JP2004100111A - Stainproofing agent for polyester fiber and stainproofing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a hydrophilic stainproofing agent produced by using a substance capable of imparting excellent stainproofness and wash resistance even under a severe environment, having excellent processing operability and safety and giving little load on the environment, and provide a method for the stainproofing treatment of a polyester fiber by using the agent. <P>SOLUTION: The stainproofing agent for polyester fibers contains at least one kind of component selected from (A) a cellulose derivative produced by methoxylating, hydroxyethoxylating or hydroxypropoxylating a part of the hydroxy group of a cellulose and having a weight-average molecular weight of 1,000-1,000,000 and (B) a cellulose graft polymer produced by the graft polymerization of an acrylic monomer to the residual hydroxy group of the component A. This invention further provides a stainproofing method using the agent and a polyester fiber treated with the agent. <P>COPYRIGHT: (C)2004,JPO

Description

【０００８】
（ＲはＨ、メチル、ヒドロキシエチル又はヒドロキシプロピルで、少なくとも１つのＲはＨ以外である。ｎは１〜１００，０００の正数を表す。）
【０００９】
式（Ａ）の構造ですべてのＲがＨとなるセルロースは水不溶性で防汚効果はないが、水酸基の少なくとも１つをメトキシ化、ヒドロキシエトキシ化、ヒドロキシプロポキシ化することにより、水溶性となり、セルロース誘導体（Ａ）の構造となる。式（Ａ）においてｎは１〜１００，０００、好ましくは２００〜１０，０００である。セルロース誘導体の重量平均分子量は１，０００〜１００万が好ましく、更には１万〜５０万、特には７万〜４０万程度がより好ましい。
セルロース誘導体（Ａ）の構造中、メトキシ化、ヒドロキシエトキシ化、ヒドロキシプロポキシ化については、それぞれほぼ同様の防汚性を示すが、水酸基の置換率は防汚性については２０〜１００％程度が好ましい。
【００１０】
セルロース誘導体（Ａ）の構造をもつ物質を利用して、さらに防汚性、洗濯耐久性を向上させる為、セルロース誘導体（Ａ）の残存水酸基にビニル系モノマーをグラフトさせることが好ましい。グラフト方法としては、セルロース誘導体（Ａ）の水溶液を硝酸で酸性とし、硝酸二アンモニウムセリウム（ＩＶ）を用いてグラフト重合させる方法。また、セルロース誘導体（Ａ）を用いて過酸化物と亜硫酸水素ナトリウム等の還元剤を用いてレドックス重合をしたものも性能的に優れたものが得られる。
ここで用いられるビニル系モノマーとしては、アクリル酸、メタクリル酸、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、２−（ジメチルアミノ）エチル（メタ）アクリレート、アクリルアミド、ポリエチレングリコール変性モノ（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、２−アクリルアミド−２−メチルプロパンスルホン酸、Ｎ−ビニル−２−ピロリドン等が例示される。中でも、防汚性、洗濯耐久性に効果的なものは、アクリル酸、ポリエチレングリコール変性モノ（メタ）アクリレート、Ｎ−ビニル−２−ピロリドン等は有効である。
