JP3847508B2 - Softener composition - Google Patents

Description

【０００９】
【化２】

【００１０】
〔式中、Ｒ¹〜Ｒ⁵及びＸ^-は前述と同一の意味を示し、Ｒ⁶は水素原子又は炭素数１〜１２のアルキル基、もしくは平均縮合度１〜２０のオキシエチレン基である。Ｙは−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−及び−Ｏ−から選ばれる基である。ｌ、ｋは同一でも異なっていてもよい１〜５の数である。〕
本発明では上記化合物の中でも（Ｉ）、（II）、（IV）、（Ｖ）が好ましく、特に（II）又は（Ｖ）が好ましい。
【００１１】
さらに本発明では、Ｒ¹及びＲ²の両方又はいずれか一方が、好ましくはいずれか一方が、エステル基又はアミド基あるいはその両方で分断されている炭素数１４〜２４のアルキル基又はアルケニル基であることが望ましく、特に
Ｒ⁷−ＣＯＺ−Ｒ⁸−、Ｒ⁷−ＺＣＯ−Ｒ⁸−
〔式中、Ｒ⁷は炭素数１３〜１９のアルキル基又はアルケニル基であり、Ｒ⁸は炭素数１〜５、好ましくは１〜３のアルキレン基である。Ｚは−Ｏ−又は−ＮＨ−を示す。〕
から選ばれる基であることが望ましい。
【００１２】
なお、（ａ）成分の化合物のうち３級アミノ基を有する化合物は、柔軟剤組成物に配合する前に酸剤により３級アミノ基を中和したものを用いることもできる。中和のための酸としては塩酸、硫酸、リン酸、脂肪酸が好ましく、特に塩酸、硫酸が好ましい。
【００１３】
（ｂ）成分
本発明の（ｂ）成分である陰イオン界面活性剤としては、アルキルベンゼンスルホン酸、アルキル硫酸、ポリオキシアルキレンアルキルエーテル硫酸、オレフィンスルホン酸、アルカンスルホン酸、飽和又は不飽和脂肪酸、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カルボン酸、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などを挙げることができる。これらの中でも炭素数１０〜３０、好ましくは１２〜２４、特に好ましくは１４〜２４のアルキル基を有するアルキル硫酸、炭素数１０〜３０、好ましくは１２〜２４、特に好ましくは１４〜２４のアルキル基を有し、エチレンオキシド平均付加モル数が１〜６、好ましくは１〜４であるポリオキシエチレンアルキルエーテル硫酸、炭素数８〜１８の飽和又は不飽和脂肪酸及びこれらの塩から選ばれる１種以上を配合することが好ましい。
【００１４】
（ｃ）成分
本発明の（ｃ）である抗菌性化合物とは、木綿金巾＃２００３に該化合物１重量％を均一に付着させた布を用いＪＩＳ Ｌ １９０２「繊維製品の抗菌性試験法」の方法で抗菌性試験を行い阻止帯が見られる化合物である。
【００１５】
（Ｉ）の抗菌性化合物としては炭素数８〜１６のジアルキルジメチル４級アンモニウム塩やモノアルキルトリメチル４級アンモニウム塩等を使用することもできるが、特に下記一般式（２）又は（３）の化合物が好ましい。
【００１６】
【化３】

【００１７】
〔式中、Ｒ²¹及びＲ³¹は炭素数５〜１６、好ましくは７〜１４のアルキル基又はアルケニル基、好ましくはアルキル基であり、Ｒ²³、Ｒ²⁴は炭素数１〜３のアルキル基又はヒドロキシアルキル基である。Ｔは−ＣＯＯ−、ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、
【００１８】
【化４】

【００１９】
である。Ｒ²²、Ｒ²⁵は、炭素数１〜６のアルキレン基又は−(Ｏ−Ｒ²⁶)_n−である。ここでＲ²⁶はエチレン基もしくはプロピレン基、好ましくはエチレン基であり、ｎは１〜１０、好ましくは１〜５の数である。さらにＺ^-は陰イオン基、好ましくはハロゲンイオン、炭素数１〜３のアルキル硫酸イオンである。ｂは０又は１である。〕
本発明の最も好ましい抗菌性４級アンモニウム化合物としては下記のものを挙げることができる。
【００２０】
【化５】

