JP4319792B2 - Soft base and soft finish - Google Patents

Description

（式中、Ｚ¹、Ｚ²、Ｚ³、Ｚ⁴は同一でも異なっていてもよく、それぞれヒドロキシル基又は下記式［４］：
【００１０】
−ＮＨＣＯＲ⁵ ［４］
で表される基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵は同一でも異なっていてもよく、それぞれヒドロキシル基を有していてもよい炭素数１１〜２３の飽和又は不飽和炭化水素基を表し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈは同一でも異なっていてもよく、それぞれ２又は３である。）
【００１１】
また、本発明の柔軟仕上剤は、上記本発明の柔軟基剤を１０〜９０重量％含有することを特徴とするものである。
【００１２】
【発明の実施の形態】
先ず、本発明の柔軟基剤について説明する。本発明の柔軟基剤は、高級脂肪酸とアミンから得られるアマイド系化合物として以下の３タイプのもの：
（Ａ）下記一般式［１］で表される化合物及びその有機酸塩からなる群から選択される少なくとも１種の第１のアマイド系化合物（環状タイプのアマイド系化合物）；
（Ｂ）下記一般式［２］で表される化合物及びその有機酸塩からなる群から選択される少なくとも１種の第２のアマイド系化合物（縮合タイプのアマイド系化合物）；及び
（Ｃ）下記一般式［３］で表される化合物及びその有機酸塩からなる群から選択される少なくとも１種の第３のアマイド系化合物（直鎖タイプのアマイド系化合物）；
を含有するものである。
【００１３】
【化３】