【００１１】
セルロースグラフト重合体（Ｂ）が、良好な汚れ離脱性および洗濯耐久性を発揮するには、グラフト率を、セルロース誘導体（Ａ）の重量に対し、１０〜１００％の割合で行なわれるのが好ましく、特にセルロースの特性を有効にするには、１０〜５０％程度が良い。
【００１２】
繊維素材へ該防汚物質を繊維へ固着させる方法としては、特に限定されないが、繊維製品製造過程において、該防汚物質を所望の濃度に水溶化し、この溶液を用いてパディング法、コーティング法、吸尽法、スプレー法等で処理することが望ましい。浴中吸尽法での、繊維の吸着助剤として、水不溶性成分（Ｃ）を加えると良い。
【００１３】
水不溶性成分（Ｃ）は特に限定されるものではないが、例えば、リモネン等の芳香族炭化水素類、エステル類、石油類、親油性界面活性剤等を用いることができるが、安全性・環境面からリモネン等の使用が好ましい。添加量としては、セルロース誘導体（Ａ）又はセルロースグラフト重合体（Ｂ）に対して、３〜１０％程度加え乳化分散させる。少なすぎると吸着能力が不足し、又多すぎると液が不安定になりむらづきが起こる。
【００１４】
セルロース誘導体（Ａ）、セルロースグラフト重合体（Ｂ）の付着量は、特に限定されないが、好ましくは、繊維素材重量に対し０．１〜１％が望ましい。また、セルロース誘導体以外に他の薬剤を併用することもできる。上記の併用薬剤としては、セルロース誘導体はノニオン性であるため、特に制限されるものではなく、ジメチロール尿素、ジメチロールジヒドロキシエチレン尿素、ジヒドロキシエチレン尿素、メチロールメラミン等の防縮剤、脂肪酸エステル、アミド系柔軟剤、抗菌防虫剤、防炎剤、帯電防止剤、染料等が例示される。
【００１５】
そして、さらに、ポリフェノール類、アクリル系、ウレタン系、イソシアネート系、エポキシ系のポリマー、ジメチロール尿素、メチロールメラミン等との併用は洗濯耐久性を著しく向上させる。
ポリフェノール類等は、不溶化物質とのさらなる併用により、より優れた洗濯耐久性を付与することができる。ポリフェノール類の好ましい例としてタンニン酸を挙げることができる。ポリフェノール類と併用する上記不溶性物質としては、多糖類、多価金属塩等が例示される。多糖類としては、澱粉、セルロース、キチン、キトサン等などが挙げられる。多価金属塩に含まれる多価金属としては、例えば亜鉛、アルミニウム、マグネシウム、カルシウム、クロム、鉄、アンチモン、ジルコニウム、チタン等が好ましい。これらの多価金属塩としては、例えば、酢酸アルミニウム、酢酸マグネシウム、酢酸カルシウム、酒石酸アンチモンナトリウム、酒石酸アンチモンカリウム等が挙げられる。
【００１６】
ワーキングウェア等の防汚性は特に洗濯耐久性を要する。セルロース誘導体（Ａ）、セルロースグラフト重合体（Ｂ）等の防汚性を保持しながら、汚れの離脱性を低下させない助剤が必要である。セルロース誘導体（Ａ）、セルロースグラフト重合体（Ｂ）を用いて洗濯回数の少ない条件においては、防汚性を保持できるが、洗濯回数が１０回、２０回と重ねるごとに防汚性は低下する。洗濯耐久性を向上させるには、セルロース誘導体（Ａ）及び／又はセルロースグラフト重合体（Ｂ）を不溶化させるための架橋剤、もしくは助剤を用いる必要がある。セルロース誘導体（Ａ）、セルロースグラフト重合体（Ｂ）を不溶化させる架橋剤としては、特に限定されるものではないが、メチロールメラミン系架橋剤、エポキシ系架橋剤、イソシアネート系架橋剤等が例示される。上記３種類の試験結果では、メチロールメラミン系架橋剤は防汚性を低下させずに耐久性を向上させることができる。しかし、風合いが硬くなりすぎたり、ホルマリンの発生などの問題点も多い。その他エポキシ系、イソシアネート系架橋剤は、防汚性を低下させるため、使用するのは好ましくない。以上の結果から、助剤として検討した結果、ポリフェノール類がセルロース誘導体（Ａ）、セルロースグラフト重合体（Ｂ）を不溶化させる助剤として有効であることを見出し、しかも防汚性を低下させず、洗濯耐久性をもたらすことを発見した。特に中でもタンニン酸は有効であり、洗濯耐久性を著しく向上させる。セルロース誘導体（Ａ）、重合体（Ｂ）の有効成分に対して、添加量は２〜１００％、好ましくは、１０〜３０％である。
【００１７】
さらに、洗濯耐久性向上として、タンニン酸とキレートする金属を用いることにより、洗濯耐久性が大幅に向上することを見出した。セルロース誘導体（Ａ）、セルロースグラフト重合体（Ｂ）に対して、タンニン酸だけを用いると水中の金属類、特に鉄分と反応して黄変となる。
