JP3883943B2 - Easy-cleaning antifouling agent composition for clothing - Google Patents

Description

【００１２】
〔式中、Ｒ¹は炭素数１２〜２６のアルキル基又はアルケニル基であり、Ｒ²は炭素数１〜６のアルキレン基であり、Ａは−ＣＯＯ−、−ＣＯＮＨ−、−ＯＣＯ−、−ＮＨＣＯ−から選ばれる基である。ａは０又は１も数であり、Ｒ³、Ｒ⁴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。〕。
【００１３】
一般式（１）において、Ｒ¹の炭素数は、好ましくは炭素数１２〜２２、より好ましくは１３〜１９、特に好ましくは１５〜１７、最も好ましくは１５である。Ａは、好ましくは−ＣＯＯ−又は−ＣＯＮＨ−であり、最も好ましくは−ＣＯＮＨ−である。Ｒ²の炭素数は、好ましくは２又は３であり、Ｒ³、Ｒ⁴は、好ましくはメチル基である。
【００１４】
本発明の最も好ましいアミンオキシド化合物としては下記一般式（１−１）の化合物または一般式（１−２）の化合物が好適である。
【００１５】
【化２】

【００１６】
〔式中、Ｒ⁵は炭素数１３〜２１、好ましくは１３〜１９、特に好ましくは１５〜１７、最も好ましくは１５のアルキル基又はアルケニル基であり、ｂ、ｃは２又は３の数である〕。
【００１７】
本発明では、炭素数１２〜２６の炭化水素基、例えば上記一般式中のＲ¹又はＲ⁵は、単独のアルキル（又はアルケニル）鎖長でもよく、異なるアルキル（又はアルケニル）鎖長を有する混合アルキル基（又はアルケニル基）であってもよい。後者の場合には、パーム油、大豆油、なたね油、綿実油から選ばれる植物油及び豚脂、牛脂、魚油から選ばれる動物油から誘導される混合アルキル（又はアルケニル）鎖長を有するものが好適である。具体的にはパルミチル基（またはパルミチン酸残基）／ステアリル基（又はステアリン酸残基、もしくはオレイル基またはオレイン酸残基）のモル比が９０／１０〜２０／８０、好ましくは９０／１０〜３０／７０であることが易洗防汚効果の点から好ましい。
【００１８】
本発明に係わる組成物は、上記アミンオキシド化合物を易洗防汚効果の点から好ましくは０．０１〜３０質量％、より好ましくは０．１〜２０質量％、特に好ましくは０．５〜１０質量％含有することが好適である。
【００１９】
本発明に係わる組成物は上記アミンオキシド化合物を水に溶解させた水溶液の形態であり、用いる水は微量に存在する金属を除去したイオン交換水や蒸留水が好ましい。水の含有量は４０〜９９．５質量％、より好ましくは６０〜９９質量％、特に好ましくは８０〜９９質量％が好適である。また、該組成物の２０℃におけるｐＨは、易洗防汚効果の点から好ましくは５〜８．５、より好ましくは６〜７．８、特に好ましくは６．５〜７．５が好適である。このようなｐＨに調整するために塩酸、硫酸、リン酸、クエン酸、コハク酸、乳酸から選ばれる酸、及び炭酸ナトリウム、炭酸カリウム、水酸化ナトリウム、水酸化カリウム、アルカノールアミンから選ばれるアルカリ剤を用いることが好ましい。本発明では特に塩酸、硫酸から選ばれる酸、及び炭酸ナトリウム、水酸化ナトリウムから選ばれるアルカリ剤を用いることが好ましい。
【００２０】
本発明に係わる組成物は上記アミンオキシド化合物以外の界面活性剤を含有することができるが、本発明の効果を妨げるおそれがあるために含有量はアミンオキシド化合物に対して好ましくは８０質量％以下、より好ましくは５０質量％以下、特に好ましくは２５質量％以下、最も好ましくは１０質量％以下である。本発明に用いることができる界面活性剤としては、炭素数８〜１５のアルキル基を有するアルキルベンゼンスルホン酸塩、炭素数８〜１６のアルキル硫酸エステル塩、平均付加モル数が１〜４、アルキル基の炭素数が８〜１６のポリオキシエチレンアルキルエーテル硫酸エステル塩から選ばれる陰イオン界面活性剤、平均付加モル数が４〜２０、アルキル基の炭素数が８〜１４のポリオキシエチレン（及び／又はポリオキシプロピレン）アルキルエーテル型非イオン界面活性剤、エステル基又はアミド基で分断されていてもよい炭素数が１２〜２２アルキル基を１つまたは２つ有する４級アンモニウム型陽イオン界面活性剤、炭素数１０〜１８のアルキル基を有するスルホベタイン型、又はカルボベタイン型両性界面活性剤を挙げることができる。
【００２１】