【００２１】
（II）の抗菌性化合物としては特にトリクロサンが好ましい。
【００２２】
（柔軟剤組成物）
本発明の柔軟剤組成物は（ａ）成分を３〜５０重量％、好ましくは３〜４０重量％、特に好ましくは５〜３５重量％含有する。また、（ｂ）成分を０．５〜３０重量％、好ましくは１〜２０重量％、特に好ましくは５〜２０重量％含有する。さらに（ｃ）成分を０．０１〜１０重量％、好ましくは０．１〜８重量％、特には０．１〜５重量％含有する。
【００２３】
また、（ａ）成分と（ｂ）成分の重量比は、（ａ）／（ｂ）＝１０／１〜１／１０、特に５／１〜１／５が風合いを改善する上で望ましく、（ａ）成分と（ｃ）成分の重量比は、防臭効果の点から、（ｃ）／（ａ）＝１／２００〜１／１、特に１／１５０〜１／２が良好である。
【００２４】
本発明の柔軟剤組成物は、上記（ａ）〜（ｃ）成分と水を含有する組成物であり、蒸留水やイオン交換水などの、水に含まれるイオン性物質を除去した水を使用することが望ましい。水は貯蔵安定性の点から４０〜９５重量％、特に５０〜９０重量％含有することが望ましい。
【００２５】
また、本発明の柔軟剤組成物は、２０℃におけるｐＨが１〜５、特に１．５〜４であることが貯蔵安定性の点から好ましい。
【００２６】
（ｄ）成分
本発明では（ｄ）成分として非イオン界面活性剤を配合することが貯蔵安定性の点から好ましい。非イオン界面活性剤としては炭素数８〜２０のアルキル基またはアルケニル基を１つ以上有するポリオキシアルキレンアルキルエーテルが好ましく、特に一般式（４）の非イオン界面活性剤が良好である。
Ｒ⁴¹−Ｔ−[(Ｒ⁴²Ｏ)_p−Ｈ]_q （４）
〔式中、Ｒ⁴¹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、Ｒ⁴²は炭素数２又は３のアルキレン基であり、好ましくはエチレン基である。ｐは平均付加モル数であり、２〜１００、好ましくは５〜４０、特に好ましくは２０〜４０の数を示す。Ｔは−Ｏ−、−Ｎ−又は−ＣＯＮ−であり、Ｔが−Ｏ−の場合はｑは１であり、Ｔが−Ｎ−又は−ＣＯＮ−の場合はｑは２である。〕。
【００２７】
一般式（４）の化合物の具体例として以下の化合物を挙げることができる。
Ｒ⁴¹−Ｏ−(Ｃ₂Ｈ₄Ｏ)_r−Ｈ
〔式中、Ｒ⁴¹は前記と同じ意味であり、ｒは平均付加モル数であり、８〜１００、好ましくは１０〜８０の数である。〕
Ｒ⁴¹−Ｏ−(Ｃ₂Ｈ₄Ｏ)_s(Ｃ₃Ｈ₆Ｏ)_t−Ｈ
〔式中、Ｒ⁴¹は前記と同じ意味であり、ｓ及びｔは平均付加モル数であり、それぞれ独立に２〜４０、好ましくは５〜４０の数であり、エチレンオキシドとプロピレンオキシドはランダムあるいはブロック付加体であってもよい。〕
【００２８】
【化６】

【００２９】
このような非イオン界面活性剤は組成物中に０．５〜１０重量％、好ましくは１〜８重量％配合されることが貯蔵安定性の面から望ましい。
【００３０】
（ｅ）成分
本発明の柔軟剤組成物には、貯蔵安定性をさらに向上させる目的で（ｅ）成分として油成分を配合することが望ましい。油成分としては炭素数８〜２０、好ましくは１０〜１８の脂肪酸と多価アルコールのエステル化合物が好ましく、特にトリグリセライド、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が好ましい。このような油成分は組成物中に０．０５〜１０重量％、特に０．１〜５重量％配合するのが好ましい。
【００３１】
本発明の柔軟剤組成物には、さらに下記式（５）から求められるδが２０〜４０、好ましくは２１〜３５、特に好ましくは２１〜２７の化合物を配合することが貯蔵安定性の点から望ましい。また、分子量が１００〜４００、好ましくは１３０〜３００、特には１５０〜３００であり、沸点が１５０℃以上、好ましくは２００〜３５０℃、特には２４０〜３５０のものが良好である。
δ＝[(１４８２０＋９９．２Ｔｂ＋０．０８４Ｔｂ²)／Ｖ]^1/2 （５）
〔式中、Ｔｂは沸点（°Ｋ）、Ｖは２０℃におけるモル容積である。〕。
【００３２】
ここで本発明のδは溶解度パラメータに近似するものであり「溶液と溶解度」（篠田耕三著、平成３年４月３０日、丸善（株）発行）の７８頁〜８２頁に記載されているものである。
【００３３】
本発明のδ値を満足する化合物として好ましい化合物は、アルキル基の炭素数が３〜８のアルキルグリセリルエーテル、ジ又はトリエチレングルコールモノフェニルエーテル、アルキル基の炭素数が２〜８のジ又はトリエチレングルコールモノアルキルエーテル、１，６−ヘキサンジオール、２，５−ヘキサンジオール、３−ペンタノン、シクロヘキサノール、２−ヘキサノール、１−オクタノールを挙げることができ、これらの中でも特にアルキル基の炭素数が２〜５のアルキルグリセリルエーテル、アルキル基の炭素数が２〜５のジ又はトリエチレングルコールモノアルキルエーテル、トリエチレングリコールモノフェニルエーテルが好ましい。
【００３４】
本発明の柔軟剤組成物には、貯蔵安定性の点から無機塩、例えば塩化カルシウムなどを０〜１０００ｐｐｍ、好ましくは１０〜５００ｐｐｍ添加することが望ましい。但し、脂肪酸塩類など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。
【００３５】
本発明の柔軟剤組成物には、通常柔軟剤組成物に配合されるシリコーン、香料、色素等の成分を配合しても差し支えない。
【００３６】
【実施例】
合成例１
メチルモノエタノールアミンとアクリロニトリルを通常の方法でマイケル付加反応を行わせた反応生成物をステンレス製オートクレーブに仕込み、溶媒としてエタノール、触媒としてラネーニッケルを加えた。オートクレーブ内を窒素置換後、水素で置換し、水素圧１０ｋｇ／ｃｍ²、温度１１０℃で３時間反応を行った。次にアミンに対して２．２モル倍のホルマリン水溶液をオートクレーブに圧入し、さらに５時間反応を継続した。冷却後、得られた反応物を蒸留してＮ−ヒドロキシエチル−Ｎ，Ｎ’，Ｎ’−テトラメチルプロパンジアミンを得た。
【００３７】
次にステアリン酸とＮ−ヒドロキシエチル−Ｎ，Ｎ’，Ｎ’−テトラメチルプロパンジアミンを通常のエステル化方法によりエステル化し、さらにエステル化物をメチルクロリドにより４級化反応を行わせ、下記構造の化合物ａ−１を得た。
【００３８】
【化７】