タンニン酸とキレート可能な金属としては、多価水溶性金属塩が有効である。亜鉛、アルミニウム、クロム、鉄、アンチモン、ジルコニウム、チタン等があるが変色等の問題から亜鉛、アルミニウムの金属塩が望ましい。添加量としては、セルロース誘導体（Ａ）、セルロースグラフト重合体（Ｂ）に対して、１０〜２００％が有効であるが、好ましくは、２０〜１００％が望ましい。１０％未満では、タンニン酸のフリー部分が多くなり、着色金属の反応が起こり、黄変がある。又２００％を超えると防汚性能が低下する。
【００１８】
本発明におけるポリエステル系繊維とは、ポリエチレンテレフタレート、ポリブチレンテレフタレートや、これらを主成分とした共重合体のポリエステル系繊維を含む織物、編物、不織布などのことをいい、ポリエステル系繊維以外の合成繊維や再生繊維あるいは天然繊維が混紡、混繊されていても良い。
【００１９】
【実施例】
次に本発明を実施例及び比較例に基づき詳細に説明するが、本発明は何等これらに限定されるものではない。
【００２０】
実施例１
セルロース誘導体（Ａ）〔メトローズ６０ＳＨ−４０００、信越化学（株）製〕であるヒドロキシプロピルメチルセルロースを固形分１重量％となるように水で希釈調液し、ポリエステル１００％の布を常温で浸漬したあと、絞り率１００％となるように脱水し、１２０℃で３分乾燥し１５０℃で１分キュアした。汚れ離脱性の試験結果を表１に示す。
（メトローズ６０ＳＨ−４０００）
メトキシ化置換度・・・１．９
ヒドロキシプロポキシ化平均置換モル数・・・０．２５
置換度・・・セルロースのグルコース環単位当たり、メトキシ基で置換された水酸基の平均個数
置換モル数・・・セルロースのグルコース環単位当たりに付加したヒドロキシプロポキシ基あるいはヒドロキシエトキシ基の平均で置換された水酸基の平均個数メトキシ基　２８〜３０％、ヒドロキシプロポキシ基　７〜１２％
【００２１】
実施例２
セルロース誘導体（Ａ）（メトローズ６０ＳＨ−４０００）であるヒドロキシプロピルメチルセルロースとＤ−リモネン〔ヤスハラケミカル（株）製〕の乳化液を２．５％ｏ．ｗ．ｆ、浴比１：２０で９０℃×１０分浴中処理で繊維に吸着させる。次に、ポリフェノール類であるタンニン酸水溶液０．２％、酢酸アルミニウム水溶液１０％の混合液を添加し、脱水して１２０℃で３分乾燥し１５０℃でキュアした。汚れ離脱性の試験結果を表１に示す。
【００２２】
実施例３
セルロース誘導体（Ａ）　〔メトローズＳＭ−４００、信越化学（株）製〕であるメチルセルロース１５ｇを水で溶解し、アクリル酸３ｇおよびメトキシポリエチレングリコール（２３モル付加）メタクリレート３ｇを溶解し窒素置換を行なった後、硝酸０．１ｃｃ及び硝酸−２−アンモニウムセリウム（ＩＶ）０．１ｇを水に溶解したものを加えて４０℃で１時間グラフト重合してセルロースグラフト重合体（Ｂ）を得た。この重合体（Ｂ）０．２５ｇ、タンニン酸０．１ｇ、酢酸アルミニウム０．３ｇを水に溶かし１００ｇの混合液を作成後、ポリエステル１００％の布を常温で浸漬し、絞り率１００％となるように脱水した。その後、１２０℃で３分乾燥し、１５０℃で１分キュアした。汚れ離脱性の試験結果を表１に示す。
【００２３】
実施例４
セルロース誘導体（Ａ）　〔メトローズＳＭ−４００、信越化学（株）製〕であるメチルセルロース１５ｇを水で溶解し、アクリル酸３ｇおよびメトキシポリエチレングリコール（２３モル付加）メタクリレート３ｇを溶解し窒素置換を行なった後、触媒として、過硫酸アンモニウム０．２ｇ及び亜硫酸水素ナトリウム０．２ｇを用いて４５℃で４時間重合を行なってセルロースグラフト重合体（Ｂ）を得た。この重合体（Ｂ）０．２５ｇ、タンニン酸０．１ｇ、酢酸アルミニウム０．３ｇを水に溶かし１００ｇの混合液を作成後、ポリエステル１００％の布を常温で浸漬し、絞り率１００％となるように脱水した。その後、１２０℃で３分乾燥し、１５０℃で１分キュアした。汚れ離脱性の試験結果を表１に示す。
（メトローズＳＭ−４００）
メトキシ化置換度・・・１．９
置換度・・・セルロースのグルコース環単位当たり、メトキシ基で置換された水酸基の平均個数
メトキシ基　２７．５％〜３１．５％
【００２４】
比較例１
未処理のポリエステル１００％布に、下記のＳＲ性試験での手順を行った。汚れ離脱性の試験結果を表１に示す。
【００２５】
比較例２
ＳＲ用ＰＥＧ変性ポリエステルエマルジョン樹脂（有効成分１０％）を固形分１重量％となるように水で希釈調液し、ポリエステル１００％の布を常温で浸漬したあと、絞り率１００％となりように脱水し、１２０℃で３分乾燥し１５０℃で１分キュアした。汚れ離脱性の試験結果を表１に示す。