本発明に係わる組成物は衣料に該組成物を接触させた後の乾燥を促進させる目的、又は該組成物の貯蔵安定性を改善する目的から、水溶性の溶剤を用いることが好ましい。具体的に好ましい溶剤としてはエタノール、プロパノール、イソプロパノール、エチレングリコール、プロピレングリコール、及びグリセリンが好適であり、特にエタノール及び／又はプロピレングリコールが好ましい。このような溶剤の比率は、組成物中に好ましくは０．１〜４０質量％、より好ましくは１〜２０質量％、特に好ましくは５〜２０質量％含有される。
【００２２】
本発明に係わる組成物は、易洗防汚効果を向上させる目的から炭素数１〜４の炭化水素基が１〜３個置換していてもよいアルキルベンゼンスルホン酸塩、又はナフタレンスルホン酸塩を含有することが好ましく、具体的に好ましい化合物としては、ｐ−トルエンスルホン酸ナトリウム、ｍ−キシレンスルホン酸ナトリウム、クメンスルホン酸ナトリウム及びナフタレンスルホン酸ナトリウムから選ばれる１種以上であり、特にｐ−トルエンスルホン酸ナトリウム及びナフタレンスルホン酸ナトリウムから選ばれる化合物が最も好ましい。このような化合物は組成物中に好ましくは０〜１０質量％、より好ましくは０．０１〜５質量％、特に好ましくは０．１〜１質量％含有される。
【００２３】
本発明では上記組成物を対象衣料に接触後乾燥させる。対象衣料は着用前の汚れが付着する前の衣料であり、洗濯時の脱水終了後の衣料、あるいは乾燥後の衣料に接触させることが易洗防汚効果を効果的に得る目的から好ましい。接触させる方法としては、該組成物に対象衣料を浸漬させる方法、スプレーヤーを用いて該組成物を対象衣料に噴霧する方法、又は布帛、不織布、スポンジ等の可撓性で吸水性の基体に含浸させたもので繊維製品を擦る方法が好ましい。特にスプレーにより噴霧する方法が簡便に易洗防汚効果を得ることができるため好ましく、スプレーはトリガー式スプレー容器が好ましく、特に実開平４−３７５５４号公報の第１図に示されているような液垂れや噴霧の均一性に優れる蓄圧式トリガーを用いることが良好である。
【００２４】
本発明の組成物に用いるのに好ましいトリガー式スプレー容器は、１回のストロークで０．２ｇ〜１．５ｇ、好ましくは０．２５〜１．２ｇ、特に好ましくは０．３〜１．０ｇ噴出するものが良好であり、特に地面に垂直に置いた対象物に１５ｃｍ離れた場所からスプレーしたときの液のかかる面積が１００〜８００ｃｍ²、好ましくは１５０〜６００ｃｍ²になる容器が好ましい。また、本発明では、上記アミンオキシド化合物が衣料１００ｃｍ²当たり好ましくは０．００１〜２ｇ、より好ましくは０．０１〜１ｇ、特に好ましくは０．０２〜０．５ｇ付着するように均一に衣料にスプレーし、好ましくは濯ぐことなく、乾燥させることが易洗防汚効果の点から好適である。
【００２５】
本発明では該組成物を対象衣料に接触後、好ましくは濯ぐことなく、乾燥を行う。乾燥は、自然乾燥や、乾燥機あるいはアイロンによる加熱乾燥が好ましく、特に、洗濯後乾燥した衣料に用いる場合には、アイロンによる加熱乾燥が最も好ましい。
【００２６】
【実施例】
白いワイシャツ（ＲＥＡＬ−ＬＩＮＥ ＦＡＳＨＩＯＭ社製ＣＲＥＡＮＥＡＲＲＯＷ）５枚を市販の衣料用洗剤（花王（株）アタック）を用いて洗濯機で洗浄し（東芝製２槽式洗濯機VH-360S1、洗剤濃度0.0667質量％、水道水30L使用、水温20℃、10分間、すすぎ２回）、自然乾燥させた。
【００２７】
花王（株）製アイロン用スムーザー４００ｍｌの中身を抜いた手動式スプレー容器を匂いが無くなるまで洗浄し、自然乾燥させたもの（１回のストロークで０．３ｇ噴出、１５ｃｍ離れた場所から噴射させたときの付着面積４２０ｃｍ²）に表１の組成物４００ｍｌを入れた。
【００２８】
上記乾燥後のワイシャツの衿の部分の半分に上記スプレーを用いてアミンオキシド化合物の付着量が０．０２ｇ／１００ｃｍ²になるようにスプレーした（ただし、比較例１、２、４は、実施例３の噴霧量と同じとした）。その後アイロンをかけて乾燥した。
【００２９】
処理後のワイシャツを５人の男性（２０〜３０代）に３６時間（１日１２時間で３日間）着用させ、着用後の衣料の衿部分を下記の基準で判定した。次に、この着用後の衣料を上記と同様の方法で洗濯し、自然乾燥させたワイシャツの衿部分を下記の基準で判定した。
【００３０】
判定基準
０：処理した部分の方が、汚れが付着していない（又は汚れが落ちている）
１：処理した部分の方が、あまり汚れが付着していない（又はやや汚れが落ちている）
２：処理した部分と処理していない部分に差がない
３：処理した部分の方が、汚れが付着している（又は汚れが落ちていない）
ワイシャツ５枚の平均を求め、平均点が０．５未満の場合を◎、０．５以上１未満を○、１以上１．５未満を□、１．５以上２未満を△、２以上を×として評価し表１に示した。