【００３９】
合成例２
ジメチルエタノールアミンとステアリン酸のエステル化反応生成物及び塩化コリンとモノクロロ酢酸とのエステル化反応生成物を通常の方法で合成した。これら２種の化合物をそれぞれ等モル量エタノールに溶解させ、還流下６時間反応させた。エタノールを減圧留去し通常の方法で精製し、下記構造の化合物ａ−２を得た。
【００４０】
【化８】

【００４１】
合成例３
ステアリン酸とＮ−ヒドロキシエチルエチレンジアミンとの脱水縮合反応を行わせ、これを加水分解し蒸留しすることでＮ−ステアロイル−Ｎ’−ヒドロキシエチルエチレンジアミンを得た。これをエタノールに溶解させ、還流下アミンに対して１．１倍当量のホルマリンを滴下し、続いてさらにアミンに対して１．１倍当量のぎ酸を滴下し５時間熟成した。反応生成物をさらにメチルクロリドにより４級化させることで、Ｎ−ステアロイルアミノエチル−Ｎ−ヒドロキシエチル−Ｎ，Ｎ−ジメチルアンモニウムクロリドを得た。この化合物とジメチルグリシンとを通常のエステル化反応を行わせることで下記構造の化合物ａ−３を得た。
【００４２】
【化９】

【００４３】
合成例４
フラスコに１−クロロアルカン（１５０ｇ、０．５２ｍｏｌ）とＮ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−プロパンジアミン（６８ｇ、０．５３ｍｏｌ）をエタノール（３５０．０ｇ）に混合させた。混合物を７２時間還流させた後、エタノールを減圧下で留去し、未反応のアミン化合物を除去した。得られた固体を、更に、常法に従い、アセトンで再結晶することで下記構造のａ−４〔Ｎ−（３−ジメチルアミノプロピル）−Ｎ−アルキル−Ｎ，Ｎ−ジメチルアンモニウムクロライド（１８０ｇ、純分９５重量％）〕を得た。
【００４４】
【化１０】

【００４５】
合成例５
ステアリルジメチルアミンの塩酸塩（１モル）とエピクロルヒドリン１モルとを５００ｍｌのイソプロパノールに溶解させ、９０℃で１時間反応させた。その後をステアリルジメチルアミン（１モル）を滴下ロートより滴下し、さらに９０℃で６時間攪拌した。冷却後、溶媒を減圧留去し、得られた固形分をアセトンにより再結晶することで下記構造の化合物ａ−５を得た。
【００４６】
【化１１】

【００４７】
実施例
＜柔軟剤組成物＞
上記ａ−１〜ａ−５及び下記の化合物を用いて表１の柔軟剤組成物を調製した。
・ａ’−１：ジオレイルジメチルアンモニウムクロリド
・ｂ−１：ステアリル硫酸エステルナトリウム
・ｂ−２：ポリオキシエチレン（エチレンオキサイド平均付加モル数２．５）ステアリルエーテル硫酸ナトリウム
・ｂ−３：ステアリン酸ナトリウム
【００４８】
【化１２】