【００２６】
以上の様に処理された布について、▲１▼加工上がり、▲２▼１０回洗濯後、▲３▼２０回洗濯後、▲３▼加工上がりの布を汚れ離脱性（ＳＲ性）の試験の汚染条件を７０℃で３時間乾燥処理した場合の、それぞれの汚れ離脱性能を測定した結果をそれぞれ表１に示す。
汚れ離脱性（ＳＲ性）の試験は以下のように行った。
ポリエステル試験布にＢ重油を２ｍｌ滴下し、４０℃で１時間乾燥させた後、試験布にバラスト布を加えて１ｋｇとし、洗剤〔アタック、花王（株）製〕２０ｇを用いて、家庭用電気洗濯機で、浴量３０Ｌ、水温２５℃として５分間洗濯し、すすぎ、脱水、乾燥させる。乾燥した試験布の残存シミの状態をＪＩＳ汚染用グレースケールで１〜５等級で測定した。ＪＩＳ汚染用グレースケールにおける１〜５級の内容は以下の通りである。例えば４−５は４級と５級の間を示す。
１級：汚染がひどい
２級：相当にシミが残っているもの
３級：わずかにシミが残っているもの
４級：シミの目立たないもの
５級：汚染がない
【００２７】
【表１】

【００２８】
これらの結果から、一般的なモーターオイルでの汚染に比べ、Ｂ重油での汚染や常温（２５℃）での家庭洗濯といった厳しい条件下において、従来の防汚加工剤（比較例２）の判定級２−３に比べて、本発明の防汚加工剤（実施例１〜４）は汚れ離脱性能判定級が４−５といった優れた汚れ離脱性能であり、また１０回、２０回の洗濯後も判定級４−５という優れた結果を示している。さらに、汚染条件を７０度３時間と厳しくした時の離脱性能は従来の坊汚加工剤（比較例２）は判定級が１と全く性能が見られないのに対して、本発明の防汚加工剤（実施例１〜４）は判定級が３及び４という顕著な差が見られる。
【００２９】
【発明の効果】
本発明にかかる防汚加工剤で処理したポリエステル系繊維は、水洗濯における防汚性能、洗濯耐久性において優れた効果を発揮する。そして、繊維加工における安全性、利便性が高く、低コストで環境にもやさしい加工が実現できる。
本発明によれば、従来の加工にまつわる問題点、すなわち加工の性能、安全性、コスト、環境配慮を考え、該防汚加工剤を用いることによりかかる問題を一挙に解決することが可能である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an antifouling agent for polyester. More specifically, the present invention relates to a hydrophilic antifouling agent for polyester having excellent antifouling property and washing durability even under severe conditions.
[0002]
[Prior art]
Polyester fibers have excellent properties such as excellent dimensional stability, strength, and low wrinkling, and are therefore used in all fields of clothing. Particularly in hospitals, food industries, offices, gas stations, and the like, they have been widely used in recent years as various uniforms.
[0003]
[Problems to be solved by the invention]
Polyester is originally a hydrophobic substance, and is therefore known to have various adverse effects. Poor water absorption and hygroscopicity, oil stains are easy to adhere, dirt once adhered is difficult to remove, easy to recontaminate during washing, furthermore, static electricity is easily generated and dust is easily adhered to various disadvantages. Have.