そして、上記一般式［１］、［２］及び［３］において、Ｚ¹、Ｚ²、Ｚ³、Ｚ⁴は同一でも異なっていてもよく、それぞれヒドロキシル基又は下記式［４］：
【００１４】
−ＮＨＣＯＲ⁵ ［４］
で表される基を表す。また、上記一般式［１］、［２］、［３］及び［４］において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵は同一でも異なっていてもよく、それぞれヒドロキシル基を有していてもよい炭素数１１〜２３の飽和又は不飽和炭化水素基を表す。炭化水素基の炭素数が１１未満では柔軟性が低く不十分となり、他方、２３を超えると柔軟仕上剤の液状化が困難となり、水への希釈性が著しく低下するおそれがある。係る飽和又は不飽和炭化水素基としては、炭素数が１５〜２１のものが好ましく、それらの炭化水素鎖は直鎖状であっても分岐鎖状であってもよい。
【００１５】
また、上記一般式［１］、［２］及び［３］において、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈは同一でも異なっていてもよく、それぞれ２又は３であり、全てが２であることが特に好ましい。これらの値が２未満では、一般式［１］で表される環状タイプのアマイド系化合物が得られ難く、他方、３を超えると柔軟仕上剤の液状化が困難となり、水への希釈性が低下するおそれがある。
【００１６】
本発明においては、前記一般式［１］、［２］、［３］で表される化合物の有機酸塩を使用すると、得られる柔軟基剤の希釈性がより向上する傾向にあるので好ましい。このような有機酸としては特に限定はないが、例えば、ギ酸、酢酸、乳酸、リンゴ酸、パラトルエンスルホン酸、グリコール酸、クエン酸、マレイン酸などが挙げられ、ギ酸、酢酸、乳酸がより好ましく、酢酸が特に好ましい。
【００１７】
本発明の柔軟基剤は、前記の（Ａ）成分である第１のアマイド系化合物（環状タイプのアマイド系化合物）、（Ｂ）成分である第２のアマイド系化合物（縮合タイプのアマイド系化合物）、（Ｃ）成分である第３のアマイド系化合物（直鎖タイプのアマイド系化合物）を、（Ａ）：（Ｂ）：（Ｃ）の重量比が５０〜９０：８〜３０：２〜２０となる範囲で含有する。（Ａ）成分の重量比率が５０未満では柔軟仕上剤の液状化が困難であり、他方、９０を超えると柔軟性が低下し繊維製品の風合が悪くなるだけでなく、白度の低下も懸念される。また、（Ｂ）成分の重量比率が８未満では繊維製品の白度の低下や色相変化が大きくなり、他方、３０を超えると水への希釈性が低下する。さらに、（Ｃ）成分の重量比率が２未満では、水への希釈性が低下するおそれがあり、他方、２０を超えると繊維製品の白度の低下や色相変化が大きくなる。
【００１８】
さらに、本発明の柔軟基剤においては、前記第１〜第３のアマイド系化合物中の飽和炭化水素基と不飽和炭化水素基との総重量比が０：１００〜５０：５０であり、０：１００〜３０：７０であることが好ましく、０：１００〜１０：９０であることがより好ましい。ここで、前記第１〜第３のアマイド系化合物中の飽和炭化水素基及び不飽和炭化水素基とは、一般式［１］、［２］及び［３］においてＲ¹、Ｒ²、Ｒ³及びＲ⁴で表される基、並びに一般式［１］、［２］及び［３］におけるＺ¹、Ｚ²、Ｚ³及びＺ⁴が下記式［４］：
【００１９】
−ＮＨＣＯＲ⁵ ［４］
で表される基の場合はそのＲ⁵で表される基をいう。上記飽和炭化水素基の重量比率が５０を超えると、柔軟仕上剤の液状化が困難となり水への希釈性が低下するだけでなく、吸水性阻害が増大する。
【００２０】
このように、本発明の柔軟基剤においては、特定の高級脂肪酸とアミンから得られるアマイド系化合物として直鎖タイプのアマイド系化合物と環状タイプのアマイド系化合物と縮合タイプのアマイド系化合物とが併せて使用され、それぞれの重量比｛（Ａ）：（Ｂ）：（Ｃ）｝が特定の割合となるように配合され、かつその中の不飽和炭化水素基の比率を特定の割合以上となっており、それによって各種繊維素材に対して優れた柔軟性を付与しかつ吸水性阻害の発生を十分に防止でき、さらに高濃度でも液状でかつ水への希釈性などの作業性に優れるという特性を有するものである。
【００２１】
次に、本発明の柔軟基剤の製造方法について述べる。
【００２２】
上記一般式［１］、［２］及び［３］で表される化合物は、いずれも、高級脂肪酸とアミンとから従来公知の方法により製造することができる。本発明において用いられる高級脂肪酸は、炭素数１２〜２４の飽和又は不飽和脂肪酸であり、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、ヒドロキシステアリン酸、アラキジン酸、ベヘニン酸などの飽和脂肪酸；ミリストレイン酸、パルミトレイン酸、オレイン酸、リノール酸、リノレン酸、リシノール酸、エルカ酸などの不飽和脂肪酸が挙げられ、これらの中でも炭素数１６〜２２のものがより好ましい。これらの高級脂肪酸は１種を単独で用いてもよいし、２種以上を併用してもよい。
【００２３】
また、本発明において用いられるアミンとしては、例えば、ジエチレントリアミン、ジ（３−アミノプロピル）アミン、Ｎ−（３−アミノプロピル）エチレンジアミン、Ｎ−（２−アミノエチル）エタノールアミンなどが挙げられ、ジエチレントリアミンが特に好適である。これらのアミンは１種を単独で用いてもよいし、２種以上を併用してもよい。
【００２４】
上記一般式［３］で表される化合物は、例えば、前記の高級脂肪酸とアミンとを、温度１４０〜１９０℃（好ましくは１５０〜１７０℃）で１〜６時間アマイド化反応させることにより、８０〜９５％の収率で得ることができる。なお、温度と反応時間によっては、副生成物として一般式［１］で表される化合物が生じる。また、アマイド化反応させる際におけるアミンと高級脂肪酸との比率は、アミノ基１当量に対してカルボキシル基が０．９〜１．１当量となるようにすることが好ましい。
【００２５】
また、上記一般式［１］で表される化合物は、例えば、前記の高級脂肪酸とアミンとを、上記と同様にアマイド化反応させた後、さらに、１８０〜２６０℃（好ましくは２２０〜２５０℃）で１〜５時間、環状化反応させることにより得ることができる。アマイド化反応及び環状化反応の進行度合いは、全アミン価、第三級アミン価の測定により追跡することができる。なお、副生成物として、一般式［３］で表される化合物が生じる。
【００２６】
さらに、上記一般式［２］で表される化合物は、例えば、前記の高級脂肪酸とアミンとを、１４０〜１９０℃（好ましくは１５０〜１７０℃）で１〜６時間アマイド化反応させた後、さらに、尿素により縮合反応させることにより得ることができる。係る縮合反応は、好ましくは１５０〜２００℃、より好ましくは１６０〜１８０℃で、３０分〜５時間反応を進行させることが好ましい。尿素の使用量は、アマイド化反応により得られる一般式［３］で表される化合物１モルに対し、０．１〜０．５モルが適当である。
【００２７】
本発明においては、上記一般式［１］、［２］及び［３］で表される化合物をそれぞれ上記の製造方法により合成し、配合して柔軟基剤を得ることができる。そして、本発明の柔軟基剤においては、上記一般式［１］、［２］及び［３］で表される化合物の製造後又は配合後に、前記の有機酸を用いて中和することが好ましい。このように一般式［１］、［２］及び［３］で表される化合物を中和する際における有機酸の添加量に特に制限はないが、得られる柔軟仕上剤のｐＨが中和点より酸性側となるようにすることが好ましい。なお、有機酸を過剰に加えても、得られる柔軟基剤の性能を阻害するものではない。
【００２８】
また、本発明においては、製造工程の簡略化、製造コストの低減を目的として、前述の高級脂肪酸とアミンとを先ず前記のようにアマイド化反応させ、続いて環状化反応させ、さらに尿素により縮合反応させるという連続した三段階の反応により、上記一般式［１］、［２］及び［３］で表される化合物を含有する柔軟基剤を得ることもできる。
【００２９】
次に、本発明の柔軟仕上剤について説明する。本発明の柔軟仕上剤は、上記本発明の柔軟基剤を含有するものであり、液状のまま前記柔軟基剤の含有量を低濃度から高濃度まで任意に調節することができるが、前記柔軟基剤を１０〜９０重量％含有することが好ましい。柔軟基剤の含有量が１０重量％未満では製造時及び輸送時のコストが上昇し、また消費者の使用性が低下する傾向にあり、他方、９０重量％を超えると高粘度状あるいは固形状となり易く、水への希釈性が低下する傾向にある。
【００３０】
本発明の柔軟仕上剤に使用される溶媒としては、炭素数１２〜１８の高級アルコールのアルキレンオキサイド付加物、ポリオキシエチレンソルビタン脂肪酸エステルなどの各種非イオン活性剤；エチレングリコール、ポリエチレングリコール、プロピレングリコール、グリセリン、ソルビトールなどの多価アルコール；エタノール、イソプロピルアルコールなどのアルコール類、水、及びこれらの混合物が好適である。
【００３１】
本発明の柔軟仕上剤には、上記の溶媒以外に、従来より柔軟仕上剤に使用されている公知の成分を、本発明に係る効果が損なわれない範囲で配合することができる。このような成分としては、例えば、グリセリン、ソルビタン、ペンタエリスリトール、ポリエチレングリコール、ポリアルキレングリコールなどの多価アルコールの脂肪酸エステル；アニオン界面活性剤（例えば、スルホコハク酸モノアルキルエステル、スルホコハク酸ジアルキルエステルなど）；第四級アンモニウム塩（アルキルトリメチルアンモニウムクロライド、アルキルトリメチルアンモニウムメチルスルホン酸など）；炭素数１２〜１８の高級アルキルアミン又は高級脂肪酸のアルキレンオキサイド付加物などの非イオン系界面活性剤（例えば、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンラウリルアミン、ポリオキシエチレンステアリルアミン）；アミノ変性シリコーン、ジメチル変性シリコーン、エポキシ変性シリコーンなどのシリコーン系化合物；塩化ナトリウム、塩化カルシウムなどの水溶性無機塩；パラフィン系炭化水素、セルロース系誘導体、酸化防止剤などが挙げられる。
【００３２】
【実施例】
以下、実施例及び比較例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。
【００３３】
実施例１〜５及び比較例１〜７
先ず、以下の実施例１〜５及び比較例１〜７に示す柔軟基剤及びそれを用いた柔軟仕上剤を調製し、得られた柔軟仕上剤を用いて以下に示す（１）水への希釈性評価、並びに（２）柔軟処理布の評価（風合、吸水性、白度、色相変化）を実施した。なお、実施例１〜５及び比較例１〜４で得られた柔軟基剤における（Ａ）成分：（Ｂ）成分：（Ｃ）成分の重量比は、全アミン価及び第三級アミン価に基づいて算出した。また、実施例１〜５及び比較例１〜４において得られた柔軟基剤及び柔軟仕上剤の組成などを表１及び表２に示す。なお、表１及び表２中、柔軟基剤の「飽和：不飽和」の欄には飽和炭化水素基と不飽和炭化水素基との総重量比を示す。
【００３４】
（実施例１）