【００４９】
・ｃ−４：トリクロサン
・ｄ−１：炭素数１２の飽和アルコールにエチレンオキサイドを平均２１モル付加さたもの
・ｄ−２：ラウリン酸のジエタノールアミドにエチレンオキシドを平均２０モル付加させたもの
・ｅ−１：ステアリン酸モノ、ジ、トリグリセリド混合物（モノ：ジ：トリ＝６０：３５：５）
・ｆ−１：Ｃ₈Ｈ₁₇ＯＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＨ（δ＝２１．９６）
・ｆ−２：トリエチレングリコールモノフェニルエーテル（δ＝２０．９２）
・ｆ−３：１，６−ヘキサンジオール（δ＝２７．２３）
・ｇ−１：塩化カルシウム
・ｇ−２：色素（アシッドブルー９）
・ｇ−３：香料。
【００５０】
＜柔軟処理方法＞
男性用肌着（木綿１００％）２枚及びバスタオル（木綿１００％）２枚を市販の弱アルカリ性洗剤（花王（株）製アタック）を用いて洗濯機で洗浄した（東芝製２槽式洗濯機ＶＨ−３６０Ｓ１、洗剤濃度０．０６６７重量％、水道水３０Ｌ使用、水温２０℃、１０分間）。その後洗浄液を排出し、１分間脱水後、３０Ｌの水道水を注水して５分間すすぎを行い、排水後１分間脱水を行った。その後再度３０Ｌの水道水を注水した後、表１の組成物７ｇを添加し５分間攪拌した。その後、脱水し、湿度７０％、２５℃の恒温室で１２時間乾燥した。
【００５１】
＜風合いの評価＞
上記処理を行ったバスタオルの風合いを１０人のパネラー（３０代男性５人、２０代女性５人）により下記の基準で評価した。これらの平均点を求め、平均点が１未満を○、１以上１．５未満を△、１．５以上を×として評価した。結果を表１に示す。
さっぱりした風合いであり油っぽさが全くない…０
やや油っぽさがあるがさっぱりした風合いがある…１
油っぽい風合いがする…２
非常に油っぽい風合いである…３。
【００５２】
＜防臭効果の評価＞
恒温室で乾燥させた衣料の臭いと、それら衣料を２０代男性５人に１２時間着用させた後の衣料の臭いを、それぞれ１０人のパネラー（３０代男性１０人）により下記の基準で判定し、平均点を求めた。平均点が１未満を○、１以上１．５未満を△、１．５以上を×として評価した。結果を表１に示す。
ほとんど臭いを感じない…０
かすかに臭いを感じるが気にならない程度である…１
臭いがする…２
顕著に臭いがする…３
【００５３】
【表１】

[0001]
[Field of the Invention]
The present invention relates to a softener composition for textile products.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, as a main softening component for softening, a compound having a long-chain alkyl group and one quaternary ammonium group or tertiary amino group is generally used. Such a softening component is adsorbed on a textile product to finish it softly, while it is known to make the fiber oily, and improvement is desired in terms of clothing texture.
[0003]
In addition, attempts have been made to add an antibacterial agent to a softener composition from the viewpoint of hygiene and deodorization of textile products. JP-A-10-512015 and WO98556886 disclose a softener composition comprising a water-insoluble quaternary ammonium compound as a softening component and a water-soluble quaternary ammonium compound as an antibacterial compound. However, such a composition is not preferable in terms of the texture of the clothing, and it also suppresses bad odors attached to the clothing such as a body odor derived from a bad odor when washed indoors after washing and a sweat when worn. It is not satisfactory in terms of deodorizing effect.
[0004]
On the other hand, Japanese Patent Application Laid-Open No. 9-111660 discloses a softener composition in which a softening component having two or more cationic groups in a molecule and an anionic surfactant are combined. The composition is not fully satisfactory in terms of the texture of the textile product.
[0005]
Therefore, the subject of this invention is providing the softening agent composition which improves the feel of a textile product, and is excellent in the deodorizing effect.
[0006]
[Means for Solving the Problems]
The present invention includes (a) two or more groups selected from a quaternary ammonium group and a tertiary amino group in the molecule, and one group selected from an alkyl group and an alkenyl group having 8 to 36 carbon atoms. The softener composition containing 3 to 50% by weight of the compound having the above, (b) 0.5 to 30% by weight of the anionic surfactant, and (c) the following antibacterial compound (I) and / or (II) .
(I) To water at 20 ° C. having at least one alkyl group and / or alkenyl group having 8 to 16 carbon atoms and any one of a quaternary ammonium group and a tertiary amino group in the molecule Antibacterial compounds (II) triclosan, bis- (2-pyridylthio-1-oxide) zinc, 2,4,5,6-tetrachloroisophthalonitrile, trichlorocarbanilide, 2- One or more antibacterial compounds selected from (4-thiocyanomethylthio) benzimidazole, polyhexamethylene biguanidine hydrochloride, chlorhexidine glucuronate, 8-oxyquinoline and polylysine
DETAILED DESCRIPTION OF THE INVENTION
(A) Component The component (a) of the present invention comprises (a) two or more, more preferably two or three, most preferably two selected from a quaternary ammonium group and a tertiary amino group in the molecule. And a compound having one or more, more preferably one or two, most preferably one selected from an alkyl group and an alkenyl group having 8 to 36 carbon atoms, and a main component for softening . In particular, the compound of the general formula (1) is preferable.
^{R 1 - [A-P]} n - [B-Q] m -C-R 2 · aX - (1)
[In the formula, at least one of R ¹ and R ² is an alkyl group or alkenyl group having 8 to 36 carbon atoms, preferably 10 to 24, particularly preferably 14 to 24, which may be separated by an ester group or an amide group. And the other is an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. A, B and C may be the same or different and each represents a group represented by —N ⁺ (R ³ ) (R ⁴ ) — or —N (R ⁵ ) —. Here, R ³ , R ⁴ , and R ⁵ may be the same or different, and are an alkyl group or a hydroxyalkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. P and Q may be separated by an ester group, an ether group or an amide group, and may be an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group or an ether group. a is the number of —N ⁺ (R ³ ) (R ⁴ ) — in A, B, and C. n is 1 to 3, preferably 1 or 2, and m is 0 to 2, preferably 0 or 1. X ⁻ is an anion, preferably a halogen ion, an alkyl sulfate ion having 1 to 3 carbon atoms, or a fatty acid ion. ]
Preferred examples of such compounds include the following compounds.
[0008]
[Chemical 1]

