with a K value greater than 1000 and less than 4000
C rank: Perfume ingredients with a K value of 4000 or more
[0092]
(2) Fragrance composition
The measured K value was divided into the following two ranks, and the yellowness value was evaluated.
“Small”: a fragrance composition having a K value of 3000 or less for the entire fragrance composition
“Large”: A perfume composition having a K value of more than 3000
The obtained results are shown in Table 1.
[0093]
[Table 1]

[0094]
In the fragrance compositions of the examples, 40% by weight or more of fragrance having a K value of 1000 or less is blended, and further, 10% by weight or less of fragrance having 4000 or more is blended. As a result, the klet value of the entire fragrance composition is suppressed to 3000 or less.
On the other hand, in the fragrance composition of the comparative example, a fragrance having a K value of 1000 or less is blended in less than 40% by weight, and a fragrance having 4000 or more is blended in an amount of more than 10% by weight. As a result, K value of the whole fragrance composition cannot be suppressed to 3000 or less.
[0095]
(Examples 11-19, Comparative Examples 11-13: Softener composition)
According to the composition shown in Table 2, using the fragrance composition of Examples 1-9 as the fragrance composition (j) of Table 2, the softener composition of Examples 11-19 and the fragrance of Comparative Examples 1-3 The softener composition of Comparative Examples 11-13 was prepared using the composition as the fragrance composition (j) in Table 2. In the softening agent compositions of Examples 11 to 19 and Comparative Examples 11 to 13, the fragrance composition (j) was blended in an amount of 0.5% by weight. Using each of the obtained softener compositions, the effect of the fragrance composition on the appearance of the softener, further performing a storage stability test and a light resistance test, changes in the K value of the softener composition after each test, In addition, the change in odor and the remaining fragrance were evaluated.
[0096]
<Preparation of softener composition>
Ion-exchanged water equivalent to 95% of the amount necessary for the finished mass of the softening agent composition to be 200 g was placed in a 300 ml beaker and heated to 60 ° C. in a water bath. While stirring (300 r / min), required amounts of component (b) and component (e) were dissolved. Next, the mixture (40 degreeC) which mixed the required amount (a) component and (d) component previously was added.
[0097]
After stirring for 5 minutes, components (c) and (f) to (h) are added sequentially. After stirring for 5 minutes, the pH is adjusted to the target with 35% aqueous hydrochloric acid and 48% aqueous sodium hydroxide, An amount of ion-exchanged water at 60 ° C. necessary for the finished mass was added. Thereafter, the mixture was stirred for 10 minutes, the beaker was transferred to a water bath containing 5 ° C. water, and cooled to 20 ° C. while stirring. In addition, pH shown in Table 2 is pH after cooling (20 degreeC).
[0098]
[Table 2]

[0099]
<Evaluation>
(Storage stability test)
The prepared softener composition was stored at 40 ° C. for 20 days, and used as a sample after a storage stability test.
(Light resistance test)
Using the prepared softener composition, Xenon Long Life Fade Meter FAL-7X-LB type manufactured by Suga Test Instruments Co., Ltd., totaling 10,000 kJ / m ² The sample was irradiated with ultraviolet rays and subjected to a light resistance test.
[0100]
1. Effect of perfume composition on appearance of softener composition
The K value of the softener composition was measured in the same manner as the yellowness evaluation of the fragrance composition, and the influence of the fragrance composition on the appearance of the softener composition was evaluated.
[Evaluation criteria]
When the K value of the softener composition was 3000 or less, the influence of the fragrance composition on the appearance of the softener composition was evaluated as “none”, and when the K value was greater than 3000, the influence was evaluated as “present”.
[0101]
2. Changes in K value of softener composition after storage stability test and light resistance test
The change in K value is evaluated as “no change” when the K value change rate between the sample immediately after preparation (compounding) and the sample after storage is less than 10%, and the sample immediately after preparation (combination) and the sample after storage When the rate of change in the K value was 10% or more, it was evaluated that there was a change.
[0102]
3. Changes in odor of softener composition after storage stability test and light resistance test
Odor changes were evaluated by 10 expert panelists immediately after preparation (combination) and after storage, with 0 points for panelers that have changed and +1 points for panelers that have not changed. The ranking was based on the total score of people. When the total score of the panelists scored 7 points or more, the change was evaluated as “none”, and when the total score was less than 7 points, the change was evaluated as “present”.
[0103]
4). Afterglow
2 kg of commercially available cotton towel and 1 kg of acrylic jersey with 3.5 ° DH hard water repeatedly washed with a commercial detergent attack (Kao Co., Ltd., registered trademark) 5 times (30 L washing machine), fiber treatment agent attached to the fiber Then, 10 ml of the softening agent composition shown in Table 2 was added and stirred at 25 ° C. for 3 minutes for treatment.
The cloth treated by the above method was air-dried indoors and then left in a constant temperature and humidity room at 25 ° C. and 65% RH for 24 hours. These fabrics were evaluated for residual fragrance properties by 10 professional panelists.
A comparison was made between the fabric treated with the softener composition of Example 1 and each sample. One panel was deemed to have an equivalent or higher residual scent, and one panel was deemed to be weaker than that. The ranking was based on the total score of 10 people.
[0104]
[Evaluation criteria]
When the total score of the panelists was 7 points or more, the remaining fragrance was evaluated as “present”, and when the total score was less than 7 points, the remaining fragrance was evaluated as “none”.
The evaluation results are as shown in Table 3.
[0105]
[Table 3]