【００３１】
【表１】

【００３２】
・アミンオキシド１：Ｎ−アルキル−Ｎ，Ｎ−ジメチルアミンオキシド（アルキル基：炭素数１６／炭素数１８＝４０／６０、モル比）
・アミンオキシド２：Ｎ−アルカノイルオキシエチル−Ｎ，Ｎ−ジメチルアミンオキシド（アルカノイル基：硬化牛脂アルキル組成）
・アミンオキシド３：Ｎ−パルミトイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンオキシド
・アミンオキシド４：Ｎ−デカノイルアミノプロピル−Ｎ，Ｎ−ジメチルアミンオキシド
・ポリアクリル酸：ナトリウム塩、重量平均分子量１００００
・陰イオン界面活性剤１：ポリオキシエチレンラウリルエーテル硫酸エステル塩、エチレンオキシド平均付加モル数２．５
ｐＨ調節は０．１規定硫酸水溶液及び０．１規定水酸化ナトリウム水溶液で行った。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a washable antifouling treatment composition for clothing and a method for treating clothing.
[0002]
[Prior art and problems to be solved by the invention]
In general, clothes are generally washed in a washing machine using a weak alkaline detergent. However, dirt derived from sebum on the heels and cuffs and mud dirt adhering to the socks are very stubborn dirt, and it is difficult to wash to a satisfactory level by ordinary washing.
[0003]
As a method for solving this problem, there has been proposed a treatment agent that imparts antifouling property to a textile product by applying or dipping the textile product after washing. For example, the textile product surface is provided with a coating agent capable of preventing contact between the textile product and dirt, and after the textile product has been used, the coating agent is removed, thereby preventing the textile product from being stained. A method is known, and examples of the coating agent include carboxymethyl cellulose, modified starch, and water-insoluble fine particles (for example, Patent Document 1). An antifouling composition containing acrylic acid and / or a methacrylic acid polymer compound (for example, Patent Documents 2 to 4) or a water-insoluble powder (for example, Patent Document 5) is used as a base material for the antifouling agent. Proposed. An antifouling agent using a polymer capable of forming a film is also known (for example, Patent Document 6). However, even with these treatment agents, a satisfactory antifouling effect cannot be obtained yet.
