JP3606700B2 - How to prevent yellowing of textile products - Google Patents
How to prevent yellowing of textile products Download PDFInfo
- Publication number
- JP3606700B2 JP3606700B2 JP7806697A JP7806697A JP3606700B2 JP 3606700 B2 JP3606700 B2 JP 3606700B2 JP 7806697 A JP7806697 A JP 7806697A JP 7806697 A JP7806697 A JP 7806697A JP 3606700 B2 JP3606700 B2 JP 3606700B2
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- Prior art keywords
- acid
- yellowing
- water
- bht
- oil repellent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、繊維製品の黄変を防止する加工方法に関する。特に、本発明は、繊維製品を撥水撥油加工する際に、撥水撥油の性能を損なわずに繊維製品の黄変を防止することのできる加工方法に関する。
【０００２】
【従来の技術】
繊維製品の包装材料などに含有される２，６−ジ−ｔ−ブチル−ｐ−クレゾール（以下、ＢＨＴと略す）を代表とするフェノール系酸化防止剤や段ボール中に存在するバニリンが原因で、包装された繊維製品が黄変する事故は過去に多く報告されており、製造物責任法（ＰＬ法）が施行された今日においてはこの防止策に関心が高まってきている。ＢＨＴによる黄変は、まず包装材料中のＢＨＴが経時で昇華し、繊維製品に付着し、このＢＨＴが酸化窒素ガスによるニトロ化などによって黄変物質に変化するために生じるとされている。ＢＨＴによる黄変の機構はＷａｇｎｅｒらによって下記のように説明されている（Ｍｅｌｌｉａｎｄ Ｔｅｘｔｉｌｂｅｒ．， ６３，２９１ （１９８２））。
【０００３】
【化１】
繊維製品の加工では、ＢＨＴや酸化窒素ガスの吸着を促進するといわれる柔軟剤、帯電防止加工剤、防汚加工剤、油剤などが使用されている。よって、特に繊維製品の仕上工程では、酸化窒素ガスによるＢＨＴの黄変を充分に考慮する必要があり、繊維製品をリンゴ酸やクエン酸などの不揮発性の酸で処理することにより、ＢＨＴのニトロ化反応を抑制し、またニトロ化して生成したニトロフェノールの黄色化を抑制している。しかし、酸化窒素ガスによるＢＨＴの黄変を防止する目的で不揮発性の酸で繊維製品を処理するという方法を採ると、フッ素系撥水撥油剤などにより撥水撥油加工する際には、撥水撥油の性能が低下するという問題が生じる。
【０００５】
その他のフェノール系酸化防止剤やバニリンについても同様に酸化窒素ガスによる繊維製品の黄変が認められ、これらの黄変防止の対策もリンゴ酸やクエン酸などの不揮発性の酸によって行われているため、撥水撥油加工を施した繊維製品の場合には、ＢＨＴの場合と同様の問題が生じる。
【０００６】
【発明が解決しようとする課題】
本発明は、撥水撥油加工を施した繊維製品に対し、その本来の撥水撥油の性能を低下させることなく、ＢＨＴを代表とするフェノール系酸化防止剤やバニリンと酸化窒素ガスに起因する黄変を防止することのできる加工方法を提供することを目的とするものである。
【０００７】
【課題を解決するための手段】
本発明者らは、上記課題を解決するため鋭意検討の結果、特定の酸のアンモニウム塩を用いることにより、撥水撥油の性能を維持し、黄変も防止できることを見出し、この知見に基づいて本発明を完成させた。
すなわち、本発明は、フッ素系撥水撥油剤で繊維製品を処理するに際して、１２０℃以上の沸点を有する不揮発性酸のアンモニウム塩から選ばれる少なくとも１種を、繊維製品に対して０．０１〜０．５重量％の量で付与することを特徴とする繊維製品の酸化窒素ガスに起因する黄変の防止加工方法を提供するものである。
【０００８】
【発明の実施の形態】
本発明に用いられるフッ素系撥水撥油剤としては、パーフルオロアルキルアクリレート共重合物を含有するフッ素系撥水撥油剤がある。これらは、例えば、ＮＫガードシリーズ〔日華化学（株）製〕、アサヒガードシリーズ〔明成化学工業（株）製〕、ディックガードシリーズ〔大日本インキ（株）製〕などの市販商品として入手することができる。
【０００９】