[0009]
[Chemical 2]

[0010]
[Wherein, R ^{1 to} R ⁵ and X ⁻ represent the same meaning as described above, and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an oxyethylene group having an average degree of condensation of 1 to 20. Y is a group selected from -COO-, -OCO-, -CONH-, -NHCO- and -O-. l and k are the numbers of 1-5 which may be the same or different. ]
In the present invention, among the above compounds, (I), (II), (IV) and (V) are preferable, and (II) or (V) is particularly preferable.
[0011]
Further, in the present invention, both or any one of R ¹ and R ² , preferably any one is an alkyl group or alkenyl group having 14 to 24 carbon atoms separated by an ester group or an amide group or both. In particular, R ⁷ —COZ—R ⁸ —, R ⁷ —ZCO—R ⁸ —
[Wherein, R ⁷ is an alkyl group or alkenyl group having 13 to 19 carbon atoms, and R ⁸ is an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. Z represents —O— or —NH—. ]
It is desirable that the group is selected from
[0012]
In addition, the compound which has a tertiary amino group among the compounds of (a) component can also use what neutralized the tertiary amino group with the acid agent before mix | blending with a softening agent composition. As the acid for neutralization, hydrochloric acid, sulfuric acid, phosphoric acid and fatty acid are preferable, and hydrochloric acid and sulfuric acid are particularly preferable.
[0013]
(B) Component As the anionic surfactant which is the component (b) of the present invention, alkylbenzene sulfonic acid, alkyl sulfuric acid, polyoxyalkylene alkyl ether sulfuric acid, olefin sulfonic acid, alkane sulfonic acid, saturated or unsaturated fatty acid, poly Examples thereof include oxyalkylene alkyl or alkenyl ether carboxylic acids, α-sulfo fatty acids, α-sulfo fatty acid esters and salts thereof. Among these, an alkyl sulfuric acid having an alkyl group having 10 to 30 carbon atoms, preferably 12 to 24, particularly preferably 14 to 24 carbon atoms, an alkyl group having 10 to 30 carbon atoms, preferably 12 to 24 carbon atoms, and particularly preferably 14 to 24 carbon atoms. 1 or more selected from polyoxyethylene alkyl ether sulfuric acid having an average number of moles of added ethylene oxide of 1 to 6, preferably 1 to 4, saturated or unsaturated fatty acids having 8 to 18 carbon atoms and salts thereof It is preferable to mix.
[0014]
(C) Ingredient The antibacterial compound (c) of the present invention is a JIS L 1902 “antibacterial test method for textile products” using a cloth in which 1% by weight of the compound is uniformly adhered to a cotton metal cloth # 2003. It is a compound that shows an inhibitory band when an antibacterial test is carried out by the method.
[0015]
As the antibacterial compound (I), a dialkyldimethyl quaternary ammonium salt having 8 to 16 carbon atoms, a monoalkyltrimethyl quaternary ammonium salt, or the like can be used. In particular, the following general formula (2) or (3) Compounds are preferred.
[0016]
[Chemical 3]

[0017]
[Wherein, R ²¹ and R ³¹ are alkyl groups or alkenyl groups having 5 to 16 carbon atoms, preferably 7 to 14 carbon atoms, preferably alkyl groups, and R ²³ and R ²⁴ are alkyl groups having 1 to 3 carbon atoms or A hydroxyalkyl group; T is -COO-, OCO-, -CONH-, -NHCO-,
[0018]
[Formula 4]