１Ｌ四ツ口フラスコにオレイン酸５６４ｇを仕込み、１００℃に昇温した後、ジエチレントリアミン１０３ｇを加えた。得られた混合物を１６０℃まで昇温した後、１時間脱水反応（アマイド化反応）させ、次いで２４０〜２５０℃に昇温した後、２時間イミダゾリン化反応（環状化反応）させた。反応終了後、その反応溶液を１２０℃まで降温して尿素３０ｇを加え、１７０〜１８０℃に昇温した後、３時間縮合反応させた。続いて、この反応溶液を９０℃以下に冷却した後、約９０ｇの酢酸で中和し、粘液状の柔軟基剤を７２０ｇ得た。
【００３５】
得られた柔軟基剤における（Ａ）、（Ｂ）及び（Ｃ）成分はそれぞれ、一般式［１］、［２］及び［３］におけるＺ¹〜Ｚ⁴が−ＮＨＣＯＲ⁵、Ｒ¹〜Ｒ⁵がオレイン酸残基（８−ヘプタデセニル基）、ａ〜ｈが２である第１〜第３のアマイド系化合物の酢酸塩であった。そして、この柔軟基剤における（Ａ）：（Ｂ）：（Ｃ）の重量比は８０：１５：５であり、飽和炭化水素基と不飽和炭化水素基との総重量比は０：１００であった。
【００３６】
次いで、この柔軟基剤８０ｇを、５ｇのジエチレングリコール、１０ｇのソフタノール１２０（（株）日本触媒、炭素数１２〜１４のアルコールのエチレンオキサイド１２モル付加物）及び５ｇの水と共に均一になるまで混合して柔軟仕上剤を得たところ、その柔軟仕上剤は粘液状のものであった。
【００３７】
（実施例２）
１Ｌ四ツ口フラスコにオレイン酸５０８ｇ及びステアリン酸５７ｇを仕込み、１００℃に昇温した後、ジエチレントリアミン１０３ｇを加えた。得られた混合物を１６０℃まで昇温した後、１時間脱水反応させ、次いで２４０〜２５０℃に昇温した後、２時間イミダゾリン化反応させた。反応終了後、その反応溶液を１２０℃まで降温して尿素３０ｇを加え、１７０〜１８０℃に昇温した後、３時間縮合反応させた。続いて、この反応溶液を９０℃以下に冷却した後、約９０ｇの酢酸にて中和し、粘液状の柔軟基剤を約７２１ｇ得た。
【００３８】
得られた柔軟基剤における（Ａ）、（Ｂ）及び（Ｃ）成分はそれぞれ、一般式［１］、［２］及び［３］におけるＺ¹〜Ｚ⁴が−ＮＨＣＯＲ⁵、Ｒ¹〜Ｒ⁵がオレイン酸残基（８−ヘプタデセニル基）又はステアリン酸残基（ヘプタデシル基）、ａ〜ｈが２である第１〜第３のアマイド系化合物の酢酸塩であった。そして、この柔軟基剤における（Ａ）：（Ｂ）：（Ｃ）の重量比は８０：１５：５であり、飽和炭化水素基と不飽和炭化水素基との総重量比は１０：９０であった。
【００３９】
次いで、この柔軟基剤を用いた以外は実施例１と同様にして柔軟仕上剤を得たところ、その柔軟仕上剤は粘液状のものであった。
【００４０】
（実施例３）
１Ｌ四ツ口フラスコにリノール酸５６０ｇを仕込み、１００℃に昇温した後、ジエチレントリアミン１０３ｇを加えた。得られた混合物を１６０℃まで昇温した後、１時間脱水反応させ、次いで２４０〜２５０℃に昇温した後、２時間イミダゾリン化反応させた。反応終了後、その反応溶液を１２０℃まで降温して尿素３０ｇを加え、１７０〜１８０℃に昇温した後、３時間縮合反応させた。続いて、この反応溶液を９０℃以下に冷却した後、約９０ｇの酢酸で中和し、粘液状の柔軟基剤を７１６ｇ得た。
【００４１】
得られた柔軟基剤における（Ａ）、（Ｂ）及び（Ｃ）成分はそれぞれ、一般式［１］、［２］及び［３］におけるＺ¹〜Ｚ⁴が−ＮＨＣＯＲ⁵、Ｒ¹〜Ｒ⁵がリノール酸残基（８，１１−ヘプタデカジエニル基）、ａ〜ｈが２である第１〜第３のアマイド系化合物の酢酸塩であった。そして、この柔軟基剤における（Ａ）：（Ｂ）：（Ｃ）の重量比は８０：１５：５であり、飽和炭化水素基と不飽和炭化水素基との総重量比は０：１００であった。
【００４２】
次いで、この柔軟基剤を用いた以外は実施例１と同様にして柔軟仕上剤を得たところ、その柔軟仕上剤は粘液状のものであった。
【００４３】
（実施例４）
１Ｌ四ツ口フラスコにオレイン酸２８２ｇ及びエルカ酸３３８ｇを仕込み、１００℃に昇温した後、ジエチレントリアミン１０３ｇを加えた。得られた混合物を１６０℃まで昇温した後、１時間脱水反応させ、次いで２４０〜２５０℃に昇温した後、２時間イミダゾリン化反応させた。反応終了後、その反応溶液を１２０℃まで降温して尿素３０ｇを加え、１７０〜１８０℃に昇温した後、３時間縮合反応させた。続いて、この反応溶液を９０℃以下に冷却した後、約１００ｇの酢酸で中和し、室温でペースト状の柔軟基剤を７８６ｇ得た。
【００４４】
得られた柔軟基剤における（Ａ）、（Ｂ）及び（Ｃ）成分はそれぞれ、一般式［１］、［２］及び［３］におけるＺ¹〜Ｚ⁴が−ＮＨＣＯＲ⁵、Ｒ¹〜Ｒ⁵がオレイン酸残基（８−ヘプタデセニル基）又はエルカ酸残基（１２−ヘンエイコセニル基）、ａ〜ｈが２である第１〜第３のアマイド系化合物の酢酸塩であった。そして、この柔軟基剤における（Ａ）：（Ｂ）：（Ｃ）の重量比は８０：１５：５であり、飽和炭化水素基と不飽和炭化水素基との総重量比は０：１００であった。
【００４５】
次いで、この柔軟基剤を用いた以外は実施例１と同様にして柔軟仕上剤を得たところ、その柔軟仕上剤は粘液状のものであった。
【００４６】
（実施例５）
１Ｌ四ツ口フラスコにオレイン酸３３８ｇ及びラウリン酸１７１ｇを仕込み、１００℃に昇温した後、ジエチレントリアミン１０３ｇを加えた。得られた混合物を１６０℃まで昇温した後、１時間脱水反応させ、次いで２４０〜２５０℃に昇温した後、２時間イミダゾリン化反応させた。反応終了後、その反応溶液を１２０℃まで降温して尿素３０ｇを加え、１７０〜１８０℃に昇温した後、３時間縮合反応させた。続いて、この反応溶液を９０℃以下に冷却した後、約１００ｇの酢酸で中和し、室温で軟固体状の柔軟基剤を７８６ｇ得た。
【００４７】
得られた柔軟基剤における（Ａ）、（Ｂ）及び（Ｃ）成分はそれぞれ、一般式［１］、［２］及び［３］におけるＺ¹〜Ｚ⁴が−ＮＨＣＯＲ⁵、Ｒ¹〜Ｒ⁵がオレイン酸残基（８−ヘプタデセニル基）又はラウリン酸残基（ウンデシル基）、ａ〜ｈが２である第１〜第３のアマイド系化合物の酢酸塩であった。そして、この柔軟基剤における（Ａ）：（Ｂ）：（Ｃ）の重量比は８０：１５：５であり、飽和炭化水素基と不飽和炭化水素基との総重量比は３２：６８であった。
【００４８】
次いで、この柔軟基剤を用いた以外は実施例１と同様にして柔軟仕上剤を得たところ、その柔軟仕上剤は粘液状のものであった。
【００４９】
（比較例１）
１Ｌ四ツ口フラスコにステアリン酸５６８ｇを仕込み、１００℃に昇温した後、ジエチレントリアミン１０３ｇを加えた。得られた混合物を１６０℃まで昇温した後、１時間脱水反応させ、次いで２４０〜２５０℃に昇温した後、２時間イミダゾリン化反応させた。反応終了後、その反応溶液を１２０℃まで降温して尿素３０ｇを加え、１７０〜１８０℃に昇温した後、３時間縮合反応させた。続いて、この反応溶液を９０℃以下に冷却した後、約９０ｇの酢酸で中和し、柔軟基剤を７２４ｇ得た。この柔軟基剤は７０〜８０℃で粘液状であり、室温では固体状となった。
【００５０】
得られた柔軟基剤における（Ａ）、（Ｂ）及び（Ｃ）成分はそれぞれ、一般式［１］、［２］及び［３］におけるＺ¹〜Ｚ⁴が−ＮＨＣＯＲ⁵、Ｒ¹〜Ｒ⁵がステアリン酸残基（ヘプタデシル基）、ａ〜ｈが２である第１〜第３のアマイド系化合物の酢酸塩であった。そして、この柔軟基剤における（Ａ）：（Ｂ）：（Ｃ）の重量比は８０：１５：５であり、飽和炭化水素基と不飽和炭化水素基との総重量比は１００：０であった。
【００５１】
次いで、この柔軟基剤を用いた以外は実施例１と同様にして柔軟仕上剤を得たところ、その柔軟仕上剤はペースト状のものであった。
【００５２】
（比較例２）
１Ｌ四ツ口フラスコにオレイン酸５６４ｇを仕込み、１００℃に昇温した後、ジエチレントリアミン１０３ｇを加えた。得られた混合物を１６０℃に昇温した後、１時間脱水反応させ、次いで２４０〜２５０℃に昇温した後、２時間イミダゾリン化反応させた。反応終了後、その反応溶液を９０℃以下に冷却した後、約９０重量部の酢酸で中和し、粘液状の柔軟基剤を７０７ｇ得た。
【００５３】
得られた柔軟基剤における（Ａ）及び（Ｃ）成分はそれぞれ、一般式［１］及び［３］におけるＺ¹、Ｚ⁴が−ＮＨＣＯＲ⁵、Ｒ¹、Ｒ⁴、Ｒ⁵がオレイン酸残基（８−ヘプタデセニル基）、ａ、ｂ、ｇ、ｈが２である第１及び第３のアマイド系化合物の酢酸塩であった。そして、この柔軟基剤における（Ａ）：（Ｂ）：（Ｃ）の重量比は８０：０：２０であり、飽和炭化水素基と不飽和炭化水素基との総重量比は０：１００であった。
【００５４】
次いで、この柔軟基剤を用いた以外は実施例１と同様にして柔軟仕上剤を得たところ、その柔軟仕上剤は粘液状のものであった。
【００５５】
（比較例３）
１Ｌ四ツ口フラスコにオレイン酸５６４ｇを仕込み、１００℃に昇温した後、ジエチレントリアミン１０３ｇを加えた。得られた混合物を１６０℃に昇温した後、１時間脱水反応させ、次いで１９０〜２００℃に昇温した後、２時間イミダゾリン化反応させた。反応終了後、その反応溶液を１２０℃まで降温して尿素３０ｇを加え、１７０〜１８０℃に昇温した後、３時間縮合反応させた。続いて、この反応溶液を９０℃以下に冷却した後、約９０ｇの酢酸で中和し、粘液状の柔軟基剤を７２９ｇ得た。
【００５６】
得られた柔軟基剤における（Ａ）、（Ｂ）及び（Ｃ）成分はそれぞれ、一般式［１］、［２］及び［３］におけるＺ¹〜Ｚ⁴が−ＮＨＣＯＲ⁵、Ｒ¹〜Ｒ⁵がオレイン酸残基（８−ヘプタデセニル基）、ａ〜ｈが２である第１〜第３のアマイド系化合物の酢酸塩であった。そして、この柔軟基剤における（Ａ）：（Ｂ）：（Ｃ）の重量比は３０：６５：５であり、飽和炭化水素基と不飽和炭化水素基との総重量比は０：１００であった。
【００５７】
次いで、この柔軟基剤を用いた以外は実施例１と同様にして柔軟仕上剤を得たところ、その柔軟仕上剤は粘液状のものであった。
【００５８】
（比較例４）
１Ｌ四ツ口フラスコにオレイン酸２２７ｇ及びステアリン酸３３８ｇを仕込み、１００℃に昇温した後、ジエチレントリアミン１０３ｇを加えた。得られた混合物を１６０℃に昇温した後、１時間脱水反応させ、次いで２４０〜２５０℃に昇温した後、２時間イミダゾリン化反応させた。反応終了後、その反応溶液を１２０℃まで降温して尿素３０ｇを加え、１７０〜１８０℃に昇温した後、３時間縮合反応させた。続いて、この反応溶液を９０℃以下に冷却した後、約９０ｇの酢酸で中和し、柔軟基剤を７２１ｇ得た。この柔軟基剤は７０〜８０℃では粘液状であり、室温で軟固体状となった。
【００５９】
得られた柔軟基剤における（Ａ）、（Ｂ）及び（Ｃ）成分はそれぞれ、一般式［１］、［２］及び［３］におけるＺ¹〜Ｚ⁴が−ＮＨＣＯＲ⁵、Ｒ¹〜Ｒ⁵がオレイン酸残基（８−ヘプタデセニル基）又はステアリン酸残基（ヘプタデシル基）、ａ〜ｈが２である第１〜第３のアマイド系化合物の酢酸塩であった。そして、この柔軟基剤における（Ａ）：（Ｂ）：（Ｃ）の重量比は８０：１５：５であり、飽和炭化水素基と不飽和炭化水素基との総重量比は６０：４０であった。
【００６０】
次いで、この柔軟基剤を用いた以外は実施例１と同様にして柔軟仕上剤を得たところ、その柔軟仕上剤はペースト状のものであった。
【００６１】
（比較例５〜７）
従来より使用されているサンフレークＡＥ−３（日華化学（株）製、固体状のアマイド系柔軟基剤）、サンソフロンＫ−２（日華化学（株）製、アマイド系柔軟仕上剤、不揮発分１８重量％の分散液）、サンソフロンＦＤ−３０４（日華化学（株）製、アマイド系柔軟仕上剤、不揮発分１６重量％の分散液）をそれぞれ比較例５〜７の柔軟仕上剤として用いた。
【００６２】
【表１】