To carry out antifouling processing on polyester having the above-mentioned properties or to perform dirt removal processing, as a conventionally performed method, a method of treating with a fluorine resin or a method of imparting hydrophilicity to fibers And so on. The method of performing a fluorine resin treatment is a method of imparting water repellency and oil repellency to fibers to prevent the penetration of dirt and exhibit antifouling properties. However, the water absorption, moisture absorption, and antistatic properties of the fibers are further deteriorated. Further, there is a disadvantage that once stained, it is difficult to remove even when washed.
[0004]
On the other hand, the method of imparting hydrophilicity is improved in water absorption, moisture absorption, antistatic properties, etc., but is still insufficient in terms of antifouling properties and washing durability. For example, when processing is performed using a polyester antifouling agent which is currently widely used, if washing is carried out immediately after adhesion of dirt, the antifouling property evaluation method specified in JIS (washing in warm water at 40 ° C.) In the case of (1), excellent antifouling properties are exhibited, but there is a drawback that dirt is extremely difficult to remove if the dirt is left unattended. In addition, there is a problem that sufficient antifouling performance is not exhibited when the evaluation is performed under the washing conditions generally used at home (washing with tap water at room temperature).
An object of the present invention is to impart not only excellent antifouling property and washing durability even under severe environmental conditions, but also excellent processing operability and safety, and hydrophilic antifouling processing using a substance having a small environmental load. An object of the present invention is to provide an agent and a method for processing a polyester fiber using the same.
[0005]
[Means for Solving the Problems]
The present invention relates to a cellulose derivative (A) having a weight-average molecular weight of 1,000 to 1,000,000, in which the hydroxyl groups of cellulose are partially methoxylated, hydroxyethoxylated, and hydroxypropoxylated. The present invention relates to an antifouling agent for polyester fibers containing at least one selected from cellulose graft polymers (B) graft-polymerized with monomers.
The present invention relates to a method for processing a polyester fiber, wherein the antifouling agent for a polyester fiber is adsorbed on the polyester fiber.
The present invention relates to a polyester fiber, wherein the antifouling agent for polyester fiber is fixed to the polyester fiber.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, a cellulose derivative (A) obtained by partially methoxylating, hydroxyethoxylating, or hydroxypropoxylating a hydroxyl group of cellulose is represented by the following formula (A).
[0007]
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[0008]
(R is H, methyl, hydroxyethyl or hydroxypropyl, and at least one R is other than H. n represents a positive number from 1 to 100,000.)
[0009]
Cellulose in which all R is H in the structure of formula (A) is water-insoluble and has no antifouling effect, but becomes water-soluble by methoxylating, hydroxyethoxylating, or hydroxypropoxylating at least one of the hydroxyl groups. It has the structure of the cellulose derivative (A). In the formula (A), n is 1 to 100,000, preferably 200 to 10,000. The weight average molecular weight of the cellulose derivative is preferably 1,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably about 70,000 to 400,000.
In the structure of the cellulose derivative (A), methoxylation, hydroxyethoxylation, and hydroxypropoxylation show almost the same antifouling properties, respectively, but the substitution rate of the hydroxyl group is preferably about 20 to 100% for the antifouling properties. .
[0010]
In order to further improve the antifouling property and washing durability by using a substance having the structure of the cellulose derivative (A), it is preferable to graft a vinyl monomer to the remaining hydroxyl groups of the cellulose derivative (A). The grafting method is a method in which an aqueous solution of the cellulose derivative (A) is acidified with nitric acid, and graft polymerization is performed using diammonium cerium (IV) nitrate. Further, those obtained by performing redox polymerization using a peroxide and a reducing agent such as sodium hydrogen sulfite using the cellulose derivative (A) can also obtain excellent performance.
The vinyl monomers used here include acrylic acid, methacrylic acid, dodecyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, acrylamide, and polyethylene Glycol-modified mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinyl-2-pyrrolidone and the like are exemplified. Above all, acrylic acid, polyethylene glycol-modified mono (meth) acrylate, N-vinyl-2-pyrrolidone and the like are effective for antifouling property and washing durability.
[0011]
In order for the cellulose graft polymer (B) to exhibit good soil release properties and washing durability, the grafting ratio is preferably 10 to 100% based on the weight of the cellulose derivative (A). In order to make the properties of cellulose particularly effective, about 10 to 50% is preferable.