本発明に用いられる１２０℃以上の沸点を有する不揮発性酸のアンモニウム塩としては、例えば、プロピオン酸、酪酸、吉草酸、シュウ酸、マロン酸、コハク酸、グルタル酸、リンゴ酸、酒石酸、クエン酸、グルコン酸、アスコルビン酸などの有機酸のアンモニウム塩、リン酸、ピロリン酸、メタリン酸、ホウ酸、メタホウ酸、硫酸などの無機酸のアンモニウム塩や下記一般式（１）〜（３）で表されるリン系有機酸のアンモニウム塩などが挙げられる。
【００１０】
【化２】
〔式中、Ｘはそれぞれ水素原子またはＰＯ（ＯＭ）２ を表す。ただし、Ｘのうちの少なくとも１つはＰＯ（ＯＭ）２ である。（Ｍはそれぞれ水素原子またはＮＨ４ を表す。ただし、Ｍのうちの少なくとも１つはＮＨ４ である。）〕
【００１２】
【化３】
（式中、ｎは０または１〜３の整数を表し、Ｍはそれぞれ水素原子またはＮＨ４ を表す。ただし、Ｍのうちの少なくとも１つはＮＨ４ である。）
【００１４】
【化４】
〔式中、Ｒは水素原子または炭素数１〜５のアルキル基を表し、Ｚはそれぞれ水素原子またはＰＯ（ＯＭ）２ を表す。ただし、Ｚのうちの少なくとも１つはＰＯ（ＯＭ）２ である。（Ｍはそれぞれ水素原子またはＮＨ４ を表す。ただし、Ｍのうちの少なくとも１つはＮＨ４ である。）〕
本発明に用いられる繊維製品としては、ポリエステル繊維、ポリアミド繊維、アクリル繊維、ウレタン繊維、アセテート繊維などの合成繊維、レーヨンなどの再生繊維、綿、ウール、絹などの天然繊維およびこれらの複合繊維からなる繊維製品が挙げられ、その繊維の形態としては糸状、不織布状、織物状、編物状などのいずれの形態であってもよい。
【００１６】
フッ素系撥水撥油剤で繊維製品を処理する場合、通常次の様な工程が採用される。処理を施そうとする繊維製品によりその処理条件も異なるが、例えば、フッ素系撥水撥油剤含有処理液をパッディング処理、スプレー処理、浸漬処理などの方法で付与し、その後１００℃前後で乾燥の後、１５０℃〜１８０℃で１〜２分間熱セットを行う。本発明における、１２０℃以上の沸点を有する不揮発性酸のアンモニウム塩を繊維製品に対して０．０１〜０．２重量％の量で付与する方法としては、上記のフッ素系撥水撥油剤含有処理液に不揮発性酸のアンモニウム塩を併用して付与するか、あるいは上記の様なフッ素系撥水撥油処理の前に予め不揮発性酸のアンモニウム塩の処理液で処理することにより付与しておく方法が挙げられる。
【００１７】
従来より行われていた不揮発性酸による処理法の場合には、フッ素系撥水撥油剤の処理浴ｐＨがかなり酸性サイドにスライドする。その結果、撥水撥油剤のエマルジョン粒子のゼータ電位が変化してしまい、本来の性能に障害が生じていた。しかし、不揮発性酸のアンモニウム塩を使用することで、撥水撥油剤の処理浴のｐＨ変化が小さくなり、撥水撥油性への影響を少なくすることができる。また、処理された繊維製品を乾燥し、セットするときに、アンモニアの一部が揮発することで、繊維製品の生地ｐＨが酸性サイドに保たれ、黄変防止効果が得られるものと推定される。
【００１８】
【実施例】
以下、本願を実施例によりさらに説明するが、本願はこれらの実施例により何ら限定されるものではない。
下記の処理条件において、処理浴組成の添加剤を表１のように変えて、撥水撥油、帯電防止および、防汚の複合機能加工を行い、下記評価方法による評価を行った。得られた結果を表１に記す。
【００１９】
１．予め仕上加工布を０．０５ｇのＢＨＴを共存させた密閉系内に５０℃で２４放置して、ＢＨＴを付着させたもの試験布として使用した。
【００２２】
２．黄変度合いは、測色機〔オートマティックカラーアイ マクベス２０２０（マクベス社製）〕にて、ハンターイエローインデックス（Ｈ．Ｙ．Ｉ．）を測定し、比較した。
【００２３】
【表１】
【発明の効果】
本発明によれば、撥水撥油性能を低下させることなく、ＢＨＴに代表されるフェノール系酸化防止剤と酸化窒素ガスによる黄変を防止できる繊維製品を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a processing method for preventing yellowing of a textile product. In particular, the present invention relates to a processing method capable of preventing yellowing of a fiber product without impairing the performance of the water / oil repellent when the fiber product is subjected to water / oil repellent finish.