[0019]
It is. R ²² and R ²⁵ are each an alkylene group having 1 to 6 carbon atoms or — (O—R ²⁶ ) _n —. Here, R ²⁶ is an ethylene group or a propylene group, preferably an ethylene group, and n is a number of 1 to 10, preferably 1 to 5. Z ^- is an anionic group, preferably a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms. b is 0 or 1. ]
The most preferable antibacterial quaternary ammonium compounds of the present invention include the following.
[0020]
[Chemical formula 5]

[0021]
As the antibacterial compound (II), triclosan is particularly preferable.
[0022]
(Softener composition)
The softener composition of the present invention contains the component (a) in an amount of 3 to 50% by weight, preferably 3 to 40% by weight, particularly preferably 5 to 35% by weight. Further, the component (b) is contained in an amount of 0.5 to 30% by weight, preferably 1 to 20% by weight, particularly preferably 5 to 20% by weight. Further, the component (c) is contained in an amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, particularly 0.1 to 5% by weight.
[0023]
The weight ratio of the component (a) to the component (b) is preferably (a) / (b) = 10/1 to 1/10, particularly 5/1 to 1/5 in order to improve the texture. The weight ratio of the component a) to the component (c) is preferably (c) / (a) = 1/200 to 1/1, particularly 1/150 to 1/2 from the viewpoint of the deodorizing effect.
[0024]
The softener composition of the present invention is a composition containing the above components (a) to (c) and water, and uses water from which ionic substances contained in water such as distilled water and ion exchange water have been removed. It is desirable to do. Water is preferably contained in an amount of 40 to 95% by weight, particularly 50 to 90% by weight from the viewpoint of storage stability.
[0025]
Moreover, it is preferable from the point of storage stability that the softening agent composition of this invention is pH 1-20 in 20 degreeC, especially 1.5-4.
[0026]
(D) Component In the present invention, it is preferable from the viewpoint of storage stability that a nonionic surfactant is blended as the component (d). As the nonionic surfactant, a polyoxyalkylene alkyl ether having at least one alkyl group or alkenyl group having 8 to 20 carbon atoms is preferable, and the nonionic surfactant of the general formula (4) is particularly preferable.
^{R 41 -T - [(R 42} O) p -H] q (4)
[Wherein, R ⁴¹ is an alkyl group or alkenyl group having 10 to 18 carbon atoms, preferably 12 to 18 carbon atoms, and R ⁴² is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. p is an average addition mole number, and shows the number of 2-100, Preferably it is 5-40, Most preferably, it is 20-40. T is —O—, —N— or —CON—. When T is —O—, q is 1, and when T is —N— or —CON—, q is 2. ].
[0027]
Specific examples of the compound of the general formula (4) include the following compounds.
R ⁴¹ —O— (C ₂ H ₄ O) _r —H
[Wherein, R ⁴¹ has the same meaning as described above, and r is the average number of moles added, which is 8 to 100, preferably 10 to 80. ]
R ⁴¹ —O— (C ₂ H ₄ O) _s (C ₃ H ₆ O) _t —H
[In the formula, R ⁴¹ has the same meaning as described above, s and t are the average number of moles added, each independently 2 to 40, preferably 5 to 40, and ethylene oxide and propylene oxide are random or block. It may be an adduct. ]
[0028]
[Chemical 6]