[0012]
The method of fixing the antifouling substance to the fiber material to the fiber is not particularly limited, but in a fiber product manufacturing process, the antifouling substance is solubilized to a desired concentration, and a padding method, a coating method, It is desirable to treat by an exhaustion method, a spray method or the like. It is preferable to add a water-insoluble component (C) as a fiber adsorption aid in the bath exhaustion method.
[0013]
The water-insoluble component (C) is not particularly limited. For example, aromatic hydrocarbons such as limonene, esters, petroleum, and lipophilic surfactants can be used. From the viewpoint, use of limonene or the like is preferable. About 3 to 10% is added to the cellulose derivative (A) or the cellulose graft polymer (B) for emulsification and dispersion. If the amount is too small, the adsorption capacity is insufficient, and if it is too large, the liquid becomes unstable and unevenness occurs.
[0014]
The adhesion amount of the cellulose derivative (A) and the cellulose graft polymer (B) is not particularly limited, but is preferably 0.1 to 1% based on the weight of the fiber material. In addition, other drugs besides the cellulose derivative can be used in combination. The above concomitant drug is not particularly limited because the cellulose derivative is nonionic, and is used as a shrinkage inhibitor such as dimethylol urea, dimethylol dihydroxyethylene urea, dihydroxyethylene urea, and methylol melamine, a fatty acid ester, and an amide-based flexible agent. Agents, antibacterial insecticides, flame retardants, antistatic agents, dyes and the like.
[0015]
Further, when used in combination with polyphenols, acrylics, urethanes, isocyanates, epoxy polymers, dimethylol urea, methylol melamine, etc., the washing durability is remarkably improved.
Polyphenols and the like can impart more excellent washing durability by further use in combination with an insolubilizing substance. Preferred examples of the polyphenols include tannic acid. Examples of the insoluble substance used in combination with polyphenols include polysaccharides and polyvalent metal salts. Examples of the polysaccharide include starch, cellulose, chitin, chitosan and the like. As the polyvalent metal contained in the polyvalent metal salt, for example, zinc, aluminum, magnesium, calcium, chromium, iron, antimony, zirconium, titanium and the like are preferable. Examples of these polyvalent metal salts include aluminum acetate, magnesium acetate, calcium acetate, sodium antimony tartrate, potassium antimony tartrate and the like.
[0016]
The antifouling property of working wear and the like particularly requires washing durability. It is necessary to use an auxiliary agent that does not decrease the soil release property while maintaining the soil resistance of the cellulose derivative (A), the cellulose graft polymer (B), and the like. The antifouling property can be maintained under conditions where the number of washings is small using the cellulose derivative (A) and the cellulose graft polymer (B), but the antifouling property decreases as the number of washings increases to 10 or 20 times. . In order to improve the washing durability, it is necessary to use a crosslinking agent or an auxiliary agent for insolubilizing the cellulose derivative (A) and / or the cellulose graft polymer (B). The crosslinking agent for insolubilizing the cellulose derivative (A) and the cellulose graft polymer (B) is not particularly limited, and examples thereof include a methylolmelamine-based crosslinking agent, an epoxy-based crosslinking agent, and an isocyanate-based crosslinking agent. . According to the results of the above three tests, the methylolmelamine-based crosslinking agent can improve the durability without lowering the antifouling property. However, there are many problems such as the texture becoming too hard and generation of formalin. Other epoxy-based and isocyanate-based cross-linking agents are not preferable because they reduce the antifouling property. From the above results, as a result of examination as an auxiliary agent, it was found that polyphenols were effective as an auxiliary agent for insolubilizing the cellulose derivative (A) and the cellulose graft polymer (B), and without reducing the antifouling property. It has been found to provide laundry durability. Particularly, tannic acid is effective, and significantly improves washing durability. The amount added is 2 to 100%, preferably 10 to 30%, based on the active ingredients of the cellulose derivative (A) and the polymer (B).
[0017]
Furthermore, they found that the use of a metal that chelate with tannic acid improves washing durability significantly. When only tannic acid is used with respect to the cellulose derivative (A) and the cellulose graft polymer (B), the tannic acid reacts with metals in water, particularly iron, and turns yellow.