【００６３】
【表２】

【００６４】
（１）水への希釈性評価
常温の水、４０℃の湯、及び７０℃の湯に対し、実施例１〜５及び比較例１〜５で得られた柔軟仕上剤をそれぞれ、１重量％、５重量％、１０重量％となるように添加し、撹拌速度約６０ｒｐｍで撹拌しながら、水への希釈性を目視にて下記の３段階に評価した。得られた結果を表３に示す。
◎：５分以内に乳化分散する、
○：５〜１０分で乳化分散する、
△：１０〜３０分で乳化分散する、
×：３０分経過しても乳化分散しない。
【００６５】
【表３】

【００６６】
表３に示した結果から明らかなように、実施例１〜５の柔軟仕上剤はいずれも、常温の水、４０℃の湯、及び７０℃の湯に対して水への希釈性が良好であって、容易に乳化分散させることができるものであった。したがって、本発明の柔軟仕上剤は、広い温度範囲において水への希釈性に優れ、作業性が良好であることが確認された。
【００６７】
また、本発明の柔軟仕上剤の水への希釈性は、柔軟基剤中の飽和炭化水素基と不飽和炭化水素基との総重量比、及び、（Ａ）成分：（Ｂ）成分：（Ｃ）成分の重量比に大きく影響されることが確認された。
【００６８】
（２）柔軟処理布の評価
供試布の準備
供試布１；綿ニット天竺（蛍光処理済み）をそのまま柔軟処理に用いた。
【００６９】
供試布２；綿ニット（綿１００％）を、反応染料（Ｄｉａｍｉｒａ Ｔｕｒｑ． Ｂｌｕｅ Ｂ、三菱化成（株））４％ｏ．ｗ．ｆ．、浴比１：２０の染色浴中で、６０℃で３０分間染色した後、水洗し、次いで９５℃で２０分間湯洗し、さらに水洗した。水洗後、ネオフィックスＲ−８００（日華化学（株）、フィックス剤）２％ｏ．ｗ．ｆ．、浴比１：２０の浴中で、５０℃で２０分間フィックス処理した後水洗し、次いで脱水及び乾燥により得られた布を柔軟処理に用いた。
【００７０】
柔軟処理
上記の供試布１及び２を、それぞれ、柔軟処理浴に４０℃で１０分間浸漬した後、遠心脱水機にてピックアップ１００％となるよう脱水し、１０５℃で５分間乾燥させ、柔軟処理布１及び２を得た。
【００７１】
なお、柔軟処理浴は、実施例１〜５及び比較例１〜７で得られた柔軟仕上剤をそれぞれ０．５％ｏ．ｗ．ｆ．（比較例６、７の柔軟仕上剤の場合は５％ｏ．ｗ．ｆ．）とし、浴比は１：２０とした。得られた柔軟処理布１及び２について、以下のようにして風合、吸水性、白度及び色相変化を評価した。得られた結果を表４に示す。なお、表４において、ブランクの欄には供試布１及び２の値を示す。
【００７２】
（２−１）風合
触感により柔軟処理布１及び２の風合を以下の５段階に評価した。数値が小さいほど粗硬であり、数値が大きくなるほど柔軟性が良好である。
【００７３】
１：強つきがある（粗硬）、
２：やや強つきがある、
３：やや柔軟である（中庸）、
４：かなり柔軟である、
５：非常にソフトな感触があり、柔軟性に優れる。
【００７４】
（２−２）吸水性
ＪＩＳ Ｌ １９０７（滴下法）に準じ、柔軟処理布１及び２に水滴を１滴滴下し、水滴が完全に消失するまでの時間（秒）を測定した。
【００７５】
（２−３）白度
積分球形光束計スペクトロフォトメーター（ＣＭ−３７００ｄ、ミノルタ製）を使用し、柔軟処理布１の白度を測定した。
【００７６】
（２−４）色相変化
積分球形光束計スペクトロフォトメーター（ＣＭ−３７００ｄ、ミノルタ製）を使用し、柔軟処理布２の色相変化（ΔＥ値）を測定した。
【００７７】
【表４】