[0029]
It is desirable from the viewpoint of storage stability that such a nonionic surfactant is blended in the composition in an amount of 0.5 to 10% by weight, preferably 1 to 8% by weight.
[0030]
(E) Component In the softener composition of the present invention, it is desirable to blend an oil component as the (e) component for the purpose of further improving storage stability. As the oil component, an ester compound of a fatty acid having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms and a polyhydric alcohol is preferable, and triglyceride, diglyceride, monoglyceride, pentaerythritol mono, di, triester and sorbitan ester are particularly preferable. Such an oil component is preferably added to the composition in an amount of 0.05 to 10% by weight, particularly 0.1 to 5% by weight.
[0031]
From the viewpoint of storage stability, the softening agent composition of the present invention may further contain a compound having a δ of 20 to 40, preferably 21 to 35, particularly preferably 21 to 27 calculated from the following formula (5). desirable. The molecular weight is 100 to 400, preferably 130 to 300, particularly 150 to 300, and the boiling point is 150 ° C. or higher, preferably 200 to 350 ° C., particularly 240 to 350.
δ = [(14820 + 99.2Tb + 0.084Tb ² ) / V] ^1/2 (5)
[In the formula, Tb is a boiling point (° K), and V is a molar volume at 20 ° C. ].
[0032]
Here, δ of the present invention approximates the solubility parameter, and is described in pages 78 to 82 of “Solution and Solubility” (published by Kozo Shinoda, April 30, 1991, published by Maruzen Co., Ltd.). Is.
[0033]
Preferred compounds satisfying the δ value of the present invention are alkyl glyceryl ethers having 3 to 8 carbon atoms in the alkyl group, di- or triethylene glycol monophenyl ether, di- or tri-alkyl having 2 to 8 carbon atoms in the alkyl group. Examples include triethylene glycol monoalkyl ether, 1,6-hexanediol, 2,5-hexanediol, 3-pentanone, cyclohexanol, 2-hexanol, and 1-octanol. Alkyl glyceryl ether having 2 to 5 carbon atoms, di- or triethylene glycol monoalkyl ether having 2 to 5 carbon atoms in the alkyl group, and triethylene glycol monophenyl ether are preferable.
[0034]
It is desirable to add 0 to 1000 ppm, preferably 10 to 500 ppm of an inorganic salt such as calcium chloride from the viewpoint of storage stability in the softener composition of the present invention. However, although surfactants such as fatty acid salts include sodium salts and potassium salts, inorganic salts mixed into the composition by using such surfactants are not subject to the above restrictions.
[0035]
In the softener composition of the present invention, components such as silicone, fragrance, and pigment usually blended in the softener composition may be blended.
[0036]
【Example】
Synthesis example 1
A reaction product obtained by subjecting methyl monoethanolamine and acrylonitrile to a Michael addition reaction by a conventional method was charged into a stainless steel autoclave, and ethanol as a solvent and Raney nickel as a catalyst were added. The autoclave was purged with nitrogen and then replaced with hydrogen, and reacted at a hydrogen pressure of 10 kg / cm ² and a temperature of 110 ° C. for 3 hours. Next, an aqueous formalin solution having a molar ratio of 2.2 with respect to the amine was injected into the autoclave, and the reaction was further continued for 5 hours. After cooling, the resulting reaction product was distilled to obtain N-hydroxyethyl-N, N ′, N′-tetramethylpropanediamine.
[0037]
Next, stearic acid and N-hydroxyethyl-N, N ′, N′-tetramethylpropanediamine are esterified by an ordinary esterification method, and the esterified product is subjected to a quaternization reaction with methyl chloride. Compound a-1 was obtained.
[0038]
[Chemical 7]

[0039]
Synthesis example 2
The esterification reaction product of dimethylethanolamine and stearic acid and the esterification reaction product of choline chloride and monochloroacetic acid were synthesized by conventional methods. Each of these two compounds was dissolved in equimolar amounts of ethanol and reacted for 6 hours under reflux. Ethanol was distilled off under reduced pressure and purified by a usual method to obtain a compound a-2 having the following structure.
[0040]
[Chemical 8]

[0041]
Synthesis example 3
A dehydration condensation reaction between stearic acid and N-hydroxyethylethylenediamine was performed, and this was hydrolyzed and distilled to obtain N-stearoyl-N′-hydroxyethylethylenediamine. This was dissolved in ethanol, 1.1-fold equivalent of formalin was added dropwise to the amine under reflux, and then 1.1-fold equivalent of formic acid was added dropwise to the amine, followed by aging for 5 hours. The reaction product was further quaternized with methyl chloride to obtain N-stearoylaminoethyl-N-hydroxyethyl-N, N-dimethylammonium chloride. Compound a-3 having the following structure was obtained by subjecting this compound and dimethylglycine to a normal esterification reaction.
[0042]
[Chemical 9]

[0043]
Synthesis example 4
In a flask, 1-chloroalkane (150 g, 0.52 mol) and N, N, N ′, N′-tetramethyl-1,3-propanediamine (68 g, 0.53 mol) were mixed with ethanol (350.0 g). It was. After the mixture was refluxed for 72 hours, ethanol was distilled off under reduced pressure to remove unreacted amine compound. The obtained solid was further recrystallized with acetone according to a conventional method to obtain a-4 [N- (3-dimethylaminopropyl) -N-alkyl-N, N-dimethylammonium chloride (180 g, Pure content of 95% by weight).
[0044]
[Chemical Formula 10]

[0045]
Synthesis example 5
Stearyldimethylamine hydrochloride (1 mol) and epichlorohydrin 1 mol were dissolved in 500 ml of isopropanol and reacted at 90 ° C. for 1 hour. Thereafter, stearyldimethylamine (1 mol) was added dropwise from a dropping funnel, and the mixture was further stirred at 90 ° C. for 6 hours. After cooling, the solvent was distilled off under reduced pressure, and the resulting solid was recrystallized from acetone to obtain Compound a-5 having the following structure.
[0046]
Embedded image

[0047]
Examples <Softener composition>
The softening agent composition of Table 1 was prepared using said a-1 to a-5 and the following compound.
A'-1: dioleyldimethylammonium chloride b-1 sodium stearyl sulfate ester b-2 polyoxyethylene (ethylene oxide average addition mole number 2.5) sodium stearyl ether sulfate b-3 stearic acid Sodium [0048]
Embedded image