As the metal capable of chelating with tannic acid, a polyvalent water-soluble metal salt is effective. There are zinc, aluminum, chromium, iron, antimony, zirconium, titanium and the like, but zinc and aluminum metal salts are desirable from the viewpoint of discoloration and the like. The amount added is 10 to 200% effective for the cellulose derivative (A) and the cellulose graft polymer (B), but preferably 20 to 100%. If it is less than 10%, the free portion of tannic acid increases, causing a reaction of a colored metal and causing yellowing. If it exceeds 200%, the antifouling performance is reduced.
[0018]
The polyester fiber in the present invention refers to polyethylene terephthalate, polybutylene terephthalate, or a woven fabric, knitted fabric, nonwoven fabric, or the like containing a polyester fiber of a copolymer containing these as a main component, and a synthetic fiber other than the polyester fiber. Or, a recycled fiber or a natural fiber may be blended or blended.
[0019]
【Example】
Next, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to these.
[0020]
Example 1
Hydroxypropylmethylcellulose, which is a cellulose derivative (A) [Metroze 60SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd.], was diluted with water so as to have a solid content of 1% by weight, and a 100% polyester cloth was immersed at room temperature. Then, it was dehydrated to a squeezing ratio of 100%, dried at 120 ° C. for 3 minutes, and cured at 150 ° C. for 1 minute. Table 1 shows the test results of the soil release property.
(Metroze 60SH-4000)
Methoxylation substitution degree: 1.9
Average number of moles of substituted hydroxypropoxylated: 0.25
Degree of substitution: Average number of hydroxyl groups substituted with methoxy groups per glucose ring unit of cellulose Molar substitution: Average number of hydroxypropoxy or hydroxyethoxy groups added per glucose ring unit of cellulose Average number of hydroxyl groups 28-30% for methoxy groups, 7-12% for hydroxypropoxy groups
[0021]
Example 2
An emulsion of hydroxypropylmethylcellulose, which is a cellulose derivative (A) (Metroze 60SH-4000), and D-limonene (manufactured by Yasuhara Chemical Co., Ltd.) was 2.5% o. w. f, Adsorption to fibers by treatment in a bath at a bath ratio of 1:20 at 90 ° C. for 10 minutes. Next, a mixed solution of a 0.2% aqueous solution of tannic acid and a 10% aqueous solution of aluminum acetate, which are polyphenols, was added, dehydrated, dried at 120 ° C. for 3 minutes, and cured at 150 ° C. Table 1 shows the test results of the soil release property.
[0022]
Example 3
Cellulose derivative (A) [Metroose SM-400, manufactured by Shin-Etsu Chemical Co., Ltd.] 15 g of methylcellulose was dissolved in water, 3 g of acrylic acid and 3 g of methoxypolyethylene glycol (23 mol added) methacrylate were dissolved and replaced with nitrogen. Thereafter, a solution prepared by dissolving 0.1 cc of nitric acid and 0.1 g of 2-ammonium cerium (IV) nitrate in water was added thereto, followed by graft polymerization at 40 ° C. for 1 hour to obtain a cellulose graft polymer (B). After dissolving 0.25 g of this polymer (B), 0.1 g of tannic acid, and 0.3 g of aluminum acetate in water to prepare a mixed solution of 100 g, a 100% polyester cloth is immersed at room temperature to obtain a squeezing ratio of 100%. Dehydrated as follows. Then, it dried at 120 degreeC for 3 minutes, and cured at 150 degreeC for 1 minute. Table 1 shows the test results of the soil release property.
[0023]
Example 4
Cellulose derivative (A) [Metroose SM-400, manufactured by Shin-Etsu Chemical Co., Ltd.] 15 g of methylcellulose was dissolved in water, 3 g of acrylic acid and 3 g of methoxypolyethylene glycol (23 mol added) methacrylate were dissolved and replaced with nitrogen. Thereafter, polymerization was carried out at 45 ° C. for 4 hours using 0.2 g of ammonium persulfate and 0.2 g of sodium hydrogen sulfite as a catalyst to obtain a cellulose graft polymer (B). After dissolving 0.25 g of this polymer (B), 0.1 g of tannic acid, and 0.3 g of aluminum acetate in water to prepare a mixed solution of 100 g, a 100% polyester cloth is immersed at room temperature to obtain a squeezing ratio of 100%. Dehydrated as follows. Then, it dried at 120 degreeC for 3 minutes, and cured at 150 degreeC for 1 minute. Table 1 shows the test results of the soil release property.