[0106]
In the softening agent compositions of Examples 11 to 19 in which the fragrance compositions of Examples 1 to 9 were perfumed, a transparent softening agent composition that did not impair the appearance of the transparent softening agent due to yellowing by the fragrance was achieved. Further, it was confirmed that this softener composition was a sample with little change even in the storage stability by heat and the light resistance test by light without impairing the residual fragrance.
[0107]
The appearances of the softener compositions of Comparative Examples 11 to 13 containing the fragrance compositions of Comparative Examples 1 to 3 were clearly below our designed level. Moreover, it was confirmed that the fragrance | flavor containing many Schiff bases was inferior in odor stability compared with the Example, and in the comparative example in which many terpene alcohols were mix | blended, the stability with respect to light was bad.
[0108]
From these, the product of the present invention is a well-balanced fragrance composition that is stable against heat and light and also has residual fragrance, and a softener, without impairing the appearance of the transparent or translucent softener composition. It was revealed to be a composition.
[0109]
【The invention's effect】
In the fragrance composition for softeners according to the present invention, the fragrance component (single fragrance) is ranked according to the K value indicating the degree of yellowness, and among them, the fragrance having a K value of 1000 or less is classified into the entire fragrance composition. 40% by weight or more, and by setting the degree of yellowness of the whole fragrance composition to a K value of 3000 or less, the yellowness is low, and the desired color of the softener is not colored, and A fragrance composition having a high residual fragrance, good stability of the fragrance composition and little deterioration of odor can be obtained. Therefore, the fragrance composition according to the present invention does not impair the appearance by light even when it is filled in a transparent container in order to enhance the commercial value especially by enhancing the transparent appearance of the transparent softener, and as designed. The incense tone can be maintained.
[0110]
Since the softener composition according to the present invention contains the fragrance composition according to the present invention, it is a transparent or translucent softener that has high residual fragrance, little odor degradation, and does not impair the appearance of the fragrance composition. It is a composition.

Claims (2)

Benzyl acetate, allyl amyl glycolate, γ-undecalactone, n-octanol, lyial, 1- (2-t-butylcyclohexyloxy) -2-butanol, phenylethyl alcohol, hexamethylhexahydrocyclopentabenzopyran, iso From camphorcyclohexanol, methyl dihydrojasmonate, tricyclodecenyl propionate, hexylcinnamic aldehyde, cyclopentadecanolide, porenate, musk ketone, limonene, methyl b-naphthyl ketone, α-isomethyl ionone, citronellol, and geraniol A fragrance composition containing 40% by weight or more of at least one fragrance component (A) selected from the group consisting of :
The total content of at least one fragrance component (C) selected from orange oil, patchouli oil, benzoin, lemon oil, and aldehyde Hyde C-12 NMA Schiff base is 10% by weight or less,
The content of the Schiff base fragrance is 0.5% by weight or less, and the content of the terpene and sesquitene alcohols having a double bond is 10% by weight or less,
A fragrance composition for a transparent softener or a translucent softener having a light transmittance of a wavelength of 660 nm of 30% or more when a quartz cell having an optical path length of 10 mm is used and ion-exchanged water is added to the control side cell. . A compound having one or more hydrocarbon groups having 12 to 36 carbon atoms, a tertiary amino group or an acid salt thereof or one or more quaternary ammonium groups thereof, and the fragrance composition according to claim 1 , A transparent or translucent softener composition having a light transmittance at a wavelength of 660 nm of 30% or more when a quartz cell having an optical path length of 10 mm is used and ion-exchanged water is added to a control side cell.