[0004]
Furthermore, a technique using a compound having a cationic group as an antifouling agent has already been proposed (for example, Patent Document 7), but even these treatment agents still cannot obtain satisfactory antifouling properties.
[0005]
Accordingly, an object of the present invention is to provide an easy-to-wash antifouling treatment agent for clothing that imparts excellent antifouling properties to textile products such as clothing and has easy-to-wash properties that can be easily removed by washing even if dirt is attached. There is to do.
[0006]
[Patent Document 1]
JP-A-10-263497 [Patent Document 2]
JP 2000-143738 A [Patent Document 3]
JP 2000-199178 A [Patent Document 4]
JP 2000-199179 A [Patent Document 5]
Japanese Patent Laid-Open No. 9-273071 [Patent Document 6]
Japanese Patent Laid-Open No. 9-273079 [Patent Document 7]
Japanese National Patent Publication No. 11-505568
[Means for Solving the Problems]
The present invention relates to a washable antifouling treatment composition for clothing containing an amine oxide compound having one hydrocarbon group having 12 to 26 carbon atoms and two hydrocarbon groups having 1 to 3 carbon atoms, and water.
[0008]
Moreover, this invention relates to the easy-cleaning antifouling processing method of the clothing which dries the easy-cleaning antifouling processing agent composition for clothing of the said invention after making contact with object clothing.
[0009]
In addition, the easy-to-wash antifouling treatment composition for clothes according to the present invention is a treatment composition for adhering antifouling ingredients to clothes by direct contact with the clothes and then drying, and is used for washing clothes. It is clearly distinguished from the common cleaning agents used.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The composition of the present invention contains an amine oxide compound having one hydrocarbon group having 12 to 26 carbon atoms and two hydrocarbon groups having 1 to 3 carbon atoms. A preferred specific example of the compound is represented by the general formula (1). Can be mentioned.
[0011]
[Chemical 1]

[0012]
[Wherein, R ¹ represents an alkyl group or alkenyl group having 12 to 26 carbon atoms, R ² represents an alkylene group having 1 to 6 carbon atoms, and A represents —COO—, —CONH—, —OCO—, — It is a group selected from NHCO-. a is 0 or 1 and R ³ and R ⁴ are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. ].
[0013]
In the general formula (1), the carbon number of R ¹ is preferably 12 to 22, more preferably 13 to 19, particularly preferably 15 to 17, and most preferably 15. A is preferably —COO— or —CONH—, and most preferably —CONH—. R ² preferably has 2 or 3 carbon atoms, and R ³ and R ⁴ are preferably methyl groups.
[0014]
As the most preferred amine oxide compound of the present invention, a compound of the following general formula (1-1) or a compound of the general formula (1-2) is suitable.
[0015]
[Chemical 2]

[0016]
[Wherein R ⁵ is an alkyl group or alkenyl group having 13 to 21, preferably 13 to 19, particularly preferably 15 to 17, and most preferably 15 carbon atoms, and b and c are 2 or 3 carbon atoms. ].
[0017]
In the present invention, the hydrocarbon group having 12 to 26 carbon atoms, for example, R ¹ or R ⁵ in the above general formula may be a single alkyl (or alkenyl) chain length or a mixture having different alkyl (or alkenyl) chain lengths. It may be an alkyl group (or alkenyl group). In the latter case, those having a mixed alkyl (or alkenyl) chain length derived from vegetable oil selected from palm oil, soybean oil, rapeseed oil and cottonseed oil and animal oil selected from lard, beef tallow and fish oil are preferred. Specifically, the molar ratio of palmityl group (or palmitic acid residue) / stearyl group (or stearic acid residue, oleyl group or oleic acid residue) is 90/10 to 20/80, preferably 90/10 30/70 is preferred from the viewpoint of easy washing and antifouling effect.