[0049]
-C-4: triclosan-d-1: an average of 21 moles of ethylene oxide added to a saturated alcohol having 12 carbon atoms-d-2: an average of 20 moles of ethylene oxide added to diethanolamide of lauric acid-e -1: Stearic acid mono, di, triglyceride mixture (mono: di: tri = 60: 35: 5)
F-1: C ₈ H ₁₇ OCH ₂ CH (OH) CH ₂ OH (δ = 21.96)
F-2: triethylene glycol monophenyl ether (δ = 20.92)
F-3: 1,6-hexanediol (δ = 27.23)
・ G-1: Calcium chloride ・ g-2: Dye (Acid Blue 9)
-G-3: A fragrance | flavor.
[0050]
<Flexible processing method>
Two men's underwear (100% cotton) and two bath towels (100% cotton) were washed with a washing machine using a commercially available weak alkaline detergent (attack made by Kao Corporation) (Toshiba 2-tank washing machine) VH-360S1, detergent concentration 0.0667% by weight, use of 30 L of tap water, water temperature 20 ° C., 10 minutes). Thereafter, the washing liquid was discharged, dehydrated for 1 minute, poured 30 L of tap water, rinsed for 5 minutes, and dehydrated for 1 minute after drainage. Thereafter, 30 L of tap water was poured again, and then 7 g of the composition shown in Table 1 was added and stirred for 5 minutes. Then, it dehydrated and dried for 12 hours in a constant temperature room with a humidity of 70% and 25 ° C.
[0051]
<Evaluation of texture>
The texture of the bath towel subjected to the above treatment was evaluated by 10 panelists (5 men in their 30s and 5 women in their 20s) according to the following criteria. These average points were determined, and the average score was evaluated as 0 for less than 1, 1 for less than 1.5, and x for 1.5 or more. The results are shown in Table 1.
Refreshing texture and no oiliness ... 0
Slightly oily but refreshing texture ... 1
Oily texture ... 2
Very oily texture ... 3.
[0052]
<Evaluation of deodorizing effect>
The smell of clothes dried in a temperature-controlled room and the smell of clothes after 12 hours of wearing these clothes by men in their twenties for 12 hours are determined by the following standards by 10 panelists (10 men in their 30s). Then, the average score was obtained. An average score of less than 1 was evaluated as ○, 1 or more and less than 1.5 as Δ, and 1.5 or more as ×. The results are shown in Table 1.
Almost no smell ... 0
I feel a slight smell but I don't mind ... 1
It smells ... 2
It smells remarkably ... 3
[0053]
[Table 1]

Claims (2)

(A) in the molecule, have a group selected from quaternary ammonium groups and tertiary amino groups at least two, and compound 3 which chromatic one group selected from alkyl and alkenyl groups having 8 to 36 carbon atoms A softener composition comprising -50% by weight, (b) 0.5-30% by weight of an anionic surfactant and (c) the following antibacterial compound (I) and / or (II).
(I) At least one alkyl group and / or alkenyl group having 5 to 16 carbon atoms is selected from the compound represented by the following general formula (2) and the compound represented by the general formula (3). An antibacterial compound (II) triclosan having a solubility in water at 20 ° C. of 2 g / 100 g or more and having either one of a quaternary ammonium group or a tertiary amino group, bis- (2-pyridylthio-1) -Oxide) zinc, 2,4,5,6-tetrachloroisophthalonitrile, trichlorocarbanilide, 2- (4-thiocyanomethylthio) benzimidazole, polyhexamethylene biguanidine hydrochloride, chlorhexidine glucuronate, 8- One or more antibacterial compounds selected from oxyquinoline and polylysine

[Wherein, R ²¹ and R ³⁶ are an alkyl group or alkenyl group having 5 to 16 carbon atoms, and R ²³ and R ²⁴ are an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms. T is -COO-, OCO-, -CONH-, -NHCO-,

It is. R ²² and R ²⁵ are an alkylene group having 1 to 6 carbon atoms or — ( O—R ²⁶ ) _n —. Here, R ²⁶ is an ethylene group or a propylene group, and n is a number from 1 to 10. Further, Z ⁻ is an anionic group. b is 0 or 1. ] The softener composition according to claim 1, wherein the component (a) is a compound of the following general formula (1).
^{R 1 - [A-P]} n - [B-Q] m -C-R 2 · aX - (1)
[In the formula, ^one of R ¹ and R ² is an alkyl group or alkenyl group having 8 to 36 carbon atoms which may be divided by an ester group or an amide group, and the other is an alkyl group having 1 to 5 carbon atoms or A hydroxyalkyl group; A, B and C may be the same or different and each represents a group represented by —N ⁺ (R ³ ) (R ⁴ ) — or —N (R ⁵ ) —. Wherein R ^3, R ^4, R ⁵ may be the same or different, it is an alkyl or hydroxyalkyl group having 1 to 5 carbon atoms. P and Q may be separated by an ester group, an ether group or an amide group, and may be an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group or an ether group. a is the number of —N ⁺ (R ³ ) (R ⁴ ) — in A, B, and C. n is a number from 1 to 3, and m is a number from 0 to 2. X ⁻ is an anion. ]