[0002]
[Prior art]
Due to the phenolic antioxidants such as 2,6-di-t-butyl-p-cresol (hereinafter abbreviated as BHT) contained in textile packaging materials and vanillin present in cardboard, Many accidents in which the packaged textile products turn yellow have been reported in the past, and interest in this preventive measure is increasing today when the Product Liability Act (PL Act) was enforced. Yellowing due to BHT is said to occur because BHT in the packaging material first sublimes over time and adheres to the textile product, and this BHT changes to a yellowing substance by nitration with nitric oxide gas or the like. The mechanism of yellowing by BHT is explained by Wagner et al. (Melliand Textilber., 63, 291 (1982)).
[0003]
[Chemical 1]
In the processing of textile products, softeners, antistatic processing agents, antifouling processing agents, oils, etc., which are said to promote the adsorption of BHT and nitric oxide gas, are used. Therefore, particularly in the finishing process of textile products, it is necessary to fully consider the yellowing of BHT caused by nitric oxide gas. By treating textile products with non-volatile acids such as malic acid and citric acid, the nitro of BHT It suppresses the nitrification reaction, and also suppresses the yellowing of nitrophenol produced by nitration. However, if the fiber product is treated with a non-volatile acid for the purpose of preventing yellowing of BHT due to nitrogen oxide gas, the water- and oil-repellent processing with a fluorine-based water- and oil-repellent agent or the like is used. There arises a problem that the performance of water / oil repellency is lowered.
[0005]
Similarly, other phenolic antioxidants and vanillin have yellowing of textiles caused by nitric oxide gas, and measures to prevent these yellowing are also implemented by non-volatile acids such as malic acid and citric acid. Therefore, in the case of a fiber product subjected to water / oil repellent finishing, the same problem as in the case of BHT occurs.
[0006]
[Problems to be solved by the invention]
The present invention is caused by phenolic antioxidants such as BHT, vanillin and nitrogen oxide gas, without reducing the performance of the original water and oil repellent for fiber products subjected to water and oil repellent processing. An object of the present invention is to provide a processing method capable of preventing yellowing.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that by using an ammonium salt of a specific acid, it is possible to maintain the performance of water and oil repellency and prevent yellowing, and based on this finding The present invention has been completed.
That is, in the present invention, when treating a textile product with a fluorine-based water and oil repellent, at least one selected from ammonium salts of nonvolatile acids having a boiling point of 120 ° C. or higher is 0.01 to there is provided a yellowing prevention processing method due to nitric oxide gas textile product characterized by imparting an amount of 0.5 wt%.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the fluorine-based water / oil repellent used in the present invention include a fluorine-based water / oil repellent containing a perfluoroalkyl acrylate copolymer. These are obtained as commercial products such as NK guard series [manufactured by Nikka Chemical Co., Ltd.], Asahi guard series [manufactured by Meisei Chemical Co., Ltd.], dick guard series [manufactured by Dainippon Ink Co., Ltd.], etc. be able to.
[0009]
Examples of the ammonium salt of a non-volatile acid having a boiling point of 120 ° C. or higher used in the present invention include propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, malic acid, tartaric acid, and citric acid. , Ammonium salts of organic acids such as gluconic acid and ascorbic acid, ammonium salts of inorganic acids such as phosphoric acid, pyrophosphoric acid, metaphosphoric acid, boric acid, metaboric acid, sulfuric acid and the following general formulas (1) to (3) And ammonium salts of phosphorous organic acids.