【００７８】
表４に示した結果から明らかなように、比較例２の柔軟仕上剤は水への希釈性は良好であるものの、実施例１〜５の柔軟仕上剤と比較して白度の低下が大きく、繊維製品の黄変の問題が生じることが確認された。
【００７９】
また、実施例１〜５の柔軟仕上剤は、繊維に良好な柔軟性を付与するだけでなく、従来のアマイド系柔軟基剤を含有するカチオン系柔軟仕上剤（比較例５〜７）に比べ、吸水性阻害が少ないことが確認された。
【００８０】
さらに、柔軟処理布２、すなわち、染色後にフィックス処理させた供試布２を柔軟処理した場合でも、実施例１〜５の柔軟仕上剤を用いた場合は吸水性が優れており、撥水傾向にあるフィックス処理に対しても積極的に吸水性を付与する効果を有することが確認された。このことは、本発明の柔軟基剤自身も液状であること、柔軟基剤中の不飽和炭化水素基の重量比率が高いことから、従来の固体状柔軟基剤に比べて柔軟基剤自身の水への親和性が高いことによるものと推察される。
【００８１】
したがって、本発明の柔軟基剤及び柔軟仕上剤においては、柔軟性、吸水性、作業性（水への希釈性など）の観点から、（Ａ）成分：（Ｂ）成分：（Ｃ）成分の重量比が５０〜９０：８〜３０：２〜２０で、かつ、飽和炭化水素基と不飽和炭化水素基との総重量比が０：１００〜５０：５０となる範囲で前記第１〜第３のアマイド系化合物を含有することが重要であることが確認された。
【００８２】
【発明の効果】
以上説明したように、本発明の柔軟基剤は、柔軟性に優れるだけでなく、従来のアマイド系柔軟基剤では得られなかった吸水性を示し、天然繊維、合成繊維などの繊維の種類を問わず各種繊維素材に幅広く利用することができる。また、本発明の柔軟基剤は、水への溶解性に優れ、高濃度であっても液状を保持するため作業性に優れ、さらに輸送時などにおけるコスト的にも有利なものである。
【００８３】
したがって、本発明によれば、吸水性阻害の発生を十分に防止しつつ各種繊維素材に対して優れた柔軟性を付与し、かつ水への希釈性が良好で作業性に優れ、高濃度であっても液状の柔軟基剤、並びにそれを含有する柔軟仕上剤を提供することが可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a soft base and a soft finish, and more particularly to a soft base and a soft finish mainly composed of an amide compound.
[0002]
[Prior art]
Conventionally, as a softener for textile products, a cationic system mainly composed of an amide type soft base and a quaternary ammonium salt type soft base; anionic surfactants (for example, sulfoalkyl succinate monoalkyl ester, dialkyl sulfosuccinate) Many nonionic soft finishes based on fatty acid esters of polyhydric alcohols (for example, glycerin, sorbitan, etc.) are known.
[0003]
In general, anionic and nonionic soft finishes exhibit relatively good flexibility with respect to natural fibers, but in fact have little effect on synthetic fibers. On the other hand, cationic softeners are described in JP-A-6-228865, JP-A-11-81137, JP-A-11-350348, and the like, and almost all of them are natural fibers and synthetic fibers. However, these conventional cationic softeners tend to reduce the water absorption of textile products, and there is a demand for water absorption such as underwear. However, it is not yet sufficient as a softening agent in certain fields.
[0004]
Liquid soft finishes are generally supplied as emulsions containing 10 to 20% by weight of the soft base as described above. Recently, cost reduction during production and transportation, and consumer use. From the standpoint of properties and the like, there is an increasing demand for a high-concentration soft finish with a high soft base content. However, the high-concentration type soft finish using the above-mentioned conventional cationic soft base tends to be highly viscous or solid due to the high concentration of the soft base. There is a problem that workability such as dilution may be significantly reduced.
[0005]
Therefore, not only gives excellent flexibility to various fiber materials, but also has less water absorption inhibition than conventional cationic flexible bases, and has good dilutability in water and workability. The development of a liquid soft base and a soft finish containing the same is desired.
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned problems of the prior art, imparts excellent flexibility to various fiber materials while sufficiently preventing the occurrence of water absorption inhibition, and is dilutable in water. It is an object of the present invention to provide a liquid soft base and a soft finish containing the same, even when the concentration is high.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that as an amide compound obtained from a higher fatty acid and an amine, a linear amide compound, a cyclic amide compound, and a condensation amide compound Each compound is compounded at a specific ratio, and the ratio of unsaturated hydrocarbon groups in the compound is not less than a specific ratio, thereby providing excellent flexibility to various fiber materials and inhibiting water absorption. It was found that a soft base capable of sufficiently preventing generation was obtained, and further, a soft finish containing the soft base was found to be liquid even at a high concentration and excellent in workability such as dilutability in water. It came to complete.
[0008]
That is, the soft base of the present invention comprises (A) at least one first amide compound selected from the group consisting of a compound represented by the following general formula [1] and an organic acid salt thereof, (B) At least one second amide compound selected from the group consisting of a compound represented by the following general formula [2] and an organic acid salt thereof, and (C) a compound represented by the following general formula [3] And at least one third amide compound selected from the group consisting of organic acid salts thereof and a weight ratio of (A) :( B) :( C) = 50 to 90: 8 to 30: 2 to 20 And the total weight ratio of saturated hydrocarbon groups to unsaturated hydrocarbon groups in the first to third amide compounds is 0: 100 to 50:50. is there.
[0009]
[Chemical formula 2]

(Where Z¹, Z², Z^Three, Z^FourMay be the same or different and each represents a hydroxyl group or the following formula [4]:
[0010]
-NHCOR^Five                              [4]
R represents a group represented by¹, R², R^Three, R^Four, R^FiveMay be the same or different and each represents a saturated or unsaturated hydrocarbon group having 11 to 23 carbon atoms which may have a hydroxyl group, a, b, c, d, e, f, g, h May be the same or different and each is 2 or 3. )
[0011]
The soft finish of the present invention contains 10 to 90% by weight of the soft base of the present invention.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
First, the flexible base of the present invention will be described. The soft base of the present invention has the following three types as amide compounds obtained from higher fatty acids and amines:
(A) at least one first amide compound selected from the group consisting of a compound represented by the following general formula [1] and an organic acid salt thereof (cyclic type amide compound);
(B) at least one second amide compound selected from the group consisting of a compound represented by the following general formula [2] and an organic acid salt thereof (condensation type amide compound); and
(C) at least one third amide compound selected from the group consisting of a compound represented by the following general formula [3] and an organic acid salt thereof (linear amide compound);
It contains.
[0013]
[Chemical 3]