[0018]
The composition according to the present invention is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and particularly preferably 0.5 to 10% by mass from the viewpoint of easy washing and antifouling effect. It is preferable to contain by mass%.
[0019]
The composition according to the present invention is in the form of an aqueous solution in which the amine oxide compound is dissolved in water, and the water used is preferably ion-exchanged water or distilled water from which a trace amount of metal is removed. The water content is preferably 40 to 99.5% by mass, more preferably 60 to 99% by mass, and particularly preferably 80 to 99% by mass. The pH at 20 ° C. of the composition is preferably 5 to 8.5, more preferably 6 to 7.8, and particularly preferably 6.5 to 7.5 from the viewpoint of easy washing and antifouling effect. is there. In order to adjust to such pH, an acid selected from hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, succinic acid and lactic acid, and an alkaline agent selected from sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and alkanolamine Is preferably used. In the present invention, it is particularly preferable to use an acid selected from hydrochloric acid and sulfuric acid, and an alkali agent selected from sodium carbonate and sodium hydroxide.
[0020]
The composition according to the present invention may contain a surfactant other than the amine oxide compound, but the content is preferably 80% by mass or less based on the amine oxide compound because the effect of the present invention may be hindered. More preferably, it is 50 mass% or less, Most preferably, it is 25 mass% or less, Most preferably, it is 10 mass% or less. As the surfactant that can be used in the present invention, an alkylbenzene sulfonate having an alkyl group having 8 to 15 carbon atoms, an alkyl sulfate ester salt having 8 to 16 carbon atoms, an average addition mole number of 1 to 4, an alkyl group Anionic surfactant selected from polyoxyethylene alkyl ether sulfates having 8 to 16 carbon atoms, polyoxyethylene having an average addition mole number of 4 to 20 and an alkyl group having 8 to 14 carbon atoms (and / or Or polyoxypropylene) alkyl ether type nonionic surfactant, quaternary ammonium type cationic surfactant having one or two alkyl groups having 12 to 22 carbon atoms which may be separated by an ester group or an amide group And sulfobetaine-type or carbobetaine-type amphoteric surfactants having an alkyl group having 10 to 18 carbon atoms. That.
[0021]
In the composition according to the present invention, it is preferable to use a water-soluble solvent for the purpose of promoting drying after the composition is brought into contact with clothing, or for the purpose of improving the storage stability of the composition. Specific preferred solvents are ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, and glycerin, with ethanol and / or propylene glycol being particularly preferred. The ratio of such a solvent is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass, and particularly preferably 5 to 20% by mass in the composition.
[0022]
The composition according to the present invention contains alkylbenzene sulfonate or naphthalene sulfonate which may be substituted with 1 to 3 hydrocarbon groups having 1 to 4 carbon atoms for the purpose of improving the easy washing and antifouling effect. Specifically, the preferred compound is at least one selected from sodium p-toluenesulfonate, sodium m-xylenesulfonate, sodium cumenesulfonate and sodium naphthalenesulfonate, and particularly p-toluenesulfone Most preferred are compounds selected from sodium acid and sodium naphthalene sulfonate. Such a compound is preferably contained in the composition in an amount of 0 to 10% by mass, more preferably 0.01 to 5% by mass, and particularly preferably 0.1 to 1% by mass.
[0023]
In the present invention, the composition is dried after contacting the target clothing. The target clothes are clothes before the dirt before wearing adheres, and it is preferable to contact the clothes after the dehydration at the time of washing or the clothes after drying for the purpose of effectively obtaining the easy-to-wash antifouling effect. Examples of the contact method include a method of immersing the target clothing in the composition, a method of spraying the composition on the target clothing using a sprayer, or a flexible, water-absorbing substrate such as a fabric, nonwoven fabric, or sponge. A method of rubbing the fiber product with the impregnated material is preferable. In particular, the spraying method is preferable because it can easily obtain an easy washing and antifouling effect, and the spray is preferably a trigger type spray container, particularly as shown in FIG. 1 of Japanese Utility Model Publication No. 4-37554. It is preferable to use an accumulator trigger that is excellent in dripping and spray uniformity.