(Metroze SM-400)
Methoxylation substitution degree: 1.9
Degree of substitution: average number of hydroxyl groups substituted with methoxy groups per glucose ring unit of cellulose methoxy groups 27.5% to 31.5%
[0024]
Comparative Example 1
The procedure of the following SR test was performed on the untreated 100% polyester cloth. Table 1 shows the test results of the soil release property.
[0025]
Comparative Example 2
A PEG-modified polyester emulsion resin for SR (active ingredient 10%) was diluted with water so as to have a solid content of 1% by weight, and a 100% polyester cloth was immersed at room temperature, and then dehydrated to a squeezing rate of 100%. Then, it was dried at 120 ° C. for 3 minutes and cured at 150 ° C. for 1 minute. Table 1 shows the test results of the soil release property.
[0026]
For the cloth treated as described above, (1) after finishing the processing, (2) after washing 10 times, (3) after washing 20 times, and (3) remove the finished cloth from the test for soil release (SR property). Table 1 shows the results of measuring the soil release performance when the soiling conditions were dried at 70 ° C. for 3 hours.
The test of the soil release property (SR property) was performed as follows.
After dropping 2 ml of heavy oil B onto the polyester test cloth and drying it at 40 ° C. for 1 hour, add ballast cloth to the test cloth to make 1 kg, and use 20 g of detergent (Attack, manufactured by Kao Corporation) for household electric power. Wash in a washing machine for 5 minutes at a bath volume of 30 L and a water temperature of 25 ° C., rinse, dehydrate and dry. The state of the remaining stain on the dried test cloth was measured on a scale of 1 to 5 using a gray scale for JIS contamination. The contents of the first to fifth grades in the gray scale for JIS contamination are as follows. For example, 4-5 indicates between quaternary and quintic.
First grade: severely contaminated Second grade: considerable stain remaining Third grade: slight stain remaining Fourth grade: less noticeable stain fifth grade: no contamination
[Table 1]

[0028]
From these results, it was found that the conventional antifouling agent (Comparative Example 2) was classified under severe conditions such as contamination with heavy oil B and home washing at room temperature (25 ° C.) as compared with contamination with general motor oil. Compared with 2-3, the antifouling agent of the present invention (Examples 1 to 4) has excellent dirt release performance such as a dirt release performance judgment class of 4-5, and even after washing 10 times and 20 times. It shows an excellent result of judgment class 4-5. Furthermore, the release performance when the contamination conditions were strictly set to 70 ° C. for 3 hours showed that the conventional soil release agent (Comparative Example 2) had a judgment grade of 1 and showed no performance. The processing agents (Examples 1 to 4) have a remarkable difference of 3 and 4 in the judgment grade.
[0029]
【The invention's effect】
The polyester fiber treated with the antifouling agent according to the present invention exhibits excellent effects in antifouling performance in water washing and washing durability. In addition, safety and convenience in fiber processing are high, and low-cost and environmentally friendly processing can be realized.
According to the present invention, it is possible to solve the problems associated with the conventional processing, that is, the performance, safety, cost, and environmental considerations of the processing, and to use the antifouling agent at once to solve such problems.

Claims (5)

Graft polymerization of a cellulose derivative (A) having a weight average molecular weight of 1,000 to 1,000,000 by partially methoxylating, hydroxyethoxylating, or hydroxypropoxylating a hydroxyl group of cellulose, and a residual hydroxyl group of (A) with an acrylic monomer. An antifouling agent for polyester fibers containing at least one selected from the cellulose graft polymers (B). The antifouling agent for polyester fibers according to claim 1, further comprising at least one selected from aromatic hydrocarbons, esters, petroleums, and lipophilic surfactants. 3. The antifouling agent for polyester fibers according to claim 1, further comprising a polyphenol. A method for processing polyester fiber, comprising adsorbing the antifouling agent for polyester fiber according to claim 1 to polyester fiber. 4. A polyester fiber, wherein the polyester fiber antifouling agent according to claim 1 is fixed to the polyester fiber.