[0010]
[Chemical 2]
[Wherein, X represents a hydrogen atom or PO (OM) 2 , respectively. However, at least one of X is PO (OM) 2 . (M represents a hydrogen atom or NH 4 , respectively, provided that at least one of M is NH 4. )]
[0012]
[Chemical 3]
(In the formula, n represents 0 or an integer of 1 to 3, and M represents a hydrogen atom or NH 4 , respectively, provided that at least one of M is NH 4. )
[0014]
[Formula 4]
[Wherein, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z represents a hydrogen atom or PO (OM) 2 , respectively. However, at least one of Z is PO (OM) 2 . (M represents a hydrogen atom or NH 4 , respectively, provided that at least one of M is NH 4. )]
The fiber products used in the present invention include synthetic fibers such as polyester fibers, polyamide fibers, acrylic fibers, urethane fibers and acetate fibers, recycled fibers such as rayon, natural fibers such as cotton, wool and silk, and composite fibers thereof. The form of the fiber may be any form such as a thread form, a non-woven form, a woven form, and a knitted form.
[0016]
When a textile product is treated with a fluorine-based water / oil repellent, the following steps are usually employed. The treatment conditions differ depending on the textile product to be treated. For example, a fluorine-containing water / oil repellent-containing treatment solution is applied by a method such as padding treatment, spray treatment, immersion treatment, and then dried at around 100 ° C. After that, heat setting is performed at 150 ° C. to 180 ° C. for 1 to 2 minutes. In the present invention, as a method of applying a non-volatile acid ammonium salt having a boiling point of 120 ° C. or higher to a fiber product in an amount of 0.01 to 0.2% by weight, the above-mentioned fluorine-based water and oil repellent is contained. Apply in combination with ammonium salt of non-volatile acid to the treatment liquid, or by pre-treatment with non-volatile acid ammonium salt treatment liquid before fluorine-based water / oil repellent treatment as described above. The method of putting is mentioned.
[0017]
In the case of a conventional treatment method using a non-volatile acid, the treatment bath pH of the fluorine-based water / oil repellent slides to the very acidic side. As a result, the zeta potential of the emulsion particles of the water / oil repellent agent was changed, and the original performance was hindered. However, by using an ammonium salt of a non-volatile acid, the pH change of the water / oil repellent treatment bath is reduced, and the influence on the water / oil repellency can be reduced. In addition, when the treated fiber product is dried and set, it is estimated that a part of ammonia is volatilized, so that the fabric pH of the fiber product is maintained on the acidic side, and the yellowing prevention effect is obtained. .
[0018]
【Example】
Hereinafter, although this application is further demonstrated by an Example, this application is not limited at all by these Examples.
Under the following treatment conditions, the additive of the treatment bath composition was changed as shown in Table 1, and water / oil / oil repellency, antistatic and antifouling combined function processing was performed, and the evaluation by the following evaluation methods was performed. The obtained results are shown in Table 1.
[0019]
[0022]
2. The degree of yellowing was measured by comparing the Hunter Yellow Index (HYI) with a colorimeter [Automatic Color Eye Macbeth 2020 (manufactured by Macbeth)].
[0023]
[Table 1]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the textiles which can prevent yellowing by the phenolic antioxidant represented by BHT and nitrogen oxide gas can be obtained, without reducing water / oil repellency performance.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7806697A JP3606700B2 (en) | 1997-03-28 | 1997-03-28 | How to prevent yellowing of textile products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7806697A JP3606700B2 (en) | 1997-03-28 | 1997-03-28 | How to prevent yellowing of textile products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10273878A JPH10273878A (en) | 1998-10-13 |
| JP3606700B2 true JP3606700B2 (en) | 2005-01-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7806697A Expired - Fee Related JP3606700B2 (en) | 1997-03-28 | 1997-03-28 | How to prevent yellowing of textile products |
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| Country | Link |
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| JP (1) | JP3606700B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103757901B (en) * | 2013-12-31 | 2015-10-28 | 苏州市轩德纺织科技有限公司 | Sweater finishing agent of a kind of water and oil repellant and preparation method thereof |
| JP6427113B2 (en) | 2014-01-16 | 2018-11-21 | 高砂香料工業株式会社 | Fragrance composition |
| KR101958578B1 (en) * | 2017-12-29 | 2019-03-14 | 효성티앤씨 주식회사 | Method of manufacturing white dope-dyed polyester fiber |
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1997
- 1997-03-28 JP JP7806697A patent/JP3606700B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH10273878A (en) | 1998-10-13 |
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