[0024]
A preferred trigger spray container for use in the composition of the present invention is 0.2 g to 1.5 g, preferably 0.25 to 1.2 g, particularly preferably 0.3 to 1.0 g in a single stroke. it is good which, in particular consuming liquid area 100～800Cm ² when sprayed from 15cm away the object placed perpendicularly to the ground, preferably a container to be 150~600cm ^2. In the present invention, the amine oxide compound is preferably uniformly applied to the garment so that it adheres to 0.001 to ² g, more preferably 0.01 to 1 g, and particularly preferably 0.02 to 0.5 g per 100 cm ² of garment. From the viewpoint of easy washing and antifouling effect, it is preferable to spray, preferably dry without rinsing.
[0025]
In the present invention, the composition is dried after contact with the target garment, preferably without rinsing. Drying is preferably natural drying or heat drying with a dryer or an iron, and particularly when used for clothes dried after washing, heat drying with an iron is most preferable.
[0026]
【Example】
5 white shirts (CREEAREARROW manufactured by REAL-LINE FASHIOM) were washed with a washing machine using a commercially available laundry detergent (Kao Attack) (Toshiba 2-tank washing machine VH-360S1, detergent concentration 0.0667 mass) %, Using 30 L of tap water, water temperature 20 ° C., 10 minutes, 2 times of rinsing) and air-dried.
[0027]
A hand-operated spray container with 400 ml of iron smoother made by Kao Co., Ltd. was washed until it became odorless and dried naturally (0.3 g was sprayed in one stroke, sprayed from 15 cm away) 400 ml of the composition shown in Table 1 was added to the adhesion area (420 cm ² ).
[0028]
The above-mentioned spray was used to spray half of the heel portion of the shirt after the drying so that the amount of the amine oxide compound deposited was 0.02 g / 100 cm ² (however, Comparative Examples 1, 2, and 4 were examples) 3). Then it was ironed and dried.
[0029]
The shirts after treatment were worn by five men (20-30s) for 36 hours (12 hours a day for 3 days), and the heel portion of the clothes after wearing was determined according to the following criteria. Next, the garment part of the shirt after washing this clothes after washing by the method similar to the above and air-drying was determined on the following reference | standard.
[0030]
Judgment criteria 0: The treated part is not contaminated (or the dirt is removed).
1: The treated part is not so dirty (or slightly dirty)
2: There is no difference between the treated part and the untreated part 3: Dirt is attached to the treated part (or the dirt is not removed)
Find the average of 5 shirts, ◎ if the average score is less than 0.5, ○ from 0.5 to less than 1, □, from 1 to less than 1.5, from 1.5 to less than 2, △, 2 or more It evaluated as x and is shown in Table 1.
[0031]
[Table 1]

[0032]
Amine oxide 1: N-alkyl-N, N-dimethylamine oxide (alkyl group: carbon number 16 / carbon number 18 = 40/60, molar ratio)
Amine oxide 2: N-alkanoyloxyethyl-N, N-dimethylamine oxide (alkanoyl group: cured beef tallow alkyl composition)
Amine oxide 3: N-palmitoylaminopropyl-N, N-dimethylamine oxide Amine oxide 4: N-decanoylaminopropyl-N, N-dimethylamine oxide Polyacrylic acid: sodium salt, weight average molecular weight 10,000
Anionic surfactant 1: polyoxyethylene lauryl ether sulfate ester salt, ethylene oxide average addition mole number 2.5
The pH was adjusted with a 0.1 N aqueous sulfuric acid solution and a 0.1 N aqueous sodium hydroxide solution.

Claims (2)

An easy-clean antifouling agent composition for clothing containing an amine oxide compound having one hydrocarbon group having 12 to 26 carbon atoms and two hydrocarbon groups having 1 to 3 carbon atoms, and water. An easy-cleaning and antifouling treatment method for clothing, wherein the easy-cleaning and antifouling treatment composition for clothing according to claim 1 is dried after contacting the target clothing.