In the general formulas [1], [2] and [3], Z¹, Z², Z^Three, Z^FourMay be the same or different and each represents a hydroxyl group or the following formula [4]:
[0014]
-NHCOR^Five                              [4]
Represents a group represented by In the general formulas [1], [2], [3] and [4], R¹, R², R^Three, R^Four, R^FiveMay be the same or different and each represents a saturated or unsaturated hydrocarbon group having 11 to 23 carbon atoms which may have a hydroxyl group. If the number of carbon atoms of the hydrocarbon group is less than 11, the flexibility is low and insufficient. On the other hand, if it exceeds 23, it becomes difficult to liquefy the soft finish and the dilutability in water may be significantly reduced. Such a saturated or unsaturated hydrocarbon group preferably has 15 to 21 carbon atoms, and these hydrocarbon chains may be linear or branched.
[0015]
In the general formulas [1], [2] and [3], a, b, c, d, e, f, g and h may be the same or different, and each is 2 or 3, Is particularly preferably 2. If these values are less than 2, it is difficult to obtain a cyclic type amide compound represented by the general formula [1]. On the other hand, if it exceeds 3, it becomes difficult to liquefy the soft finish and the dilutability to water is low. May decrease.
[0016]
In the present invention, it is preferable to use organic acid salts of the compounds represented by the general formulas [1], [2], and [3] because the dilutability of the resulting soft base tends to be further improved. Examples of such organic acids include, but are not limited to, for example, formic acid, acetic acid, lactic acid, malic acid, paratoluenesulfonic acid, glycolic acid, citric acid, and maleic acid, and formic acid, acetic acid, and lactic acid are more preferable. Acetic acid is particularly preferred.
[0017]
The flexible base of the present invention includes the first amide compound (cyclic type amide compound) as the component (A) and the second amide compound (condensation type amide compound) as the component (B). ) And (C) the third amide compound (linear amide compound), the weight ratio of (A) :( B) :( C) is 50 to 90: 8 to 30: 2 It contains in the range used as 20. When the weight ratio of the component (A) is less than 50, it is difficult to liquefy the soft finish. On the other hand, when it exceeds 90, not only does the flexibility deteriorate and the texture of the fiber product deteriorates, but also the whiteness decreases. Concerned. On the other hand, when the weight ratio of the component (B) is less than 8, the decrease in whiteness and hue of the fiber product is increased. Furthermore, if the weight ratio of the component (C) is less than 2, the dilutability in water may be reduced, and if it exceeds 20, the decrease in whiteness and the change in hue of the fiber product will increase.
[0018]
Furthermore, in the soft base of the present invention, the total weight ratio of the saturated hydrocarbon group and the unsaturated hydrocarbon group in the first to third amide compounds is 0: 100 to 50:50, : 100 to 30:70 is preferable, and 0: 100 to 10:90 is more preferable. Here, the saturated hydrocarbon group and the unsaturated hydrocarbon group in the first to third amide compounds are R in the general formulas [1], [2] and [3].¹, R², R^ThreeAnd R^FourAnd Z in the general formulas [1], [2] and [3]¹, Z², Z^ThreeAnd Z^FourIs the following formula [4]:
[0019]
-NHCOR^Five                              [4]
In the case of a group represented by^FiveThe group represented by these. When the weight ratio of the saturated hydrocarbon group exceeds 50, it becomes difficult to liquefy the soft finish and not only the dilutability in water decreases, but also the water absorption inhibition increases.
[0020]
As described above, in the flexible base of the present invention, a linear amide compound, a cyclic amide compound, and a condensation amide compound are combined as an amide compound obtained from a specific higher fatty acid and an amine. Are used so that each weight ratio {(A) :( B) :( C)} is a specific ratio, and the ratio of the unsaturated hydrocarbon groups therein is a specific ratio or more. Therefore, it provides excellent flexibility to various fiber materials, can sufficiently prevent the occurrence of water absorption inhibition, and is excellent in workability such as being liquid even at high concentrations and diluting into water. It is what has.
[0021]
Next, the manufacturing method of the soft base of this invention is described.
[0022]
Any of the compounds represented by the above general formulas [1], [2] and [3] can be produced by a conventionally known method from a higher fatty acid and an amine. The higher fatty acid used in the present invention is a saturated or unsaturated fatty acid having 12 to 24 carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, arachidic acid, behenic acid, etc. Unsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid, etc. Among these, those having 16 to 22 carbon atoms are more preferred. These higher fatty acids may be used alone or in combination of two or more.
[0023]
Examples of the amine used in the present invention include diethylenetriamine, di (3-aminopropyl) amine, N- (3-aminopropyl) ethylenediamine, N- (2-aminoethyl) ethanolamine, and the like. Is particularly preferred. These amines may be used alone or in combination of two or more.
[0024]
The compound represented by the general formula [3] can be obtained by, for example, reacting the higher fatty acid and amine with an amide reaction at a temperature of 140 to 190 ° C. (preferably 150 to 170 ° C.) for 1 to 6 hours. It can be obtained in a yield of ˜95%. Depending on the temperature and reaction time, a compound represented by the general formula [1] is produced as a by-product. Moreover, it is preferable that the ratio of the amine and the higher fatty acid in the amidation reaction is such that the carboxyl group is 0.9 to 1.1 equivalents relative to 1 equivalent of the amino group.
[0025]
In addition, the compound represented by the general formula [1] is, for example, after the above higher fatty acid and amine are subjected to an amide reaction in the same manner as described above, and further 180 to 260 ° C (preferably 220 to 250 ° C). ) For 1 to 5 hours. The progress of the amidation reaction and the cyclization reaction can be monitored by measuring the total amine value and the tertiary amine value. In addition, the compound represented by General formula [3] arises as a by-product.
[0026]
Furthermore, the compound represented by the general formula [2] is, for example, an amide reaction of the higher fatty acid and amine at 140 to 190 ° C. (preferably 150 to 170 ° C.) for 1 to 6 hours, Further, it can be obtained by a condensation reaction with urea. The condensation reaction is preferably 150 to 200 ° C., more preferably 160 to 180 ° C., and the reaction is preferably allowed to proceed for 30 minutes to 5 hours. The amount of urea used is suitably 0.1 to 0.5 mol per 1 mol of the compound represented by the general formula [3] obtained by the amide reaction.
[0027]
In the present invention, the compounds represented by the above general formulas [1], [2] and [3] can be synthesized by the above production methods and blended to obtain a flexible base. And in the soft base of this invention, it is preferable to neutralize using the said organic acid after manufacture of a compound represented by the said general formula [1], [2] and [3], or after mix | blending. . Thus, there is no particular limitation on the amount of the organic acid added when neutralizing the compounds represented by the general formulas [1], [2] and [3], but the pH of the resulting soft finish is the neutral point. It is preferable to be on the acidic side. In addition, even if it adds organic acid excessively, the performance of the soft base obtained is not inhibited.
[0028]
In the present invention, for the purpose of simplifying the production process and reducing the production cost, the above higher fatty acid and amine are first subjected to an amide reaction as described above, followed by a cyclization reaction, and further condensed with urea. A flexible base containing the compounds represented by the above general formulas [1], [2] and [3] can also be obtained by a continuous three-stage reaction of reacting.
[0029]
Next, the soft finish of the present invention will be described. The soft finish of the present invention contains the soft base of the present invention, and the content of the soft base can be arbitrarily adjusted from a low concentration to a high concentration in the liquid state. It is preferable to contain 10 to 90% by weight of the base. If the content of the soft base is less than 10% by weight, the cost during production and transportation tends to increase and the usability for consumers tends to decrease. On the other hand, if the content exceeds 90% by weight, it is highly viscous or solid. This tends to reduce the dilutability in water.
[0030]
Examples of the solvent used in the softener of the present invention include various nonionic active agents such as alkylene oxide adducts of higher alcohols having 12 to 18 carbon atoms and polyoxyethylene sorbitan fatty acid esters; ethylene glycol, polyethylene glycol, propylene glycol Polyhydric alcohols such as glycerin and sorbitol; alcohols such as ethanol and isopropyl alcohol, water, and mixtures thereof are suitable.
[0031]
In the soft finish of the present invention, in addition to the above-mentioned solvents, known components conventionally used in soft finishes can be blended within a range that does not impair the effects of the present invention. Examples of such components include fatty acid esters of polyhydric alcohols such as glycerin, sorbitan, pentaerythritol, polyethylene glycol, and polyalkylene glycol; anionic surfactants (for example, sulfosuccinic acid monoalkyl esters and sulfosuccinic acid dialkyl esters) Quaternary ammonium salts (alkyltrimethylammonium chloride, alkyltrimethylammonium methylsulfonic acid, etc.); nonionic surfactants such as higher alkylamines having 12 to 18 carbon atoms or alkylene oxide adducts of higher fatty acids (eg, poly Oxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurylamine, polyoxyethylene stearylamine); amino-modified silicone Dimethyl-modified silicone, silicone-based compounds such as epoxy-modified silicone: sodium chloride, water-soluble inorganic salts such as calcium chloride; paraffinic hydrocarbons, cellulosics, and antioxidants.
[0032]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited at all by these Examples.
[0033]
Examples 1-5 and Comparative Examples 1-7
First, the softening base shown in the following Examples 1-5 and Comparative Examples 1-7 and the softening finishing agent using the same were prepared, and using the resulting softening finishing agent, the following (1) to water Dilution evaluation and (2) evaluation of the soft cloth (texture, water absorption, whiteness, hue change) were performed. In addition, the weight ratio of (A) component: (B) component: (C) component in the soft bases obtained in Examples 1-5 and Comparative Examples 1-4 is the total amine value and the tertiary amine value. Based on the calculation. In addition, Tables 1 and 2 show compositions of the soft base and the soft finish obtained in Examples 1 to 5 and Comparative Examples 1 to 4. In Tables 1 and 2, the “saturation: unsaturation” column of the flexible base indicates the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups.
[0034]
Example 1
564 g of oleic acid was charged into a 1 L four-necked flask and heated to 100 ° C., and 103 g of diethylenetriamine was added. The resulting mixture was heated to 160 ° C., dehydrated (amidation reaction) for 1 hour, then heated to 240 to 250 ° C., and then subjected to imidazoline reaction (cyclization reaction) for 2 hours. After the completion of the reaction, the reaction solution was cooled to 120 ° C., 30 g of urea was added, the temperature was raised to 170 to 180 ° C., and a condensation reaction was performed for 3 hours. Subsequently, the reaction solution was cooled to 90 ° C. or lower and then neutralized with about 90 g of acetic acid to obtain 720 g of a viscous liquid base.
[0035]
The components (A), (B), and (C) in the obtained soft base are Z in the general formulas [1], [2], and [3], respectively.¹~ Z^Four-NHCOR^Five, R¹~ R^FiveAre the oleic acid residues (8-heptadecenyl group) and a to h are 2, and the acetates of the first to third amide compounds. In this flexible base, the weight ratio of (A) :( B) :( C) is 80: 15: 5, and the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups is 0: 100. there were.
[0036]
Next, 80 g of this flexible base was mixed with 5 g of diethylene glycol, 10 g of softanol 120 (Nippon Catalyst Co., Ltd., 12 mol of ethylene oxide 12 mol adduct of alcohol having 12 to 14 carbon atoms) and 5 g of water until uniform. When a soft finish was obtained, the soft finish was a viscous liquid.
[0037]
(Example 2)
A 1 L four-necked flask was charged with 508 g of oleic acid and 57 g of stearic acid, heated to 100 ° C., and 103 g of diethylenetriamine was added. The resulting mixture was heated to 160 ° C. and then subjected to dehydration reaction for 1 hour, and then heated to 240 to 250 ° C. and then subjected to imidazolination reaction for 2 hours. After the completion of the reaction, the reaction solution was cooled to 120 ° C., 30 g of urea was added, the temperature was raised to 170 to 180 ° C., and a condensation reaction was performed for 3 hours. Subsequently, the reaction solution was cooled to 90 ° C. or lower and then neutralized with about 90 g of acetic acid to obtain about 721 g of a viscous liquid base.
[0038]
The components (A), (B), and (C) in the obtained soft base are Z in the general formulas [1], [2], and [3], respectively.¹~ Z^Four-NHCOR^Five, R¹~ R^FiveAre the oleic acid residues (8-heptadecenyl group) or stearic acid residues (heptadecyl group), and the acetates of the first to third amide compounds in which a to h are 2. In this flexible base, the weight ratio of (A) :( B) :( C) is 80: 15: 5, and the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups is 10:90. there were.
[0039]
Next, when a soft finish was obtained in the same manner as in Example 1 except that this soft base was used, the soft finish was a viscous liquid.
[0040]
(Example 3)
After charging 560 g of linoleic acid into a 1 L four-necked flask and raising the temperature to 100 ° C., 103 g of diethylenetriamine was added. The resulting mixture was heated to 160 ° C. and then subjected to dehydration reaction for 1 hour, and then heated to 240 to 250 ° C. and then subjected to imidazolination reaction for 2 hours. After the completion of the reaction, the reaction solution was cooled to 120 ° C., 30 g of urea was added, the temperature was raised to 170 to 180 ° C., and a condensation reaction was performed for 3 hours. Subsequently, the reaction solution was cooled to 90 ° C. or lower and then neutralized with about 90 g of acetic acid to obtain 716 g of a viscous liquid base.
[0041]
The components (A), (B), and (C) in the obtained soft base are Z in the general formulas [1], [2], and [3], respectively.¹~ Z^Four-NHCOR^Five, R¹~ R^FiveIs the linoleic acid residue (8,11-heptadecadienyl group), and the acetates of the first to third amide compounds in which a to h are 2. In this flexible base, the weight ratio of (A) :( B) :( C) is 80: 15: 5, and the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups is 0: 100. there were.
[0042]
Next, when a soft finish was obtained in the same manner as in Example 1 except that this soft base was used, the soft finish was a viscous liquid.
[0043]
(Example 4)
A 1 L four-necked flask was charged with 282 g of oleic acid and 338 g of erucic acid, heated to 100 ° C., and 103 g of diethylenetriamine was added. The resulting mixture was heated to 160 ° C. and then subjected to dehydration reaction for 1 hour, and then heated to 240 to 250 ° C. and then subjected to imidazolination reaction for 2 hours. After the completion of the reaction, the reaction solution was cooled to 120 ° C., 30 g of urea was added, the temperature was raised to 170 to 180 ° C., and a condensation reaction was performed for 3 hours. Subsequently, the reaction solution was cooled to 90 ° C. or lower and neutralized with about 100 g of acetic acid to obtain 786 g of a paste-like flexible base at room temperature.
[0044]
The components (A), (B), and (C) in the obtained soft base are Z in the general formulas [1], [2], and [3], respectively.¹~ Z^Four-NHCOR^Five, R¹~ R^FiveAre oleic acid residues (8-heptadecenyl group) or erucic acid residues (12-heneicosenyl group), and a to h are acetates of the first to third amide compounds. In this flexible base, the weight ratio of (A) :( B) :( C) is 80: 15: 5, and the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups is 0: 100. there were.
[0045]
Next, when a soft finish was obtained in the same manner as in Example 1 except that this soft base was used, the soft finish was a viscous liquid.
[0046]
(Example 5)
A 1 L four-necked flask was charged with 338 g of oleic acid and 171 g of lauric acid, heated to 100 ° C., and 103 g of diethylenetriamine was added. The resulting mixture was heated to 160 ° C. and then subjected to dehydration reaction for 1 hour, and then heated to 240 to 250 ° C. and then subjected to imidazolination reaction for 2 hours. After the completion of the reaction, the reaction solution was cooled to 120 ° C., 30 g of urea was added, the temperature was raised to 170 to 180 ° C., and a condensation reaction was performed for 3 hours. Subsequently, the reaction solution was cooled to 90 ° C. or lower and neutralized with about 100 g of acetic acid to obtain 786 g of a soft solid soft base at room temperature.
[0047]
The components (A), (B), and (C) in the obtained soft base are Z in the general formulas [1], [2], and [3], respectively.¹~ Z^Four-NHCOR^Five, R¹~ R^FiveAre oleic acid residues (8-heptadecenyl group) or lauric acid residues (undecyl groups), and acetates of the first to third amide compounds in which a to h are 2. And the weight ratio of (A) :( B) :( C) in this flexible base is 80: 15: 5, and the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups is 32:68. there were.
[0048]
Next, when a soft finish was obtained in the same manner as in Example 1 except that this soft base was used, the soft finish was a viscous liquid.
[0049]
(Comparative Example 1)
568 g of stearic acid was charged into a 1 L four-necked flask, heated to 100 ° C., and 103 g of diethylenetriamine was added. The resulting mixture was heated to 160 ° C. and then subjected to dehydration reaction for 1 hour, and then heated to 240 to 250 ° C. and then subjected to imidazolination reaction for 2 hours. After the completion of the reaction, the reaction solution was cooled to 120 ° C., 30 g of urea was added, the temperature was raised to 170 to 180 ° C., and a condensation reaction was performed for 3 hours. Subsequently, the reaction solution was cooled to 90 ° C. or lower and then neutralized with about 90 g of acetic acid to obtain 724 g of a flexible base. This soft base was viscous at 70-80 ° C. and became solid at room temperature.
[0050]
The components (A), (B), and (C) in the obtained soft base are Z in the general formulas [1], [2], and [3], respectively.¹~ Z^Four-NHCOR^Five, R¹~ R^FiveIs an acetate of the first to third amide compounds in which stearic acid residues (heptadecyl group) and a to h are 2. In this flexible base, the weight ratio of (A) :( B) :( C) is 80: 15: 5, and the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups is 100: 0. there were.
[0051]
Next, when a soft finish was obtained in the same manner as in Example 1 except that this soft base was used, the soft finish was a paste.
[0052]
(Comparative Example 2)
564 g of oleic acid was charged into a 1 L four-necked flask and heated to 100 ° C., and 103 g of diethylenetriamine was added. The resulting mixture was heated to 160 ° C. and then subjected to dehydration reaction for 1 hour, then heated to 240 to 250 ° C. and then subjected to imidazolination reaction for 2 hours. After completion of the reaction, the reaction solution was cooled to 90 ° C. or lower and then neutralized with about 90 parts by weight of acetic acid to obtain 707 g of a viscous soft base.
[0053]
The components (A) and (C) in the obtained soft base are Z in the general formulas [1] and [3], respectively.¹, Z^Four-NHCOR^Five, R¹, R^Four, R^FiveAre acetates of the first and third amide compounds in which oleic acid residue (8-heptadecenyl group) and a, b, g, and h are 2. And the weight ratio of (A) :( B) :( C) in this flexible base is 80: 0: 20, and the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups is 0: 100. there were.
[0054]
Next, when a soft finish was obtained in the same manner as in Example 1 except that this soft base was used, the soft finish was a viscous liquid.
[0055]
(Comparative Example 3)
564 g of oleic acid was charged into a 1 L four-necked flask and heated to 100 ° C., and 103 g of diethylenetriamine was added. The obtained mixture was heated to 160 ° C. and then subjected to dehydration reaction for 1 hour, and then heated to 190 to 200 ° C. and then subjected to imidazolination reaction for 2 hours. After the completion of the reaction, the reaction solution was cooled to 120 ° C., 30 g of urea was added, the temperature was raised to 170 to 180 ° C., and a condensation reaction was performed for 3 hours. Subsequently, the reaction solution was cooled to 90 ° C. or less and then neutralized with about 90 g of acetic acid to obtain 729 g of a viscous liquid base.
[0056]
The components (A), (B), and (C) in the obtained soft base are Z in the general formulas [1], [2], and [3], respectively.¹~ Z^Four-NHCOR^Five, R¹~ R^FiveAre the oleic acid residues (8-heptadecenyl group) and a to h are 2, and the acetates of the first to third amide compounds. And the weight ratio of (A) :( B) :( C) in this flexible base is 30: 65: 5, and the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups is 0: 100. there were.
[0057]
Next, when a soft finish was obtained in the same manner as in Example 1 except that this soft base was used, the soft finish was a viscous liquid.
[0058]
(Comparative Example 4)
A 1 L four-necked flask was charged with 227 g of oleic acid and 338 g of stearic acid, heated to 100 ° C., and 103 g of diethylenetriamine was added. The resulting mixture was heated to 160 ° C. and then subjected to dehydration reaction for 1 hour, then heated to 240 to 250 ° C. and then subjected to imidazolination reaction for 2 hours. After the completion of the reaction, the reaction solution was cooled to 120 ° C., 30 g of urea was added, the temperature was raised to 170 to 180 ° C., and a condensation reaction was performed for 3 hours. Subsequently, the reaction solution was cooled to 90 ° C. or lower and then neutralized with about 90 g of acetic acid to obtain 721 g of a flexible base. This soft base was a viscous liquid at 70 to 80 ° C. and became a soft solid at room temperature.
[0059]
The components (A), (B), and (C) in the obtained soft base are Z in the general formulas [1], [2], and [3], respectively.¹~ Z^Four-NHCOR^Five, R¹~ R^FiveAre the oleic acid residues (8-heptadecenyl group) or stearic acid residues (heptadecyl group), and the acetates of the first to third amide compounds in which a to h are 2. And the weight ratio of (A) :( B) :( C) in this flexible base is 80: 15: 5, and the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups is 60:40. there were.
[0060]
Next, when a soft finish was obtained in the same manner as in Example 1 except that this soft base was used, the soft finish was a paste.
[0061]
(Comparative Examples 5-7)
Conventionally used Sunflakes AE-3 (manufactured by Nikka Chemical Co., Ltd., solid amide soft base), Sansoflon K-2 (manufactured by Nikka Chemical Co., Ltd., amide softener, non-volatile) 18% by weight dispersion), Sansoflon FD-304 (manufactured by Nikka Chemical Co., Ltd., amide-based soft finish, non-volatile content 16% by weight dispersion) are used as the soft finishes of Comparative Examples 5-7, respectively. It was.
[0062]
[Table 1]

[0063]
[Table 2]

[0064]
(1) Dilutability evaluation in water
The softening agents obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were 1% by weight, 5% by weight, and 10% by weight, respectively, with respect to normal temperature water, 40 ° C. hot water, and 70 ° C. While being stirred at a stirring speed of about 60 rpm, the dilutability in water was visually evaluated in the following three stages. The obtained results are shown in Table 3.
A: Emulsified and dispersed within 5 minutes.
○: Emulsified and dispersed in 5 to 10 minutes.
Δ: Emulsified and dispersed in 10 to 30 minutes.
X: It does not emulsify and disperse even after 30 minutes.
[0065]
[Table 3]

[0066]
As is apparent from the results shown in Table 3, all of the softeners of Examples 1 to 5 have good dilutability in water with respect to normal temperature water, 40 ° C hot water, and 70 ° C hot water. Therefore, it can be easily emulsified and dispersed. Therefore, it was confirmed that the softener of the present invention was excellent in dilutability in water over a wide temperature range and had good workability.
[0067]
Further, the dilutability of the soft finish of the present invention into water is determined by the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups in the soft base, and (A) component: (B) component: ( It was confirmed that the weight ratio of component C) was greatly affected.
[0068]
(2) Evaluation of flexible treatment cloth
Preparation of test cloth
Specimen 1: Cotton knit sheeting (fluorescence treated) was used as it was for softening treatment.
[0069]
Test cloth 2: Cotton knit (cotton 100%) was reacted with reactive dye (Diamira Turq. Blue B, Mitsubishi Kasei Co., Ltd.) 4% o. w. f. After dyeing at 60 ° C. for 30 minutes in a dyeing bath having a bath ratio of 1:20, washing was performed with water, followed by washing with hot water at 95 ° C. for 20 minutes, and further with water. After washing with water, Neofix R-800 (Nikka Chemical Co., Ltd., fixative) 2% o. w. f. In a bath having a bath ratio of 1:20, a fixed treatment was performed at 50 ° C. for 20 minutes, followed by washing with water, and then a cloth obtained by dehydration and drying was used for the softening treatment.
[0070]
Flexible processing
Each of the above test cloths 1 and 2 is immersed in a softening treatment bath at 40 ° C. for 10 minutes, then dehydrated to 100% pick-up with a centrifugal dehydrator, dried at 105 ° C. for 5 minutes, and the softening treatment cloth. 1 and 2 were obtained.
[0071]
In addition, the softening treatment bath was prepared by applying 0.5% o. w. f. (In the case of the softeners of Comparative Examples 6 and 7, 5% owf.), And the bath ratio was 1:20. About the obtained flexible treatment cloths 1 and 2, texture, water absorption, whiteness, and hue change were evaluated as follows. Table 4 shows the obtained results. In Table 4, blank values indicate the values of the test cloths 1 and 2.
[0072]
(2-1) Feel
The texture of the flexible fabrics 1 and 2 was evaluated according to the following five levels. The smaller the numerical value, the harder the hardness, and the larger the numerical value, the better the flexibility.
[0073]
1: Strong (coarse),
2: Slightly strong,
3: Slightly flexible (moderate),
4: Pretty flexible,
5: Very soft feel and excellent flexibility.
[0074]
(2-2) Water absorption
In accordance with JIS L 1907 (drop method), one drop of water was dropped on the flexible treatment cloths 1 and 2, and the time (seconds) until the water drop completely disappeared was measured.
[0075]
(2-3) Whiteness
The whiteness of the flexible treatment cloth 1 was measured using an integrating sphere photometer spectrophotometer (CM-3700d, manufactured by Minolta).
[0076]
(2-4) Hue change
Using an integrating sphere photometer spectrophotometer (CM-3700d, manufactured by Minolta), the hue change (ΔE value) of the flexible fabric 2 was measured.
[0077]
[Table 4]

[0078]
As is clear from the results shown in Table 4, although the soft finish of Comparative Example 2 has good dilutability in water, the decrease in whiteness is large compared to the soft finishes of Examples 1 to 5. It was confirmed that the problem of yellowing of the textile products occurred.
[0079]
In addition, the soft finishes of Examples 1 to 5 not only give good flexibility to the fibers, but also compared to a cationic soft finish (Comparative Examples 5 to 7) containing a conventional amide soft base. It was confirmed that there was little water absorption inhibition.
[0080]
Furthermore, even when the softened fabric 2, that is, the test fabric 2 that has been fixed after dyeing, is softened, when the soft finishes of Examples 1 to 5 are used, the water absorption is excellent and the water repellent tendency It was confirmed that it has an effect of positively imparting water absorption even to the fix treatment in the above. This is because the soft base of the present invention is also liquid and the weight ratio of unsaturated hydrocarbon groups in the soft base is high, so that the soft base itself has a higher proportion than the conventional solid soft base. This is probably due to the high affinity for water.
[0081]
Therefore, in the soft base and soft finish of the present invention, from the viewpoint of flexibility, water absorption, workability (such as dilutability in water), (A) component: (B) component: (C) component In the range where the weight ratio is 50 to 90: 8 to 30: 2 to 20 and the total weight ratio of the saturated hydrocarbon group and the unsaturated hydrocarbon group is 0: 100 to 50:50, It was confirmed that it was important to contain 3 amide compounds.
[0082]
【The invention's effect】
As described above, the flexible base of the present invention not only has excellent flexibility, but also exhibits water absorption that cannot be obtained with conventional amide-based flexible bases. It can be used widely for various fiber materials regardless. Further, the flexible base of the present invention is excellent in solubility in water, is excellent in workability because it maintains a liquid state even at a high concentration, and is advantageous in terms of cost during transportation.
[0083]
Therefore, according to the present invention, it is possible to impart excellent flexibility to various fiber materials while sufficiently preventing the occurrence of water absorption inhibition, and has good dilutability in water, excellent workability, and high concentration. Even if it exists, it becomes possible to provide a liquid soft base and a soft finish containing it.

Claims (2)

(A) At least one first amide compound selected from the group consisting of a compound represented by the following general formula [1] and an organic acid salt thereof, (B) represented by the following general formula [2] At least one second amide compound selected from the group consisting of a compound and an organic acid salt thereof, and (C) selected from the group consisting of a compound represented by the following general formula [3] and an organic acid salt thereof Containing at least one third amide compound in a weight ratio of (A) :( B) :( C) = 50 to 90: 8 to 30: 2 to 20; A flexible base (wherein the first to third compounds are characterized in that the total weight ratio of saturated hydrocarbon groups and unsaturated hydrocarbon groups in the third amide compound is 0: 100 to 50:50) The saturated hydrocarbon group and unsaturated hydrocarbon group in the amide compound of [1], ^R 1 in [2] and ^[3], R 2, groups represented by ^{R 3} and ^{R 4,} as well as the following general formula [1], ^Z 1 in [2] and [3], Z ² , when Z ³ and Z ⁴ are a group represented by the following general formula [4], it means a group represented by R ⁵ in the formula ) .

(In the formula, Z ¹ , Z ² , Z ³ and Z ⁴ may be the same or different, and each represents a hydroxyl group or the following formula [4]:
—NHCOR ⁵ [4]
Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and each of them may have a hydroxyl group, a saturated or unsaturated group having 11 to 23 carbon atoms. Represents a saturated hydrocarbon group, and a, b, c, d, e, f, g, and h may be the same or different and each is 2 or 3. )   A softening agent comprising 10 to 90% by weight of the softening base according to claim 1.